Advances in Colloid and Interface Science, 38 (1992) 99-142 99

Elsevier Science Publishers B.V., Amsterdam

DEVELOPMENT OF METHODS FOR SURFACE FREE

ENERGY DETERMINATION USING CONTACT ANGLES OF
LIQUIDS ON SOLIDS*

JAN KLOUBEK

The J. Heyrovsky Institute ofPhysical Chemistry and Electrochemistry,

Czechoslovak Academy of Sciences, 182 23 Prague 8, Czechoslovakia

CONTENTS

Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
1. Introduction ..................................... 99
2. Surface Free Energy and Surface Tension .................... 100
3. Problems of Wetting ................................ 103
4. Grain Boundary Groove Method ......................... 105
5. Critical Surface Tension of Wetting ........................ 105
6. The Interaction Parameter ............................ 108
7. Hypothesis on Minimization of the Interaction Energy ............. 110
8. Wu’s Equation of State ............................... 112
9. Neumann’s Equation of State ........................... 112
10. Fowkes’Theory ................................... 117
11. The Extended Fowkes’ Equation ......................... 121
12. Evaluation of Solid-Liquid-Liquid Systems ................... 128
13. Induction and Acid-Base Interactions ...................... 134
14. Conclusion ..................................... 138
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138

ABSTRACT

Methods for the surface free energy determination of solids based on wetting by liquids
are reviewed. Some critical remarks and new ideas are included.

1. INTRODUCTION

The intermolecular interactions at interfaces are an important topic

of research. Papers dealing with the attraction originating in these
interactions often appear in the literature; they concern adhesion, adsorp-
tion, wetting and other phenomena or applications such as chromatog-
raphy. A basic property of materials, which causes the interaction, is the

* Dedicated to Professor A. Scheludko on the occasion of his 70th birthday.

OOOl-8888,‘92/$15.00 0 1992 - Elsevier Science Publishers B.V. All rights reserved.

100

surface free energy. Many methods are available for a precise determina-
tion of the surface free energy of liquids but no direct measurement is
known which would yield a reliable value of the surface free energy of
solids. Therefore, this important characteristics is mostly calculated from
the contact angles of various liquids on the respective solid. However,
controversies concerning the correctness of the calculation methods can
be found in the literature. Many papers appeared in which some of the
methods were misinterpreted or misused. A convenient survey about the
calculation might be useful for research workers who are not sufficiently
familiar with this field. Therefore, the following review has been written.
It does not offer an explicit recommendation of which method should be
correctly used because this is not yet definitely known. However, it is
hoped that this review will incite further research and support a develop-
ment to clarify this question.

2. SURFACE FREE ENERGY AND SURFACE TENSION

Nearly all monographs on surface chemistry begin with the surface

tension and the surface free energy. Consequently, it seems unnecessary
to give any references to the literature on these terms and their defmi-
tions. Nevertheless, they are often confused or interchanged and there-
fore a little attention should be paid to them.
A surface is the region between the condensed and gas phases. Simi-
larly, an interface is the region between two adjacent phases. These
regions cannot be considered as separate phases because they are only
several molecular diameters thick and their properties change with the
perpendicular distance from the bulk phase. The molecules in the bulk of
an isotropic condensed phase are in a symmetrical force field, i.e. the
attractive forces between molecules are the same in all directions. The
molecules on the surface are attracted into the bulk by all the neighbour-
ing molecules of the same phase and the resultant sum of the forces points
perpendicularly towards the surface plane because the attraction from
the gas phase is zero. This creates an asymmetric force field with a surface
excess energy called the surface free energy. The tendency to decrease
this asymmetry accounts for adsorption, adhesion and wetting phenom-
ena.
The forces at the interface of two condensed phases are usually
unbalanced and give rise to the inter-facial free energy. Both the surface
and interfacial free energies will be denoted by the symbol y. The higher
the surface free energies and the smaller the interfacial energy of the
adjoining phases, the higher is their work of adhesion, IV,. This is
 101

expressed by the Dupre equation which, for the interface between a solid
(S) and a liquid (L), is expressed as:

WA= YS + k - k

All values of y and WAwill be given here in mJ mV2without any further

indication of the units.
According to the definition, the surface tension, CT,
is a tangential force
acting per unit length on the surface. The unit used for o is mN m-l and
the values are the same as for the earlier units of dyne cm-’ or g secm2.
The surface tension reduces the surface area of liquids to a minimum.
This value should just be exceeded to stretch the area under equilibrium,
reversible and isothermal conditions. A reversible extension of the surface
at constant o is only possible with liquids because of the unhindered
translational motion of molecules between the surface region and the
bulk. This makes the arrangement on the surface independent of changes
in the surface area. The work needed for extension of the surface by dA
equals the work for translation of molecules from the bulk into the surface
region, which increases the energy of the liquid phase at constant T, V
and n by dF. Hence, under equilibrium and reversible conditions,

0 = w/c-w,,.
9 ,
(2)

The same relationship is valid for the interfacial tension at the liquid-
liquid and solid-liquid interfaces. The higher the surface or interfacial
tension, the larger the work that is needed to create a new surface or
interface, respectively.
The measured CTvalue of the liquid agrees with its y value not only
because it has the same units, mN m-’ = mJ ms2, but also because it equals
the energy with which the molecules are attracted from the surface region
into the bulk. This energy has the same value as the work for the
translation of molecules from the bulk to the surface, or the energy with
which the molecules are attracted from the gas phase to the liquid surface.
It equals one half of the work of cohesion when the arrangement of
molecules in the surface region is the same as in the bulk. Also the
measured o between two liquids agrees with the value of the inter-facial
free energy. The reversible work for the extension of the interface equals
the work of molecular translation from both phases to the interfacial
region and also equals the average work of cohesion decreased by the work
of adhesion, i.e.
 The same definition is valid for the surface free energy and the surface
tension of liquids. Equation (3) is identical to Eqn (1) for solid-liquid
interfaces if ys = os. Because both the work of cohesion of the gas phase
and the work of adhesion are equal to zero, Eqn (3) yields e = We /2.
The surface tension can change under dynamic conditions or mechani-
cal stress. Then,

dF/dA = d(oAYdA = o + da/d(ln A) (4)

where the differential do refers to a reversible change in the composition

or ordering of the surface layer of liquids. Hence, the dynamic surface
tension is equal to o + Aa and Ao is a function of the rate of the surface
area increase, AA/At.
The surface area of non-elastic solids cannot be increased reversibly.
The work needed to create a new surface is usually larger than dF/dA
because of the irreversible destruction of intermolecular bonds or reorien-
tation ofthe original molecular arrangement. The surface tension, i.e. the
force acting parallel to the surface, is not a measurable quantity for solids.
The molecules cannot move from the bulk into the surface region and
cannot take an equilibrium position as they do in the liquid state. The
second term on the right-hand side of Eqn (4) is zero with liquids at
equilibrium but it has a constant value with solids because of the immo-
bility of molecules. Therefore, attraction forces at the solid surface can
differ from those corresponding to the equilibrium liquid surface, e, and
are equal to e + Ao. The phase transition can either increase or decrease
o to y [1,21 because Ao can be either positive or negative. Hence, an
extrapolation of the measured dependence of o on the temperature,
Tdo/dT, of liquids cannot be used to determine yafter their transition into
solid state. For water, for example, o = 75.6 at 0°C while a distinctly higher
y value for ice was calculated from the contact angle of water on ice surface
[3]. To prevent any misunderstanding, the values of y are further used in
this paper for both solids and liquids.
The meaning of the particular y values is defined by various indexes
which, it is hoped, are easily understandable to readers. The subscripts
denote the surface free energy of solids (ys), liquids (~3, or of some
particular compounds, elements and molecular sections, e.g. hydro-
carbons (yH),water (yw),mercury (~~1,difluoromethylene group <ycr? etc.
The inter-facial free energy between two phases is denoted by two numer-
als (y12),or by capitals relating to the particular interfaces, e.g. solid-liq-
 103

uid <ysJ, solid-hydrocarbon (y&, solid-solid (yss), water-other liquid

(ywL), water-mercury(yw,) etc. If one liquid phase is saturated with
another liquid the index for the latter is in parentheses (y&. A solid
surface with adsorbed vapours has the surface free energy ysv and that
covered with an adsorbed film has ySf(to comply with the cited authors).
The critical surface tension is yc. The superscripts refer to the theory
which separates the surface free energy into components and elements.
The original notation of the cited authors is mostly preserved here
although it may differ in some cases.
Theoretical estimates of ys values are based on the work of cohesion,
ys = IV, /‘2, and they use the calculated number of interrupted bonds per
m2 as well as the bond energy. The values cannot be strictly correct since
no allowance is made for surface distortion. The assumptions employed
can cause high differences. For the (100) plane of NaCl, e.g. values of ys
ranging from 33 to 129 141or to 158 El were calculated at 0 K. However,
such differences make the results dubious. All mechanical methods such
as shrinkage or zero creep, healing of scratches, and crushing or peeling,
were criticized as lacking a sufficient theoretical basis [61. The results
sometimes differ by an order of magnitude. As a result the calculation of
ys using the experimental data of wetting by liquids became increasingly
popular.

3. PROBLEMS OF WE’ITING

Wetting is characterized by the contact angles 8 of liquids on solids.

The liquid spreads completely on the solid surface if 8 is zero. In this case,
adsorption of liquid vapours continues at their saturated pressure, ps,
until ys decreases to yL.Then, adsorption is followed by condensation, the
thickness of the adsorption layer is unlimited and the surface attains the
quality of the liquid phase with ysv = yL.For small 8, a limited adsorption
of vapours can be expected which changes ys to a lower value, ysv. Liquid
drops on solids with ysv display the 0 which is given by the Young
equation:

ysv = YL cos8 + YSL 6)

It follows from Eqn (5) that ysL > 0 when ysv > yLand 8 = 0. The validity
of Eqn (5) is limited; it cannot be applied when ysv < yL and 8 = 0.
Furthermore, ysv can relate to the wetting liquid and/or to water adsorbed
from the atmosphere. The difference between ys and ysv is called the
spreading pressure, x, i.e.
104

Jc= Ys - Ysv (6)

and can be calculated from the adsorption isotherm [73using the equation

p*
x = RT r d(lnp) (3
s
0

For contact angles larger than lo”, x is usually neglected [81 and ys is
substituted for ysv in the Young equation. Then,

Ys = YL Cm30 + YSL 03)

Justification of the Young equation is often demonstrated by drawing

the vectors of o tangentially to the respective surfaces and interface.
However, as shown above, crsneed not be equal to ys. The latter quantity
cannot be substituted in the scheme mentioned for the vector os.
Nevertheless, Eqn (8) is correct and can be substantiated by an equi-
librium between the tendencies of the liquid to wet the solid (which is
given by the work of immersion, WI = ys - y&l and to contract to its
smallest surface (which can be expressed by oL cos 0 = yLcos 9).
Combination of Eqns (1) and (8) yields the Young-Dupre equation

Iv, = y& + cos 0)

from which Wk can be evaluated using the accessible quantities yr,and 9.

As will be shown later, ys and ysLcan be calculated from W,.
The uncertainty in the significance of 0 values should be considered
when using Eqn (9) because of the adsorption and contact angle hyster-
esis. A deviation of the apparent 8 value from the thermodynamic (or the
Young) value, caused by roughness or heterogeneity of the solid surface,
can lead to serious errors in the WA determination. A comprehensive
review of contact angles, their interpretation, application and measure-
ment has been published by Neumann [Zl and another review appeared
recently E91.Contact angles should be measured on smooth and homo-
geneous sutiaces. However, hysteresis seems to be possible even on such
surfaces DO,111.Unfo~una~ly, most authors only determine and use the
advancing angles which do not guarantee the true thermodynamic
values. Hence, the results of calculations, in which these values of 8 are
used, can be incorrect even when the method applied is correct.
 105

4. GRAIN BOUNDARY GROOVE METHOD

Bailey and Watkins WI measured angles created by two crystals of

the same solid. The plane of their contact has the energy yss, their angle
toward the liquid phase is 2a and toward the saturated vapor phase is
26. A drop of this liquid on the smooth crystal surface has the contact
angle 8. The respective equations for the force equilibrium are

Yss = 2YSL cma (10)

and

Yss = 2YscosP (11)

Combining Eqns (8), (10) and (11) yields

ysL = yL cos 8 cost p/(cos a - cos PI (12)

Unfortunately, this method has limited application and the results ex-
hibit considerable scattering. For example, for the ice-water interface ysL
= 33 * 3 [131and 41* 9 1141were determined. Such a difference can simply
be caused by deviations of 6, e.g. for water on ice, the values 6 = 1” and
27.5” were found [13,151; taken with ys = 106.0 131and yL = 75.6 in Eqn
(81, the values ysL = 30.4 and 38.9, respectively, are obtained.

5. CRITICAL SURFACE TENSION OF WETTING

In 1950 1161published the first of his extensive studies in

Zisman
which he obtained the critical surface tension of solids, yc, by linear
extrapolation of the cos 8 dependence on yL to cos 9 = 1 according to
equation

case= 1+ My,-yd (13)

in which b is a constant for a given set of liquids. The experimental results

of Zisman and his co-workers were used by many other authors. The
significance of his papers lies not only in the number of valuable meas-
urements made but also because they led to interest in the problems of
wetting and their interpretation. Zisman reviewed his results (see Refs.
[17,181).
106

Values of yCvary according to the set of liquids used for its determina-
tion. For polyethylene, for example, pure liquids gave yC= 33.5 while
aqueous solutions of 1,4-dioxane, ethanol or butanol, and fluorocarbon
surfactants yielded yC= 31.5, 27.5 1171and 20.0 [191 respectively. For
polytetrafluoroethylene, yC = 18.6 was obtained using pure liquids;
aqueous solutions of ethanol or butanol yielded a similar value, yC= 18.5
while aqueous solutions of 1,Cdioxane gave yC= 22.5 D71. This indicates
that adsorption can significantly influence the yCvalues and that solu-
tions cannot be reliably used to obtain a characteristic quantity for solids
1201.Nevertheless, many authors later ignored this fact and used various
solutions for contact angle measurements. Even pure liquids do not yield
the same value of yCon one solid surface, e.g. for polytetrafluoroethylene
the data of Zisman 1181with the hydrogen-bonding liquids can be extrapo-
lated to yC= 23.3 while n-alkanes from heptane to hexadecane yield yC=
18.2. The first three alkanes forming finite contact angles, i.e. hexane,
heptane and octane, give yC= 17.5.
Zisman admitted the empirical nature of yCand acknowledged that it
would be useful to replace yCby a thermodynamic parameter 117l. Later,
he equated yCwith the dispersion component of the surface free energy
[211 (see Section 10 - Fowkes’ theory). Some other authors also tried to
deduce a relationship between yCand ys. Wolfram 1221 combined the
Antonow rule (for yL > ys),

YSL = YL - Ys (14)

with the Young equation (8) for cos 8 = 1, from which he obtained yC= ys.
However, this relationship cannot be valid because Eqn (14) has been
shown to be incorrect [231.
Girifalco and Good [24,251 consider yCto be equivalent to ys when
systems are used in which the cohesive forces in both the liquids and the
respective solid are of the same type as the adhesive forces. They call such
interfaces regular. The ratio between yCand ys depends on the interaction
parameter, $I(see Section 61,

Ys = YA2 (15)

Regular interfaces with (I = 1 are rare and, usually, 4 < 1.

Gardon demonstrated a correlation between the solubility parameter
and yCbut he did not find a functional relationship [261. The solubility
parameter is the square root of the cohesive energy density (c.e.d.) which
equals the heat of vaporization of volatile materials. For a non-volatile
 107

material the c.e.d. has the same value as the solvent which dissolves this
material without adsorbing heat. Relationships between y and c.e.d. have
been found by Beerbower W7.land Panzer 1281. However, while the c.e.d.
refers to interactions in the dissolved state, the crystallinity of solids can
significantly change this value.
Dann considered the value of yc determined by using a series of pure
hydrocarbons equal to the dispersion component of the surface free
energy [29,301. He also showed that the dependence of cos 8 on yL need
not be linear and that solutions of polar liquids yield lower values of yc.
Hartkopf found a linear dependence between yc determined on liquid
substrates and their yL [311. He agrees that ‘(c on these substrates equal
the dispersion component of their yL.
Rhee 1321combined Eqns 03) and (13) and obtained the relationship:

ysL = ys - yc + (1 - cos 8)/b cos 8 (16)

according to which ysLdecreases parabolically with increasing cos 8 and

yc = (2 cos 8 - 1)/b (17)

because d&d cos 0 = 0 for minimal ysL. Using yc and b determined

empirically according to Eqn (13) and cos 8 from Eqn (17) and assuming
ysL = 0, Eqn (16) yields ys. In his subsequent paper, Rhee derived from
Eqn (16) 1331that

ys = (by, + 1J2/4b (18)

He shows that ysL is not zero at cos 8 = 1 but ranges from 0.1 to 3.4.
However, Rhee did not mention in his paper that his procedure, from
which he derived Eqn (181, also has a second solution leading to yc = ys.
Furthermore, Eqn (16) for cos 8 = 1 gives a trivial result, yc = ys - ysL,
which agrees with Eqn (8). Therefore, calculations of ys from Eqns (16)
and (18) do not seem to give reliable results.
Zisman concluded [171that some of his ycvalues are characteristics for
parts of molecules forming a solid surface. For example, he found that yc
= 6 for the -CF, group, 18 for -CF,-, 22-22 for -CHs and 31-33 for -CH,-.
These ycvalues deviate (except for that for methylene) from the respective
group contributions to the surface free energy determined recently, i.e.
9.5 for -CF,, 22.6 for -CF,- [341,15.8 for -CHs, and 32.8 for -CH2- 1351.
Comparison of the ‘(c values can indicate the composition of various
solid surfaces. Oxidation of polyethylene increases its ‘(c from 31 to 50
108

1361.After oxidative exposure to the laboratory atmosphere, yc = 51 was

found for polyacetylene 1371.Based on the similarity of these ycvalues, it
was concluded that both the solids have a similar composition on their
surfaces and contain hydroxyl groups 1381.For a less oxidized or unoxi-
dized polyacetylene, Yc= 40 was found experimentally 1391while ys = 25
was calculated [381.
It can be concluded that Ycvalues yield interesting information on solid
surfaces. The assumption that Yc= & (the dispersion component of the
surface free energy) for values determined by a set of non-polar liquids
seems to be the most acceptable. However, long extrapolations of yL on
cos 8 dependences to cos 8 = I can be erroneous because the dependence
need not be linear. Short extrapolations of data with 0 < 10” can be
influenced by JC.Therefore, because of the variability of yc, its empirical
nature, and uncertainty about its physical meaning, the continued use of
Ycas a characteristic quantity for solid surfaces cannot be recommended.
In particularly, solutions of liquids should not be used for this purpose.

6. THE INTERACTIONPARAMETER

Important progress in the history of the development of knowledge about

inter-facialinteractions was made by Good [24,25,40421. The oldest relation-
ship for the interfacial free energy between phases 1 and 2 (for y1 > y2),

Y12 = Y1- Yz (19)

(see also Eqn (1411,was suggested by Young 1431and about a hundred

years later promoted by Antonow 1441;it is known as the Antonow rule.
This rule was discussed in many papers and evidence was furnished 1231
that it cannot be generally valid. Lord Rayleigh 1451suggested another
relationship,

l/2= yl112- y21'2

Y12 (20)

from which the interfacial free energy is

yiz = Y1+ Yz- 2(YlY2)1’2 cm

According to Eqn (211, the work of adhesion (see Eqn (1)) equals the
geometric mean of the works of cohesion and y12= 0 for y1 = y2. Equation
(21) holds for the regular interfaces mentioned in the previous chapter;
such an interface is very exceptional.
 109

Good introduced a correction factor (I (called the interaction para-

meter) into Eqn (21):

m
Y12 = Yl + Y2 - WY1Y2) (22)

He investigated 137 pairs of liquids 1241and found $I= 1 in only two cases
(water-butyronitrile and water-monochloroacetone). The +values varied
from 0.32 (water-mercury) up to 1.17 (water-di-n-propylamine) and only
15% of the investigated pairs had 4 in the range 0.95-1.05. Liquids of the
same kind have similar inter-facial interactions and similar (I values for
their interaction, e.g. for the interface of aliphatic and aromatic hydrocar-
bons with mercury 4 = 0.61 * 0.07, for aliphatic hydrocarbons with water
4 = 0.56 f 0.02, w hi1e for aromatic hydrocarbons with water, (I= 0.70 kO.02,
and for alcohols with water (I = 1.09 kO.04.
Substituting Eqn (8) into Eqn (22) for the solid-liquid interface yields

ys = y# + cos 8)2/4@ (23)

A similarity between the interaction at solid-liquid and liquid-liquid

interfaces of the same type can be assumed and the values of 41found for
liquid-liquid interfaces can be employed for the respective solid-liquid
interface. Thus, the contact angles of mercury and water, respectively, on
polyacetylene with the respective values of (I for aromatic hydrocarbons
in Eqn (23) yield different values (ys = 22.7 and 64.0), while similar values
(ys = 25.0 and 26.4) are obtained for the $I values for alcohols. This
indicates that the investigated polyacetylene surface was oxidized and/or
hydrated and had alcohol-like properties K331.
The $Iparameter can be theoretically calculated using the equations
given by Good 141,421.

9=+&A c.24

(p, = 4(v,v,)“3/(1,‘:‘3 + v;‘3,2 (25)

+A = 42&~422)“~ (26)

A,, = 3a,a2C,C2/2(C, + C,) + cc&; + cz$~ + 2&;/3kT (27)

and

Aii = 3a~Ci/4 + 2aiCL~

+ 2CL~/3” Cm
110

where Vis the volume of spherical molecules, a is the polarizability, C is

a constant determined from the dispersion of the refraction index, and ~1
is the dipole moment of the molecules. The value of $A can be as low as
about 0.5. If the dipole moments are very small, 4A reduces to
2(C1C2)v2/(C1 + C2>= 2U,12)1’2/u1+ 12) where I is the ionization energy.
If the cohesive forces in both phases are solely London forces or, on the
contrary, if dipole-dipole forces predominate, then $A approaches unity.
With molar volume ratios of 1:2 or 15, $v = 0.99 or 0.93, respectively.
Good I421calculated I$values for liquids on perfluoro compounds and
he determined average values of ys = 21 or 24 for polytetrafluoroethylene,
with a surface composed of -CF,- groups, depending on the chosen l.~=
0.0 or 1.2, respectively. These values are higher than yc but they agree
reasonably well with the -CF,- group contribution to the surface free
energy of liquid perfluorohydrocarbons, yCF = 22.6 [34]. For polyhexa-
fluoropropylene and perfluorolauric acid m&olayer with surfaces com-
posed of -CF, groups he obtained ys = 19 and 13, respectively. These ys
values are higher than the respective -CFs group contribution (ycr = 9.5).
The reason can lie in the unsuitably chosen parameters in Eqns (27) and
(28).
Ja&zuk and Bialopiotrowicz I461also calculated (I values using Eqn
(26) for interactions of solids with liquids which yielded in Eqn (23) ys =
27.70 f 2.92 for paraffin, 21.72 f 1.24 for polytetrafluoroethylene, 34.55
* 1.98 for polyethylene, 40.31 * 2.25 for poly(ethylene terephthalate) and
41.38 f 2.05 for poly(methy1 methacrylate). The 9 and ys values varied,
e.g., for paraffin from 0.5364 to 1.0000 and from 26.57 to 53.93, respec-
tively. Therefore, it seems that the calculated 4 values can yield mislead-
ing results. However, the empirical 4 based on a similarity of interactions
at the liquid-liquid and solid-liquid interfaces of the same kind can yield
a reasonably good approach to the true ys values. Furthermore, these $
values can be used to obtain ys from the ycvalues in Eqn (15).

7. HYPOTHESIS ON MINIMIZATION OF THE INTERACTION ENERGY

Elton I471combined Eqns (8) and (14) to obtain

ys =y# + cos 8112 cm

He calculated ys for paraffin using yL and 9 for water, glycerol and
ethylene glycol in Eqn (29). The results obtained were in very good
agreement, ys = 27.2 f 0.2; however, this value seems to be low. Using the
same yLand 8 of water with Q = 0.56 in Eqn (23) yields a higher value, ys
 111

= 32, which is in good agreement with the value corresponding to the

-CH, groups (ys = 32.8 1351).
In the next paper, Mitchell and Elton 1481extrapolated the measured
temperature dependence of yL for hexadecane and octadecane to their
melting points. They compared these values with ys obtained from Eqn
(29) and found ys values about 3 units lower than the respective yLvalues
at the same temperature. They explained this difference in terms of a loss
in the surface energy as a part of the general loss occurring on solidifica-
tion. However, calculation according to Eqn (23) using the data of Mitchell
and Elton and $I= 0.56 gives ys values which are higher by about 1.0 than
the respective yLvalues. Hence, Eqn (29) seems to yield incorrect lower
values.
There was a long discussion in the literature as to whether the
Antonow rule, i.e. Eqns (14) and (19), is valid. Lipatov and Feinerman
1491tried to give these equations a theoretical basis. They suggested a
hypothesis on the minimization of the work of adhesion according to
which it equals the work of cohesion of the phase with the lower surface
free energy, i.e.

w, = w,, = 2y2 (30)

for two adjoining mutually insoluble phases with cohesive energies WC,
> WC,. Equation (30) substituted in the Dupre equation (1) gives Eqn (19)
(or Eqn (14)) and, with the Young equation (8), yields Eqn (29) [501.
Lipatov and Feinerman say that the true values of ys are obtained from
Eqn (29) only for contact angles of liquids with yL > ys. The corresponding
dependence of ys on yL,e.g. using data for liquids on polytetrafluoroethy-
lene from the literature 1511,confirms the finding of the above authors.
After an increase of ys with increasing yL up to yL = 35, a reasonably
constant value of ys = 27.2 ? 1.3 is obtained by using organic liquids with
higher yL.However, this ys seems to be too high compared with the value
of 21.7 from the preceding Section. Extrapolation of yL for liquid per-
fluoroalkanes yields the value 23.9 1511and the calculation based on
evaluation of their orientation gives 22.6 1341for the surface composed of
-CF,- groups.
All the values in Eqn (19) should be related to the mutually saturated
phases and deviations can be caused by neglecting this fact. Feinerman
and Lipatov 1521assume that a change in the orientation and density of
molecules at the interface can also lead to an error. Such changes have
been demonstrated for aliphatic hydrocarbons at the interface with water
1531.However, even after taking them into account, it has been shown
112

1231that the hypothesis on minimization of the interaction energy and

Eqn (19) are not valid. Therefore, Eqn (29) is not theoretically substan-
tiated and ys values obtained using it cannot be correct.

8. WU’S EQUATION OF STATE

Wu 1511substituted yC/$2 from Eqn (151 into Eqn (23) and obtained

yc = )(l + cos ej2/4 (31)

Here, yCis not the Zisman extrapolated value for a set of liquids but is a
function of 4 and ys according to Eqn (15). Wu calls the relationship shown
in Eqn (31) an equation of state. He draws a smooth curve below which
all points on the plot of yCvs. yLlie and he equates the maximum of this
curve, y,(max), to ys. He obtained ys = 35.9 for polyethylene, which is
higher than Zisman’s value (yC= 31) and which agrees with the extrapo-
lated values of 34.7 for the liquid homolog series and 35.7 from the
temperature dependence of melts. Similarly, his ys = 22.6 for polytetra-
fluoroethylene is higher than Zisman’s yC = 18 and approaches the
extrapolated value 23.9 obtained from liquid homologs.
The method of Wu seems to give reasonable results. Unfortunately, it
is very tedious. Furthermore, no reasons have been given as to why the
maximum of the curve should equal ys. The equality y,(max) = ys can be
true for Eqn (23) only when 4 = 1. In contrast, the highest yCvalue was
obtained for paraffin wax and poly(methy1 methacrylate) with the same
liquid [511.The interaction of these two solids with the same liquid cannot
correspond to the same value of 4 and, at least in one case, I$should deviate
from 1.

9. NEUMANN’S EQUATION OF STATE

Neumann et al. [541suggested that, in addition to the Young equation

(81, a relationship between ys, yLand ysL,

YSL = f (YSPYd (32)

should exist, which they call the equation of state. They assumed that the
parameter of interaction is only a function of ysL and they empirically
found the linear relationship

@ = -cI'YSL
+1 (33)
 113

in which a = 0.0075 (m2 mJ_‘). By inserting Eqn (33) into Eqn (22), they
eliminated 4 and obtained the explicit formulation of the equation of state,

ysL = (ysv2- yL1’2)2/[1- 2a(ysy3V21 (34)

In the next paper [!%I, they combined Eqns (8) and (34) and obtained

cos 8 = [2(ays - l)(ysy~)“~ + yJ/yJa(YsYL)“2

- 11 (35)

They also gave instructions on how to calculate ys from the available yL

and 8 values. Instructions for solving Eqn (35) were also given in their
next communication [561.The following procedure can be recommended:

A = (2 + 2ayL cos 8jU2 (36a)

cos cp= 0.3182 ~~~‘~(1+ cos CO/A3 (36b)

21)= cp/3+ 60 (36~)

ys = (9.4294A cos $I2 (36d)

Calculation is not possible if a(ysyL)1’2in Eqn (35) approaches 1. In that

case the complementary angle, 180 - 8, is substituted for 8 and the same
method yields ysLinstead of ys.
Neumann [2,57,581 explained two methods with which the linear
dependence of Qon ysLand the value of a were verified. In the first method,
the dependence of yL cos 8 vs. yL was plotted and resulted in a smooth
curve of the same general shape for all the investigated solids. The
limiting line slope at yL = yL(lim) and cos 8 = 1 was d(yL cos 8)/dyL = 0.
Because ys is a constant, it follows from Eqn (8) that

lim (cos 8 -+ 1) d(yL cos WdyL = -dysJdyL = 0 (37)

i.e., ysL has a minimum value at y#im) and cos 8 = 1. It was assumed
that this minimum ysLequals zero. Hence, yL(lim) = ys according to Eqn
(8). (In fact, yL(lim) also equals the Zisman critical surface tensions, yc.)
Then, ysLvalues were obtained from Eqn (8) using yLand 8 for the liquids
together with yL(lim) = ys. The respective (pvalues were calculated from
Eqn (23). The dependence between these Cpand ysLvalues is a straight
line with the slope a = 0.0075 and with 4 = 1 at ysL = 0. There were only
very small deviations of this average a in all the investigated cases.
114

In the second method verifying the linear relationship shown in Eqn

(331, Ys was used as an adjustable parameter. Values of ysL were calcu-
lated from Eqn (8) using the chosen Ysand the experimental yLand cos 6
values. The respective Cpvalues were obtained from Eqn (23) and the
straight line dependence of 4 on YsL was plotted. The correct ys was
assumed to be given by the dependence which intersected 4 = 1 at ysL =
0. The same a value was obtained as with the first method.
A drawback of Eqn (35) is the already mentioned discontinuity in the
ys dependence on cos 8 for a(ysydu2 approaching 1. For this reason, Li
and Neumann 1591developed a new equation of state,

ysL = ys + yL - 2(ys3,P2
exd-Ph - 19~1 cm
which, when combined with Eqn (81, yields

(1 + cos e>/2 = (Ydyr,P2expl-6YL2(I - Yslr321 (39)

From the same data as in Ref. L571,f3= 0.000115 (m2 mJ-‘)2 was
determined. The authors also gave practical instructions for solving Eqn
(39). The results obtained from the above equation agree with those from
Eqn (35). There is no discontinuity in Eqn (39) and, therefore, the results
in the respective region are more accurate.
Validity of the equation of state was verified from the theoretical point
of view using both thermodynamic arguments 1601and some experimen-
tal results 1611.The contact angles of pairs of liquids on a single solid were
found to be equal when their yL values were the same and their other
properties differed. Seven liquids with dipole moments from zero (pen-
tadecane) up to 2.77 (benzaldehyde) and with the percentage of the
dispersion component of the solubility parameter from 100 (pentadecane)
down to 56 (benzaldehyde and methyl salicylate) on polytetrafluoroethy-
lene and on siliconized glass were examined. Furthermore, ys values were
calculated for many solids. For polytetrafluoroethylene, ys = 18.8 f 0.3
was determined as the average of 24 measurements with various liquids
[551,which agrees with the Zisman yCvalue. However, the average ys with
polar liquids (water, formamide, glycerol and 1,2,6-hexanetriol) deviates
to a lower value and, with hydrocarbons, to a higher value. Deviations of
YCwere of opposite sign. For (17-perfluoroheptyl)heptadecanoic acid ys =
13.0 f 0.3 1621and for perfluorolauricacid ys = 12.3 f 0.2 1631which agrees
with ys = 13 calculated by Good 1411for a perfluorolauric acid monolayer
using I$computed from Eqn (22). However, the equation of state yielded
ys = 30.8 k 0.8 for poly(chlorotrifluoroethylene1 [631while Good obtained
 115

ys = 38 1411.Th e 1owest ys value, 8.8 f 0.3, was calculated from Eqn (35)
for perfluorostearic acid [631 which resembles the result obtained with
liquid perfluoroalkanes for the -CFs group, i.e. ys = 9.5 [341. Similarly,
the calculated value for polyethylene, 32.2 1631, agrees with that for
-CH, groups, 32.8 1351.
The advantage of the equation of state lies in the possibility of obtain-
ing ys from a single measurement with one liquid. Thus, the temperature
dependence of ys was determined for a polyamide from the contact angles
of water 1641.A set of polar liquids was used in Eqn (35) to determine how
the substrate, on which the polyesters solidified, influences the surface
free energy of these polymers 1651,e.g. their surfaces formed on mica had
ys of about 10 to 17 higher than those formed on teflon. The real adhesion
of some varnishes on various substrates was compared with the calcu-
lated surface and inter-facial free energies [661. The spreading pressure
of ethylene glycol on polymers was evaluated from the results of ys
obtained using Eqn (35) 1671.The parameter of interactions was calcu-
lated from Eqn (33) [31.The equation of state was shown to be applicable
for lipid-oil-water interfaces [681. The results obtained from Eqn (35)
were used to explain the particle engulfment by solidifying melts 169,701
and to interpret the platelet adhesion 1711.The usefulness of the equation
of state was supported by results including heats of wetting [721, suspen-
sion stability [73,741, sedimentation volume [751,protein adsorption 1761,
particle and cell adhesion [77,781 and phagocytic cell ingestion 1791.
Agreement was found between a direct measurement of the interaction
forces between a monolayer of dimethyldioctadecylammonium on mica
and water DOI and the value of ys calculated by Eqn (35) 1811. Other
examples of using the Neumann equation of state can be found in the
literature.
The Neumann method and theory were also criticized. For the liquid-
liquid interface, a in Eqns (33)-(35) was found not to be a constant
l82-841. Neumann et al. [851explained it by extending the classical phase
rule to interfaces. They deduced that the number of degrees of freedom
for two components and a three phase system with a liquid-liquid
interface is 3 and, with a solid-liquid interface, 2. Therefore, Eqn (32)
cannot be valid for the former system while it is confirmed for the latter.
Two degrees of freedom mean that two independent variables, ys and yL,
are sufficient to determine the third one, ysL. However, Ja&zuk and
Bialopiotrowicz 1461found that a may depend on the type of solid-liquid
interface and it may only be considered constant for interfaces with a
similar kind of interaction.
116

Phillips and Riddiford [861 did not agree with the assumptions yL(lim)
= ys, x = 0 and ysL = 0 when 8 = 0, for which there is no experimental
evidence. They deduced from Eqn (23) that (d4/dys&, =,-,must be indeter-
minate if, as found by Neumann et al., (dyddy& =o is infinite. Therefore,
Eqn (33) is inconsistent with Eqn (23) and a can be valid only over the
experimental range used to obtain it. As a consequence, Eqns (34) and
(35) with constant a cannot be generally valid.
Van Oss et al. [831argued against the above confirmation of Eqn (35)
using liquids of the same yLwhich gave the same values of 8 1611.They
showed contradictory examples with liquids of different yLwhich yielded
the same 8 on the same solid. According to Eqn (35), they should have
given different 8. Furthermore, water had rather different 8 on solids with
nearly the same ys, which van Oss et al. explained by different polarities
of the respective solids, i.e. by a factor not involved in Eqn (35).
Johnson and Dettre [841 showed the dependences of cos 8 on yL for
n-alkanes on polytetrafluoroethylene and stearic acid. The straight lines
cross at yL = 26 and the difference in their slope was considered by the
authors to be outside the experimental error. According to the equation
of state, the lines should superimpose when one liquid has the same 8 on
both the solids. Further, the opponents questioned the assumption of ysL
= 0 at cos 8 = 1. As a contradictory argument, they used the unsuitable
example of the hexane-water interface with the zero contact angle and
an interfacial free energy of 51. However, the equivalent to cos 8 from
Eqn (8) is (yi - yi2)/y2,which yields either 1.18 (a value outside the Young
equation validity) or -0.45 (inconsistent with the argument). They also
criticized the general thermodynamic approach with respect to the Gibbs
phase rule. The above objections were disproved in the reply of Neumann
et al. [87]. It was shown that the superimposition for the mentioned solids
is possible within experimental error if the deviations caused by JCnear
to cos 9 = 1 are considered. The problem of the phase rule had already
been explained in the preceding paper [851.
Morrison [88] centred his critique on the thermodynamic basis of the
equation of state. As in the previous case, the phase rule was discussed.
Furthermore, the interfacial energy cannot be a function of temperature
and the chemical potential of the liquid only, as seems to follow from the
Neumann relationship, y = y(T,p&. It should depend on both the liquid
and the solid and on the nature of these phases. Hence, ysL should be a
function of more variables than ys and yL.In the reply of Neumann et al.
[89], it is explained that pz in the respective derivation of the equation of
state is not the chemical potential of the bulk liquid but an inter-facial
quantity which reflects the properties of both the adjacent phases.
 117

The equation of state cannot be applied in the case of the acid-base

interaction which influences adsorption from solutions on solids. It was
shown that basic solutes adsorb more on acid solids and this adsorption
does not depend on the yL value of the solvent but on its acid-base
character 1901.This also means that the work of adhesion and ysL do not
exclusively depend on ys and yL.
The Neumann equation represents an elegant way to obtain the
experimentally inaccessible quantities ys and ysL. Unfortunately, a reli-
able method which could bring a convincing and definite decision as to
whether the theory and results are correct is not yet available. It can be
expected that this controversy will continue because the theoretical basis
seems to be incompatible with the Fowkes method predominantly used
by other authors (see Section 10). At this juncture it seems useful to cite
Neumann et al. 1881:“It does not readily appear to us that the two schools
of thought are mutually exclusive; rather, they are simply limited.
Ideally, in a perfect, fully cognizant world one would be able to evaluate
the complete collection of intermolecular interactions and thus evaluate
surface energies or tensions without recourse to phenomenal approaches.
Surface thermodynamics, like its volume thermodynamics cousin, would
acquire the status of a useful phenomenal discipline that would enhance
practical calculation. In reality, however, the status of the molecular
approach does not lend itself to a level of practicality required in many
applications.”

10. FOWKES’ THEORY

The most frequently used method for calculation of ys is based on

Fowkes’ concept 1911that the surface free energy consists, in general, of
the sum of its components and intermolecular attraction occurs exclu-
sively between components of the same kind. Saturated hydrocarbons (H)
have only a London (dispersion) component, yH = y$. Water (w) has a yw
value composed of qw and hydrogen bond, pw, components, i.e. yw = & +
Fw. Mercury (M) has y& and metallic, y$, components, i.e. yM = & + y&
Briefly, the y for all compounds always consists of 4 and possibly some
other components. If the interaction is a result of only the dispersion
forces at the liquid-liquid interface, molecules of the first liquid are
attracted into their own phase by a force of y1 and this attraction is
decreased from the direction of the adjoining phase by a force which
Fowkes expressed by the geometric mean of the dispersion components
d Ii2 . Similarly, molecules of the second liquid are
of both the liquids, (#yp)
attracted from the interface into its bulk by y2less the force <yty$)‘/”acting
118

in the opposite direction. The sum of all these forces yields the inter-facial
free energy, i.e.

Y12 = y1- cy&!y'" + Y2 - cy:ry2 = Yl + Y2-2(YtYy2 (40)

Fowkes applied this theory to the W-H and M-H interfaces and, from the
known YH, YW, YM, YWH and YMHvalues, he obtained y$ = 21.8 f 0.7 and
y$,,= 200 * 7 using Eqn (40). These two values in Eqn (40) yielded for the
water-mercury interface the value of ywMwhich agrees with the experi-
mentally determined value.
In his subsequent papers, Fowkes 192-941 used Eqn (40) to evaluate
the spreading coefficient, S, of liquids with yL= yt on water,

s = ‘(w - yL - ywL = 2(Y$YLP2 - 2YL (41)

Then, he applied Eqn (40) to the solid-liquid interface, which, together

with Eqns (1) and (8), yields

w* = y# + cos 0) = 2(y;y;P2

(when interaction occurs between the dispersion components alone). He

evaluated the & values for some solids using Eqn (42), e.g. y$ = 19.5 for
polytetrafluoroethylene, 25.5 for paraffin wax, 35.0 for polyethylene and
10.4 for perfluorododecanoic acid on platinum. These values are slightly
higher than the corresponding yCvalues (see Section 5) but the difference
is not significant. In addition, the ys values obtained by the other methods
described above are similar.
Analogous to the spreading coefficient, Fowkes mentioned that the
total reduction in the surface energy, -AG, of solids resulting from
unlimited vapor adsorption of liquids with yL = ?p at their saturated
pressurep, (leading to the formation of a thick layer with the surface free
energy yd is

-AG = ys-yL-ysL = ~(Y$~YL)'~--YL

The value of -AG can be obtained from the adsorption isotherm,

-AG = W’/VA) j- u d(Znp) (44)

0
 119

where V is the molar volume, A is the surface area of the solid, u is the
adsorbed volume, T is temperature, p pressure and R is the gas constant
(cf. Eqns (6) and (7) for limited adsorption). Similarly as with Eqn (43),
yg can be obtained from the heat of adsorption. The heat of immersion can
also be used. The change in the free energy of immersion, AF, is

AF = ys - ysL = 2(yd,YdV2
- YL (45)

Fowkes found that a polar interaction also takes place at interfaces of

water with various organic liquids. He evaluated it as an excess interac-
tion, E, from the equation

y12 = Yl + Y2 - w&y2 -4312 (46)

which he also applied to solid-liquid interfaces. He wrote

w, = y# + cos 0) = wd, + ESL (47)

where

(48)

Fowkes I951 later separated E into several parts corresponding to the

work of adhesion and, accordingly, he wrote

w, = wd,+ wp+v* +wi,+vcm,b

+ ... (49)

Similarly, he separated y into its components,

y = yd + rp + yh + y’ + Y”b+ ... 60)

where the superscripts d, p, h, i and ab denote the dispersion (London),

polar (Keesom), hydrogen bond, induction (Debye) and acid-base forces,
respectively. The dispersion components for liquids can be determined
from their contact angles on solids with ys = yg and y$ can be obtained
from the contact angles of liquids with yL = yf using Eqn (42).
It was not clear whether the separation of y into components is correct.
The surface free energy includes the entropy term which was the subject
of discord and criticism of Eqn (50) 196,971. However, Tamai [98,99]
showed that y can also be composed of the respective entropy terms. He
arrived at the relationship
120

y= (l/zA)(AWd+ hTAK%&,,l+ (l/zA)(AwP

+ kZ'AP/'&,) (51)

where A is the surface area occupied by one molecule, AWis the difference
between the molecular energy on the surface and in the bulk, AK is the
difference between the force constants for isotropic vibration in the bulk,
Kb, and for vibration normal to the surface. Thus, Eqn (51) containing the
entropy terms AK/K,, is equivalent to Eqn (50) (for y with d and p
components).
Fowkes’ theory on surface free energy components and Eqn (48) were
accepted by many authors. Zisman [171first considered Fowkes’approach
which relates his yCto y,$,as especially promising, but later concluded [181
from earlier results [100,1011 that it was an unreliable and pseudo-
theoretical method. It was suggested that the geometric mean, (y$$)l’z,
can be replaced by the arithmetic, (yf + &/2 11021,quadratic U(y 1 ’ +
d’d c? d
<y$>WP, anharmonic [(Y$~ + (y$)211($+ $1, or han-mnic 2yly2/(yl + ~2)
mean [1031. However, in addition to the geometric mean, only the har-
monic mean was used in practice.
Spelt and Neumann [lo41 admitted that such surface free energy
components as ydand ypmight well exist but they cannot be determined
from the contact angles because the equation of state (32) predicts the
same contact angle on a given solid for two liquids with the same yLand
different polarities. They demonstrated these results. Therefore, the
quantities which were stated to be dispersion and polar components
should be merely artifacts.
Fowkes determined 1911y& = 21.8 f 0.7 using the data for the interface
between water and some n-alkanes. A higher value with a higher stand-
ard deviation of ywd - 22.3 f 2.4 [823 was obtained using additional data
for YH and YWH with saturated hydrocarbons. Johnson and Dettre [lo51
found that the (yw - yWH)/yH dependence on l/yHvz for n-alkanes is linear
but does not pass through the point (0; -1) as required by the relationship

(yw - yWH)/yH = -1 + 20’&)“2/YH1’2 (52)

corresponding to Eqn (40). They concluded that only part of ‘(His involved
in the interaction, e.g. for hexadecane they found @yyH = 0.87 instead of
1 as assumed by Fowkes. Gillap et al. I1061 stated that y$ in Eqn (52)
decreases linearly with increasing length of the n-alkane chain, which
also does not agree with the Fowkes theory. This raises the question of
whether the value yw d -- 21 .8 is correct and whether y$ is a characteristic
constant at all.
 121

On the basis of the interactions of water with many other liquids, Good
and Elbing 11071considered the value 21.8 to be about 10% overestimated.
Aveyard et al. [108,1091 tried to explain the & dependence on the alkane
chain length by separating the work of adhesion and yH into the parts
corresponding to the CH, and CH, groups. They obtained we_, < WC,
and YCH, ’ kHS- Substituting these values for W, and yn in Eqn 953), 2

(53)

yielded &,, = 20.8 and 19.5 for the interactions with the CHs and CH,
groups, respectively. They considered these results to be similar enough
to confirm the validity of constant & in Eqn (53). A hypothesis on the
orientation of molecules with chain structure at interfaces 1531led to the
conclusion that the yH value related to the surface differs from the
effective force at the interface with water, y’ . Substitution of the calcu-
lated y’H VdUeS for yH in Eqn (53) yielded & = 19.1 independent of the
chain length. This value agrees with y!$,= 19.2 derived by Padday and
Uffrndel [llOl who used a modified Moelwyn-Hughes equation for the
dispersion interaction and the Hamaker method to derive the total
interaction across a plane interface. Accordingly, the original, generally
used Fowkes’ value should be corrected. Also the dispersion component
of mercury, yMd - 200, was corrected to the value 190.6 1821.
Some remarks on the basic Fowkes’ equation (40) can also be found in
the next section.

11. THE EXTENDED FOWKES’ EQUATION

Equations (46) and (47) have been used by a number of authors. Dann
1301found that I& for the polymer-liquid interface is a linear function
of ye = yL- yi and the slopes of the EsL vs. $ straight lines depend on the
kinds of polymer. Other authors tried to extend Eqn (46) and substituted
the geometric mean of the non-dispersion components for E,,. Owens and
Wendt 11111introduced

w* = 2,y$$V + 2(y:y:Y’2 64

Dahlquist 11121and Kaelble et al. [X3-1151 wrote

IV* = 2(y$J$1’2 + 2(Y~$Y2 (55)

122

Harder et al. 11061used the same equation but they mentioned that Yp
corresponds mainly to hydrogen bonding. Both polar and hydrogen bond
components were used by Kitazaki and Hata 11171

w* =204yp’2+2(yyyg1’2
+2(y#1’2 66)

All the non-dispersion components were also denoted by the superscript

n and their interaction was expressed 182,118,1191 by the equation

(57)

A sum of the short-range forces including the hydrogen and covalent

bonds was also used to represent the interaction 11201(see Section 13).
Fowkes assumed 1951that the $ and qLvalues for some liquids often
used in the ys evaluation (water, glycerol, formamide, ethylene glycol and
2-ethoxyethanol) are negligibly small compared with &. He did not agree
with the idea of expressing the contribution of the hydrogen bonds to the
work of adhesion by the geometric mean, K$ = 2($j$1’2. However, he
admitted 1901 that there is some reason to equate the dipoledipole
interactions with the geometric mean,

68)

The interaction energy between two dipoles is -2&@3kTr~2. If the

distance between the dipole, r12, is the geometric mean of rll, and r22,
then Eqn (58) should be correct.
Wu 1121-1231 found that the reciprocal (harmonic) mean ofthe surface
free energy components yields results for solid polymers with smaller
deviations than the geometric mean and he used the equation

(59)

There is no other reason for using the harmonic mean rather than a
purpose-designed mathematical method. However, Fowkes’ geometric
mean corresponds to the Berthelot hypothesis according to which the
attractive constants for identical molecules, A 11and A,,, yield the attrac-
tive constant for unlike molecules, A i2,

Al2 = ol,lA22~“2
 123

The appropriateness of the geometric mean can also be supported by

the following arguments. It can be assumed that the interfacial free
energy originates in the difference between the values of attractive forces.
This can be expressed for the dispersion components by

(y:2)l/2 = (yy2 - (y!y2 (61)

(cf. Eqn (20)). A more illustrative concept can be based on Eqn (3). W,
would be zero if no inter-facial attraction existed. Then for the dispersion
components, the inter-facial free energy equals the average work of
cohesion,

yt2 = yf + y; = (y$“2(y$1’2 + (yy2(y$Y2 (62)

However, adhesion decreases the cohesion of phase 1 through attraction

from the direction of phase 2. Then, the relationship (#)“2[(#‘2 -
($) ‘j21 instead of ($) “2($) l/2 can be assumed to be valid. Similar forces
are active on the other side of the interface, leading to the equation

y& = (yy2uyy2 - ($11 + (y;)1’2[(yy’2- tyy21 (63)

Both Eqns (61) and (63) yield the same result, i.e.

yt2 = yf + y; - 2(ygY2 (64

or

wd, = 2(yfy$P2 (65)

The same procedure can be employed for the polar (Keesom) interaction,
leading to Eqn (58). Eqns (54)~(59) often fail probably because neither
the geometric nor the other means for the hydrogen bond and acid-base
components corresponds to the interaction mechanism. The interaction
through the polar (Keesom) components can be negligibly small and is
incorrectly interchanged for the former types of interactions.
The results obtained from Eqns (55) and (59) were repeatedly com-
pared [123,125-1281. A combination of the geometric and harmonic
means was also used 11231,i.e.

Iv* = 2(y&$Y’2 + 4ygye/c* + ve) (66)

124

or from Ref. L281

(67)

Wu ]1231 concluded that Eqn (59) is suitable for polymers, while Eqn (66)
should be preferred for high energy systems such as mercury, glass, metal
oxides and graphite. He considered Eqn (55) to be unsuitable. Dalal[126],
however, found that the geometric mean according to Eqn (55) fits the
polymer interactions better than the harmonic mean according to Eqn
(59).
The results obtained from the geometric and arithmetic means were
also compared. Dorris and Gray [1291 determined x for n-alkanes on
cotton cellulose by gas chromatography using Eqn (7). They substituted
this x into Eqn (40) which yields

yL(l + cos (3)= 2(y”syd31’2

- Jc (68)

(cf. Eqn (42) where x is omitted) and, for cos 0 = 1 and yL= yk,they obtained

y; = (2y, + d2/4YL (69)

Similarly, they used the arithmetic mean <y$+ yJ instead of the geometric
mean in Eqn (48) to express wd, and they obtained

yg = YL + x (70)

They found that the results from Eqn (70) were better than those from
Eqn (69). However, the Young equation (8) was incorrectly used in both
the above equations because ysv can be smaller than yL + ysL and ysL + 0
at cos 6 = 1. Furthermore, -AG from Eqn (43) should have been used here
rather than JCfrom Eqn (6). Nonetheless, the method of inverse gas
chromatography using the adsorption of n-alkanes to obtain y$ is very
auspicious and it was adopted and further developed by other authors
]130-1361.
The chromatographic method investigates pulverized solids while
contact angles should usually be measured on large smooth surfaces,
which are not always available. However, 0 can also be determined using
powders. The results calculated from Eqn (59) for poly(methy1 methacry-
late) sheet and powder agreed well 11371.The average values of y& $ and
ys obtained for seven pairs of liquids were 17.7 f 0.8,17.9 f 0.8 and 35.6
* 0.3 for the sheet and 17.7 * 0.5, 18.2 f 0.4 and 35.9 * 0.1 for powder,
 125

respectively. However, the results for polytetrafluoroethylene exhibited

higher deviations both between the values for single pairs of liquids and
between the mean values for the sheet and powder. The authors found
&, 6 and ys 10.0 + 2.5, 7.0 f 2.1 and 17.0 f 1.2 for the sheet and 13.7 f
4.5,5.0 f 4.9 and 18.7 * 2.5 for the powder, respectively. The $$values are
improbably high so that the results are in doubt.
Krause and Kildsig 11381 evaluated ys for m-acetotoluide from the
solubility of the powder. First, they determined yds= 28.0 from the 6 value
for decalin on the smooth solid surface by using Eqn (42). Then they
substituted Eqn (42) into the Ostwald-Freundlich equation relating the
particle size to the solubility and they obtained ys = 34.4 from the
relationship

log (S,/S, = (2V/2.3RTrI) [yL+ ys - 2(&yd31’? (71)

where S, and S, are the solubilities of particles with radii rl and r2,
respectively, for r2 > > rl, and u is the molar volume of the solid.
Many examples of the use of Eqns (541, (55) and (57) can be found in
the literature. They were mostly employed for low-energy polymers.
Polymers with a different structure having a long unbranched side chain
exhibit a dependence of ys on the number of carbon atoms, n, in the chain
[139]. For n = 21 down to 12, $j remains below 1 and ys slowly increases
by about 2. For a further increase in n, ys and $j suddenly increase to
limiting values of about 40 and 7, respectively.
The wettability of polymers was improved by various methods of
surface treatment, e.g. by corona discharge 11401.This increased 6 while
storage at a higher temperature decreased $$.
Ja&zuk and Bialopiotrowicz WY31used Eqns (55), (59) and (66) to
investigate the surface free energy of polymers and they asked whether
the determined components have a physical meaning and are related to
a given kind of molecular interaction. They arrived at the conclusion that
the components are characteristic constants which agree for various
systems but are not exactly related to the actual molecular interactions.
The dispersion components obtained also include non-dispersion forces
and the polar components include specific and non-specific forces. How-
ever, the same authors [1411 found that Eqn (57) yields good results
despite existing hydrogen bond interaction.
Equation (55) was employed to evaluate the surface free energy com-
ponents for ice 131,coal [142, 1431, adsorption layers of amine fluorides
on glass [1441, etc. The spreading pressure JCaccording to Eqn (7) was
used to calculate the surface free energy of high-energy solids. However,
126

relationships for the spreading coefficient or immersion were employed

instead of JC,similarly as in Eqns (43) and (451, i.e.

-AG = ys - yL - YsL = %Y$J’$~‘~ + %,%t) v2 - 2yL (72)

and

AF = “(s- yc& = 20$gw2 + 2(&w2 - YL (73)

and the calculated y& yg and ys values have been published for galena
11451,quartz 11461,marble [1471 and porous glass [148,1491.
Most authors used equations with two kinds of interactions, i.e. with
dispersion and non-dispersion (or polar) terms. Equation (56) was used
only exceptionally. The values y&,= 14.7 and & = 36.3 were determined
[821 for water from a modified version of Eqn (56).
Other papers, many of which give valuable data on wetting, can also
be quoted here. However, considering that the actual meaning of the
calculated y$ and y/$or y!$values has been questioned 11281and that other
new hypotheses have been suggested (see below), the results based on
Eqns (54)-(59), (661, (67), (72) and (73) do not seem to be reliable and it
cannot be recommended that such values be given without new, relevant
justification.
Doubts may also be raised in connection with some other results given
in the literature. Chibowski et al. [150-1533 tried to evaluate x from zeta
potential measurements and to calculate y$for solids from these x values.
However, their method has been criticized and it was shown that the
results obtained from the electrokinetic data cannot equal either x or -AG
or AF’ [154,1551. Therefore, their use of Eqns (69) and (70) was incorrect.
Equations for evaluation of the solid-liquid adhesion have been
developed 191,921 and tested [82,1281 on liquid-liquid systems. Let us
consider the limits within which these two systems may be evaluated
when only the London forces and the Keesom forces are considered to
interact. For the insoluble solid-liquid interface, the work of adhesion,
W,, is given by Eqn (1). However, in addition, the equation

w* = ysv + yL-YSL = Ys + YL-YSL_Jc

can be considered if x > 0 and the initial state after the vapor adsorption
on the solid is chosen. For W,, in accordance with Eqn (551, we have

wA=yS+yL- ysL = 2(y;ydLY2+ 2<Y~ye)“2 (75)

 127

As the left-hand side of Eqn (75) gives the difference between the initial
(ys + 73 and final (ysJ states of adhesion, the right-hand side of the
equation should also refer to both the initial and final states. This
condition is fulfilled when 3c= 0 and all the dispersion and polar com-
ponents are the same after adhesion as they were before it.
It may seem that a similar relationship can be used for IV’* from Eqn
(74), i.e.

w, = ysv + yL - ysL = 2(4&V2 + 2,~&P2 (76)

However, the right-hand side of Eqn (76) is incorrect because the inter-
action across the interface takes place between the solid and liquid phases
and not between the adsorption layer (with ysv = y&, + &) and the liquid.
The adsorption layer of the liquid on the solid surface influences the
contact angle 0 but not ysL.It is a part of the solid surface but it vanishes
or changes its properties at the solid-liquid interface. Therefore, the
correct relationship, which follows from Eqns (74) and (75), is

w, = ysv + yL - y&!L= 2(y;y;Y’2 + 2,ygyfY2 -x (77)

For the liquid-liquid interface, Eqn (55) is valid when the two phases
are mutually insoluble. For partially soluble and mutually saturated
liquids, y1 chess to y1(2),y2 to Ye, and y’i2 refers to the saturated phases.
Then, the equations for the work of adhesion can be written

IV* = y1 + y2- y’1.2= 2(y:y$“2 + 2(YpY5)“2 (78)

using the initial state before dissolving (yl + y& and the final equilibrium
state (Y’~~),or

IV, = Yi(2)+ Y2(1)- Y’12 = %Yf(2) Y&1y2 + 2%2, Y&l) P2 (79)

using the already saturated phases as the initial state. However, the
right-hand side of Eqn (78) cannot be valid because it does not include
the final interaction forces at the interface in equilibrium. Equation (79)
is correct because all the components are the same before and after
adhesion. Unfortunately, they are not related to the pure liquids and are
valid just for the special case under consideration, i.e. they are useless
for other applications. In addition, Eqn (79) cannot be solved as it contains
four unknowns. Therefore, liquid-liquid systems have limited application
in verification of the relationships for solid-liquid systems.
128

For aqueous solutions of alcohols, Ja&zuk et al. 11561suggested the

equation,

w, = yL(l + cos e) = 2(y&y;)1’2 + 2(ynsfynL)1’2+Ys

- YSf (80)

in which ySfis the surface free energy of the solid with an adsorbed film
of alcohol molecules. However, comparison of Eqns (77) or (79) with Eqn
(80) indicates that the latter is incorrect.
A special case occurs when the interaction force is changed by orien-
tation of the molecules at the interface. Let us consider only the simplest
case of the interaction between the dispersion components of two in-
soluble phases, the first of which has y1 = y$ but where orientation of its
molecules changes the attraction force at the interface from y1 to a
different value. Then, the equation

iv* = y1 + y2 - y12 = 2(Y’,y;P2 (81)

can be written in which yll is an effective value which should involve both
the initial and final attraction force&.%&s case was already mentioned
in connection with the determination of the y$ [531 (see Section 10).
The interaction can be influenced by the time of contact between the
two phases. Lowe and Riddiford [157l found the contact angle of water
on polytetrafluoroethylene to be 109” under static conditions and at an
advance velocity ofthe meniscus below 0.06 cm min-‘. At velocities higher
than 0.7 cm min-‘, the contact angle had a constant value of 115”. They
interpreted this difference by assuming that the polar interaction takes
place after orientation of the water molecules, which requires some time.
Therefore, at high meniscus advance velocities, only dispersion forces
interact while, under static conditions, both dispersion and polar forces
are present. Accordingly, the respective 8 values in Eqns (42) and (55)
yield y$ = 20.3 and s = 0.2. Other results in the literature also confirm
that ys for polytetrafluoroethylene contains a non-dispersion component
of a value between 0.05 [1581 and 2.0 [1131.

12. EVALUATION OF SOLID-LIQUID-LIQUID SYSTEMS

Equilibrium at the solid @)-water (WI-hydrocarbon (H) interface is

given by the Young equation

YSH = YSW + YWH C0s e

 129

in which 8 is the contact angle measured between the WH and SW

interfaces across the water phase. Tamai et al. 11591suggested evaluation
of the dispersion component of solids, $$, using a combination of Eqn (82)
with twice Eqn (46). For hydrocarbons, Eqn (46) can be written as

YSH = YS + YH - 2(&H)1'2 (83)

and, for water,

ysw = ys + yw - 2(Y&$y2 -Esw (84

Subtraction of Eqn (84) from (83) and substitution of YwHcos 8 from Eqn
(82) for ysH- ysw yields

YWH ms 0 = YH - ‘(W + d 1’2[(&1’2- (yH)“2]+Esw

2(ys) (85)

from which y$ can be calculated after elimination of Esw by using Eqn

(85) for two different hydrocarbons and then subtracting one from the
other. This method makes it possible to obtain y$ for high-energy solids
which are completely wetted by single liquids. Tamai et al. 11591deter-
mined y!$= 160,313,437 and 449 from the contact angles of water drops
in n-hexane, n-octane and cyclohexane on iron, cadmium, copper and
aluminium, respectively, using the known values of yH,YwHand y$ = 21.8.
They also applied this method to polymers. In a subsequent paper, Tamai
and Kobayashi 11601used the same method for quartz and they found
yt = 19.4 and Esw = 101. These values correspond to those for water and,
accordingly, the quartz surface was covered with a multilayer of adsorbed
d but, considering the discussion of Eqn
water. In fact, they determined ysv
(76), this value cannot be correct.
Hamilton [1611 noticed that n-octane has ‘(H= y$ = 21.8. Therefore, the
n-octane under-water contact angles should have the same value on all
solids with ys = yg because Eqn (85) yields

cos 8 = (YH- YW)/YWH (86)

and 0 does not depend on ys. Hamilton calculated 0 = 130” from Eqn (86)
using ywn = 43.8 and, instead of yw, the value for water saturated with
n-octane, ?(w(n)= 51.6. His procedure is, in principle, correct, as follows
from Eqn (79) in the previous chapter. The y$ value should be the same
for ?(w(n)as for yw because y$,, = yn. If ys contains a polar component
interacting with water, 6 should decrease according to Eqn (85) to give
130

COS 8 = (YH - yW + &W)hWH (87)

Hamilton found that 8 = 130” for polyethylene and polytetrafluoroethy-

lene, in agreement with Eqn (861, while a value of 40” for nylon 6,6
indicates that it is a highly polar solid.
Bagnall and Green I1621 pointed out that Hamilton used incorrect
1(W(H)and ywHvalues. They recalculated Eqn (86) using yw = 72.6 and ywH
= 50.8 and obtained 8 = 180” on solids with ys = y$. However, the accurate
values of yw(H)= 71.77, ywH= 51.69, yH= 21.64 [531yield 8 = 169.9“.
Hamilton I1631 substituted Eqn (58) into (87) and he obtained the
following equation for the solid-water-n-octane system

YwH ws 8 + yw - YH = 2(ybk)1’z
in which he substituted ywH= 50.8, yH= 21.8, yw(H)= 51.6 (instead of ti)
and yl$, = 50.2. He investigated the increase in yg after oxidation of
polymers and compared these values with the increase in the strength of
adhesion to a polar adhesive determined experimentally.
Schultz et al. I1641 applied Eqn (85) to muscovite mica. They used
water and aliphatic hydrocarbons (hexane, octane, decane and hexa-
decane) and from the plot of yw- yH+ ywHcos 8 vs. <y&j” - (y#’ obtained
a straight line with the intersection Esw at yH = y$ and the slope (y$@.
They used yw = 72.6 and y& = 21.6 in the calculation, which yielded Es,
= 100 and y$ = 30. The y!$value was verified by Eqn (42) from the contact
angles of mercury, tricresylphosphate and a-bromonaphthalene, which
gave the average of yi = 31.8.
In their next paper, Schultz et al. 11651substituted polar liquids for
hydrocarbons to investigate muscovite mica. Equation (84), the analogous
equation for polar liquids,

ysL = ‘(s + YL - 2(Yhv'2 - ESL

and the respective Young equation,

YSL = YWL cose+Ysw (90)

yield

EsL = yL- ywLcos 0 - 2(y#dV2 + C (91)

 131

where C = Esw + 2(&y"wP2 - yw is the value obtained from measurements

with water and aliphatic hydrocarbons in their previous paper 11641.The
partial solubility of water with some of the liquids used led to a change
of 8 with time. Therefore, the authors extrapolated 8 to zero time of
contact and used ti and yLfor pure liquids. They then calculated EsLfrom
Eqn (91) using the $ values which are also given in their paper. The plot
of EsL vs.($)'"yielded a straight line. Accordingly, EsL equals W, and
$ = 90 was determined from Eqn (58). However, this value does not agree
with s = 49 from Esw in their previous paper.
Schultz et al. 11661applied this two-liquid method to carbon fibres.
They used formamide (F) instead of water as the polar liquid and n-al-
kanes and decalin as the non-polar liquids. They found the condition
under which the hydrocarbon is entirely replaced on the fibre surface by
formamide without leaving a thin film when the fibre advances from the
hydrocarbon into the formamide:

Es. > 2[($j)“2 - (rH)“21[(r~)“~ - (Y$)“21 (92)

In the opposite direction of fibre movement, the hydrocarbon displaces

the formamide if

Es&’ < yt - [(y;)“2 - (y$1’21

[($)1’2- (Y”)“2] (93)

The authors did not show how they arrived at Eqns (92) and (93). The
absence of a thin film of one liquid under the other is an important
condition for determining the true properties of the solid surface. How-
ever, the results obtained for a carbon fibre, ?ps= 24 and $ = 16, are typical
for low-energy polymers and not for a carbon surface. Therefore, they may
correspond to a fibre surface coating.
Andrade et al. 11671used the water-n-octane system on poly(hydrox-
yethyl methacrylate) polymers. They determined Esw from Eqn (87), &
from the contact angle of water according to Eqns (47) and (48), and @
from Esw = Wp,in Eqn (58). In the next paper, Andrade et al. [1681
employed the harmonic mean according to Eqn (59), instead of the
geometric mean, in combination with Eqn (82).
Ko et al. [1691 obtained rather different results for mixtures of 2-hy-
droxyethyl methacrylate and ethyl methacrylate when they calculated
ys, & and $Jfrom the contact angles of single liquids according to Eqn (55)
or (59) and from the contact angles of hydrocarbons under water. Mat-
sunaga and Ikada I1701investigated hydrophilic polymers using the data
for various combinations of hydrocarbons (n-hexane, n-heptane, n-octane,
132

iso-octane and cyclohexane) with polar liquids (water, glycerol, forma-

mide and ethylene glycol) in Eqn (85). The slope of the dependence
between yw - yH+ ywHcos 8 and 2[(&)1’2 - (YH)‘~I=was the same for all
the polar liquids as for water and gave the y$ values 29, 30 and 37 for
poly(viny1 alcohol), cellulose and poly(methy1 methacrylate), respectively.
However, the dependence of EsL vs. ($)l” was not linear, showing that
Eqn (58) cannot be employed to calculate 3.
Ja/nczuk and Chibowski 11711suggested the equation

20&&Y’2 = yw + YH+ YWH C0s ’ (94)

for the condition that the non-polar liquid spreads under the water
droplet. They did not describe the derivation of this equation but obtained
reasonable values of yds= 24.0 and 127.6 for polytetrafluoroethylene and
graphite, respectively. Ja&zuk et al. [1721used Eqn (85) and determined
yi = 64.0 for marble. Then they determined 3cfor water by integrating the
adsorption isotherm according to Eqn (7) up to pressure p corresponding
to the formation ofthe second statistical monolayer. They interpreted this
x = 76.6 as -AG on a polar solid

_AG = ys - yw - ysw = 2(yds?pw)1’2

+ 2($$ &)1’2 - 2yW (95)

(for a non-polar solid, see Eqn (43)) and they obtained $ = 106.6. However,
it can hardly be assumed that the second statistical monolayer has the
properties of liquid water and, therefore, the calculation using Eqn (95)
was probably incorrect. Also, the other results obtained by using the
solid-liquid-liquid method cannot be accepted without some doubts. The
$, values for various carbons and the y$ change after the plasma treat-
ment were determined by Donnet et al. [1731. One sample yielded y$ = 62
which increased to 168 after the treatment, the other sample yielded &
= 68 which decreased to 9 after the same procedure. Such a difference
seems to be dubious.
Ja&zuk and Bialopiotrowicz 11741evaluated yg for the clay minerals
using Eqn (85). They obtained yi values by the following procedure. They
calculated the value of the dispersion component, y&,of the solid surface
covered with an adsorbed water film, using the equation

y; - y$f = 20$$y$JP2- 2YfiJ (96)

Then they measured the contact angle of water, ew, on the solid and
calculated yEfusing the relationship
 133

y,cos 8 = y& + y& - 2(y&&rP2

- xy&~)“2 (97)

Finally, they obtained $ from the equation

(98)

However, Eqns (96)-(98) do not seem to be correct in the light of the

discussion of Eqns (76) and (77). Furthermore, the derivation of Eqn (97)
is not clear.
Most results were obtained using the dependence of yw - YH- Ywncos
d 1/2- (~n)‘~l according to Eqn (85). In this way, Yuk and Jhon
8 vs. 2Kyw)
11751determined y$ and ~8for polymer hydrogels at various temperatures
and, from the temperature dependence, they found the surface entropies,
d@dT and yI$,/dT.Tagawa et al. 11761 measured the advancing and
receding contact angles to determine yg from the former and $ from the
latter angle on carbon fibres [1761 and on other fibrous materials [177].
They obtained a linear dependence between Esw and $$ from Eqn (58).
Tsutsumi et al. 11781 also investigated carbon fibres but they used
formamide instead of water. They determined the surface ratio of oxygen
to carbon by ESCA which was related closely but not linearly to the
surface polarity expressed by wys for yg from Eqn (58).
The method using the solid-liquid-liquid system has the advantage
in comparison with the solid-liquid-air system that the surface free
energy components of high energy solids, on which the single liquids
spread, can be obtained. Unfortunately, new difficulties arose from the
possibility of film formation of one liquid under the other and from the
solubilities of the liquids. Furthermore, as in the previous Section, it is
not clear whether the use of the extended Fowkes’ equation is correct.
Some results seem to confirm relationship (58) while others do not. It was
shown 167,821that Eqns (54)-(57) are compatible with the Girifalco and
Good equation (22). The relationship between the interaction parameter
and the surface free energy components is

(99)

where d = yd/y,p = rplr and h = p/y. This relationship shows that, in

principle, Eqns (54)-(57) can be used but it does not confirm that the
components yPand yh, calculated from these equations, have a physical
meaning and that these equations represent the interaction mechanism.
This review suggests that the above equations were often misused.
134

13. INDUCTION AND ACID-BASE INTERACTIONS

As shown in Eqn (49), Fowkes I911separated the work of adhesion into

a variety of interactions among which he also included the induction,
I@*, and acid-base, wAb,parts. Accordingly, he also included the induc-
tion, y, and acid-base, yb, components of the surface free energy, which
was also later mentioned by other authors 1128, 146,148l. Van Oss et al.
[1201combined y’ with ydand yi’into a single component which they called
the apolar or Lifshitz-van der Waals component and denoted this com-
ponent as Fw. In fact, y’ can only be a negligibly small component of the
total yvalue if the phase consists of one type of molecule, as in pure liquids.
However, j can play an important role in the interaction across the
interference of two phases. This was shown in only one paper 1821;
otherwise WAwas neglected. Component y’ can be evoked in molecules at
an interface by polar molecules of the other phase. The interaction across
the interface can have either dipole-dipole or acid-base character includ-
ing the hydrogen bond. The induction force immediately disappears when
the molecule is not in the immediate vicinity of the polar molecule which
initiated the induction.
The induction interaction was demonstrated, for example at the inter-
faces between mercury (Ml and organic liquids (L) 1821.If yL = 6, then
the equation

YM + ‘(L - YML = 2(&YL)1'2

should hold because the solubility does not complicate the system. The
value of y$ = 190.6 was determined from interaction with hydrocarbons
using Eqn (100). However, it yielded either lower or higher y&values for
other liquids. The former case, as found for benzene and alcohols, results
when yL is higher than yt and only dispersion forces interact. A high y$
as found for some halogen compounds and organic acids, is obtained when
other interactions occur in addition to those between the dispersion
forces. Then a polar component induced in mercury was assumed to
interact with the polar component of the liquid.
The acid-base interaction, wAb, was demonstrated by Fowkes and
Mostafa 1901. However, Fowkes denied that it could be expressed by
relationships such as wAb = 2(flb$b)1’2 or PAb = 2($y$“’ [911. Van Oss
et al. 11201 combined the hydrogen bond and acid-base components,
called them short-range forces and denoted them as ysR.They expressed
the interaction by the equation
 135

Iv* = 2($w$wP2 + 2@Ry$RY’2 (101)

which is identical in form to Eqns (541, (55) and (57) but the significance
of the terms differs. Equation (101) was criticized by Spelt and Neumann
1811for the same reasons as the previous equations employing the division
of the surface free energy into components.
In their next paper 11791as well as in all their subsequent work 183,
180-1861, van Oss et al. divided the ysRcomponent into acid, y+,and base,
y-, parameters on the basis of the relationship

,,= = 2(y+y-)‘/2 (102)

They assumed that the short-range force interactions at the interface

take place between the acid parameter of one phase and the base para-
meter of the other phase. Accordingly, they wrote the equation,

w,=2(yy&w)“~ + 2(y&)“2 + 2ty7y;Y2 (103)

Compounds which have a FR component are called bipolar. Compounds

with y = Fw can have either y+or y- parameters and can interact either
as proton donors (electron acceptors) or proton acceptors (electron
donors), respectively; they are called monopolar.
It seems that the idea of the acid-base interaction according to Eqns
(102) and (103) can help to remove the objections against the previously
used terms for the polar and hydrogen bond interactions. The acid and
base parameters of monopolar compounds can be compared with the
induction component. However, the permanent dipoles of one phase can
interact across the interface only with the permanent or induced dipoles
of the other phase. Therefore, the combination of the London and Keesom
components into one yLwcomponent is, in principle, incorrect even when
the contribution of the dipole interactions to the adhesion is negligible.
The Keeson forces should be involved in the acid-base interaction. There-
fore, it was recommended 11241that the surface free energy be divided
into dispersion component, yd, as originally suggested by Fowkes 1911,and
the acid-base component, Fb, which is composed of the acid, f, and base,
yb, elements according to a relationship analogous to Eqn (1021,

r”b = 2(yayY2 (104)

An equation analogous to Eqn (103) has been derived 11241. For the
dispersion forces, the derivation is shown in this paper in Eqn (63).
136

Similarly, the acid-base interaction of the element $ consists of cohesion

on one side of the interface, ($$‘)1’2, which is decreased by the adhesive
attraction from the other side, ($y2) b ‘I2 . This can be written together as
($)“2[($)“2 - ($)1’21. Summation of all similar interactions for $, y!,
$, $ and Eqn (104) yield the acid-base component of the inter-facial
energy, &!.

yy; = yp + $b - 2(ygv2 - xy;yy2 (105)

which, combined with Eqn (64), gives

IV* = 2(~~$3”2 + 2(y;$)“2 + 2(&Y2 (106)

Larionov et al. 11871studied intermolecular interactions for adsorption

in gas chromatography and they evaluated the total energy of adsorption
as the sum of particular contributions,

AU=Aud+Ati+AU’+A@ (107)

They expressed the hydrogen bonding part of the adsorption energy, Avh,
by the equation

Auh = vsIybA+ @fl (108)

in which the enthalpy constants Ware specified by subscripts S and A for

sorbent and adsorbate, and by superscripts a and b for acid and base
components, respectively. Equation (108) is in accord with the acid-base
interaction according to Eqn (106).
In addition to attraction, the new hypothesis [1241 also assumes
repulsion at the interface. The acid-base attraction across the interface
takes place when the opposite elements approach closely to one another.
However, permanent elements of the same kind approach at the interface
with the same probability, which causes their repulsion. Therefore, the
complete interaction of the element $ should be ($)1’2[(yt)1’2 - ($)“2 +
(y$‘/? and the summation of all similar interactions yields

,,$ = $b + $b - 2($,9”2 - 2(y;$) 1’2 + 2($~$)“~ + 2(Y%)“2 (109)

and
 137

w* = Z(y$y!j)“2 + 2(fly!j))“2 + 2(y99”2 - 2,$fiP2 - 2c$$p2 (110)

It is interesting to note that Eqn (110) can be rewritten as

w* = 2(y!y!$i’2 + 2[($)“2 - ($P21 Ky;Y2 - ($9”21 (111)

which is similar to Eqn (57) where ($)‘I2 and ($)‘I2 are substituted for
($)‘j2 - (y$‘12 and (Y;)“~ - ($)“2, respectively.
While Eqn (110) is valid for permanent elements, Eqn (106) becomes
valid for induced elements because they do not cause repulsion. Of course,
Eqns (106) and (110) can be reduced according to the components and
elements which are available. If phase 1 has yl = yf + sb and phase 2 in
monopolar with y2 = y$,then Eqn (110) reduces to

w* = 2(yfy;)“2 + 2($$Y2 - 2cY;Y;)1'2 (112)

or

W* = 2(yty;)“2 + 2(y;yy2 - 2($$Y2 (113)

If the component in phase 2 is only induced, then Eqn (106) yields

W* = 2(y~y;)“2 + 2($jzbP2 (114)

or

W* = 2(y~y$)“2 + 2(y;#P (115)

Superscript ‘i’ is added to distinguish the induced from the permanent

element. The interaction between the two monopolar phases with the
opposite elements proceeds according to equation
W* = 2(yty;)“2 + 2(fiy;)1’2 (116)
The values of elements determined according to this new hypothesis
11241for water are y$, = 67.7 and yw b = 10.6. Benzene and diethyl ether
were found to be monopolar bases with yk = 4.4 and 18.8, respectively.
Mercury is also monopolar and has yh = 3.0. Some other compounds were
investigated and their elements were also determined. It was shown that
the new hypothesis fits well for perfluoro compounds 1341and explains
their high hydrophobicity. However, more results are needed to make a
reliable decision about its validity.
138

14.CONCLUSION

This review covers a 40-year period in the development of methods for

the surface free energy determination for solids based on their wettabil-
ity. During this time a great many ideas and concepts, their alteration
and modification, and also a large number of greater or smaller errors
appeared. Not all the papers published on the subject could be mentioned
here, but a selection has been made. It is hoped that all the important
ideas are included.
There is no point in summarizing the contents of the review or in
pointing out the usefulness or insufficiencies of the particular methods,
as this has been done in the previous sections and an abbreviated
statement of the main points can often have a misleading effect, dispro-
portionately favouring or suppressing some questionable ideas. I have
criticized some methods which I do not think to be correct. However, I do
believe that they were useful in the development of new ideas. On the
other hand, many papers published earlier or recently only increase the
confusion by applying old, incorrect methods to new materials. May this
review help to stop the further propagation of such papers and to chal-
lenge research workers to try to explain all the vague questions connected
with the surface free energy of solids! A definite and definitive solution
is still not available.

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