Review

Addressing the Apparent Controversies Between the Contact

Angle-Based Models for Estimation of Surface Free Energy:
A Critical Review
Georgi As. Georgiev 1, *, Stanislav Baluschev 1,2 , Petar Eftimov 3 , Mihaela Bacheva 1 and Katharina Landfester 2

1 Department of Optics and Spectroscopy, Faculty of Physics, Sofia University “St. Kliment Ohridski”,
1164 Sofia, Bulgaria; [email protected] (S.B.); [email protected] (M.B.)
2 Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany;
[email protected]
3 Department of Cell and Developmental Biology, Faculty of Biology, Sofia University “St. Kliment Ohridski”,
1164 Sofia, Bulgaria; [email protected]
* Correspondence: [email protected]

Abstract: The most popular contact angle (CA)-based approaches for determination of solid surface
free energy (SFE) are considered: (i) single liquid methods, mainly of Neumann and Chibowski, (ii) the
multiple liquids approach of Owens–Wendt–Rabel–Kaelble (OWRK), and (iii) van Oss-Chaudhury–Good
(vOCG) acid–base model. Evaluations based on Neumann and Chibowski models agree between each
other. Under the assumption of equilibrium “wet wetting” (i.e., presence of saturated precursor film
ahead of the drop), the model of Chibowski transforms in Lipatov’s interfacial equilibrium rule, i.e.,
the Antonow rule derived for the ternary point solid–liquid–gas. Very good agreement is observed
between single and multiple liquids models where OWRK/vOCG values can be viewed as a mean
of the individual SFE adopted by the solid with each of the wetting probes. Both approaches (single
and multiple liquids) can be used in conjunction to evaluate SFE dispersion and polar components
and to elucidate hydrophobicity and hydrophilicity. The implementation of apparently fully non-polar
liquids (diiodomethane, bromonaphthalene) in OWRK and vOCG is practically and theoretically suspect.
Citation: Georgiev, G.A.; Baluschev, CA-based estimates represent apparent SFE determined by the interactions of both the solid surface
S.; Eftimov, P.; Bacheva, M.; and the probing liquid, which are very useful to elucidate the energy, chemistry and dynamics of the
Landfester, K. Addressing the solid surface.
Apparent Controversies Between the
Contact Angle-Based Models for Keywords: surface free energy; contact angle models; single and multiple probe liquid methods
Estimation of Surface Free Energy: A
Critical Review. Colloids Interfaces
2024, 8, 62. https://doi.org/10.3390/
colloids8060062 1. Introduction
Academic Editor: Georgi G. Gochev Surface free energy (SFE) is among the most important characteristics of solid materials
implemented in industry and medicine such as polymers, ceramics, implants, etc. [1–3].
Received: 14 October 2024
This is because the recognition of SFE allows, among other things, (i) the elucidation of
Revised: 8 November 2024
Accepted: 13 November 2024
what type of functional groups (dipoles, donors or acceptors of H-bonds) are present at the
Published: 18 November 2024
solid surface (crucial information, as surface and bulk compositions differ even for simple
polymers) and (ii) the prediction of the (bio)adhesion of coatings and (bio)materials to cells,
tissues, implants and other relevant interfaces [4–8].
The most popular methods for SFE determination are based on the measurement of
Copyright: © 2024 by the authors. the contact angle (CA) between a fluid probe (water and other liquids with diverse polar
Licensee MDPI, Basel, Switzerland. and nonpolar as well as acid/base properties) and the solid surface of interest (Figure 1).
This article is an open access article Although other methods for SFE determination exist (inverse gas chromatography, calorimetric,
distributed under the terms and spectroscopic, ellipsometric, charge transfer, etc.), CA-based approaches are dominant due to
conditions of the Creative Commons
their affordability and relative simplicity, and also, CA-based models remain the most suitable
Attribution (CC BY) license (https://
available tool “for determining the individual interactive force components of the solid surface
creativecommons.org/licenses/by/
such as the dispersion, polar, hydrogen bonding” [4].
4.0/).

Colloids Interfaces 2024, 8, 62. https://doi.org/10.3390/colloids8060062 https://www.mdpi.com/journal/colloids

Colloids Interfaces 2024, 8, x FOR PEER REVIEW 2 of 38

Colloids Interfaces 2024, 8, 62 remain the most suitable available tool “for determining the individual interactive 2force
of 36
components of the solid surface such as the dispersion, polar, hydrogen bonding” [4].

Figure 1.
Figure 1. The contact angle of a liquid
liquid drop
drop onon solid
solid surface
surface can
can (a)
(a) adopt
adopt variety
variety of
of metastable
metastable
values;however,
values; however,a amost
most stable
stable value
value exists
exists that that approximates
approximates the equilibrium
the equilibrium contactcontact
angle ofangle of
Young.
Young. This value can be accessed via sessile drop (b) or from the advancing and receding
This value can be accessed via sessile drop (b) or from the advancing and receding contact angles of contact
angles of a sliding drop (c) via the equation of Tadmore (d). While most models assume “dry wet-
a sliding drop (c) via the equation of Tadmore (d). While most models assume “dry wetting”, the
ting”, the Frumkin–Derjaguin theory (e) by default assumes “wet wetting” where very thin precur-
Frumkin–Derjaguin theory (e) by default assumes “wet wetting” where very thin precursor film is
sor film is present ahead of the drop.
present ahead of the drop.

IfIfvapor
vaporadsorption
adsorption occurs
occurs at at
thethe solid
solid surface
surface (so-called
(so-called “wet“wet wetting”),
wetting”), then
then the the bal-
balance of
ance of interfacial tensions that determines the contact angle can be described
interfacial tensions that determines the contact angle can be described as (Figure 1) [9–11]as (Figure
1) [9–11]
γs − πe = γsl + γlv cos θ, (1)
𝛾 − 𝜋 = 𝛾 + 𝛾 cos 𝜃, (1)
Here,
Here,θθisisthe theequilibrium
equilibrium (Young)
(Young) contact
contactangle, γlv is𝛾 theissurface
angle, tension
the surface of the probe
tension of the
liquid from which the sessile droplet
probe liquid from which the sessile droplet is formed,is formed, π e is the 𝜋 is the spreading (or film) pres-
spreading (or film) pressure due
to vapor adsorption,
sure due to vapor adsorption, γ sv is the 𝛾 is the solid vapor surface tension
solid vapor surface tension and γ s and 𝛾 s(where
(where γ = γ sv 𝛾πe=
+ )
𝛾 the
is + 𝜋surface
) is thetension
surface of the solid
tension of theinsolid
equilibrium with its
in equilibrium own
with itsvapor
own vapor without stressstress
without [11].
It is customary
[11]. It is customary for thefor surface
the surfacetension
tensionof the solid
of the solid to tobebedenoted
denotedasassurface
surfacefree
free energy
energy
(although,
(although,as aswill
willbebediscussed
discussed further,
further,thisthis
might be abe
might bitainaccurate
bit inaccuratefromfroma thermodynamic
a thermody-
point of view for CA-based estimates). Nowadays, it
namic point of view for CA-based estimates). Nowadays, it is commonly (although is commonly (although not without not
debate) [12,13] accepted that for CA > 10 ◦ , the contribution of the spreading pressure is
without debate) [12,13] accepted that for CA > 10°, the contribution of the spreading pres-
very
sure low
is veryandlowcanandbe neglected (so-called
can be neglected “dry wetting”
(so-called [9,14–16]),
“dry wetting” which leads
[9,14–16]), which to γleads
s = γsvto
(i.e., γ
γs = γsv becomes
sv (i.e., 𝛾
a measure for the SFE of the solid) and to the
becomes a measure for the SFE of the solid) and to the classic Young classic Young equation
(Figure
equation 1b)(Figure 1b)
γsv = γsl + γlv cos θ (2)
𝛾 = 𝛾 + 𝛾 cos 𝜃 (2)
The base assumption in these equations is that θ is the so-called thermodynamic contact
angleThe base assumption
of Young, characteristic in these equations
for the lowest isenergy
that θ state
is the of
so-called thermodynamic
a chemically homogeneous con-
tact angle of Young, characteristic for the lowest energy state
absolutely smooth surface [10,11]. Of course, real solid surfaces are not like that, but it wasof a chemically homogene-
ous absolutelythat
demonstrated smooth surface [10,11].
if the chemical groups Of arecourse,
uniformly realdistributed
solid surfacesacross are not
the like that,
surface but
and the
it wassurface
mean demonstrated
roughness that if the
is less thanchemical
500 nm,groups
the Young areequation
uniformly candistributed across the
be applied [17,18]. sur-
If there
face
is and the
strongly mean surface
pronounced roughness
chemical is less thanheterogeneity,
or topographical 500 nm, the Young then theequation
equationcan be ap-
of Young
plied [17,18].
cannot be directlyIf there is strongly
implemented, and pronounced chemical
these peculiarities or surface
of the topographical
must beheterogeneity,
accounted for
then
in the equation
advance of Young
via the models cannot be directly
of Cassie–Baxter implemented,
or Wenzel [19,20]. The and these peculiarities
application of the
of these models
is reviewed in multiple publications and is beyond the scope of the current analysis.
In the equation of Young, γlv and θ are readily experimentally determinable, but γsl
cannot be measured. Thus, as there are two unknowns (γsl and γsv ) in it, Equation (2)
Colloids Interfaces 2024, 8, 62 3 of 36

cannot be directly solved for γsv . Therefore, the equation of Young is usually combined
with the equation of Dupre for the work of adhesion Wa between the liquid drop and the
solid (i.e., the work necessary to separate the liquid from the solid to give both solid and
liquid phases in equilibrium with the vapor phase):

Wa = γsv + γlv − γsl (3)

This leads to the equation of Young–Dupre:

Wa = γlv (1 + cos θ) (4)

so that the work of adhesion is only given as a function of the liquid surface tension and
the contact angle [14–16]. As the work of adhesion is directly measurable, the analysis of
its relationship with γsv allows us to calculate the value of γsv (which equals γs if “dry
wetting” is assumed) and eventually the underlying contributions of the intermolecular
interactions to it.
In the current review, we will focus on the most commonly used models for CA-based
estimation of SFE, as already identified in the recent literature: (i) single probe liquid (fre-
quently water) methods with major focus on the approaches developed by Neumann [21]
and Chibowski [22], (ii) the multiple liquids approach developed by Owens–Wendt–Rabel–
Kaelble (OWRK) [23], and (iii) the multiple probe liquids acid–base approach of van
Oss–Chaudhury–Good (vOCG) [24]. We will not particularly consider the mathemati-
cal derivation of the equations, as this information is already available to the interested
reader in papers devoted specifically to Neumann equation of state (EoS) [21], OWRK [25],
vOCG [24,26]. A number of recent studies were also dedicated to the challenges associated
with the numerical accuracy and statistical consistency of the models originating from the
use of best fit parameters in EoS and the uncertainty of the surface tension components
ascribed to the wetting liquids in OWRK and especially in vOCG [27–34] (these issues will
be concisely mentioned by us as well). Instead, we will focus on (i) the base assumptions
behind the approaches, (ii) some key controversies (apparent or real) between the models,
(iii) recent (and some well-forgotten) developments in the evaluation of the intermolecu-
lar interaction contributions to the value of SFE which might facilitate the application of
CA-based techniques, as well as (iv) analysis of the consistency of the results obtained by
the various models (i.e., of the models’ mutual compatibility). Also, a brief overview will
be performed of the key equations, which might be used to predict the adhesion between
two (bio) interfaces interacting through aqueous (or other) solution utilizing the SFE values
calculated with the CA-based models.

2. Models for Determination of SFE

2.1. Models That Measure SFE from Single Liquid Contact Angle
The major advantage of the methods that utilize a single probe liquid is that they
are easier to perform experimentally and are the least laborious. A major criticism of
these approaches is that it is considered that (i) no information about the surface energy
components (dispersive, hydrogen bonding, etc.) can be derived from the SFE values
obtained in this manner and that (ii) it is thought to be complicated to compare SFE
estimates from single liquid studies to the ones calculated via multiple probe liquid models
(OWRK and vOCG). In this and in the subsequent sections, we will try to show that these
criticisms are to a significant extent unfounded.

2.1.1. Neumann Equation of State

The work of adhesion has been expressed by Good and Girifalco (1960) [35] in the
same way as the Hamaker constant via the Berthelot’s geometric mean combining rule
of the surface tensions, an approach adopted not only by the Neumann Equation of State
Colloids Interfaces 2024, 8, 62 4 of 36

(EoS) but also by most of the models to be reviewed further, including the ones of OWRK
and vOCG:
√
Wa = γlv (1 + cos θ) = 2ϕSL γsv γlv (5)
where Φ is the Girifalco–Good interaction parameter, 0.5 < Φ < 1.15 (Φ decreases further
away from unity with the increase in the contact angle between the liquid and the solid)
Good and Girifalco provided analytical expression for the calculation of Φ, which
requires knowledge of the molar volume, molecular radii and the London constants (or
corresponding) for all types of intermolecular forces (dispersive, polar, acid–base, etc.) both
for the liquid and for the solid [36]. Such information is often available for pure liquids;
however, it is very challenging to obtain for most solids and attempts to achieve this have
frequently resulted in misleading results. Therefore, it was realized from the early stages
that it is worth looking for a way to calculate Φ on the basis of reliable and easy-to-obtain
experimental data.
CA-based models which utilize single probe liquid assume that to elucidate the value
of Φ (and of SFE), it is sufficient to know only the surface tension of the probe liquid and the
equilibrium contact angle between the h liquid and the isolid. Neumann assumed that Φ can
2
be approximated as − β(γl −γs ) or as 1 − β 1 (γl − γ5 )2 , which resulted in the derivation of
equations of state [37]. r
γsv − β(γlv −γsv )2
cos θγ = −1 + 2 (6)
γlv
and r
γsv  
cos θγ = −1 + 2 1 − β 1 (γlv − γsv )2 (7)
γlv
(As frequently specific meanings were coined for them, here and further, the notation
for SFE/solid surface tension, γs or γsv , is intentionally preserved as originally chosen by
the authors of the considered equations and models.)
To determine the value of γsv and of the two parameters β and β1 , the equations were
fitted to contact angle data on solids with a diverse range of SFE presented in the format
γlv × cos(θ) vs. γlv and the following best fit estimates were produced [37]:
- β = 0.0001247 (95% confidence interval: 0.000114–0.000133) (m2 /mJ)2 ;
- β1 = 0.0001057 (95% confidence interval: 9.70 × 10−5 –0.000118) (m2 /mJ)2 .
It turns out that the confidence intervals of β and β1 are quite narrow and alterations
of the best fit parameters within that range had minimal impact on surface free energy, and
thus, “surface tensions with an accuracy of ~1–2 mJ/m2 could be obtained for polymer
films” [38].
Completely independently analyzing γlv × cos(θ) vs. γlv data by Neumann et al. and
by other teams, Gerson derived an alternative expression for the Girifalco–Good interaction
parameter ϕ = exp[γsl ( aγsv + b)], which leads to the formulation of another equation of
state [39]:
γlv (cos θ + 1)
√ − exp [ (γsv − γlv cos θ )( aγsv + b)] = 0 (8)
2 γlv γsv
where the best fit values of the parameters are a = 6.5 (±1.0) × 10−5 and b = −0.010 ± 0.001.
As can be seen in Figure 2a, for all practical purposes, the γsv values calculated for the
entire range of water contact angles with the help of Equations (6)–(8) essentially coincide
as “the absolute discrepancies between the γsv values obtained by the different EoS do not
exceed the value of ±1.3 mJ/m2 ” [27].
Colloids Interfaces 2024, 8, x FOR PEER REVIEW 5 of 38

Colloids Interfaces 2024, 8, 62 as “the absolute discrepancies between the γsv values obtained by the different EoS do
5 ofnot
36
exceed the value of ±1.3 mJ/m2” [27].

Figure 2.
Figure 2. (a)
(a)Values
ValuesofofSFE
SFEasasfunction ofof
function water contact
water angle
contact calculated
angle with
calculated Equations
with (6)–(8)
Equations (es-
(6)–(8)
timates essentially coincide for all practical purposes); (b) dependence of the power coefficient n in
(estimates essentially coincide for all practical purposes); (b) dependence of the power coefficient
Equation (12) on the surface tension of the wetting liquid as calculated via Equation (12a); (c) Equa-
n in Equation (12) on the surface tension of the wetting liquid as calculated via Equation (12a);
tion (12) provides good fit of the iterative numerical solutions of Equation (6) for various wetting
(c) Equation (12) provides good fit of the iterative numerical solutions of Equation (6) for various
liquids.
wetting liquids.
Another EoS was developed by Kwok and Neumann [40] who tested various alter-
Another EoS was developed by Kwok and Neumann [40] who tested various alterna-
natives to Berthelot’s combining rule, and found that contact angle data were well fit by
tives to Berthelot’s combining rule, and found that contact angle data were well fit by an
an equation based on a generalized form Hudson and McCoubrey combining rule:
equation based on a generalized form Hudson and McCoubrey combining rule:
( ) /
( / ) /
cos 𝜃 = −1 + 2 /
 (kγsv )2/3 (9)
r ( / )1/3
γsv  4(γsv /γlv )
cos θγ = −1 + 2 (9)

n o2 
where k=1170 m2/J was an empirical γlv constant.
1 + (γsv /γlv )1/3
Neumann EoS gained significant popularity (especially Equation (6)) and proved rel-
evant for the determination of SFE of a variety of low- and high-energy solids [37,38,41].
where k = 1170 m2 /J was an empirical constant.
One of the criticisms of Neumann EoS was their semi-empirical nature, as they contain
Neumann EoS gained significant popularity (especially Equation (6)) and proved
best fit parameters
relevant that were of
for the determination notSFE
derived analytically.
of a variety of low-Recently, Neumann
and high-energy attempted
solids to
[37,38,41].
address this. An expression similar to Equation (6) was derived on the basis
One of the criticisms of Neumann EoS was their semi-empirical nature, as they contain of molecular
parameters
best and a density
fit parameters depletion
that were theory
not derived at the interface,
analytically. which
Recently, provided
Neumann a physical
attempted to
explanation for β as a measure for the molecular packing of the solid interface
address this. An expression similar to Equation (6) was derived on the basis of molecular at the three-
phase contact
parameters andline [21].
a density depletion theory at the interface, which provided a physical
explanation for β as a measure for the molecular packing of the solid interface at the
three-phase contact line [21]. ( ) (10)
𝛾 (1 + cos 𝜃) ≈ 2 𝛾 𝛾 𝑒
2
√ − kδ T (γsv −γlv cosθ )
where δ2 is the area occupied
γlv (1 +by
cosan
θ )atom
≈ 2 in
γlνthe
γsνliquid–solid
B interface, kB is Boltzmann’s
(10)
constant, and T is temperature.
where δ2 is the area occupied by an atom in the liquid–solid interface, kB is Boltzmann’s
constant, and T is temperature.
Colloids Interfaces 2024, 8, 62 6 of 36

Another frequent complaint by practitioners is that Neumann EoS cannot be analyti-

cally solved for γsν , and instead, the value of SFE is obtained by numerical iterations via
some of the many available nonlinear optimization solvers. In order to address this issue,
polynomials are typically fitted to the EoS-calculated SFE values and generalized fifth-order
polynomial expressions were developed recently [42] to fit Equation (7):

PMγsv (θ, γlν ) = A(γlν ) × θ 5 + B(γlν ) × θ 4 + C (γlν ) × θ 3 + D (γlν ) × θ 2 + E(γlν ) × θ 1 + E(γlν ) (11)
where each of the coefficients (A–F) itself is a fifth-order polynomial of the probe liquid
surface tension. Apart from being quite cumbersome, this approach has some additional
limitations, as (i) it represents a fit of another function to the EoS-calculated values and
(ii) it cannot fit EoS for contact angles higher than 130◦ .
A somewhat more physical and practically convenient approximation exists
(Figure 2b,c) for the exponential form of the Neumann EoS (Equation (6)), which allows
us to fit the EoS over the entire range of possible contact angles. It is based on expression
derived [43,44] through Taylor series expansion of Equation (6):
   s  2
1 n θ 1 n
θ 1 2
γsν = γlν + sec − γlν + sec − − γlv (12)
4βγlv 2 4βγlv 2 2β

where the exponent n is a third-order polynomial of the probe liquid surface tension
3 2
n = −0.0000004383522γlv − 0.00003881γlv + 0.0016991γlν + 3.98253552 (12a)

The mean discrepancy between the values obtained by iterative solution of Equation (6) and
the Taylor series approximation (Equation (12)) is less than 0.4 mJ/m2, which is well within the
inherent ~1–2 mJ/m2 accuracy of the EoS and provides better fit than third-order polynomials [45].

2.1.2. Model of Chibowski Based on the Hysteresis of the Contact Angle

If the solid surface is tilted, the liquid drop starts to slide (see Figure 1c) and hysteresis
(CAH, i.e., difference in values where θ a > θ r ) is observed between the advancing and
receding contact angles of the drop, which can be attributed to the modification of the solid
surface behind the receding edge of the drop due to the deposition of a liquid film on top
of it. Therefore, the surface energy (γs ) of the bare (in a state of “dry wetting”) solid in front
of the advancing edge of the drop

γs = γsl + γl cos θ a (13)

is different from the surface energy (γs f ) of the film-covered solid behind the receding edge
of the drop
γs f = γsl + γl cos θr (14)
Then, the free energy of the film-covered surface can also be expressed as:

γs f = γs + π (15)

where π is the film pressure.

Works of adhesion can be calculated from the advancing and receding contact angles:

WαA = γl (1 + cos θ a ),WαR = γl (1 + cos θr ) (16)

And it is easily shown that:

π = WαR −WαA = γl (cos θr − cos θ a ) (17)

Colloids Interfaces 2024, 8, 62 7 of 36

From the Berthelot’s geometric mean combining rule:

√
WαA = 2Φ γs γl WαR = 2Φ γs f γl
p
(18)

Thus: √
WαA 2Φ γs γl 1 + cosθ a
= √ = (19)
WαR 2Φ γs f γl 1 + cosθr
This expression can be solved for γs to obtain [46,47]:

γl (1 + cosθ a )2
γs = (20)
2 + cos θr + cos θ a

“In the derivations of this model no assumption has been done as for the film state. It
was only assumed that retreating the contact line of liquid drop the solid surface could not
be left completely bare, because at least the London dispersion interactions are present. The
more in real systems, where solid surface practically always possesses some imperfections
(micro heterogeneity) and roughness, some amount of the liquid will be left behind the
drop, which forms the film. If this model works, total surface free energy of a solid can
be evaluated from three measurable parameters, i.e., probe liquid surface tension and its
advancing and receding contact angles measured on the investigated solid surface” [22].
The model of Chibowski is elegant and entirely analytical (i.e., no best fit parameters in it)
and has gained significant traction and popularity.
It is interesting to see how the values of SFE obtained from Equation (20) compare to
the values of SFE calculated by Neumann EoS (Equation (6)).
To perform such a comparison, it is necessary to convert the advancing and receding
contact angles to the equilibrium contact angle of Young required by the EoS. The equations
relating these quantities were derived by Tadmore on the basis of the line tension model [48–50]:

Γ A cosθ A + Γ R cosθ R
 
θ = arccos (21)
Γ A + ΓR

where
!1/3 !1/3
sin3 θ R sin3 θ A
ΓR ≡ and Γ A ≡ (21a)
2 − 3cosθ R + cos3 θ R 2 − 3cosθ A + cos3 θ A

The comparison is performed with a dataset of advancing and receding contact angle
values measured for variety of surfaces where CAH ≤ 20◦ , as higher hysteresis indicates an
exceedingly rough or heterogeneous surface where the Young equation cannot be applied
directly and Cassie–Baxter or Wenzel models should be first used to account for these
effects [51,52].
As can be seen (Figure 3), excellent agreement is observed between the SFE values
obtained by the two models, in line with previous reports [13,53]. The mean discrepancy is
within ±2.52 mN/m, and this is well within the expected effect of the uncertainty in the
determination of the advancing and receding CA (typically 2–5◦ ) on calculation of SFE [54].
oids Interfaces 2024, 8, x FOR PEER REVIEW 8 of
Colloids Interfaces 2024, 8, 62 8 of 36

FigureFigure 3. Excellent
3. Excellent agreementexists
agreement exists between
between thethe
surface free energies
surface calculated
free energies via the equations
calculated via the equatio
of Neumann and Chibowski as shown by the dependance
of Neumann and Chibowski as shown by the dependance of SFE on the Tadmoreof SFE on the Tadmore contactcontact
angle angle
(a) strong
and the and the correlation
strong correlation between
between thethe values
values obtained via
obtained via the
the two
twoapproaches
approaches (R is
(RPearson
is Pearson lin
linear correlation coefficient; p is the probability of the value of R being due to chance; p < 0.05
correlation coefficient; p is the probability of the value of R being due to chance; p < 0.05 deno
denotes statistical significance) (b). All data are from published studies (values and sources listed in
statistical significance) (b). All data are from published studies (values and sources listed in Supp
Supplementary file S1_CA_data.xlsx).
mentary file S1_CA_data.xlsx).
This agreement can be well explained by the fact that both models assume the
2.1.3.“dry
Drywetting”
vs. Wetparadigm
Wetting:forThe
the Problem
solid in front
of of the advancing
Accounting foredge of theFilm
Liquid drop.Beyond the
Advancing Edge
2.1.3. Dry of the
vs. Wet Drop.
Wetting: TheCA-Based
Problem of SFE Estimates
Accounting as a Function
for Liquid Film Beyond ofthe
Wetting Liquid
Surface Tension
Advancing Edge of the Drop. CA-Based SFE Estimates as a Function of Wetting Liquid
Surface Tension
Now let us return to Figure 1. As already mentioned, all the models considered up
Now let us return to Figure 1. As already mentioned, all the models considered up to
now and
now andthe the
models models ofofOWRK
OWRK and vOCG
and vOCG to to
be be reviewed
reviewed in subsequent
in subsequent sections sections
share the share t
assumption
assumption of of
“dry“drywetting”,
wetting”, when when for θfor θ ≥, the
≥ 10 ◦ 10°, theofvalue
value of spreading
spreading pressure πe ispressure
negligible πe is n
and
ligible andγsv 𝛾≈ γ≈ 𝛾 . From
s . From one side,
onesuchside,ansuch
assumption is convenient,
an assumption as it greatly simplifies
is convenient, the
as it greatly simp
assessment of SFE, especially as unambiguous experimental
fies the assessment of SFE, especially as unambiguous experimental or theoretical estimor theoretical estimation of π e is
challenging. Also, it was supported by sensible physical justification [1,10,14]. From a statistical
tion of πe is challenging. Also, it was supported by sensible physical justification [1,10,1
mechanical point of view, Good [55] estimated that the spreading pressure will be small for
Fromliquids
a statistical
that formmechanical
a non-zero contactpoint of on
angle view, Good
a solid, [55] estimated
“provided that the solid that
is notthe spreading pr
appreciably
sure will
roughbe orsmall for liquids
heterogeneous that form ascale
on a microscopic non-zero contact angle
and the molecules on a solid,
of the liquid “provided
are at least as th
symmetrical as n-alkanes”. Van Oss [16] calculated the interfacial
the solid is not appreciably rough or heterogeneous on a microscopic scale and the mo work of solvation, vapor
pressures and the equilibrium association constant for the adsorption of various liquids on a
cules of the liquid are at least as symmetrical as n-alkanes”. Van Oss [16] calculated t
moderately polar solid (polymethylmethacrylate) and concluded that the adsorption of liquid
interfacial
moleculesworkfromofthe solvation,
vapors to the vapor pressures
solid is minimal (<4% andofthe equilibrium
the surface association
is affected, corresponding constant
◦
the adsorption
to <1 effect on ofCA).
various
Similarliquids
estimates on a moderately
were also provided by polar solid (polymethylmethacryla
Wu [15].
However, a gradually growing body of theoretical
and concluded that the adsorption of liquid molecules from the vapors and experimental worktosuggests
the solid is m
that, as convenient as it is to assume that the value of π e is always negligible compared
imal (<4% of the surface is affected, corresponding to <1° effect on CA). Similar estima
to that of γsv , this might be an excessive oversimplification. As pointed out by Douillard
wereetalso provided
al. [56], by Wu [15].
“these assumptions are in disagreement with modern theories of vapor adsorp-
However,
tion science”aasgradually growing
“there is always body of
an adsorbed theoretical
quantity upon the and experimental
solid, even if the solid work
has sugge
that, very
as convenient
weak attractive as itforces.
is to This
assume that the
adsorption valuevalue
is due oftoπmolecular
e is always negligible
forces acting in compared
the
that of 𝛾 , this might be an excessive oversimplification. As pointed out by Douillard
fluid near saturation pressure, often called “lateral forces””. However, “measurement of
the film pressure is achievable only for solids available as powders with a nonnegligible
al. [56], “these assumptions are in disagreement with modern theories of vapor adsorpti
specific surface area” [57] and in all other cases, the determination of π e is unreliable and
science” as “there
error-prone, is alwaysinan
as explained adsorbed
detail elsewhere quantity
[16]. upon the solid, even if the solid has ve
weak attractive
It shouldforces.
be noted This
that adsorption
the assumption value
of “dry is wetting”
due to molecular forcesanacting
is also considered oversim- in the flu
plification in the Frumkin–Derjaguin theory of wetting [58]
near saturation pressure, often called “lateral forces””. However, “measurement of t (Figure 1e), which assumes that
at the three-phase contact line, the meniscus of bulk liquid coexists with the substrate at
film pressure is achievable only for solids available as powders with a nonnegligible sp
equilibrium, which is in general not dry, but coated with a liquid film formed by diffusion
cific surface area”
of liquid from the[57] andalong
droplet in all
theother
surfacecases,
(i.e., anthe determination
intrinsic process that doesof πnot
e is unreliable a
require
error-prone, as explained in detail elsewhere [16].
vapor adsorption), the so called precursor film, which emanates from the three-phase
It should
contact line be
regionnotedand that the assumption
instantaneously spreads of ahead“dry wetting”
of the is also considered an ov
latter [59].
simplification in the Frumkin–Derjaguin theory of wetting [58] (Figure 1e), which assum
that at the three-phase contact line, the meniscus of bulk liquid coexists with the substr
at equilibrium, which is in general not dry, but coated with a liquid film formed by diff
sion of liquid from the droplet along the surface (i.e., an intrinsic process that does n
Colloids Interfaces 2024, 8, 62 9 of 36

Here, Chibowski and coworkers [22,47,60,61] mentioned an interesting opportunity

that may provide an analytical approach to the estimation of the solid surface tension in the
case of “wet wetting” when a film of liquid molecules is present ahead of the advancing
edge of the drop.
The premise of the Tadmore equation is that it provides the Young contact angle, θ0,
reached in thermodynamic equilibrium when the liquid and the solid are in equilibrium with
their own saturated vapors. As the equilibrium state is the most thermodynamically favorable
one, this means that the contact angle hysteresis will also disappear, i.e., θa = θr = θ0 [47,61],
which, within the model of Chibowski, will happen only if liquid film is present both on
the solid surface behind the retreating and in front of the advancing edges of the drop, i.e.,
in the case of “wet wetting”. Of course, CAH is also affected by roughness, and as recent
reduction to absurdity ultra-large-scale molecular dynamic simulations [62,63] revealed, it
disappears only for absolutely smooth surfaces, while even the minimum, i.e., atomic roughness,
is great enough to cause some hysteresis. Another reason for the existence of hysteresis might
be that the establishment of thermodynamic equilibrium is a slow process, and if it has not
been reached, then CAH will occur [64]. This explains why even clean molecularly smooth
surfaces (mica, polished Teflon, etc.) show some, albeit minimal, hysteresis (≤5◦ ) [22]. However,
moderate roughness is known to not affect the equilibrium contact angles determined by sessile
drops [17,18] and therefore should not affect the angle calculated by the Tadmore equation.
Thus, assuming “wet wetting” and θa = θr = θ0 at thermodynamic equilibrium, the equation of
Chibowski adopts a notably simple form [22,47,60,61]:

γl Wa
γs = (1 + cos θ a ) = (22)
2 2
It was supposed that “surface free energy values obtained from the equilibrium contact
angles (i.e., with Equations (21) and (22)) provide more realistic information allowing
description of energetic properties of the examined surfaces” [61].
Remarkably, Chibowski and Terpilowski appear to have overlooked that in the case of
“wet wetting”, assuming that θ a = θ r = θ 0 (i.e., that there is identical film of liquid molecules
over prewetted surface and in front of the advancing edge of the drop), the equation
of Chibowski transforms to the rule of Anotonow [65], thus addressing the criticism of
Kwok and Neumann that Antonow’s rule is empirical and “never having been derived in
any fashion” [37]. The Antonow rule states that at thermodynamic equilibrium:

γsl = |γlv − γsv | (23)

Indeed, if Antonow’s rule is plugged in the equation of Young and the resultant
expression is solved for the value of γsv , Equation (22) is obtained.
This result agrees with the studies of Lipatov [66–70] who, based on rigorous formal
derivation and experimental evidence, suggested that when a finite contact angle is ob-
served, i.e., γlv > γs (if γlv < γs , the liquid spreads to completely wet the solid, θ = 0◦ ), and
precursor liquid film is present ahead of the drop edge (“as the process of establishment
of interfacial equilibrium involves at least some tens of monolayers, then near the ternary
point the mutual saturation of phases is always seen to take place” [66]), the Antonow rule
is valid when expressed as an interfacial equilibrium rule:
γl
γs = γlv − γsl = (1 + cos θ ) (24)
2
γs = f (γlv ) (24a)
Here, γs is the surface tension of a polymer (or other solid) in the ternary point
solid–liquid–gas, i.e., in the zone of interfacial nonuniformity.
As such, in contrast to γsv calculated under the assumption of “dry wetting”, which
is commonly perceived as a thermodynamic characteristic of the solid, γs estimated by
the interfacial equilibrium rule (i.e., at “wet wetting” when the presence of liquid film
Colloids Interfaces 2024, 8, x FOR PEER REVIEW 10

Colloids Interfaces 2024, 8, 62 10 of 36

and depends not only on the properties of the solid but also on the surface tension of
wetting liquid 𝛾 = f(𝛾 ) , in line with the premises of Frumkin–Derjaguin theory of wett
adsorbed
[58], over the solid
considering the is accounted for)
equilibrium CA is as
thearesult of allbetween
balance 𝛾 and interactions
types of interfacial the surface forces
and depends not only on the properties of the solid but also on the surface tension of
pressed as disjoining pressure. Thus, 𝛾 should be considered not as a surface energy
the wetting liquid γs = f ( γlv) , in line with the premises of Frumkin–Derjaguin theory of
rather
wettingas a surface
[58], consideringtension of the solid
the equilibrium CAinasthe ternary
a balance point γsolid–liquid–gas,
between as also
lv and the surface
cently suggested
forces expressed as by Law and
disjoining Zhao [71].
pressure. Thus, γs should be considered not as a surface
energy Based on experiments
but rather with diverse
as a surface tension probe
of the solid liquids
in the ternaryand pointvariety of low-, mid-
solid–liquid–gas, as and h
also recently
SFE polymers, suggested
Lipatov by obtained
Law and Zhao [71].
the following generalized (Figure 4) form of the 𝛾 =
dependence [67], which consists of three zones. Ifand
Based on experiments with diverse probe liquids 𝛾 >> variety of low-,
𝛾 , the mid- and zone
depolarization
high-SFE polymers, Lipatov obtained the following generalized (Figure 4) form of the
pears; when 𝛾 << 𝛾 , a zone of additional polarization occurs; in the zone where 𝛾 ≈
γs = f ( γlv) dependence [67], which consists of three zones. If γs >> γsl , the depolarization
(at
zone contact
appears; angles
when close
γs << toγsl 90°), theofpolarization
, a zone of the molecules
additional polarization occurs; inofthethe solid
zone stays the s
where
as it was
γs ≈ γsl (atatcontact
the solid–air interface.
angles close to 90 ), “It
◦ the may be seenofthat
polarization the effects
the molecules of of
thepolarization-depo
solid stays
ization
the sameare as itconnected with the
was at the solid–air fact that
interface. at the
“It may pointthat
be seen of the
ternary
effects contact the surface f
of polarization-
depolarization
field solid-airare is connected
substituted withbythethefact thatsolid-liquid
field at the point of(𝛾 ternary
). Onecontact
has notthe surface
to forget that
force field solid-air is substituted by the field solid-liquid (γ ). One
field of the surface forces is an anisotropic one. In this sense, the physical meaning
sl has not to forget that se
the field of the surface forces is an anisotropic one. In this sense, the physical meaning
rather clear” [67]. “This effect is determined by polarizability of molecules of both ph
seems rather clear” [67]. “This effect is determined by polarizability of molecules of both
in the in
phases interphase region
the interphase duedue
region to tothe
thechanges
changes in inthe
thesurface
surface force
force fieldfield of wetting
of wetting of of s
polymer
solid polymer by liquids
by liquidshaving
havingvarious
various surface tensions”
surface tensions” [70].
[70].

Figure
Figure 4.4.Generalized
Generalizeddependence γs = f 𝛾
dependence ( γlv) (𝛾 a) for
= ffor a polymer
polymer surfacesurface
(adapted(adapted
from [67]).from [67]).

Remarkably, analyzing the wetting of polymer surfaces via Equations (6) and (20),
Remarkably, analyzing the wetting of polymer surfaces via Equations (6) and
Chibowski also observed that γs = f ( γlv) , i.e., the phenomenon is not dependent on the
Chibowski also
choice of “dry” observed
or “wet” wetting 𝛾 = f(𝛾 [22,47,60,61].
thatequations ), i.e., the phenomenon is not dependent on
Thus, within the framework of
choice of “dry”
Chibowski’s orEquation
model, “wet” wetting
(20) (andequations [22,47,60,61].
Equation (6), as good agreementThus,iswithin
observedthewith
framewor
Chibowski’s model,provides
Equation (20) [13,53]) Equation SFE(20)
for(and Equation
hysteretic (θ a > θ(6),
r ) as good
surfaces, agreement
while Equation is observed
(22) w
sets the upper
Equation (20)possible
[13,53])limit of SFE inSFE
provides the (somewhat
for hystereticideal)(θcase ofr)nonhysteretic
a > θ (θ a = Equation
surfaces, while θr)
sets the upper possible limit of SFE in the (somewhat ideal) case of nonhysteretic (θa
surface where 𝛾 = f(𝛾 ) (i.e., the interaction between the solid surface and the precu
film at the ternary point) is universally observed (both in presence or absence of CAH
These results are in accordance with the hypothesis of Kloubek [72], “which st
that at the interface, besides the interaction between the surface free energy compon
Colloids Interfaces 2024, 8, 62 11 of 36

surface where γs = f ( γlv) (i.e., the interaction between the solid surface and the precursor
film at the ternary point) is universally observed (both in presence or absence of CAH).
These results are in accordance with the hypothesis of Kloubek [72], “which states
that at the interface, besides the interaction between the surface free energy components of
the same type existing in separated phases, also an interaction between a non-dispersion
component of one phase and the component of the same type induced in the region of the
interface of the other phase may take place”. In 2007, Carré [73] proposed a model for the
calculation of SFE which also assumed that γs = f ( γlv) as the polar contributions to the
surface tension of the solid are induced by the contacting liquid and are thus proportional
to the polar component of γlv . Indeed, this induced surface polarity model provided a
better fit of the experimental data than OWRK and vOCG. Carré appeared to be unaware
of the studies of Chibowski, Lipatov and Kloubek and instead quoted Fowkes “that the
polar energy of interaction between polar liquids (the classical series of liquid probes
used in wetting studies) and polymers including polystyrene, polyamides, polyesters
and poly(vinyl chloride) was proportional to the liquid polarity quantified by the polar
component of the liquid surface free energy” [74].
The utility of the interfacial equilibrium rule was recently confirmed by the newly
proposed Altay–Ma–Fleming (AMF) method for calculation of surface free energy [75].
Here, Equation (5) is rearranged to:

cos4 2θ
γsv = γlv 2
(25)
ϕsl

where the Girifalco–Good interaction parameter is calculated as:

2 θ
ϕsl = αcos2 (26)
2
so that
cos2 2θ γ
γsv = γlv = (1/α) l (1 + cosθ ) (27)
α 2
The authors assumed that in order for a finite contact angle to exist, the Antonow rule
should be modified to a strict inequality

γsl < γlv − γsv (28)

when α is calculated from the expression

∆γlν
   
1 2 θ
1−α = 2 + cos + sin θ∆θ (29)
2cos2 2θ γlv 2

where ∆ denotes the standard deviations of the corresponding quantities.

Obviously, the further α decreases away from unity, the higher is the drift away from
the equality assumed by the interfacial equilibrium rule (curiously, it appears that the
authors of the AMF model were not acquainted with the related research of Chibowski
and Lipatov, as these were not referenced in their study). The experimental data revealed
that α varied in a very narrow range, with a median value of 0.978 and 95% confidence
interval 0.97–0.99. The deviation from the interfacial equilibrium rule is so minimal that
the SFE estimates produced by the two approaches essentially coincide and the interfacial
equilibrium rule accurately fits the experimental data (Figure 5) of Altay et al. [75].
The minimal departure of α from unity (α = 0.978 instead of α = 1) can be due to
the fact that the establishment of thermodynamic equilibrium is a slow process, and thus,
for practical purposes, it might be optimal to formulate the interfacial equilibrium rule
as γsl →γlv − γsv (i.e., γsl approximates but remains negligibly lower than (γlv − γsv )), in
agreement with a recently proposed geometric interpretation of Antonow’s rule [76].
 θwater = 113.9°, calculated πe = 7.56 mN/m (experimental value 6.6–8.2 mN/m) [77]; PVC,
θwater = 84°, calculated πe = 6.84 mN/m (experimental value 5.0–6.4 mN/m) [77]); talc, θwater
= 64.4°, calculated πe = 6.12 mN/m (experimental value 6 mN/m) [57]; graphon, θwater = 82°,
Colloids Interfaces 2024, 8, 62 calculated πe = 6.77 mN/m (experimental value 6 mN/m) [78]; PMMA, θwater = 76°, 12 of 36
calcu-
lated πe = 7.82 mN/m (experimental value 9.2 mN/m) [15].

Figure 5.
Figure 5. Excellent
Excellentagreement
agreementisisobserved
observed between
between Lipatov’s
Lipatov’s interfacial
interfacial equilibrium
equilibrium rule rule (Equation
(Equation (24),
(24), solid lines) and AMF method (Equation (27); data points from Table 3 in [75]). See the
solid lines) and AMF method (Equation (27); data points from Table 3 in [75]). See the main text formain text
details.
for details.
From the discussion above, it is evident that the difference between the values of the
2.2. Models
solid surfaceThat Implement
tensions Multiple
obtained viaProbe Liquidsequilibrium
interfacial for the Estimation of SFEwetting”) and the
rule (“wet
Neumann From EoS (“dry wetting”)
the molecular may provide
interaction an estimate
standpoint, of the spreading
the equations which determinepressureSFEπ e ,from
and
indeed, there is agreement with some of the experimentally
experiments with a single probe liquid did not explicitly consider any dispersion, polar, determined values: PTFE,
◦ , calculated π = 7.56 mN/m (experimental value 6.6–8.2 mN/m) [77]; PVC,
water = 113.9
θhydrogen bond, or acid–base e interactions in formulating 𝛾 . Although, in his late re-
= 84 ◦ , calculated = 6.84
θsearch,
water Neumann did not edeny π themN/m (experimental
possibility of quantifying value 5.0–6.4
these mN/m)via
interactions [77]); talc,
surface
θtension = 64.4 ◦ , calculated π = 6.12 mN/m (experimental value 6 mN/m) [57]; graphon,
water components (STCs),e he considered the approach as adding unnecessary complex-
◦ , calculated π = 6.77 mN/m (experimental value 6 mN/m) [78]; PMMA, θ
θity to =
water 82calculation
the of eSFE, and that any attempt to do so ”within the context of these water
= 76 ◦ , calculated π = 7.82 mN/m (experimental value 9.2 mN/m) [15].
e
theories would have to involve a collapse into a much simplified version” [21]. Chibowski
has shown that very good quantitative agreement exists between the estimates obtained
2.2. Models That Implement Multiple Probe Liquids for the Estimation of SFE
via the different approaches, as SFE computed with STC models (OWRK and vOCG) rep-
resentsFrom an the
average molecular
from theinteraction
SFE valuesstandpoint,
calculated thevia
equations
his equationwhich (ordetermine
via NeumannSFE fromEoS)
experiments with a single probe liquid did not explicitly consider
for the same solid when wetted by different probe liquids (see Section 3) [46,53,79,80]. any dispersion, polar,
hydrogen
Although bond, calculationor acid–base interactions
of the total value ofinSFEformulating sv . Although,
is indeedγachievable in in his late research,
a simpler manner,
Neumann
the knowledge did not of deny the possibility
this aggregate of quantifying
quantity might not these interactions
be sufficient via surface
to predict tension
and properly
components (STCs), he considered the approach as adding unnecessary complexity to the
understand the (bio)adhesion between coatings and surfaces or between (bio)interfaces
calculation of SFE, and that any attempt to do so “within the context of these theories would
interacting through aqueous (or other) media. In such cases, it might be valuable to esti-
have to involve a collapse into a much simplified version” [21]. Chibowski has shown that
mate the balance between the nonpolar (dispersion) and polar (non-dispersive, i.e., hy-
very good quantitative agreement exists between the estimates obtained via the different
drogen bonding and other) interactions. This leads us to the STC models for estimation of
approaches, as SFE computed with STC models (OWRK and vOCG) represents an average
SFE and we will focus on the two most popular approaches: OWRK and vOCG.
from the SFE values calculated via his equation (or via Neumann EoS) for the same solid
when wetted by different probe liquids (see Section 3) [46,53,79,80]. Although calculation
2.2.1. OWRK Model
of the total value of SFE is indeed achievable in a simpler manner, the knowledge of
The separation
this aggregate quantity of the totalnot
might value
be of liquid and
sufficient solid surface
to predict tensionsunderstand
and properly into individual the
components was first performed by Fowkes [81]. When
(bio)adhesion between coatings and surfaces or between (bio)interfaces interacting studying the work of adhesion
through
between n-alkanes
aqueous (or other) (i.e., liquids
media. capable
In such of interacting
cases, it might beexclusively
valuable tovia Londonthe
estimate dispersion
balance
forces) and
between thepolar
nonpolar liquids like water and
(dispersion) and polar
mercury (i.e., liquids whose
(non-dispersive, molecules
i.e., hydrogen are capable
bonding and
of bothinteractions.
other) dispersive This and leads
polar,us non-dispersive,
to the STC models interactions between
for estimation of SFE each
andother andfocus
we will with
foreign
on the two molecules),
most popular he found that the OWRK
approaches: interfacial
andtension
vOCG.between the two types of liquids

2.2.1. OWRK Model

The separation of the total value of liquid and solid surface tensions into individual
components was first performed by Fowkes [81]. When studying the work of adhesion
between n-alkanes (i.e., liquids capable of interacting exclusively via London dispersion
forces) and polar liquids like water and mercury (i.e., liquids whose molecules are capable
Colloids Interfaces 2024, 8, 62 13 of 36

of both dispersive and polar, non-dispersive, interactions between each other and with
foreign molecules), he found that the interfacial tension between the two types of liquids
is determined solely by the dispersion interactions, as these are the only ones in which
n-alkanes can take part. Thus, using the relation
q
γ12 = γ1 + γ2 − 2 γ1d γ2d (30)

and as γ1 = γalkane = γ1d , it becomes possible to estimate the dispersion component con-
tribution to the surface tension of polar liquids. It became evident that for polar liquids
capable of electron donor–acceptor interactions γ2d < γ2 , and hence, the surface tension of
these liquids consists also of another component distinct from the London forces. Thus, in
the general case, the surface tension consists of a dispersion component, γd , and another
non-dispersion, polar component γp .
Over time, Fowkes provided a detailed view of the additive contributions that sum up
to yield the liquid and solid surface tension [74,82].

γ = γd + γi + γ pD + γh + γπ + γ ad + γe (31)

Here, the superscript d relates to the London dispersion interaction, i refers to inductive
dipole–dipole, pD- to permanent dipole–dipole, h- to hydrogen and π- to π-bonds or interactions
by formation of π-complexes, e- to electrostatic, and ad to donor–acceptor interaction.
How to distribute these contributions between the dispersion, non-polar, component
and the non-dispersion, polar, component of γ had been a matter of certain debate and of
quite perplexing use of symbols. Particularly, the label attached to the non-dispersion polar,
γp , component has changed over time and between authors, and terms like hydrogen-
bonding, γh , and acid–base, γAB , component had been coined for it (the latter becoming
most popular in recent years), which resulted in great confusion on what the best practices
to apply the OWRK model should be.
Here is a brief outlook to the various formulations of the two-component model of
SFE, which assumes that for adhesion to take place, the dispersion and non-dispersion
components of the solid and of the wetting liquid must match (please see Figure 2 in [83]):
- Owens and Wendt [23]

γl (1 + cos θ )
q q
= γsd γld + γsh γlh (32)
2
- Kaelble and Rabel [84]

γl (1 + cos θ )
q q
p p
= γsd γld + γs γl (33)
2
In both formulations, γd denoted the London dispersion forces, but Owens and Wendt
assumed that the non-dispersion interaction is dominated by hydrogen bonding, while
Kaelble attributed it to the Keesome dipoles.
- And within the framework of the theory of Lifshitz, the two-component model be-
comes [85–87]:
q q 
LW AB
Wa = γl (1 + cos θ) = W +W =2 γsLW γlLW + γsAB γlAB (34)

γ LW = γd + γi + γ pD and γ AB = γh + γπ + γ ad + γe (34a)
As γdand γh
are considered an order of magnitude higher compared to the rest of
the contributions, these are thought to determine the values of the dispersion and non-
dispersion component of γ, respectively, thus approximating the original definition of
Owens and Wendt.
Colloids Interfaces 2024, 8, 62 14 of 36

Whatever symbols and terms are chosen, in all cases, the same dispersion and non-
dispersion components of wetting liquid surface tension are used for solving Equations (32)–(34),
which means that in the context of Equations (32)–(34), for all practical purposes γLW ≈ γd and
γAB ≈ γh ≈ γp [85–87].
The Lifshitz theory allowed us to gain a better understanding of what the non-
dispersive, polar, component accounts for, and here, a very important (and still often
ignored) warning was given from Fowkes back in 1978 [82]; while expressing the dis-
persion interaction between the liquid and the solid as geometric mean is theoretically
grounded, this is not the case for the non-dispersive interactions (especially hydrogen
bonding). Thus, the OWRK qmodel is semiempirical and there are limits to its proper appli-
cation, namely as γ AB = 2 γ+ γ− (γ− and γ+ denote electron donor and electron acceptor
contributions, respectively), only bipolar (i.e., with non-zero γ+ and γ− ) but not monopolar
(γ+ = 0 or γ− = 0) probe liquids should be used when solving Equations (32)–(34). This is
so, as although monopolar liquids are not able to self-aggregate via hydrogen bonds, they
can potentially do so with the foreign molecules of the solid, and thus, assuming γp = 0 for
monopolar probes will fallaciously ignore possible hydrogen bonding between the liquid
and the solid. Apparently, fully non-polar liquids (γ+ = 0 and γ− = 0) can be used, but as
will be discussed further, this comes with its own set of practical and theoretical problems.
The OWRK model contains two unknowns, and therefore, to solve it, the contact
p
angle of at least two probe liquids with known γld and γl should be measured. In practice,
d p
however, it is best that the values of γs and γs be overdetermined by application of multiple
p
probe liquids with diverse γld /γl ratios (at least five liquids are recommended) [84,88,89].
Why this is so is evident when OWRK is rearranged into a linear form [90,91] where the
components of SFE represent the slope and the intercept of the dependence:
!1
[1 + cos(θ )]  d 1/2 γld
2  1/2
p
γlv
1/2 = γs p + γs (35)
2 γlP γl

p
Obviously, the more data points, the more precise will be the estimation of γsd and γs
p
(the linear form cannot be used for test liquids with γl = 0).

2.2.2. Are the SFE Estimates of OWRK and Neumann EoS Inherently Incompatible? On the
Possibility of Estimating SFE Components from Single Liquid Measurements.
Considerations on the Definition of Hydrophilicity and Hydrophobicity
There have been plenty of conflicting reports on the issue that have led some authors
to reject the soundness of OWRK or of the Neumann EoS, depending on their school of
thought. At the same time, others [53,60,79,85–87,92] demonstrated very good agreement
between the two approaches when analyzing a variety of datasets.
The most unambiguous approach to probe the compatibility between the EoS and
OWRK is the numerical simulation method proposed by Ahadian et al. [93]:
- Assuming that EoS is correct, and that the SFE of the solid remains constant when
accessed with different probes, the contact angles corresponding to each chosen
wetting liquid are calculated via the EoS (i.e., Equation (6) is solved in reverse:
from SFE to CA, and not from CA to SFE) for the range of SFE values from 72.8 to
11.6 mN/m. The value of 11.6 mN/m is chosen, as it corresponds to θ water = 120◦ , i.e.,
the maximum possible water contact angle for molecularly smooth surface (i.e., the
limit to which the condition about smoothness of the surface imposed by the Young
equation is valid). In order for a finite contact angle to occur, γlv > γs .
- Based on the calculated contact angle, the SFE energy of each of the simulated samples
is calculated via OWRK.
- If the EoS and OWRK are compatible, then similar or identical SFE values should be obtained.
The probe liquids used for simulation with their surface tension data are summarized
in Table 1. Those liquids were chosen, as (i) they were recently recommended as contact
Colloids Interfaces 2024, 8, x FOR PEER REVIEW 15 of 38
Colloids Interfaces 2024, 8, 62 15 of 36

angle probes
angle probes that
that are
arenonvolatile,
nonvolatile, nontoxic,
nontoxic, nonswelling
nonswelling andand notnotchemically
chemically interactive
interactive
with the substrate [90] and (ii) as, in agreement with the recommendation of
with the substrate [90] and (ii) as, in agreement with the recommendation of Fowkes, they Fowkes, they
have a clearly
have clearly defined
definedpolar
polarcomponent
componentand andtheir polarity
their (γ (γ
polarity p p
/γ) /γ)
spans a broad
spans rangerange
a broad from
0.7 to0.70.18.
from The The
to 0.18. popular, andand
popular, frequently
frequentlyconsidered
consideredasasentirely
entirely nonpolar probes,
nonpolar probes,
diiodomethane (DIM)
diiodomethane (DIM) and
and α-bromonaphthalene
α-bromonaphthalene (BN), (BN), were
were excluded
excluded due
due toto reports
reports on
on
their toxicity
their toxicityand
andononfundamental
fundamentalgrounds
groundsto tobe
bediscussed
discussedfurther.
further.

Table1.1.STC
Table STCof
ofsome
someCA
CAprobe
probeliquids
liquidsat 20◦°C.
at20 C.
𝒅 𝒑
Liquids
Liquids 𝜸𝒍 , mN/m γd , mN/m
γl , mN/m 𝜸𝒍 , mN/m
𝜸𝒍 , mN/m γ , mN/m p Polarity
Polarity
l l
water
water 72.8
72.8 21.8
21.8 51
51 0.700549
0.700549
DMSO
DMSO 44 44 36 36 8 8 0.181818
0.181818
Glycerol
Glycerol 64 64 34 34 30 30 0.46875
0.46875
Formamide
Formamide 58 58 39 39 19 19 0.327586
0.327586
Ethylene glycol 48 29 19 0.395833
Ethylene glycol 48 29 19 0.395833

Hereare
Here arethe
thevalues
valuesofofthe
the
SFESFE calculated
calculated from
from thethe numerical
numerical simulation
simulation datadata
withwith
the
the two approaches (Figure
two approaches (Figure 6a). 6a).

Figure 6.6.Very
Figure Verygoodgoodagreement
agreement is obtained
is obtained (a) between
(a) between thevalues
the SFE SFE values calculated
calculated (i) from(i) fromcontact
water water
contactvia
angles angles via the Neumann
the Neumann equation equation
(Equation(Equation (6))
(6)) and (ii) andOWRK
from (ii) from OWRK (35))
(Equation (Equation
based (35)) based
on contact
on contact
angles anglesbycalculated
calculated by for
Equation (6) Equation
the test(6) for the
liquids test 1;liquids
(Table γs remains 1; 𝛾 remains
(Tableconstant for eachconstant for
CA probe).
each CA probe). There is concordance (b) in the estimates of dispersion and non-dispersion SFE
There is concordance (b) in the estimates of dispersion and non-dispersion SFE components calculated (i)
components calculated (i) by Kloubek equations (Equations (36) and (37)) from γSV obtained with
by Kloubek equations (Equations (36) and (37)) from γSV obtained with Equation (6) from water contact
Equation (6) from water contact angles only and (ii) by OWRK where the accuracy decreases with
angles only and
the reduction in(ii)
theby OWRKofwhere
number the accuracy
test liquids (i.e., at decreases
𝛾 > 44 mN/m, with the
as inreduction
order forinθ the
> 0°number of test
to be obtained
liquids (i.e., at > 44 mN/m, as in order for > 0 ◦ to be obtained from Equation (6), γ must be higher
from Equation s(6), 𝛾 must be higher than 𝛾 ).
γ θ lv
than γs ).
As can be seen, the surface energies estimated from EoS and OWRK essentially
As can be seen, the surface energies estimated from EoS and OWRK essentially
coincide within the accuracy of the EoS (1–2 mN/m due to the uncertainty in the value of
coincide within the accuracy of the EoS (1–2 mN/m due to the uncertainty in the value of
β as explained by Neumann) and the uncertainty in 𝛾 and 𝛾 p (to be discussed further),
β as explained by Neumann) and the uncertainty in γld and γl (to be discussed further),
which proves, as supposed elsewhere, that the estimates of the two approaches are
which proves, as supposed elsewhere, that the estimates of the two approaches are mutually
mutually compatible. Attempting similar numerical simulation, Ahadian reached
compatible. Attempting similar numerical simulation, Ahadian reached opposite results
opposite results (see Figure 4 in [93]) that led to the conclusion that OWRK (and vOCG)
(see Figure 4 in [93]) that led to the conclusion that OWRK (and vOCG) is physically
is physically unsound, as some of the SFE values calculated from it are much lower than
unsound, as some of the SFE values calculated from it are much lower than the EoS
the EoS estimates (which match with the Zisman critical surface tension, and therefore set
estimates (which match with the Zisman critical surface tension, and therefore set the
the lowest theoretically possible boundary of SFE). The reason for the results obtained by
lowest theoretically possible boundary of SFE). The reason for the results obtained by
Ahadian et al. is that in their study, (i) 2–4 probe liquids were used, which is not enough
Ahadian et al. is that in their study, (i) 2–4 probe liquids were used, which is not enough to
to provide accurate estimation of SFE from OWRK, and (ii) following a popular
provide accurate estimation of SFE from OWRK, and (ii) following a popular misconception,
misconception,
DIM was included DIMas awas included
contact angle as a contact
probe angle probe
and assumed to be and assumed
entirely to beThe
non-polar. entirely
non-
non-polar.
polarity (γl The
p non-polarity
= 0) of (𝛾 = 0) ofonDIM
DIM was questioned was questioned
multiple oncontinues
occasions but multipletooccasions but
be accepted
continues to be accepted by default in many publications. As emphasized
by default in many publications. As emphasized by a recent study of the correlation of by a recent
study ofsolubility
Hansen the correlation of Hansen
parameters (HSPs)solubility parameters
with the STC of probe(HSPs) with
liquids, “DIMthepossesses
STC of probe
two
liquids, “DIM possesses two iodine atoms in a single molecule. Iodine atoms
iodine atoms in a single molecule. Iodine atoms can act as a hydrogen bond acceptor, can act asisa
so it
hydrogen bond acceptor, so it is understandable that the polar or hydrogen component of
Colloids Interfaces 2024, 8, 62 16 of 36

understandable that the polar or hydrogen component of HSP can be nonzero. In fact, data
analysis indicates that the commonly used STC values for DIM may be misleading” and
p
based on the relationship with HSP, three possible values of γDI M are proposed: 5.9 mN/m,
8 mN/m and 17.1 mN/m (γDI M = 50.8 mN/m) [94]. From analysis based on Panayiotou
partial solvation parameters, it also follows that “diiodomethane is not an apolar molecule
and in no way we may consider it interacting with dispersion forces only” and instead,
DIM surface tension contains non-dispersion contribution of 17.21 mN/m [95,96]. These
p
suggestions are in remarkable agreement with various experimental estimates of γDI M , i.e.,
2.3 mN/m [73], 4 mN/m [97,98], 6.7 mN/m [99], and with a very recent report that DIM
does not behave as a nonpolar fluid when interacting with water and instead performs as
an electron acceptor (or Lewis acid) with γ+ = 1.55 mN/m due to the iodine ions being
weak oxidizing agents [100]. Similarly, bromonaphthalene (another probe liquid often
assumed to be entirely nonpolar in OWRK and vOCG calculations) has a bromine atom
as a hydrogen bond acceptor and should probably be considered as weakly polar with
p
γl = 0.9 mN/m [101,102]. It should be noted that calculations based on HSP or on partial
solvation parameters attribute significantly higher non-dispersion contribution to the BN
surface tension [95,103].
A frequently overlooked possibility regarding the calculations of the nonpolar and polar
component of SFE energy is the equations provided by Kloubek (Equations (36) and (37)) [104,105],
p
which allow the calculation of γs and γsd from CA measurement with single probe liquid with
known STC as far as solid SFE is also known (it can be calculated from the CA of a single liquid
by any of the EoS in Section 2.1).
v " #
u p γs  [1 + cos θ ] 2
u
[ 1 + cos ]
q q
θ
γsd = γld ± t γl − (36)
2 γl 2
v "
u  2 #
p [1 + cos θ ] [ 1 + cos ]
q q
p
u γ s θ
γs = γl ∓ tγld − (37)
2 γl 2

The approach was demonstrated to be successful for the analysis of the surface properties
of polymers and woods [104–114] and allows the comparison of the values of SFE polar and
disperse component obtained in the numerical simulation, as estimated by OWRK solved for
multiple liquids and by solving Kloubek equations for water used as probe liquid.
As can be seen (Figure 6b), excellent agreement is observed via the two approaches.
The scatter of the values obtained via OWRK at γs > 44 mN/m is because for high SFE,
the OWRK fit should be performed with a small number of liquids (two or three, as in
Equation (6) for θ > 0, γl > γsv ) and the reliability of OWRK estimates becomes lower.
The equations of Kloubek provide an alternative opportunity (compared to simple or
p
multiple linear regression fits) to calculate γs and γsd as an average of the values obtained
with the different wetting liquids (Table 2). This mode of calculation reveals a very peculiar
feature; although, in the numerical simulation, the total SFE of the solid is kept constant for
p
any probing liquid, the values of γs and γsd vary depending on the test liquid for which
the calculation is performed. Although this may reflect true surface chemistry information,
another probable reason for such a discrepancy is the uncertainty in the STC coefficients
for the probe liquids.
Colloids Interfaces 2024, 8, 62 17 of 36

Table 2. Dispersive and non-dispersive SFE components (γs = 41.71 mN/m) computed with Kloubek
equations (Equations (36) and (37)) using CA calculated from Equation (6) for various test liquids.
p
Liquid θ, ◦ γsd , mN/m (Equation (36)) γs , mN/m (Equation (37))
water 70 31.75 9.96
DMSO 18.91 35.255 6.458
Glycerol 58.83 35.213 6.45
Formamide 50.14 36.712 5
Ethyleneglycol 31.21 29.137 12.57
AVERAGE 33.613 8.1
STDEV 2.924 2.93

It is the established practice that these coefficients are quoted as precisely determined
constants (without standard deviations), although STCs (used in both OWRK and vOCG)
are the subject of significant uncertainty, which often cannot be identified in the literature.
Here are some of the reported uncertainties that were occasionally disclosed [115]:
p
- water γl = 51 ± 1.57 mN/m, γld = 21 ± 0.70 mN/m;
- glycerol γld = 34.0 ± 4 mN/m;
- formamide γld = 39.0 ± 7 mN/m.
Also, it should be noted that some authors suggested different dispersive and non-
p
dispersive STC for γwater : γld = 26.2 mN/m, γl = 46.6 mN/m [116]; γld = 26.85 mN/m,
p p
γl = 45.95 mN/m [117]; γld = 29.1 mN/m, γl = 42.7 mN/m [118,119]. Evidently the
uncertainty of STC coefficients can account for the apparent discrepancies observed in
p
γs and γsd estimated from different probe liquids. Of course, the scatter may vary depending
on the technique used to measure STC or on the purity grade and the brand of the probe
liquids; however, this information is typically missing and not accounted for in the literature.
The problem was clearly stated in a recent review: “problem inherent in the vOCG (and
OWRK) model is that it requires some rather aggressive number-crunching. In essence, one
needs to solve simultaneous equations based on coefficients that might not be completely
accurate. As a consequence, there is potential for errors to become magnified. . . such
problems might be at least partly overcome by the design and preparation of specialized
probe liquids” [120].
Still, there is very good agreement between the values obtained via Neumann EoS com-
bined with Kloubek equations and the classic OWRK method (Figure 6b). Similar conclusions
on very good quantitative agreement between EoS, OWRK and vOCG were reached by Della
Volpe and Siboni based on the analysis of contact angle data for a range of probe liquids on
various polymer surfaces. This allows us to calculate β in Neuman EoS from the disperse and
polar components of SFE and the surface tension of the probe liquid as:
 √ 
log γlv (1 + cos θ )/2 γlv γsv
β=− (38)
(γlv − γsv )2

The values calculated were in excellent agreement with the best fit estimate provided
by Newmann (0.0001247). “It is quite surprising that one of the fundamental parameters
of the EoS theory can be recalculated from the vOCG (and OWRK) theory. . . There is,
however, an important difference. If we try to calculate from the vOCG theory the value of
β for a couple of completely dispersive liquid and solid, the value of β is zero, since in this
case the logarithm operand is 1. This fact would suggest that it is not completely correct
to accept that in the vOCG (and OWRK) theory a material can be completely dispersive,
but that even for materials as PTFE or hydrocarbons very low acid–base components
“must” exist, as repeatedly suggested, e.g., for some liquids commonly considered totally
dispersive” [121]. Hence, apart from the experimental uncertainty on the (non)polarity
of DIM (and BN), there are also fundamental theoretical objections to the assumption of
completely nonpolar liquids and surfaces in the frameworks of OWRK and vOCG models.
 It turns out that the estimates obtained by the application of Kloubek’s equations to
SFE obtained by Newman EoS capture the trend observed in real-world data (information
about the dataset in the Supplementary file S1_CA_data.xlsx) very well (Figure 8). The
scatter of the experimental points around the curves is easy to explain, as in the
Colloids Interfaces 2024, 8, 62 experimental studies, (i) often DIM and BN were used and considered as 18 totally
of 36
dispersive, which is practically and theoretically suspicious, (ii) sometimes the values are
calculated from two or three probe liquids, which diminishes the accuracy of OWRK
In agreement
estimates, (iii)with that observation,
interactions betweenstatistical
the probeanalysis
liquidsshows
and thethat the use
solid are of DIM and
possible dueBN to
under
induced thepolarization
assumption of andnonpolar liquids
molecular results in notable
rearrangement at theworsened statistical
solid surface significance
and (iv) often no
of OWRK andis vOCG
information estimations
available of SFE [85–87].
on solid surface roughness or whether the systems were allowed
to approach thermodynamic equilibrium by
A very interesting opportunity provided the equations
[17,18,64]. of Kloubek
Considering all(Equations (36) and
these sources (37))
of noise,
isthe
to analytically estimate the dependence of dispersion and polar components of
agreement between the trends of the data and the analytically calculated curves is SFE (total value
calculated
remarkably with Equation (6) from θwater) on water contact angle (Figure 7a).
good.

Figure7.7.(a)
Figure (a)Dependence
DependenceofofSFESFEand
anditsits component
component asas calculated
calculated from
from Equations
Equations (6),(6),
(36)(36)
andand
(37)(37)
on
on the water contact angle of the solid surface. (b) Dependence of SFE components
the water contact angle of the solid surface. (b) Dependence of SFE components and of (bio)adhesion and of
(bio)adhesion (illustrative qualitative curve) [122,123] on the total SFE.
(illustrative qualitative curve) [122,123] on the total SFE.

A question
Such that emerges
dependence from Figures
is potentially 7 and 8 is
very important onthe
for theelucidation
definition of
of the
hydrophobicity
mechanism
behind the phenomena of biofouling and bioadhesion (Figure 7b) [122,123]. as hydrophilic
and hydrophilicity. Obviously, the still commonly used division of surfaces
(θwater
A <very
90°)interesting
and hydrophobic
question (θ how> these
iswater 90°) is too phenomenological
analytically and cannot
derived dependencies be
score
against real-world data.
It turns out that the estimates obtained by the application of Kloubek’s equations to SFE
obtained by Newman EoS capture the trend observed in real-world data (information about
the dataset in the Supplementary file S1_CA_data.xlsx) very well (Figure 8). The scatter
of the experimental points around the curves is easy to explain, as in the experimental
studies, (i) often DIM and BN were used and considered as totally dispersive, which is
practically and theoretically suspicious, (ii) sometimes the values are calculated from two
or three probe liquids, which diminishes the accuracy of OWRK estimates, (iii) interactions
between the probe liquids and the solid are possible due to induced polarization and
molecular rearrangement at the solid surface and (iv) often no information is available on
solid surface roughness or whether the systems were allowed to approach thermodynamic
 assessment was based on the expression proposed by van Oss.

Δ𝐺 = Δ𝐺 + Δ𝐺 = −2𝛾 − 2𝛾 (39)

Here, the degree of hydrophobicity (ΔGiwi) is expressed as the free energy of

Colloids Interfaces 2024, 8, 62 interaction between two identical entities, where: 19 of 36

𝛾 = 𝛾 −𝛾 and 𝛾 = 2 𝛾 𝛾 + 𝛾 𝛾 − 𝛾 𝛾 (40)
equilibrium [17,18,64]. Considering all these sources of noise, the agreement between the
trends of the
(the sense of data
theseand the analytically
parameters calculated in
will be explained curves
detailisinremarkably
the vOCG good.
section).

Figure8.8.Correspondence
Figure Correspondence of of
real-world datadata
real-world (available in supplementary
(available file and
in supplementary obtained
file by solving
and obtained by
OWRK
solving from
OWRK contact
fromangles
contactof angles
multiple
of wetting
multipleliquids)
wettingand the analytical
liquids) and the dependences estimated
analytical dependences
estimated
by by (6),
Equations Equations (6),
(36) and (36)
(37) andwater
from (37) from water
contact contact
angles. angles.
Solid Solid
red and red lines
green and green lines are
are calculated
p
calculated with 𝛾 = 51 mN/m
d and 𝛾 = 21.8 mN/m, dashed p
lines
with γwater = 51 mN/m and γwater = 21.8 mN/m, dashed lines with γwater = 45.95 mN/m with 𝛾 = 45.95
and
mN/m
d and 𝛾
γwater = 26.85 mN/m. For data and publication sources, see Supplementary file S1_CA_data.xlsx.file
= 26.85 mN/m. For data and publication sources, see Supplementary
S1_CA_data.xlsx.
A question that emerges from Figures 7 and 8 is on the definition of hydrophobicity
Based on the onset
and hydrophilicity. of long-range
Obviously, the still hydrophobic
commonly used interactions,
division ofVogler
surfaces[127] suggested a
as hydrophilic
cutoff of θ ◦ ≈ 65°. ◦
(θ water < 90 ) and hydrophobic (θ water > 90 ) is too phenomenological and cannot be
water

Overall,
accepted the analysis
as scientifically supportsIndeed,
grounded. and provides 40◦ , dispersive
at θ water >theoretical justification for the
interactions much
dominate
more nuanced classification of surface hydrophilicity/hydrophobicity empirically
over the non-dispersive, polar, component of SFE. The result agrees with the estimate that derived
by Arkleswith
surfaces [128]: θ water > 50◦ [124–126] cannot be considered hydrophilic. This assessment
was
­ based on the expression
Super-hydrophilic below proposed
10°; by van Oss.
­ Hydrophilic below 20°; LW AB LW AB
­ Normal from 30° ∆G iwi = ∆Gℶwℶ + ∆Gℶwℶ = −2γiw − 2γiw
to 90⁰; (39)
­ Hydrophobic from 90° to 120°—θwater = 120° is the theoretical maximum contact angle
Here, the degree of hydrophobicity (∆Giwi ) is expressed as the free energy of interaction
for water on a smooth surface [129];
between two identical entities, where:
­ Super-hydrophobic from 150° and greater—requires rough micro-textured or micro-
patterned
LW surfaces [130].LW
q  q q q 
LW AB + − + − − +
γiw = γi − γw and γiw = 2 γi γi + γ w γ w − γi γ w (40)

(the sense of these parameters will be explained in detail in the vOCG section).
Based on the onset of long-range hydrophobic interactions, Vogler [127] suggested a
cutoff of θwater ≈ 65◦ .
Overall, the analysis supports and provides theoretical justification for the much more
nuanced classification of surface hydrophilicity/hydrophobicity empirically derived by
Arkles [128]:
- Super-hydrophilic below 10◦ ;
- Hydrophilic below 20◦ ;
- Normal from 30◦ to 90◦ ;
Colloids Interfaces 2024, 8, 62 20 of 36

- Hydrophobic from 90◦ to 120◦ —θ water = 120◦ is the theoretical maximum contact20angle
Colloids Interfaces 2024, 8, x FOR PEER REVIEW of 38
for water on a smooth surface [129];
- Super-hydrophobic from 150◦ and greater—requires rough micro-textured or micro-
patterned surfaces [130].
2.2.3. Can OWRK Model Be Used to Estimate the Acid/Base Balance in the Non-
Dispersion
2.2.3. Component
Can OWRK Modelof BeSFE
Used to Estimate the Acid/Base Balance in the
Non-Dispersion Component of SFE
As was already mentioned, the non-dispersion component of SFE can be represented
as a As was already
geometric meanmentioned,
𝛾 = 2p 𝛾the 𝛾 non-dispersion component
[24,82] of the basic of donor
electron SFE can(γbe represented
−) and the acid
as a geometric mean γ AB = 2 γ+ γ− [24,82] of the basic electron donor (γ− ) and the acid
electron acceptor (γ++) contributions. To account for this, the vOCG model was developed,
electron acceptor (γ
which, however, ) contributions.
comes with its ownTosetaccount for this, A
of challenges. therelevant
vOCG model was
question developed,
that emerges
which,
is the following: Can the simpler OWRK model be used to estimate the balance emerges
however, comes with its own set of challenges. A relevant question that between
is
γ+the
andfollowing:
γ−? Can the simpler OWRK model be used to estimate the balance between
γ+ and γ− ?
Berger, in 1999 [131], attempted to propose a methodology in this regard. EoS
Berger, in 1999 [131], attempted to propose a methodology in this regard. EoS assumes
assumes that the value of CA is determined solely by the surface tension of the probe
that the value of CA is determined solely by the surface tension of the probe liquid and of
liquid and of the solid. If the surface of the solid remains unperturbed, its SFE will also
the solid. If the surface of the solid remains unperturbed, its SFE will also remain the same,
remain the same, and therefore, for probe liquids with similar surface tensions (γformamide =
and therefore, for probe liquids with similar surface tensions (γformamide = 57.5 mN/m vs.
57.5 mN/m vs. γglycerol = 63.7 mN/m; γaniline = 43.2 mN/m vs. γphenol = 40.4), similar contact
γglycerol = 63.7 mN/m; γaniline = 43.2 mN/m vs. γphenol = 40.4), similar contact angles are
angles are to be expected. However, it turns out that for many polymers, the differences
to be expected. However, it turns out that for many polymers, the differences between
between θformamide vs. θglycerol and θformamide vs. θglycerol are much higher than what can be
θ formamide vs. θ glycerol and θ formamide vs. θ glycerol are much higher than what can be expected
expected from the difference between the surface tensions of the probe liquids (Figure 9).
from the difference between the surface tensions of the probe liquids (Figure 9).

Figure9.9.Illustrative
Figure Illustrativedepiction
depictionof of
thethe scatter
scatter produced
produced in OWRK
in OWRK plot
plot by by wetting
wetting of the of thewith
solid solidLewis
with
Lewisand
acids acids
Lewisandbases.
Lewis
Thebases. Thecircles
colored colored circles
denote denote thethat
the datapoints datapoints
originatethat
fromoriginate
the wettingfrom the
of the
wetting
solid withofLewis
the solid
acidswith
andLewis
Lewis acids
bases,and Lewis bases,
as required as required
to calculate to calculate
Berger’s Berger’s
D (Equations D (Equations
(41) and (42)). The
(41) and (42)). The gray circles depict data from other wetting liquids (to be chosen by the analyst)
gray circles depict data from other wetting liquids (to be chosen by the analyst) used to calculate γSd via
used to calculate 𝛾 via the OWRK method (Equations (32)–(35); see main text for details).
the OWRK method (Equations (32)–(35); see main text for details).
This can
This can be
be attributed
attributed primarily
primarily to
to the
the different
different affinity
affinityof of the
the solid
solid surfaces
surfaces toto Lewis
Lewis
bases (aniline,
bases (aniline, formamide)
formamide) and and Lewis
Lewis acids
acids (phenol,
(phenol, glycerol)
glycerol) liquids,
liquids, asas obviously,
obviously, basic
basic
surfaceswill
surfaces willprefer
prefer(i.e.,
(i.e.,lower
lower θ)
θ)acidic
acidicfluids
fluidsand
andvice
viceversa.
versa.Thus,
Thus, after
after estimation
estimationof of the
the
dispersion and non-dispersion components of SFE via the OWRK method
dispersion and non-dispersion components of SFE via the OWRK method (at least seven (at least seven
probeliquids
probe liquidsare
arerecommended),
recommended),ititisispossible
possibleto tocalculate
calculatethe
theBerger’s
Berger’sDDparameter:
parameter:

𝐷=2 𝛾 (𝐴𝑛𝑖𝑙𝑖𝑛𝑒) + 𝛾 (𝐹𝑜𝑟𝑚𝑎𝑚𝑖𝑑𝑒) − 2 𝛾 (𝑃ℎ𝑒𝑛𝑜𝑙) + 𝛾 (𝐺𝑙𝑦𝑐𝑒𝑟𝑖𝑛𝑒) (41)

 D > 0 corresponds to acid and D < 0 to basic character of the surface [132].
The ability of surfaces of various polymers (or other solids) to adhere to each other is
Colloids Interfaces 2024, 8, 62 21 of 36
estimated via:

∆𝐷 = 𝐷 −𝐷 (42)
q High values
q of ∆𝐷 suggest
 complimentary
q acid–base
q interaction
 between the
D=2 γSAB (opposing
Aniline) + γSAB (and
surfaces Formamide AB
) − 2toPhenol
γS (to
were shown
relate ) + and
stronger
AB ( Glycerine
γS more durable (41)
) adhesion [132–
135]. Despite its successful use cases, Bergers’s approach should be used with caution as
D > 0 corresponds to acid and D < 0 to basic character of the surface [132].
some of its premises appear uncertain. Particularly, although Berger and most of the
The ability of surfaces of various polymers (or other solids) to adhere to each other is
vOCG scales (see Section 2.2.4) consider formamide as a base, according to current
estimated via:
solvatochromic estimations, formamide adhesive is a dipolarsubstrate
solvent containing a carbonyl group
∆D = D −D (42)
and an amino group, and thus, can accept and donate H-bonds [136]. Nevertheless, the
principle
High(acids
valuespreferentially
of ∆D suggest adhere to bases and
complimentary vice versa)
acid–base is valid,between
interaction and thethe
method can
opposing
be enhanced
surfaces by itsshown
and were implementation via CA probes
to relate to stronger and morewith clearly
durable defined[132–135].
adhesion chemical Despite
nature.
For example, ituse
its successful was shown
cases, that theapproach
Bergers’s basic DMSO strongly
should be used adheres to the predominantly
with caution as some of its
acidic
premises appear uncertain. Particularly, although Berger and most of the vOCGtoscales
polyvinyl chloride (PVC) and displays much weaker adhesion the
predominantly basic poly(methyl methacrylate) (PMMA) surface, while
(see Section 2.2.4) consider formamide as a base, according to current solvatochromic in contrast, the
acidic liquid pyrrole
estimations, formamide behaves in reverse
is a dipolar and favors
solvent PMMA
containing [137].
a carbonyl group and an amino
group, and thus, can accept and donate H-bonds [136]. Nevertheless, the principle (acids
2.2.4. vOCG Model
preferentially adhere to bases and vice versa) is valid, and the method can be enhanced by
its implementation via CA
To account in detail forprobes with clearly
the possible defined chemical
complimentary nature.
(see Figure For example,
10) Lewis acid–baseit
was shown that the basic DMSO strongly adheres to the predominantly
interactions among the non-dispersive components of solid and liquid surface tensions acidic polyvinylin
chloride (PVC)
adhesion, and displays
the vOCG model wasmuch weaker adhesion
developed [24]: to the predominantly basic poly(methyl
methacrylate) (PMMA) surface, while in contrast, the acidic liquid pyrrole behaves in
reverse and favors𝑊 =PMMA cos θ) = 2(𝛾 𝛾 ) / + 2(𝛾 𝛾 ) / + 2(𝛾 𝛾 ) /
𝛾 (1 + [137]. (43)

2.2.4. vOCG Model 𝛾 =𝛾 +2 𝛾 𝛾 (44)

To account in detail for the possible complimentary (see Figure 10) Lewis acid–base
interactions among the non-dispersive 𝛾 = components
2 𝛾 𝛾 of solid and liquid surface tensions in
(45)
adhesion, the vOCG model was developed [24]:
The AB component of SFE is presented as a geometric mean and includes (i) basic,
 1/2
1/2
1/2accounting
electron donor,
Wa =(γγl)(and
− (ii) θacidic,
1 + cos ) = 2 electron
γlLW γsLW acceptor,
+ 2 γ(γ
++) −
contributions, thus
+ 2 γs+ γl− (43)
l γs
for hydrogen bonding and p-electron interactions [138]. As shown in Equations (43)–(45),
it is assumed that considering the non-dispersion q contribution to the work of adhesion,
LW + −
the acidic character of the probe γliquids = γs interacts
+ 2 γwith
s γs the basic character of the solid,(44)
/
2(𝛾 𝛾 ) , and the basic character ofABthe liquid interacts with the acidic nature of the
q
solid, 2(𝛾 𝛾 ) / . γ = 2 γs+ γs− (45)

Figure 10.
Figure Van der
10. Van der Waals
Waals (solid
(solid arrows)
arrows) and
and acid–base
acid–base (dashed
(dashed arrows)
arrows) intermolecular
intermolecular interactions
interactions
within and
within andbetween
betweenmaterials
materialsofofdifferent
differentpolarity:
polarity:(a)(a) between
between non-polar
non-polar liquid
liquid andand
any any solid;
solid; (b)
(b) between bipolar liquid and dispersive solid; (c) between monopolar liquid and complimentary
mono- or bipolar solid; (d) between bipolar liquids and solids.

The AB component of SFE is presented as a geometric mean and includes (i) basic,
electron donor, (γ− ) and (ii) acidic, electron acceptor, (γ+ ) contributions, thus accounting
for hydrogen bonding and p-electron interactions [138]. As shown in Equations (43)–(45),
Colloids Interfaces 2024, 8, 62 22 of 36

it is assumed that considering the non-dispersion contribution to the work of adhesion,

the acidic character of the probe liquid interacts with the basic character of the solid,

1/2
2 γl+ γs− , and the basic character of the liquid interacts with the acidic nature of the

1/2
solid, 2 γs γl−
+ .
In the vOCG framework, liquids and solids are considered as fully non-polar
(γLW > 0; γAB = γ+ = γ− =0), monopolar (γLW > 0; γAB = 0; γ+ = 0 or γ− =0) and bipolar
(γLW > 0; γAB > 0, γ+ > 0; γ− > 0). The molecules of bipolar materials can form hydrogen
bonds between each other (self-aggregation) and with molecules of other mono- and bipolar
specimens, while molecules of monopolar materials cannot form hydrogen bonds each with
other (i.e., no self-aggregation, and hence, γAB = 0) but can do so with the molecules of other
bipolar or monopolar materials (if the monopolar substances are of complementary nature,
i.e., γl+ with γs− or γl_ with γs+ ) [139,140]. As mentioned in Section 2.2.2, it is reasonable to
assume that within the vOCG framework, it is not acceptable to consider a material (solid
or liquid) to be entirely dispersive, and some, if even very low, acid–base components
“must” exist [121].
As vOCG contains three unknowns, contact angles with at least three probe liquids
(liquid triplets) with known STC are needed to obtain γsLW , γs− , γs+ , and γs ; however,
similarly to OWRK, to reach reliable estimates of SFE and its components, they should
be overdetermined by measurements with a larger number of liquids (7–14 are recom-
mended) [135].
The values of γlLW and γlAB are generally the same as the ones accepted in the OWRK
model for the dispersion and non-dispersion STC of probe liquids. However, a major
bottleneck encountered by the vOCG model was how to determine reliable values of
γl+ and γl− (i.e., of the subcomponents of γlAB ) of the probe liquids. Initially, a computation
procedure was adopted which (i) used water as the standard by which to judge the relative
− +
Lewis acidity and basicity of all other liquids, assuming γwater = γwater = 25.5 mN/m based on (ii)
the liquid contact angles over poly(methyl methacrylate) (PMMA) and polyvinyl chloride (PVC),
assumed to be monopolar basic and acid surface, respectively [139,140]. It was considered that
− +
although the γwater = γwater assumption is not rigorous, it will not affect the estimations of
adhesion between liquids and solids [24]. As emphasized by Della Volpe and Siboni [141], “The
meaning of this choice must be clear; it does not mean that water is equally strong as a Lewis
acid and as a Lewis base. No definition of “strength” of acids and bases is given in vOCG.
In other words, one cannot compare the acid and base components of the same solvent, but,
eventually, the acid (or base) components of different solvents can be compared”. Furthermore,
IR-spectroscopy and quantum chemical analysis suggested that PMMA and PVC are not entirely
monopolar surfaces, i.e., PMMA shows preferential basicity (due to the carbonyl group) and
includes a number of acid sites as well, while PVC is primarily acidic due to methylene chloride
but is also prone to limited self-assembly due to the weak basicity of chlorine atoms [142].
Surface composition depends on the polymer grade and the sample preparation protocol, and
other reports suggest that at the PMMA surface, only basic -CH3 and C=O groups are found
(i.e., PMMA might be viewed as monopolar) [117]. Yet, Kollman quantum chemical calculations
suggested that to some extent, each substance shows both acid and base properties [143], and
all polymers, excluding saturated hydrocarbons, such as polyethylene and polypropylene,
have both acidic and basic functional groups [144]. The use of the pioneer liquid STC values
(see Supplementary file S2_vOCG_Scales.xlsx) obtained in the manner described above resulted
in the so-called “basic catastrophe”, i.e., it turned out that when analyzed with the vOCG model,
almost every solid surface of interest is overwhelmingly basic (γs− >> γs+ ), including surfaces
like polyvinylchloride that are well known to be predominantly acidic. This seriously led to
the question “Is the world basic?” where obviously one cannot readily agree [145,146]. Janczuk
et al. [117] (see Supplementary file S2_vOCG_Scales.xlsx) performed a series of very precise
measurements of interfacial tensions and contact angles with probe liquids, thus attempting
− +
to improve the initial estimates of van Oss, while keeping with the assumption γwater = γwater ;
however, when these newly calculated liquid STCs were used, for the most part, the world
remained basic. As summed up by Greiveldinger and Shanahan [147], under the assumption
Colloids Interfaces 2024, 8, 62 23 of 36

− +
γwater = γwater , the mathematical formalism of the vOCG equation is inadequate, as indicated by
the appearance of physically untenable square roots of negative numbers (sqrt (γs− ) or sqrt(γs+ ))
and the predominance of basic surfaces, possibly due to the arbitrary nature of taking water to be
equally acidic and basic. Furthermore, ‘inverting’ the method and using accepted solid surface
characteristics to ‘rederive’ surface free energy parameters for probe liquids proved inconsistent.
They concluded that, “although from a philosophical point of view the acid/base or electron
acceptor/donor theory seems valid and constitutes a useful addition to the understanding of
interfacial free energies, in its present form, it seems clear that the mathematical presentation is
inadequate, and modifications would seem to be necessary in order to achieve self-consistency”.
Attempts were made to fix that problem by better conditioning of the system needed to solve
the vOCG equation via selection of optimal probe liquids on the basis of the difference in their
Qr ratio (γl+ /γl− ) and condition number (to ensure simultaneous use of highly polar and highly
non-polar CA probes) [116,148,149]. Although it was possible to cure the “negative square
roots” problem, statistical analysis of the quality of the fits obtained under the assumption
− +
γwater = γwater showed that the non-zero value of γs− or γs+ often may be attributed to chance
(i.e., the statistical significance of the model is inadequate) [85–87].
− +
Thus, it appears that γwater = γwater = 25.5 mN/m might be problematic, and it will be
worth looking for a scale on which the electron donor and electron acceptor parameters of
many solvents are put into such a form that one can compare the two parameters for the
same solvent. The first attempt to reconsider it was made by Lee [150] who, based on the
correlation among the coefficients of solvatochromic scale and the coefficients of the vOCG
− +
theory, suggested that water is predominantly acidic (γwater = 19 mN/m, γwater = 34.2 mN/m)
and recalculated the liquid STC accordingly. Although the world continued to be mostly basic,
more realistic estimates of acid/base properties of solids were obtained. Based on the similarity
between the Taft–Abraham scale and vOCG theory, Della Volpe and Siboni [141] also concluded
− +
that water is predominantly acidic (γwater = 10 mN/m, γwater = 65 mN/m, later revised to
− +
γwater = 11.2 mN/m, γwater = 48.5 mN/m). The explanation is that “in common pure water a
fast equilibrium (in about 10–20 min) with atmospheric carbon dioxide is established; the final
pH is about 5.5–6, which corresponds to a strong excess of hydrogen ions, about 900 times more
concentrated than OH− ions” [116].
In an attempt to derive the STC of probe liquids (see Supplementary file S2_vOCG_Scales.xlsx)
in an assumption-free manner, Della Volpe and Siboni attempted to solve the system [151]:
q
LW + −
γl,i = γl,i +2 γl,i γl,i , ∀i = 1, 2, . . . , l
q
LW + −
γs,j = γs,j + 2 γs,j γs,j , ∀i = 1, 2, . . . , s
q q q 
LW γ LW + + − − +


γl,i 1 + cos θi,j = 2 γl,i s,j γl,i γs,j + γl,i γs,j , ∀i, j (46)

The only preliminary information is the total surface tensions of the liquids, and the
contact angles adopted by them at the test solid surfaces. The parameters γlLW , γl+ and
γl− for the liquids and γs , γsLW , γs+ and γs− for the polymer (solid) surfaces are unknown.
However, certain problems persisted, as (i) some of the STCs obtained appear non-physical,
and especially (ii) due to the multiple degrees of freedom provided by the many unknowns,
it turned out that no unique solution exists even when γ+ /γ− for water is supplied to
the system. Instead, different liquid STCs can be obtained depending on the sequence of
insertion of the equations and the algorithm used to solve the system.
To address the problem, Starostina and Stoyanov [132–135,152,153] proposed the
“simplified system” approach:
- The value of γlLW is provided based on the reliable published data used in the OWRK
model (or is determined independently by OWRK).
- Equilibrium contact angles of the probe liquids are measured on two precisely characterized
polymer surfaces, PTFE (γs = 24.35 mN/m; γsd = 24.14 mN/m) and PVC (γs = 38.7 mN/m;
γsd = 36.9 mN/m). The solid SFE is determined via the OWRK model.
Colloids Interfaces 2024, 8, 62 24 of 36

- Using the relationship valid for the STC of both liquids and solids,

γ = γ LW + 2
p
γ+ γ− (47)
it is possible to express γ− via γ+ and the already known values of γ and γLW

2
2
γ − γ LW γ − γ LW
γ− = or γ+ = (48)
4γ+ 4γ−
- Now, it becomes possible to solve a much more simplified system consisting of
equations like:
v
LW
s
u γsj − γsj γli − γliLW +

q u
γli 1 + cos θij LW LW +
− γli γsj = γli
t
+ + γsj (49)
2 4γsj 4γli+

This system is computationally better defined and the following (Table 3) STC compo-
nents are determined (see also Supplementary file S2_vOCG_Scales.xlsx) and they match
the chemical nature of some liquids: ethylene glycol and glycerol are predominantly acidic,
while DMSO is overwhelmingly basic.

Table 3. Acid–base parameters of some commonly used wetting liquids at 20 ◦ C.

Simplified System Approach Van Oss Assumption

Liquid − +
(Starostina et al. [132–135,152,153]) γwater = γwater = 25.5 mN/m
γ+, mN/m γ−, mN/m γ+, mN/m γ−, mN/m
Glycerol 16.38 14 3.92 57.4
DIM 1.32 0 0 0
BN 0.05 0 0 0
Formamide 5.25 39.89 2.28 39.6
Water 61.45 10.58 25.5 25.5
DMSO 1.25 14 0.52 32
Aniline 0.02 43.91 NA NA
Ethylene glycol 12.37 7.3 1.92 47.0

The liquid STC derived by Starostina and Stoyanov proved useful to predict the
adhesive strength of polymer coatings [132–135]. The statistical analysis confirms that the
non-zero values of solid SFE and its components, determined when solving vOCG equation
with these liquid STCs, are not due to chance (i.e., the model is statistically significant). In
order to obtain reliable estimates of γs and its components, at least seven probe liquids are
necessary, and these must include bases (γ− > γ+ ) and acids (γ+ > γ− ) [132–135,152,153].
It should be noted that the quest for the best liquid STC values is an open topic among vOCG
practitioners and each of the proposed scales (see Supplementary file S2_vOCG_Scales.xlsx) has its
adherents. As recently pointed out, “it appears that almost all calculations of interaction energies
presently in the literature have been based on the earlier arbitrary scale of acidity and basicity
assumed in the vOCG model. However, without having a firm basis upon which to define a
new acid-base scale, there does not yet appear to be sufficient reason to adopt the approach of
Della Volpe et al. (2004) as a way to process data. Rather, the results can be regarded as a signpost
indicating likely inaccuracies of work done to date using limited sets of acid and base probe
liquids. Though a better overall fit can be achieved by using an updated scale of basicity and
acidity, the results for a given analysis still are likely to depend on an arbitrary selection of probe
liquids” [120]. Chibowski also considered that, especially at room temperature, it is not justified to
regard water as a predominantly acidic liquid, but rather as an amphoteric one [47]. Overall, due
to the extreme difficulty of unambiguously determining liquid STC experimentally, a theoretical
framework for their calculation might be the most convenient solution to tackle the challenge. A
quantum mechanics-based approach was proposed by Panayiotou on the basis of partial solvation
Colloids Interfaces 2024, 8, 62 25 of 36

− +
parameters [95,96]. Within this framework, γwater = γwater = 25.84 (or 23.72) mN/m (in agreement
with van Oss and in contrast to later proposals), and at the same time, the probe liquid acid–base
parameters are “more balanced” compared to the van Oss–Good parameters, i.e., for glycol,
glycerol and formamide, the base/acid ratio of the PSP-based surface tensions is in the range
1.1–1.5 versus 15–25 for the same compounds with the van Oss–Good method. The results
obtained in SFE calculations from these parameters proved relevant and they warrant further tests.
Still, it should be noted that none of the proposed γl+/γl− scales in the vOCG method resembles
the acidity and basicity estimates provided by the well-established solvatochromic scales of
polarity of pure solvents (Reinhardt, Abraham, Kamlet–Taft etc.) [154–156]. A possible explanation
might be the reorientation of liquid molecules at surfaces (as solvatochromic parameters are
measured in the liquid bulk); however, additional research is needed in this regard
A further peculiarity mentioned by Etzler [85–87] is that the values of solid SFE
and its components obtained via solving of the vOCG equation depends on the chosen
computational approach; (i) if it is solved subject to constraints that γLW alone or together
with γAB should be equal to the estimates of the OWRK model, then of course the total SFE
is close to the value obtained via OWRK, while (ii) if the vOCG equation is solved without
constraints, then often different (usually higher) SFE is obtained. The possible physical
meaning of this peculiarity requires further study.
Another challenge in the current state of the vOCG approach is that the uncertainty
of the STC of probe liquids is virtually impossible to find, as no data on standard devia-
tions/errors or confidence intervals of liquid STC are reported. Thus, the solution of the
vOCG equation bears the risk of transforming into an error propagation pipeline where the
accuracy of the estimated solid SFE and its components is impossible to estimate [120].

3. On the Compatibility of EoS, OWRK and vOCG Models: A Practical Example

Here are the contact angles of different probe liquids (STC data in Tables 1 and 3)
on Poly(methyl methacrylate) (PMMA) surfaces, as reported by Chibowski [60]. Table 4
summarizes the excellent agreement between Chibowski’s equation and Neumann EoS.

Table 4. Contact angle data of wetting probes on PMMA with calculations of SFE based on the
equation of Chibowski and Neumann.

Liquids θADV , ◦ ΘREC , ◦ ΘTadmore , ◦ γsChibowski , mN/m Neumann , mN/m

γsv
water 62.21 54.79 58.46 51.4 49.64
glycerol 63.06 53.33 58.13 44.3 42.64
Formamide 54.7 46.6 50.63 44.2 41.83
EG 54.08 41 47.5 36.2 35.28
DMSO 34.61 23.17 28.99 39.1 38.97
Mean 43.04 41.67
Standard deviation 5.81 5.31

As shown on Figure 11, there is a strong and statistically significant correlation of γs

p p
on γl and γs on γl (while γsd does not depend on the liquid surface tension) in accordance
with the induced surface polarization theory (see Section 2.1.3).
 vOCG Assuming γwater− = γwater+ = 25.5
OWRK vOCG with STC of Starostina
mN/m
𝛾 , 𝛾 , 𝛾 , 𝛾 , 𝛾 , 𝛾 , 𝛾 , 𝛾 , 𝛾 ,
𝛾 , mN/m 𝛾 _ , mN/m
mN/m
Colloids Interfaces mN/m
2024, 8, 62 mN/m mN/m mN/m mN/m mN/m mN/m mN/m 26 of 36
39.25 ± 2.8 23.14 ± 1.5 16.11 ± 1.2 39 ± 3 34.64 ± 1.4 0.17 ± 0.2 26.582 ± 1.1 40 ± 2 21.16 ± 1.05 7.12 ± 0.8 14.03 ± 1

Figure 11.
Figure 11. Dependance of solid SFE andand itsits components
components (calculated from Equations (35) and (36))
on surface
on surface tension
tension parameters
parameters of
of test
test liquids.
liquids. RR is
is Pearson
Pearson linear
linear correlation
correlation coefficient;
coefficient; pp is
is the
the
probabilityof
probability ofthe
thevalue
value of
ofRRbeing
beingduedueto tochance;
chance;pp<< 0.05
0.05 denotes
denotes statistical
statistical significance.
significance.

The values
Table 5 shows ofthetheestimates
total SFEobtained
are in excellent
via OWRK agreement,
and vOCGwithin experimental
(with the liquid STC as
accuracy, with
suggested by van theOss mean[24]values
and byobtained
Starostina byetthe
al. equations
[153]). of Chibowski and Neumann,
which can be further improved by increasing the number of contact angle probes [153].
The values
Table 5. SFE ofofPMMA
the dispersive
from OWRK andand non-dispersive
vOCG models. components vary between the various
approaches (OWRK and vOCG (using different liquid STC coefficients)), which is
OWRK vOCGmanyAssuming − =γ +
reported timesγwater
[85–87] and=is25.5
water mN/mto greatly depend
shown vOCG with on STC
the of
typeStarostina
and number of
p LW , +, −, LW , +
γs , γsd , γs , the probeγs , liquidsγchosen and son the calculation ,
protocol (these s,
subjectsγwill be γas_ ,topic
mN/mof
s γ γs γ s γs
mN/m mN/m mN/m mN/m mN/m mN/m mN/m mN/m mN/m mN/m
our subsequent publications).
39.25 ± 23.14 ± 16.11 ± The ±
34.64 agreement 26.582 ± 21.16 ±
39 ± very
3 good 0.17 ± in0.2 the estimates of40the ± 2total SFE reveals that
7.12 in terms
± 0.8 14.03of ± the
1
2.8 1.5 1.2 1.4 1.1 1.05
models of Chibowski and Neumann (allowing determination of SFE from CA
measurements with single probe), the SFE values obtained via OWRK and vOCG
The values
represent of the total
the average SFEindividual
of the are in excellent
apparentagreement,
SFE adoptedwithin by thethe
experimental
solid surface accuracy,
when
with
wettedthebymeaneach values
of the obtained
individualby the equations
liquids. of Chibowski
Chibowski and Neumann,
and others had shown which
that can thisbeis
further
valid for improved
a very by increasing
broad rangethe ofnumber
surfaces, of contact
from highly angle probes
polar [153].
(glass,The values
θwater ≈ 30°) of theto
dispersive
exceedingly and non-dispersive
hydrophobic (i.e.,components
Teflon andvary between with
polystyrene the various
θwater >approaches (OWRK
100°) [53,60,79,85–
and vOCG (using different liquid STC coefficients)), which is reported
87,92]. This is in excellent agreement with the premises of Lipatov’s interfacial equilibrium many times [85–87]
and is shown to greatly depend on the type and number
rule and the related induced surface polarization models considering that the surfaceof the probe liquids chosen and
on the calculation
tension of the solidprotocol
depends(theseon the subjects
surfacewill be a of
tension topicthe of our subsequent
wetting liquid (seepublications).
Section 2.1.3).
The
Based very
on good agreement
this example andinthe thediscussions
estimates of in thethe total SFE reveals
previous sections,that the in terms
peculiar
of the models of Chibowski and Neumann (allowing
features and limitations of the single and multiple liquid CA-based models for SFE determination of SFE from CA
measurements with single probe),
determination are summarized in Table 6. the SFE values obtained via OWRK and vOCG represent
the average of the individual apparent SFE adopted by the solid surface when wetted
by each of the individual liquids. Chibowski and others had shown that this is valid
for a very broad range of surfaces, from highly polar (glass, θ water ≈ 30◦ ) to exceedingly
hydrophobic (i.e., Teflon and polystyrene with θ water > 100◦ ) [53,60,79,85–87,92]. This is
in excellent agreement with the premises of Lipatov’s interfacial equilibrium rule and the
related induced surface polarization models considering that the surface tension of the
solid depends on the surface tension of the wetting liquid (see Section 2.1.3).
Based on this example and the discussions in the previous sections, the peculiar
features and limitations of the single and multiple liquid CA-based models for SFE deter-
mination are summarized in Table 6.
As each of the approaches has its intrinsic strengths and limitations, the choice of a
particular CA-based model for SFE determination is a matter of informed choice of the
analyst. Although laborious, as also recommended elsewhere [53,60,79,85–87,92], it makes
sense to apply all the models and to analyze the mutually complimentary information that
they provide for the solid surface of interest. The values of SFE obtained via Neumann EoS
and the model of Chibowski combined with Kloubek’s equations (Equations (36) and (37))
allow us to probe the dynamics of the dispersion and non-dispersion functionality of the
solid surface when treated by wetting liquids of different polarity. This information will in
Colloids Interfaces 2024, 8, 62 27 of 36

turn facilitate the interpretation of the SFE estimates obtained via the approaches of OWRK
and vOCG.

Table 6. Features and limitations of single and multiple liquid CA-based models for solid SFE determination.

SFE Models Features Limitations

1. The parameter β in Neumann EoS
1. SFE can be determined from CA is a best fit estimate and is not
measurements with single liquid obtained analytically. The good
of interest agreement of the EoS with the fully
analytically derived equation of
2. SFE depends not only on the Chibowski reaffirms the confidence
properties of the solid but also on in β = 0.0001247 (m2 /mJ)2 estimate
the surface tension and properties of
the wetting liquid (particularly for 2. Chibowski’s equation requires the
Single liquid models: polar CA probes) values of both advancing and
Neumann EoS (Equation (6)) receding CA. CAH can be sensitive
and Chibowski CAH model 3. Ergonomic (smaller number of not only to the chemistry but also to
(Equation (20)) measurements) and ensures better the roughness of the surface, which
(narrower) confidence interval of should be accounted for particularly
the SFE value compared to OWRK at CAH > 20◦
and vOCG
3. Considered to not provide
4. SFE values can be used for information on SFE components,
thermodynamic predictions of which can be mitigated to a
(bio)adhesion (see Equations (51) significant extent with the help of
and (52), Section 4) Kloubeck’s equations
(Equations (36) and (37))
1. As SFE values calculated via
OWRK/vOCG are essentially an
1. Fit a single SFE value and its average of the individual SFE
components (dispersion and adopted by the solid when wetted
non-dispersion) based on all CA with various CA probes, the
measured with various OWRK/vOCG estimates are often
wetting liquids less statistically robust (broader
confidence interval) and may show
2. vOCG aims to elucidate the significant dependence on the
balance between the acid and basic selection of wetting liquids
properties of the solid surface.
Adaptation of OWRK model along 2. STC components of test liquids in
the lines of Bergers’ method might +
OWRK and vOCG (especially γliquid
provide a more robust (although −
and γliquid ) may not be precisely
less detailed) characterization of the
acid/base character of the determined. Particularly the choice
solid surface of acid–base scale and the values of
Multiple liquids models: γ+ and γ− of CA probes in vOCG is
OWRK (Equation (33)) and 3. The OWRK/vOCG SFE values a matter of significant debate and
vOCG (Equation (44)) can be viewed as an average of the may strongly influence the
individual SFE obtained by numerical value, the statistical
Neumann or Chibowski equations significance and the interpretation
with each of the individual of the results. The practitioner
wetting liquids should be acquainted with each of
the suggested scales and its
4. Can be used for thermodynamic advantages and limitations.
predictions of (bio)adhesion (see
Equations (53) and (54), Section 4) 3. The latter problem can be at least
partially addressed if the
5. vOCG SFE estimates can be recommendation of Della Volpe and
plugged into xDLVO theory to Siboni is followed that at the current
probe and tune the interfacial force state of vOCG, one cannot compare
balance and the potential energy the acid and base components of the
barriers that may otherwise hamper same material, but, eventually, the
(bio)adhesion (see Section 4) acid (or base) components of
different materials can be compared
between each other

4. Values of the Solid Surface Free Energy as Predictors for (Bio)adhesion, a Brief
Remark on the Most Popular Approaches
A major reason for the interest in CA-based determination of SFE of solids is that
these values can be used to analyze and predict the (bio)adhesion of biological entities
Colloids Interfaces 2024, 8, 62 28 of 36

(bacteria, cells, microalgae, etc.) to other surfaces (polymers, implants, contact lenses,
nanoparticles, etc.) when these are brought in contact in aqueous (or other) environments,
like biofluids [157,158].
The thermodynamic concept is that for the (bio)adhesion to take place, the interfacial
tension of the adhesive contact should be lower than the sum of the interfacial tensions of
the free (non-adhered) surfaces in solution [159,160].

∆Gadh = γbs − γbl − γsl (50)

where γbs , γbl , and γsl are the interfacial free energies of the biological entity−solid,
biological entity−liquid, and solid−liquid interface (∆Gadh is the change in Gibbs free
energy; for (bio)adhesion to be thermodynamically favorable, ∆Gadh < 0).
The calculation based on the estimates from the Neumann EoS uses the following
equations [159]:

lv 2 lv 2 sv 2
q q q
bv sv bv
∆Gadh = 2 γbv γlv e− β(γ −γ ) +2 γsv γlv e− β(γ −γ ) − 2 γbv γsv e− β(γ −γ ) − 2γlv (51)
where
sv 2
q
bv
γ = γ + γ − 2 γbv γsv e− β(γ −γ )
bs bv sv

lv 2
q
bv
γbl = γbv + γlv − 2 γbv γlv e− β(γ −γ )
lv 2
q
sv
γsl = γsv + γlv − 2 γsv γlv e− β(γ −γ ) (52)
The equations based on the OWRK are as follows [160,161]:
q q q q 
LW
∆G adh = −2 LW −
γbv LW
γlv LW −
γsv LW
γlv

q q q q 
AB
∆G adh = −2 AB −
γbv AB
γlv AB −
γsv AB
γlv (53)

The acid–base interactions can be estimated in further detail from the vOCG parame-
ters [160,161]:
q q q q  q q q q  q q q q 
AB + + − − + + − − + + − −
∆G adh =2 γbv − γsv γbv − γsv −2 γbv − γlv γbv − γlv −2 γsv − γlv γsv − γlv (54)

The thermodynamic approaches have been successful on many occasions but bear the
inherent limitation that they cannot predict whether a potential energy barrier (i.e., local
maximum of repulsive forces) exists that can greatly delay the realization of (bio)adhesion.
The analysis of the variety of interactions (electrostatic, van der Waals, acid–base, etc.)
between approaching surfaces as a function of the distance between them, the geometry
and charge of the particles and the liquid environment parameters is possible via DLVO
and xDLVO theories, which also utilize the SFE data obtained for the solid surfaces. A
detailed summary of the advantages and limitations of each of these approaches is available
in the papers of Rao and some recent reviews [162–166].

5. Concluding Remarks
The field of SFE determination continues to evolve. There are some major points that
can be considered in future developments:
- An important practical consideration is how contact angles are measured, as these
serve as a base of all subsequent calculations. Apart from the model of Chibowski
using dynamic, advancing and receding, CA, all other models require the equilibrium
contact angle of Young. While for real surfaces in the real world, thermodynamic equi-
librium might be challenging to achieve, methods have been developed to measure
the so-called most stable CA that is a good approximation of the Young CA. Some of
Colloids Interfaces 2024, 8, 62 29 of 36

these required the implementation of vibrations [167]; however, simpler resolutions

are possible. In the most used sessile drop technique, it is recommended that the value
of the CA should remain constant (within ±1◦ ) for one minute after the deposition
of the liquid droplet on the solid surface. For diiodomethane, ethylene glycol, and
water, this happens within a second after deposition, while for formamide, glycerol,
aniline, and 88% phenol solution, a stable value is reached two minutes after the
deposition [153]. Such information is usually not provided in publications and may
add an additional source of uncertainty.
- The experiments should be performed with precise control of the parameters (tem-
perature, relative humidity, etc.) of the drop microenvironment, and the design and
availability of the proper measurement chamber is an ongoing challenge [168].
- The models of Chibowski and Neumann are generally in good agreement in their SFE
assessments. Multiple experiments have shown that CA-based estimates of solid SFE depend
on the surface tension and chemical nature of the wetting liquid [53,60,79,85–87,92,169,170].
The very same trend is also observed for OWRK and vOCG, where the selection of CA
probes (as well as computational routine) is of crucial importance for the SFE value to
be obtained. Still there is excellent quantitative agreement between single wetting probe
(Chibowski, Nuemann) and multiple wetting probe (OWRK and vOCG) models, where SFE
calculated from OWRK/vOCG represents the mean value of the individual SFE attained
by the solid when wetted by each distinct CA probe. As emphasized by Chibowski, the
CA-based SFE values (computed by any model) are apparent energies that are nevertheless
useful, as they tell us a lot about the energy and the chemistry of the solid surface [170,171].
- Under the assumption of saturated precursor film present ahead of the drop (i.e., a
pillar of the Frumkin–Derjaguin theory of wetting), the model of Chibowski transforms
into the interfacial equilibrium rule derived by Lipatov. It assumes that SFE is a
function of γL due to a phenomenon of induced surface polarization that was also
assumed by some other models. It is notable that the dependence γS = f (γL ) is
observed independently of the equations used to compute SFE (Equations (6) and (20)
or Equation (24)), i.e., both in “dry” and “wet” wetting. The induced polarization
models have been shown to provide a particularly good fit to the experimental data
and deserve further analysis and development.
- Based on the relative contribution of dispersive and non-dispersive components to the
SFE of solids, the designation of hydrophobicity as θ water > 90◦ looks arbitrary. The
cutoff values of θ water > 50◦ or θ water > 65◦ appear better grounded [124–127].
- The knowledge of the STC of CA probe liquids needs to be improved. The uncer-
tainty of liquid STC should be determined and become available to practitioners.
Furthermore, these parameters will be dependent on the purity and grade of the test
liquid (as even ultrapure liquids contain minor admixtures that tend to vary between
manufacturers). As recently suggested, it makes sense to develop and make available
a standardized wetting kit, i.e., high purity standard and designer liquids with pre-
cisely characterized STC at different temperatures and conditions (now, such data are
available essentially only at standard conditions).
- The assumption of the implementation of non-polar liquids, like DIM and BN, in
OWRK and vOCG needs to be critically reevaluated. Analysis of Hansen solubility
parameters (HSPs) and of experimental data casts doubt on the non-polarity assump-
tion, and particularly, DIM may have considerable non-dispersive STC. Indeed, in
p
high-profile references, DIM was frequently considered to have γDI M = 2–7 mN/m,
although this remained overlooked in most publications. Furthermore, as pointed out
by Della Volpe and Siboni, the utilization of non-polar liquids and solids might be
theoretically suspicious within the framework of vOCG and OWRK models [121].
- In line with the previous points, it is important to develop unambiguous (experimental
and analytical) methods for the determination of the STC of wetting liquids. There has
been considerable progress in recent years to correlate liquid STC to HSP [94,172–174] or
Colloids Interfaces 2024, 8, 62 30 of 36

PSP [95,96]. This is a promising direction, as the vast database of precisely determined HSP
can provide a powerful base for the unambiguous estimation of liquid STC.

Supplementary Materials: The following supporting information can be downloaded at: https:
//www.mdpi.com/article/10.3390/colloids8060062/s1, Supplementary files: (i) S1_CA_data.xlsx
present the data used for Figures 3 and 8, and (ii) S2_vOCG_Scales.xlsx shows the various STC scales
proposed for vOCG method.
Author Contributions: Conceptualization, G.A.G. and S.B.; methodology, G.A.G., P.E. and M.B.;
validation, G.A.G., S.B. and K.L.; formal analysis, G.A.G., P.E. and M.B.; investigation, P.E. and
M.B.; data curation, G.A.G., P.E. and M.B.; writing—original draft preparation, G.A.G., S.B. and K.L.;
writing—review and editing, G.A.G., S.B., K.L. and P.E.; visualization, P.E. and M.B.; supervision,
G.A.G. and S.B. All authors have read and agreed to the published version of the manuscript.
Funding: G.As.G: S.B. and M.B. acknowledge the support of the European Union NextGenerationEU,
through the National Recovery and Resilience Plan of the Republic of Bulgaria (Project No.: BG-RRP-
2.004-0008-C01). The research is also supported partially by the Operational Programme “Science and
Education for Smart Growth”, co-funded by the European Union through the European structural and
investment funds: Project “Clean technologies for sustainable environment—water, waste, energy for
circular economy” (Clean&Circle CoC) by the provision of equipment.
Data Availability Statement: Data available upon reasonable request.
Conflicts of Interest: The authors declare no conflicts of interest.

Abbreviations

CA, θ Contact angle

CAH Contact angle hysteresis
SFE Surface free energy
EoS Equation of State
OWRK Owens-Wendt-Rabel-Kaelble model
vOCG Van Oss-Chaudhury-Good model
HSP Hansen solubility parameters
PSP Partial solvation parameters
DIM Diiodomethane
BN α-bromonaphthalene
STC Surface tension components
Symbols

θ contact angle
θ0 equilibrium (Young) contact angle
Θa advancing contact angle
Θr receding contact angle
γlv surface tension of the probe liquid
γsv solid vapor surface tension
γs surface tension of the solid in equilibrium with its own vapor without stress/surface
tension of a polymer (or other solid) in the ternary point solid–liquid–gas, i.e.,
in the zone of interfacial nonuniformity
γ− contribution of electron donor
γ+ contribution of electron acceptor
γsf surface tension of the film covered solid behind the receding edge of the drop
γd contribution of London dispersion interaction,
Colloids Interfaces 2024, 8, 62 31 of 36

γi contribution of inductive dipole–dipole interaction

γpD contribution of permanent dipole–dipole interaction
γh contribution of hydrogen bonds
γπ contribution of π-bonds or interactions by formation of π-complexes
γad contribution of donor–acceptor interaction
γAB contribution of acid–base interaction
γe contribution of electrostatic interaction
γLW contribution of Lifshitz–van der Waals interaction
πe spreading pressure due to vapor adsorption
Wa work of adhesion
WαA work of adhesion form advancing contact angle
WαR work of adhesion form receding contact angle
Φ Girifalco–Good interaction parameter
a, β, β1 , b Parameters, defining Φ
δ2 area occupied by an atom in the liquid–solid interface
A–F fifth-order polynomial of the probe liquid surface tension
n third-order polynomial of the probe liquid surface tension
R Pearson linear correlation coefficient
p the probability of R being due to chance
∆Giwi free energy of interaction between two identical entities
D Berger’s parameter (D > 0 corresponds to acid and D < 0 to basic character
of the surface)

References
1. Karbowiak, T.; Debeaufort, F.; Voilley, A. Importance of Surface Tension Characterization for Food, Pharmaceutical and Packaging
Products: A Review. Crit. Rev. Food Sci. Nutr. 2006, 46, 391–407. [CrossRef] [PubMed]
2. Palencia, M. Surface free energy of solids by contact angle measurements. J. Sci. Technol. Appl. 2017, 2, 84–93. [CrossRef]
3. Kanduč, M.; Schneck, E.; Netz, R.R. Understanding the “Berg limit”: The 65◦ contact angle as the universal adhesion threshold of
biomatter. Phys. Chem. Chem. Phys. 2024, 26, 713–723. [CrossRef] [PubMed]
4. Bangera, A.E.; Appaiah, K. A conditional justification for the determination of surface energy of solids using contact angle
methods. Mater. Chem. Phys. 2019, 234, 168–171. [CrossRef]
5. Rouxhet, P.G. Contact Angles and Surface Energy of Solids: Relevance and Limitations. In Advances in Contact Angle, Wettability
and Adhesion; Scrivener Publishing LLC: Beverly, MA, USA, 2013; pp. 347–375.
6. Eftimov, P.; Yokoi, N.; Peev, N.; Georgiev, G.A. Impact of Air Exposure Time on the Water Contact Angles of Daily Disposable
Silicone Hydrogels. Int. J. Mol. Sci. 2019, 20, 1313. [CrossRef]
7. Eftimov, P.B.; Yokoi, N.; Peev, N.; Paunski, Y.; Georgiev, G.A. Relationships between the material properties of silicone hydrogels:
Desiccation, wettability and lubricity. J. Biomater. Appl. 2021, 35, 933–946. [CrossRef]
8. Neumann, A.W.; David, R.; Zuo, Y. Applied Surface Thermodynamics; CRC Press: Boca Raton, FL, USA, 2010. [CrossRef]
9. Hansen, F.K. The Measurement of Surface Energy of Polymers by Means of Contact Angles of Liquids on Solid Surfaces. A Short Overview
of Frequently Used Methods; University of Oslo: Oslo, Norway, 2004; Available online: https://www.ramehart.com/surface_
energy_finn.pdf (accessed on 16 November 2024).
10. Kloubek, J. Development of methods for surface free energy determination using contact angles of liquids on solids. Adv. Colloid
Interface Sci. 1992, 38, 99–142. [CrossRef]
11. Fortes, M.A. Wettability of Polymer Surfaces. In Physicochemical Aspects of Polymer Surfaces: Volume 1; Mittal, K.L., Ed.; Springer:
Boston, MA, USA, 1983; pp. 107–139.
12. Schrader, M.E. Contact Angle and Vapor Adsorption. Langmuir 1996, 12, 3728–3732. [CrossRef]
13. Jańczuk, B.; Zdziennicka, A. Importance of surface layers in solid surface free energy determination. Surf. Innov. 2014, 2, 173–183.
[CrossRef]
14. Morra, M.; Occhiello, E.; Garbassi, F. Knowledge about polymer surfaces from contact angle measurements. Adv. Colloid Interface
Sci. 1990, 32, 79–116. [CrossRef]
15. Wu, S. Polymer Interface and Adhesion; Routledge: New York, NY, USA, 1982. [CrossRef]
16. van Oss, C.J.; Giese, R.F.; Wu, W. On the Degree to which the Contact Angle is Affected by the Adsorption onto a Solid Surface of
Vapor Molecules Originating from the Liquid Drop. J. Dispers. Sci. Technol. 1998, 19, 1221–1236. [CrossRef]
17. Drelich, J.W. Contact angles: From past mistakes to new developments through liquid-solid adhesion measurements. Adv. Colloid
Interface Sci. 2019, 267, 1–14. [CrossRef] [PubMed]
18. Rudawska, A. Assessment of surface preparation for the bonding/adhesive technology. In Surface Treatment in Bonding Technology;
Chapter 9; Rudawska, A., Ed.; Academic Press: Cambridge, MA, USA, 2019; pp. 227–275.
19. Jiang, Y.; Lian, J.; Jiang, Z.; Li, Y.; Wen, C. Thermodynamic analysis on wetting states and wetting state transitions of rough
surfaces. Adv. Colloid Interface Sci. 2020, 278, 102136. [CrossRef] [PubMed]
Colloids Interfaces 2024, 8, 62 32 of 36

20. Erbil, H.Y.; Cansoy, C.E. Range of Applicability of the Wenzel and Cassie−Baxter Equations for Superhydrophobic Surfaces.
Langmuir 2009, 25, 14135–14145. [CrossRef] [PubMed]
21. David, R.; Neumann, A.W. Contact Angle Patterns on Low-Energy Surfaces. Adv. Colloid Interface Sci. 2014, 206, 46–56. [CrossRef]
22. Chibowski, E. Surface free energy of a solid from contact angle hysteresis. Adv. Colloid Interface Sci. 2003, 103, 149–172. [CrossRef]
23. Owens, D.K.; Wendt, R.C. Estimation of the surface free energy of polymers. J. Appl. Polym. Sci. 1969, 13, 1741–1747. [CrossRef]
24. Van Oss, C.J.; Chaudhury, M.K.; Good, R.J. Interfacial Lifshitz-van der Waals and polar interactions in macroscopic systems.
Chem. Rev. 1988, 88, 927–941. [CrossRef]
25. Kusano, R.; Kusano, Y. Symmetric expressions of surface tension components. J. Adhes. 2023, 99, 2381–2401. [CrossRef]
26. Starostina, I.A.; Ulitin, N.V.; Stoyanov, O.V. Current State of the Problem of Adhesive Interaction Estimation Using Thermody-
namic Characteristics. Polym. Sci. Ser. D 2022, 15, 354–358. [CrossRef]
27. Schuster, J.M.; Schvezov, C.E.; Rosenberger, M.R. Analysis of the general uncertainty propagation and calculation of the systematic
uncertainty of the Neumann equation of state for surface free energy determination. Int. J. Adhes. Adhes. 2024, 129, 103582.
[CrossRef]
28. Kusano, R.; Kusano, Y. Vector methods and matrix equations applied to symmetric expressions for three-component surface
tension determination. Colloids Surf. A Physicochem. Eng. Asp. 2024, 702, 135002. [CrossRef]
29. Rudawska, A.; Jacniacka, E. Analysis for determining surface free energy uncertainty by the Owen–Wendt method. Int. J. Adhes.
Adhes. 2009, 29, 451–457. [CrossRef]
30. Rudawska, A.; Jacniacka, E. Evaluating uncertainty of surface free energy measurement by the van Oss-Chaudhury-Good method.
Int. J. Adhes. Adhes. 2018, 82, 139–145. [CrossRef]
31. Volpe, C.D.; Siboni, S. Limitations of Multicomponent Theories in Surface Thermodynamics and Adhesion Science. In Progress in
Adhesion and Adhesives; Scrivener Publishing LLC: Beverly, MA, USA, 2024; pp. 1–36.
32. Weng, M.; Shen, Q. Effect of liquid surface tension data on the validity and accuracy of solid surface tension components and
parameters in the application of the van Oss–Chaudhury–Good approach. J. Adhes. Sci. Technol. 2014, 28, 2248–2268. [CrossRef]
33. Żenkiewicz, M. Methods for the calculation of surface free energy of solids. J. Achiev. Mater. Manuf. Eng. 2007, 24, 137–145.
34. Żenkiewicz, M. Comparative study on the surface free energy of a solid calculated by different methods. Polym. Test. 2007, 26,
14–19. [CrossRef]
35. Good, R.J.; Girifalco, L.A. A theory for estimation of surface and interfacial energies. III. Estimation of surface energies of solids
from contact angle data. J. Phys. Chem. 1960, 64, 561–565. [CrossRef]
36. Good, R.J. Theory for the Estimation of Surface and Interfacial Energies. In Contact Angle, Wettability, and Adhesion; American
Chemical Society: Washington, DC, USA, 1964; Volume 43, pp. 74–87.
37. Kwok, D.Y.; Neumann, A.W. Contact angle measurement and contact angle interpretation. Adv. Colloid Interface Sci. 1999, 81,
167–249. [CrossRef]
38. Tavana, H.; Neumann, A.W. Recent progress in the determination of solid surface tensions from contact angles. Adv. Colloid
Interface Sci. 2007, 132, 1–32. [CrossRef]
39. Gerson, D.F. An empirical equation-of-state for solid-fluid interfacial free energies. Colloid Polym. Sci. 1982, 260, 539–544.
[CrossRef]
40. Zhang, J.; Kwok, D.Y. An improved combining rule for solid-liquid adhesion and intermolecular potentials: Formulation and
application. J. Adhes. 2004, 80, 745–765. [CrossRef]
41. Huang, K.; Goddard, J.M. Stability of nonfouling electroless nickel-polytetrafluoroethylene coatings after exposure to commercial
dairy equipment sanitizers. J. Dairy Sci. 2015, 98, 5983–5994. [CrossRef] [PubMed]
42. Schuster, J.M.; Schvezov, C.E.; Rosenberger, M.R. Polynomial functions for direct calculation of the surface free energy developed
from the Neumann equation of state method. Int. J. Adhes. Adhes. 2023, 124, 103370. [CrossRef]
43. Kavale, M.S.; Karande, S.S.; Pushpanjali, G.M. Estimation of the Surface Free Energy of Hydrophobic Monolithic Silica Aerogels.
Macromol. Symp. 2020, 392, 2000113. [CrossRef]
44. Mahadik, D.B.; Rao, A.V.; Rao, A.P.; Wagh, P.B.; Ingale, S.V.; Gupta, S.C. Effect of concentration of trimethylchlorosilane (TMCS)
and hexamethyldisilazane (HMDZ) silylating agents on surface free energy of silica aerogels. J. Colloid Interface Sci. 2011, 356,
298–302. [CrossRef]
45. Deshmukh, R.R.; Shetty, A.R. Comparison of surface energies using various approaches and their suitability. J. Appl. Polym. Sci.
2008, 107, 3707–3717. [CrossRef]
46. Chibowski, E.; Ontiveros-Ortega, A.; Perea-Carpio, R. On the interpretation of contact angle hysteresis. J. Adhes. Sci. Technol. 2002,
16, 1367–1404. [CrossRef]
47. Chibowski, E. On some relations between advancing, receding and Young’s contact angles. Adv. Colloid Interface Sci. 2007, 133,
51–59. [CrossRef]
48. Tadmor, R. Line Energy and the Relation between Advancing, Receding, and Young Contact Angles. Langmuir 2004, 20, 7659–7664.
[CrossRef]
49. Tadmor, R.; Yadav, P.S. As-placed contact angles for sessile drops. J. Colloid Interface Sci. 2008, 317, 241–246. [CrossRef] [PubMed]
50. Tadmor, R. Line energy, line tension and drop size. Surf. Sci. 2008, 602, L108–L111. [CrossRef]
51. Law, K.-Y. Contact Angle Hysteresis on Smooth/Flat and Rough Surfaces. Interpretation, Mechanism, and Origin. Acc. Mater.
Res. 2022, 3, 1–7. [CrossRef]
Colloids Interfaces 2024, 8, 62 33 of 36

52. Eral, H.B.; ’t Mannetje, D.; Oh, J.M. Contact angle hysteresis: A review of fundamentals and applications. Colloid Polym. Sci. 2013,
291, 247–260. [CrossRef]
53. Chibowski, E.; Terpilowski, K. Comparison of apparent surface free energy of some solids determined by different approaches. In
Contact Angle, Wettability and Adhesion; CRC Press: Boca Raton, FL, USA, 2009; Volume 6, pp. 283–299.
54. Drelich, J.W.; Boinovich, L.; Chibowski, E.; Della Volpe, C.; Hołysz, L.; Marmur, A.; Siboni, S. Contact angles: History of over
200 years of open questions. Surf. Innov. 2020, 8, 3–27. [CrossRef]
55. Good, R.J. Spreading pressure and contact angle. J. Colloid Interface Sci. 1975, 52, 308–313. [CrossRef]
56. Douillard, J.M.; Médout-Marère, V. A New Interpretation of Contact Angle Variations in View of a Recent Analysis of Immersion
Calorimetry. J. Colloid Interface Sci. 2000, 223, 255–260. [CrossRef]
57. Douillard, J.M.; Zajac, J.; Malandrini, H.; Clauss, F. Contact Angle and Film Pressure: Study of a Talc Surface. J. Colloid Interface
Sci. 2002, 255, 341–351. [CrossRef]
58. Churaev, N.V.; Sobolev, V.D. Prediction of contact angles on the basis of the Frumkin-Derjaguin approach. Adv. Colloid Interface
Sci. 1995, 61, 1–16. [CrossRef]
59. Popescu, M.N.; Oshanin, G.; Dietrich, S.; Cazabat, A.M. Precursor films in wetting phenomena. J. Phys. Condens. Matter 2012,
24, 243102. [CrossRef]
60. Chibowski, E.J. Surface free energy and wettability of silyl layers on silicon determined from contact angle hysteresis. Adv. Colloid
Interface Sci. 2005, 113, 121–131. [CrossRef] [PubMed]
61. Terpiłowski, K.; Rymuszka, D.; Goncharuk, O.; Yakovenko, L. Equilibrium Contact Angle and Determination of Apparent Surface
Free Energy Using Hysteresis Approach on Rough Surfaces. In Advances in Contact Angle, Wettability and Adhesion; Scrivener
Publishing LLC: Beverly, MA, USA, 2018; pp. 331–347. [CrossRef]
62. Giacomello, A.; Schimmele, L.; Dietrich, S. Wetting hysteresis induced by nanodefects. Proc. Natl. Acad. Sci. USA 2016, 113,
E262–E271. [CrossRef] [PubMed]
63. Liu, Q.; Yu, J.; Wang, H. The role of the substrate roughness in contact angle hysteresis and dynamic deviation. Int. J. Heat Mass
Transf. 2020, 148, 118985. [CrossRef]
64. Yaminsky, V.V. Molecular mechanisms of hydrophobic transitions. J. Adhes. Sci. Technol. 2000, 14, 187–233. [CrossRef]
65. Antonow, G.N. Sur la tension superficielle à la limite de deux couches. J. Chim. Phys. 1907, 5, 372–385. [CrossRef]
66. Feinerman, A.E.; Lipatov, Y.S. The Rule of Interfacial Equilibrium. J. Adhes. 1997, 60, 99–112. [CrossRef]
67. Feinerman, A.E.; Lipatov, Y.S.; Minkov, V.I. Interfacial Interactions in Polymers: The Dependence of the Measured Surface Tension
of Solid Polymer on the Surface Tension of Wetting Liquid. J. Adhes. 1997, 61, 37–54. [CrossRef]
68. Feinerman, A.E.; Lipatov, Y.S.; Min’kov, V.I. On the Hysteresis of Polymer Wetting. J. Adhes. 1996, 56, 97–105. [CrossRef]
69. Lipatov, Y.S. Adhesion at the polymer blend-solid interface. Compos. Interfaces 2000, 8, 151–165. [CrossRef]
70. Lipatov, Y.S. Polymer Reinforcement; ChemTec Publishing: Toronto, ON, Canda, 1995.
71. Law, K.-Y.; Zhao, H. Determination of Solid Surface Tension by Contact Angle. In Surface Wetting: Characterization, Contact Angle,
and Fundamentals; Law, K.-Y., Zhao, H., Eds.; Springer International Publishing: Cham, Switzerland, 2016; pp. 135–148.
72. Kloubek, J. Interaction at interfaces and induction of surface free energy components. Collect. Czechoslov. Chem. Commun. 1987, 52,
271–286. [CrossRef]
73. Carré, A. Polar interactions at liquid/polymer interfaces. J. Adhes. Sci. Technol. 2007, 21, 961–981. [CrossRef]
74. Fowkes, F.M. Donor-Acceptor Interactions at Interfaces. J. Adhes. 1972, 4, 155–159. [CrossRef]
75. Altay, B.N.; Ma, R.; Fleming, P.D.; Joyce, M.J.; Anand, A.; Chen, T.; Keskin, B.; Maddipatla, D.; Turkani, V.S.; Kotkar, P.R.; et al.
Surface Free Energy Estimation: A New Methodology for Solid Surfaces. Adv. Mater. Interfaces 2020, 7, 1901570. [CrossRef]
76. Nosonovsky, M.; Ramachandran, R. Geometric Interpretation of Surface Tension Equilibrium in Superhydrophobic Systems.
Entropy 2015, 17, 4684–4700. [CrossRef]
77. Erbil, H.Y. Determination of spreading pressure and its effect on polymer surface tension from contact angle data. Combination
of the two-liquid contact angle method with the one-liquid contact angle method. J. Adhes. Sci. Technol. 1989, 3, 29–38. [CrossRef]
78. Zettlemoyer, A.C. Hydrophobic surfaces. J. Colloid Interface Sci. 1968, 28, 343–369. [CrossRef]
79. Radelczuk, H.; Hołysz, L.; Chibowski, E. Comparison of the Lifshitz–van der Waals/acid–base and contact angle hysteresis
approaches for determination of solid surface free energy. J. Adhes. Sci. Technol. 2002, 16, 1547–1568. [CrossRef]
80. Chibowski, E. Contact angle hysteresis due to a film present behind the drop. In Contact Angle, Wettability and Adhesion, 2nd ed.;
Mittal, K.L., Ed.; CRC Press: Boca Raton, FL, USA, 2002; pp. 265–288.
81. Fowkes, F.M. Attractive Forces at Interfaces. Ind. Eng. Chem. 1964, 56, 40–52. [CrossRef]
82. Fowkes, F.M.; Mostafa, M.A. Acid-Base Interactions in Polymer Adsorption. Ind. Eng. Chem. Prod. Res. Dev. 1978, 17, 3–7.
[CrossRef]
83. Surface Free Energy (SFE), Surface Energy. Available online: https://www.kruss-scientific (accessed on 16 November 2024).
84. Kaelble, D.H.; Uy, K.C. A Reinterpretation of Organic Liquid-Polytetrafluoroethylene Surface Interactions. J. Adhes. 1970, 2, 50–60.
[CrossRef]
85. Etzler, F.M. Determination of the Surface Free Energy of Solid Surfaces: Statistical Considerations. In Advances in Contact Angle,
Wettability and Adhesion; Scrivener Publishing LLC: Beverly, MA, USA, 2018; pp. 299–329.
86. Etzler, F.M. Determination of the surface free energy of solids: A critical review. Rev. Adhes. Adhes. 2013, 1, 3.
Colloids Interfaces 2024, 8, 62 34 of 36

87. Etzler, F.M. Determination of the Surface Free Energy of Solid Surfaces: Can the Best Model be Found. In Advances in Contact
Angle, Wettability and Adhesion; Scrivener Publishing LLC: Beverly, MA, USA, 2019; pp. 73–98.
88. Clint, J.H. Adhesion and components of solid surface energies. Curr. Opin. Colloid Interface Sci. 2001, 6, 28–33. [CrossRef]
89. Bouali, B.; Ganachaud, F.; Chapel, J.-P.; Pichot, C.; Lanteri, P. Acid–Base Approach to Latex Particles Containing Specific Groups
Based on Wettability Measurements. J. Colloid Interface Sci. 1998, 208, 81–89. [CrossRef] [PubMed]
90. Zhang, Z.; Wang, W.; Korpacz, A.N.; Dufour, C.R.; Weiland, Z.J.; Lambert, C.R.; Timko, M.T. Binary Liquid Mixture Contact-Angle
Measurements for Precise Estimation of Surface Free Energy. Langmuir 2019, 35, 12317–12325. [CrossRef]
91. Kaelble, D.H.; Dynes, P.J.; Cirlin, E.H. Interfacial Bonding and Environmental Stability of Polymer Matrix Composites. J. Adhes.
1974, 6, 23–48. [CrossRef]
92. Chibowski, E. Apparent Surface Free Energy of Superhydrophobic Surfaces. J. Adhes. Sci. Technol. 2011, 25, 1323–1336. [CrossRef]
93. Ahadian, S.; Moradian, S.; Amani Tehran, M. Assessing the equation of state and comparing it with other relationships used for
determining the surface tension of solids. Appl. Surf. Sci. 2010, 256, 1983–1991. [CrossRef]
94. Kusano, Y.; Kusano, R. Critical assessment of the correlation between surface tension components and Hansen solubility
parameters. Colloids Surf. A Physicochem. Eng. Asp. 2023, 677, 132423. [CrossRef]
95. Panayiotou, C.G. Inverse gas chromatography and partial solvation parameters. J. Chromatogr. A 2012, 1251, 194–207. [CrossRef]
96. Panayiotou, C.G. Adhesion and Wetting: A Quantum Mechanics–Based Approach, In Handbook of Surface and Colloid Chemistry; CRC
Press: Boca Raton, FL, USA, 2015; pp. 601–622.
97. Otsuka, H.; Nagasaki, Y.; Kataoka, K. Dynamic wettability study on the functionalized PEGylated layer on a polylactide surface
constructed by the coating of aldehyde-ended poly(ethylene glycol) (PEG)/polylactide (PLA) block copolymer. Sci. Technol. Adv.
Mater. 2000, 1, 21–29. [CrossRef]
98. Jańczuk, B.; Białlopiotrowicz, T. Surface free-energy components of liquids and low energy solids and contact angles. J. Colloid
Interface Sci. 1989, 127, 189–204. [CrossRef]
99. Shimizu, R.N.; Demarquette, N.R. Evaluation of surface energy of solid polymers using different models. J. Appl. Polym. Sci. 2000,
76, 1831–1845. [CrossRef]
100. Guo, J.; Wang, R.; Zhang, S.; Antao, D.S. Temperature Dependency of the Apolar Surface Tension Component for Water and Its
Role in Classifying Apolar and Polar Interfacial Interactions. J. Phys. Chem. C 2023, 127, 18167–18175. [CrossRef]
101. Jańczuk, B.; Wójcik, W.; Zdziennicka, A. Determination of the Components of the Surface Tension of Some Liquids from Interfacial
Liquid-Liquid Tension Measurements. J. Colloid Interface Sci. 1993, 157, 384–393. [CrossRef]
102. Hołysz, L. Investigation of the effect of substrata on the surface free energy components of silica gel determined by thin layer
wicking method. J. Mater. Sci. 2000, 35, 6081–6091. [CrossRef]
103. Jarray, A.; Wijshoff, H.; Luiken, J.A.; den Otter, W.K. Systematic approach for wettability prediction using molecular dynamics
simulations. Soft Matter 2020, 16, 4299–4310. [CrossRef]
104. Kloubek, J. Calculation of surface free energy components of ice according to its wettability by water, chlorobenzene, and carbon
disulfide. J. Colloid Interface Sci. 1974, 46, 185–190. [CrossRef]
105. Kloubek, J. Interaction of Polar Forces and Their Contribution to the Work of Adhesion. J. Adhes. 1974, 6, 293–301. [CrossRef]
106. Liptáková, E.; Kúdela, J. Analysis of the Wood-Wetting Process. Holzforschung 1994, 48, 139–144. [CrossRef]
107. Kúdela, J. Wetting of wood surface by a liquids of a different polarity. Wood Res. 2014, 59, 11–24.
108. Liptáková, E.; Kúdela, J.; Paprzycki, O. The adhesion of polystyrene to wood. Holz Als Roh-Werkst. 1991, 49, 31–37. [CrossRef]
109. Kudela, J.; Wesserle, F. Wood wetting with various liquids. Ann. Wars. Univ. Life Sci.-SGGW For. Wood Technol. 2013, 83, 156–161.
110. Kúdela, J.; Wesserle, F.; Baksa, J. Influence of moisture content of beech wood on wetting and surface free energy. Acta Fac.
Xylologiae Zvolen Res Publica Slovaca 2015, 57, 25–35.
111. Liptáková, E.; Kúdela, J.; Sarva, J. Study of the System Wood—Coating Material. I. Wood—Liquid Coating Material. Holzforschung
2000, 54, 189–196. [CrossRef]
112. Liptáková, E.; Kúdela, J. Study of the System Wood—Coating Material. Part 2.Wood—Solid Coating Material. Holzforschung 2002,
56, 547–557. [CrossRef]
113. Kúdela, J.; Kubovský, I.; Andrejko, M. Surface Properties of Beech Wood after CO2 Laser Engraving. Coatings 2020, 10, 77.
[CrossRef]
114. Kudela, J. Wood fibreboard paraffin hydrophobization and the impact of this treatment on the board surface finishing quality.
Ann. Wars. Univ. Life Sci.-SGGW For. Wood Technol. 2019, 107, 115–123. [CrossRef]
115. Dann, J.R. Forces involved in the adhesive process: I. Critical surface tensions of polymeric solids as determined with polar
liquids. J. Colloid Interface Sci. 1970, 32, 302–320. [CrossRef]
116. Della Volpe, C.; Siboni, S. Acid–base surface free energies of solids and the definition of scales in the Good–van Oss–Chaudhury
theory. J. Adhes. Sci. Technol. 2000, 14, 235–272. [CrossRef]
117. Zdziennicka, A.; Krawczyk, J.; Szymczyk, K.; Jańczuk, B. Components and parameters of liquids and some polymers surface
tension at different temperature. Colloids Surf. A Physicochem. Eng. Asp. 2017, 529, 864–875. [CrossRef]
118. Jie-Rong, C.; Wakida, T. Studies on the surface free energy and surface structure of PTFE film treated with low temperature
plasma. J. Appl. Polym. Sci. 1997, 63, 1733–1739. [CrossRef]
119. Saito, M.; Yabe, A. Dispersion and Polar Force Components of Surface Tension of Oily Soils. Text. Res. J. 1984, 54, 18–22. [CrossRef]
Colloids Interfaces 2024, 8, 62 35 of 36

120. Hubbe, M.A.; Gardner, D.J.; Shen, W. Contact angles and wettability of cellulosic surfaces: A review of proposed mechanisms
and test strategies. BioResources 2015, 10, 8657–8749. [CrossRef]
121. Siboni, S.; Della Volpe, C.; Maniglio, D.; Brugnara, M. The solid surface free energy calculation: II. The limits of the Zisman and of
the “equation-of-state” approaches. J. Colloid Interface Sci. 2004, 271, 454–472. [CrossRef] [PubMed]
122. Baier, R.E. Surface behaviour of biomaterials: The theta surface for biocompatibility. J. Mater. Sci. Mater. Med. 2006, 17, 1057–1062.
[CrossRef]
123. Liber-Kneć, A.; Łagan, S. Surface Testing of Dental Biomaterials—Determination of Contact Angle and Surface Free Energy.
Materials 2021, 14, 2761. [CrossRef]
124. van Oss, C.J.; Giese, R.F. The Hydrophilicity and Hydrophobicity of Clay Minerals. Clays Clay Miner. 2024, 43, 474–477. [CrossRef]
125. Henriques, M.; Gasparetto, K.; Azeredo, J.; Oliveira, R. Experimental methodology to quantify Candida albicans cell surface
hydrophobicity. Biotechnol. Lett. 2002, 24, 1111–1115. [CrossRef]
126. Bernardes, P.C.; de Andrade, N.J.; Ferreira, S.O.; de Sá, J.P.; Araújo, E.A.; Delatorre, D.M.; Luiz, L.M. Assessment of hydrophobicity
and roughness of stainless steel adhered by an isolate of Bacillus cereus from a dairy plant. Braz. J. Microbiol. 2010, 41, 984–992.
[CrossRef]
127. Vogler, E.A. Structure and reactivity of water at biomaterial surfaces. Adv. Colloid Interface Sci. 1998, 74, 69–117. [CrossRef]
128. Arkles, B. Hydrophobicity, Hydrophilicity and Silanes. Paint. Coat. Ind. 2006, 22, 114.
129. Tuteja, A.; Choi, W.; Mabry, J.M.; McKinley, G.H.; Cohen, R.E. Robust omniphobic surfaces. Proc. Natl. Acad. Sci. USA 2008, 105,
18200–18205. [CrossRef]
130. Puntervold, T.; Strand, S.; Mamonov, A.; Piñerez, I.D.T. Chapter 3—Enhanced oil recovery by Smart Water injection in sandstone
reservoirs. In Recovery Improvement; Wang, Q., Ed.; Gulf Professional Publishing: Oxford, UK, 2023; Volume 3, pp. 109–184.
131. Berger, E.J. A method of determining the surface acidity of polymeric and metallic materials and its application to lap shear
adhesion. J. Adhes. Sci. Technol. 1990, 4, 373–391. [CrossRef]
132. Kraus, E.; Horvat, S.; Deubel, C.; Staudigel, C.; Baudrit, B.; Heidemeyer, P.; Bastian, M.; Starostina, I.; Stoyanov, O. Relevance of
the acid–base approach in prediction of adhesion properties in two-component injection moulding. J. Appl. Polym. Sci. 2016,
133, 43048. [CrossRef]
133. Kraus, E.; Orf, L.; Sitnik, V.; Perelygina, R.; Burdova, E.; Starostina, I.; Stoyanov, O. Composition and surface energy characteristics
of new petroleum resins. Polym. Eng. Sci. 2017, 57, 1028–1032. [CrossRef]
134. Kraus, E.; Orf, L.; Baudrit, B.; Heidemeyer, P.; Bastian, M.; Bonenberger, R.; Starostina, I.; Stoyanov, O. Analysis of the low-pressure
plasma pretreated polymer surface in terms of acid–base approach. Appl. Surf. Sci. 2016, 371, 365–375. [CrossRef]
135. Kraus, E.; Orf, L.; Starostina, I.; Efimova, A.; Perelygina, R.; Stoyanov, O. Composite materials based on polyolefins with new
petroleum resins. Polym. Eng. Sci. 2018, 58, 2288–2292. [CrossRef]
136. Ozkanlar, A. Intermolecular interactions in binary mixtures of formamide and acetone. Fluid Phase Equilibria 2022, 560, 113517.
[CrossRef]
137. Vrbanac, M.D.; Berg, J.C. The use of wetting measurements in the assessment of acid-base interactions at solid-liquid interfaces.
J. Adhes. Sci. Technol. 1990, 4, 255–266. [CrossRef]
138. Janczuk, B.; Chibowski, E.; Bruque, J.M.; Kerkeb, M.L.; Caballero, F.G. On the Consistency of Surface Free Energy Components as
Calculated from Contact Angles of Different Liquids: An Application to the Cholesterol Surface. J. Colloid Interface Sci. 1993, 159,
421–428. [CrossRef]
139. Van Oss, C.J.; Good, R.J.; Chaudhury, M.K. Additive and nonadditive surface tension components and the interpretation of
contact angles. Langmuir 1988, 4, 884–891. [CrossRef]
140. Berg, J.C. The importance of acid-base interactions in wetting, coating, adhesion and related phenomena. Nord. Pulp Pap. Res. J.
1993, 8, 75–85. [CrossRef]
141. Della Volpe, C.; Siboni, S. Some Reflections on Acid–Base Solid Surface Free Energy Theories. J. Colloid Interface Sci. 1997, 195,
121–136. [CrossRef] [PubMed]
142. Starostina, I.A.; Makhrova, N.V.; Stoyanov, O.V.; Aristov, I.V. On the Evaluation of the Acidity and Basicity Parameters of the
Surface Free Energy of Polymers. J. Adhes. 2012, 88, 751–765. [CrossRef]
143. Kollman, P. A general analysis of noncovalent intermolecular interactions. J. Am. Chem. Soc. 1977, 99, 4875–4894. [CrossRef]
144. Fowkes, F.M. Quantitative characterization of the acid-base properties of solvents, polymers, and inorganic surfaces. J. Adhes. Sci.
Technol. 1990, 4, 669–691. [CrossRef]
145. Mittal, K.; Etzler, F. Is the world basic? Lessons from surface science. Ann. Univ. Mariae Curie-Skłodowska 2008, 63, 1–16. [CrossRef]
146. Mittal, K.; Etzler, F.M. Is the world basic? Lessons from surface science. In Contact Angle, Wettability and Adhesion; CRC Press:
Boca Raton, FL, USA, 2009; Volume 6, pp. 111–123.
147. Greiveldinger, M.; Shanahan, M.E.R. A Critique of the Mathematical Coherence of Acid/Base Interfacial Free Energy Theory.
J. Colloid Interface Sci. 1999, 215, 170–178. [CrossRef]
148. Holländer, A. On the Selection of Test Liquids for the Evaluation of Acid-Base Properties of Solid Surfaces by Contact Angle
Goniometry. J. Colloid Interface Sci. 1995, 169, 493–496. [CrossRef]
149. Combe, E.C.; Owen, B.A.; Hodges, J.S. A protocol for determining the surface free energy of dental materials. Dent. Mater. 2004,
20, 262–268. [CrossRef] [PubMed]
Colloids Interfaces 2024, 8, 62 36 of 36

150. Lee, L.-H. Correlation between Lewis Acid−Base Surface Interaction Components and Linear Solvation Energy Relationship
Solvatochromic α and β Parameters. Langmuir 1996, 12, 1681–1687. [CrossRef]
151. Della Volpe, C.; Maniglio, D.; Brugnara, M.; Siboni, S.; Morra, M. The solid surface free energy calculation: I. In defense of the
multicomponent approach. J. Colloid Interface Sci. 2004, 271, 434–453. [CrossRef] [PubMed]
152. Kraus, E.; Orf, L.; Heilig, M.; Baudrit, B.; Starostina, I.; Stoyanov, O. Characterization of Polymer Surfaces by the Use of Different
Wetting Theories Regarding Acid-Base Properties. Int. J. Polym. Sci. 2017, 2017, 4350470. [CrossRef]
153. Starostina, I.A.; Stoyanov, O.V.; Deberdeev, R.Y. Polymer Surfaces and Interfaces: Acid-Base Interactions and Adhesion in Polymer-Metal
Systems; CRC Press: Boca Raton, FL, USA, 2014.
154. Kamlet, M.J.; Abboud, J.L.M.; Abraham, M.H.; Taft, R.W. Linear solvation energy relationships. 23. A comprehensive collection
of the solvatochromic parameters, .pi.*, .alpha., and .beta., and some methods for simplifying the generalized solvatochromic
equation. J. Org. Chem. 1983, 48, 2877–2887. [CrossRef]
155. Jessop, P.G.; Jessop, D.A.; Fu, D.; Phan, L. Solvatochromic parameters for solvents of interest in green chemistry. Green Chem.
2012, 14, 1245–1259. [CrossRef]
156. Gutmann, V.; Resch, G.; Linert, W. Structural variability in solutions. Coord. Chem. Rev. 1982, 43, 133–164. [CrossRef]
157. Achinas, S.; Charalampogiannis, N.; Euverink, G.J. A Brief Recap of Microbial Adhesion and Biofilms. Appl. Sci. 2019, 9, 2801.
[CrossRef]
158. Eskhan, A.; AlQasas, N.; Johnson, D. Interaction Mechanisms and Predictions of the Biofouling of Polymer Films: A Combined
Atomic Force Microscopy and Quartz Crystal Microbalance with Dissipation Monitoring Study. Langmuir 2023, 39, 6592–6612.
[CrossRef]
159. Zhang, X.; Zhang, Q.; Yan, T.; Jiang, Z.; Zhang, X.; Zuo, Y.Y. Quantitatively Predicting Bacterial Adhesion Using Surface Free
Energy Determined with a Spectrophotometric Method. Environ. Sci. Technol. 2015, 49, 6164–6171. [CrossRef]
160. Sharma, P.K.; Rao, K.H. Analysis of different approaches for evaluation of surface energy of microbial cells by contact angle
goniometry. Adv. Colloid Interface Sci. 2002, 98, 341–463. [CrossRef] [PubMed]
161. Sharma, P.K.; Hanumantha Rao, K. Adhesion of Paenibacillus polymyxa on chalcopyrite and pyrite: Surface thermodynamics
and extended DLVO theory. Colloids Surf. B Biointerfaces 2003, 29, 21–38. [CrossRef]
162. Wang, M.; Lu, T.; Chen, W.; Zhang, H.; Qi, W.; Song, Y.; Qi, Z. Enhanced role of humic acid on the transport of iron oxide colloids
in saturated porous media under various solution chemistry conditions. Colloids Surf. A Physicochem. Eng. Asp. 2020, 607, 125486.
[CrossRef]
163. van Oss, C.J. Chapter Three—The Extended DLVO Theory. In Interface Science and Technology; van Oss, C.J., Ed.; Elsevier:
Amsterdam, The Netherlands, 2008; Volume 16, pp. 31–48.
164. Vilinska, A.; Rao, K.H. Surface Thermodynamics and Extended DLVO Theory of Cells Adhesion on Pyrite and Chalcopyrite.
Open Colloid Sci. J. 2009, 2, 1–14. [CrossRef]
165. Vilinska, A.; Rao, K.H. Surface thermodynamics and extended DLVO theory of Leptospirillum ferrooxidans cells’ adhesion on
sulfide minerals. Min. Metall. Explor. 2011, 28, 151–158. [CrossRef]
166. Zhang, T.; Wang, Q.; Yang, Y.; Hou, L.; Zheng, W.; Wu, Z.; Wang, Z. Revealing the contradiction between DLVO/XDLVO theory
and membrane fouling propensity for oil-in-water emulsion separation. J. Hazard. Mater. 2024, 466, 133594. [CrossRef]
167. Rodríguez-Valverde, M.A.; Montes Ruiz-Cabello, F.J.; Cabrerizo-Vílchez, M.A. A new method for evaluating the most-stable
contact angle using mechanical vibration. Soft Matter 2011, 7, 53–56. [CrossRef]
168. Lößlein, S.M.; Merz, R.; Müller, D.W.; Kopnarski, M.; Mücklich, F. An in-depth evaluation of sample and measurement induced
influences on static contact angle measurements. Sci. Rep. 2022, 12, 19389. [CrossRef]
169. Schuster, J.M.; Schvezov, C.E.; Rosenberger, M.R. Analysis of the Results of Surface Free Energy Measurement of Ti6Al4V by
Different Methods. Procedia Mater. Sci. 2015, 8, 732–741. [CrossRef]
170. Chibowski, E.; Jurak, M. Comparison of contact angle hysteresis of different probe liquids on the same solid surface. Colloid
Polym. Sci. 2013, 291, 391–399. [CrossRef]
171. Chibowski, E. Some problems of characterization of a solid surface via the surface free energy changes. Adsorpt. Sci. Technol. 2017,
35, 647–659. [CrossRef]
172. Murase, M.; Nakamura, D. Hansen Solubility Parameters for Directly Dealing with Surface and Interfacial Phenomena. Langmuir
2023, 39, 10475–10484. [CrossRef] [PubMed]
173. AlQasas, N.; Johnson, D. The use of neural network modeling for the estimation of the Hansen solubility parameters of polymer
films from contact angle measurements. Surf. Interfaces 2024, 44, 103721. [CrossRef]
174. AlQasas, N.; Eskhan, A.; Johnson, D. Hansen solubility parameters from surface measurements: A comparison of different
methods. Surf. Interfaces 2023, 36, 102594. [CrossRef]

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual
author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to
people or property resulting from any ideas, methods, instructions or products referred to in the content.