Surface Free-Energy Components of Liquids and Low Energy

Solids and Contact Angles

B R O N I S L A W JAIqCZUK AND T O M A S Z B I A L O P I O T R O W l C Z
Department of Physical Chemistry, Institute of Chemistry, Maria Curie-Sktodowska
University, 20-031 Lublin, Poland
Received August 19, 1987;acceptedNovember 17, 1987

Employingthe values of organicliquid surfacetension and interfacial surfacetension of water-organic

liquid, valuesof dispersion and nondispersioncomponentsofthese liquidswere calculatedand compared
with those obtained in another way. For these organicliquids and water, the values of the contact angle
on paraffin wax, polytetrafluoroethylene, polyethylene, polyethylene terephthalate, and polymethyl
methacrylate were measured. The values of dispersion and nondispersion components of surface free
energy of these polymers and paraffin wax were calculated using the measured values of the contact
angle for diiodomethane and water and the calculated values of the componentsof their surfacetension.
These calculated data were in agreement with the literature data. Taking our values of free energy
components of liquids and solids, the values of the contact angle for these solids were calculated and
compared with those measured, obtaining good agreement. On the basis of the measurements and cal-
culations it was found that dispersion and nondispersion componentsof surface free energy of liquids
and solids "work well" in the systems studied. © 1989AcademicPress,Inc.

INTRODUCTION and (3)

For the last 30 years many experimental and
theoretical studies have been carried out deal-
ing with surface free energy of liquids and sol-
ids on the basis of the Young equation. One
of the main problems of using the Young
equation for this purpose is in expressing the
interfacial free energy of solid-liquid as a
function of the surface free energy of a solid
and a liquid.
There are two basic approaches to this
problem. The first of Fowkes (1, 2) is based
on the assumption that the surface free energy
of a solid and a liquid can be divided into
many parts, the parts due to dispersion inter-
action (d), dipole-dipole interaction (pl), di-
pole induced-dipole interaction (i), hydrogen
bonding (h), 7r-bonding (~r), electrostatic in-
teraction (e), and acceptor-donor interaction
(ad), and interfacial free energy (3'12) which
can be expressed in the form
712 ~- 71 ~- 7 2 -- WA(12)
d i
WA(12) ---- WA(12) -~ WPAI(12) "~- WA(12 )
..~ h ~r e ad
WA(12 ) -~- WA(12 ) -~- WA(12 ) -~- WA(12),
[Ib]
where 7~ and 3'2 are the surface free energy of
phases 1 and 2, respectively, and WA(12) i s the
work of adhesion of phase 1 to phase 2. Fowkes
claims (3) that only W Ad( I 2 ) c a n be expressed
as a double geometric mean of the dispersion
components of 71 and 72. Owens and Wendt
(4), however, have used the geometric mean
of hydrogen bonding components of two
phases in contact to determine the surface free
energy components of polymeric solids. Kae-
ble and co-workers ( 5 - 7 ) employed the geo-
metric mean of dispersion and polar interfacial
interactions in their studies to determine the
work of adhesion. Kitazaki and Hata (8) di-
vided surface free energy into three parts, the
parts due to dispersion interaction, polar in-
teraction, and hydrogen bonding, and they
[la] used the geometric mean for all these parts to

189
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Journal of Colloid and Interface Science, Vol. 127, No. 1, January 1989 All fights of reproductionin any form reserved.
190
express interracial free energy in the interpre-
tation of the wetting and adhesion processes.
Although Wu (9-14) recognized the divi-
sion of the surface free energy of a solid or
liquid into two components (dispersion and
polar), he proposed that the "harmonic mean"
of these components, as well as the "harmonic
mean" for the dispersion components and the
"geometric mean" for polar components, ex-
presses the interfacial free energy of a solid-
liquid and liquid-liquid. Next Wu (9-14) and
Hata and Kasemura (15 ) tested the usefulness
of the harmonic mean and geometric mean
equations by measuring the interfacial tension
between polymer melts and liquids (12-16).
The second point of view is represented by
Good, Neumann, and co-workers (17-23).
They did not divide surface free energy of a
solid and liquid into components but ex-
pressed the work of adhesion by the geometric
mean of the total surface free energies con-
tacting the phase corrected by a parameter ~,
which is a unique property of the pair of sub-
stances (20). Since for many solid-liquid sys-
tems the calculation of • is impossible or very
difficult, Neumann and co-workers (22, 23)
assumed a linear relationship between inter-
facial free energy of a solid-liquid and ~ pa-
rameter and proposed a so-called state equa-
tion for calculations of interfacial free energy
of a low energy solid-liquid.
Of the two approaches, the one dividing the
surface free energy of a solid and liquid is, in
our opinion, the most convenient way and, in
many cases, the only way using the Young
equation of determining the surfacial prop-
erties of a given solid. This method has been
confirmed in studies by many authors
(24-39).
However, we think that this problem has
not been solved completely as yet because a
few questions remain: (i) Do the determined
components of surface free energy have phys-
ical significance? (ii) Are they related to given
kinds of molecular interactions? (iii) Do these
components determined for one system work
well in the other systems?
Journal of Colloid and Interface Science, Vol. 127, No. 1, January 1989
JA/qCZUK AND BIALOPIOTROWICZ
One of the reasons there are such doubts
concerning surface free energy components is
the lack of systemization of the experimental
data of contact angles in the solid-liquid-air
system for many liquids and solids. Therefore,
we measured contact angles for a series of liq-
uids on the surface of polytetrafluoroethylene
(PTFE), polyethylene (PE), polyethylene
terephthalate (PET), polymethyl methacrylate
(PMMA), and paraffin wax. We also used cal-
culated components of surface free energy
from the literature (20) dealing with the wa-
ter-organic liquid system for this series of liq-
uids. Next, measured contact angle values were
compared with those calculated for the same
system using the calculated values of surface
free energy components of the liquids studied.
THEORY
According to Fowkes (1-3), surface free
energy of a solid and a liquid can be expressed
in the form
,y = ,yd + ,~i .~_ ,)/Pl dl- ,yh
+ 3 , ~ + 7 ~ + 7 aa, [2]
where index d refers to dispersion, i to induced
dipole-dipole, Pl to dipole-dipole, h to hy-
drogen bonding, ~r to a--bonding, e to electro-
static, and ad to acceptor-donor interaction,
respectively.
From a practical point of view one can write
3' = 7 d + 7 p, [3]
where "yP is the nondispersion component of
surface free energy of a solid and a liquid,
which we shall call the polar component.
Practically, this polar component is the sum
of one or more nondispersion components
arising from different types of molecular in-
teractions.
Using the geometric mean or harmonic
mean of the dispersion (9-16 ) and the polar
or harmonic mean of the dispersion and the
geometric mean of the polar (4-I I) interracial
interactions, interfacialfree energy for a water-
 SURFACE FREE ENERGY COMPONENTS t91

organic liquid can be expressed in the respec- • = 3'w + 3'o - 3`wo [10]
tive forms: 2V3"w3"o
3"wo = 3"w + 3"o - 2 ~ Combining Eqs. [4 ] and [ 9 ] or [ 5 ] and [ 9 ]
or [6] and [9] gives, respectively,
- 2V3"(v3"~ [41
P P
• = V3'~w3`~ + V3"w3"o [11]
43'dw3"g
3"wo=3'w+3"0 3`dw + 3 " ~ ~f3"w3"o

O=
23"dw3`d
43'~v3`~
[5] (3" w + 3"g)V3"w3"o
23"(v3`~
43"dw3`d 2f~W---W3"~, + [12]
3`WO=3"W+3`O 3"dw + 3 ` ~ (3"(v + 3"DV3"w3"o
[6] O= 23"dw3`~
where index W refers to water and O to an (3" w + )V w3'o
organic liquid. For aliphatic hydrocarbons
when 3"0 ~- 3' d (2), then from Eqs. [ 4 ], [ 5 ], + 3"b. [131
and [ 6 ] the results are V 3"w3"o
From Eq. [ 8] it appears that
(3`d)1/2 ____3"W -~- 3 ' 0 - - " Y w o
2(3`0) 1/2 [7] O2-20\/3"~3`g- 1 3"._~_~w 3"do [14]
V 3"w3'o 3"w 3'o
3" v = (3"w + 3"0 - ,wo)3"o [81 Given 3'w = 72.8 mN/m:3"aw = 21,8 m N / m
3"1o - 3"w + 3"wo and 3`~v -- 51 m N / m (2) for a given organic
Fowkes, employing Eq. [ 5 ] for 3"w = 72.8 m N / liquid in contact with water (at low mutual
m and using the values of 3"0 and Ywo for solubility), Eq. [14] may be simplified to the
eight different aliphatic hydrocarbons, calcu- form
/ . . . . . . . -

lated the dispersion component of water sur-

• 2 - 1.0940 \ / 3 " ~ = 0.701 - 3"---a°-a° [15]
face tension, the mean value of which equals V 3"0 3"0
21.8 m N / m (2). In turn, introducing the
Next, employing in Eqs. [ 12 ] and [ 13 ] 3"w
same 3"o, 3"w, and 3"wo values to Eq. [ 8 ] we ob- = 72.8 m N / m , 3`dw= 22.13 m N / m , and 3'~
tain the mean value of 3"~w equal to
= 50.67 m N / m , we obtain, respectively,
22.13 m N / m .
These values may be useful for calculations O=
of dispersion and polar components of a given 3,4/2(4.266 + 0.1933, d)
organic liquid in contact with water (assuming
3"~v = 3`w - 3`dw) if the values of 3"o and 3`wo 3"o - 3'~
have been measured. + 3'4/2[4.266 + 0.0842(3`o - 3`~)] [16]
According to Good's theory (17-21), the
0=
interfacial tension of a water-organic liquid 3,4/2(4.266 + 0.1933'do)
can be presented in the form
+0.834\/1 3"d. [17]
3"wo = 3`w + 3'o - 20V3`w3"o, [9] 3`0
V
where • is the parameter of interfacial inter- From Eqs. [10] and [15] or [10] and [16] or
actions. Hence, we have [ 10 ] and [ 17 ] we can determine the dispersion

Journal of Colloid and Interface Science, Vol. 127, No. 1, January 1989
192 JA/qCZUK AND BIALOPIOTROWlCZ

and polar components of surface tension of where 0 o is the contact angle for the organic
an organic liquid employing the measured liquid drop measured through the organic liq-
values of 3"o and 3"wo. uid phase. Introducing Eq. [ 18 ] into Eq. [ 21 ]
Knowing 3"dw, 3"(v, 3"~, 3"~ and the mea- we can write
sured contact angle values of the solid-water 3"0(cos 0o + 1)
drop-air and solid-organic liquid drop-air
systems, we can calculate the dispersion - V3"~/3"~v3"w(COSOw + 1)
(3's~) 1/2 = . [241
p d p
(3"ds) and polar (3"~) components of surface 2 ( ~ f ~o - V3"o3"W/3"w)
free energy of the solid (3's) if 3"s ~< 3"w and
Given 3'w = 72.8 m N / m , 3"~v- 21.8 m N / m ,
3"s < 3"0 (4) (,re ~ 0 (2), where *re is the
and 3'(v = 51 m N / m (2), Eq. [24] may be
decrease of the solid surface free energy by the
simplified to the form
adsorbed film of liquid vapor). Employing the
geometric mean of dispersion (2) and polar 3'o(COS Oo + 1)
(4-8) interfacial interactions according to the - 10.194 ~f~o(COS 0w + 1)
Young equation, the equilibrium state of the (3"~),/2 = . [251
solid-water drop-air system is described by 2 ( ~ f ~o - 0.654 ~f~o)

3"wCOS0w = -3"w + 2 ~d d p p
+ 2V3"s3"w, Unfortunately, determination of 3,sd by com-
bining Eq. [ 19 ] and [ 22 ] or Eq. [ 20 ] and [ 23 ]
[18]
leads to equations of very complicated form,
where 0w is the contact angle of the water drop which are easy to solve only numerically, so
measured through the water phase. we have not cited them. Therefore, by mea-
In turn, using the harmonic mean for dis- suring the contact angle for the water drop
persion and the polar (9-16) or the harmonic and the organic liquid drop resting on a given
mean for dispersion (9-16), and the geometric solid surface, one can calculate its dispersion
mean for polar (9-11) interfacial interactions and polar components of surface free energy
from the Young equation, it appears, respec- from Eq. [25] and Eq. [18] or [19] and Eq.
tively, that [22 ] or [ 20 ] and Eq. [ 23 ]. The dispersion and
4 d polar components of surface free energy can
3'w3"sd
3"wCOS0w = -3"w + 3"d
w + 3"~ be determined, of course, on the basis of mea-
sured contact angles of any two organic liquids
p P
43"w3"s if the dispersion-polar components of their
+ - - [19] surface tension are known to be sufficiently
different and when the condition 3"s ~< 3'o is
43"~3"sa fulfilled.
3"wCOSOw = -3"w + - -

P P
+ 21/3'w3"s. [20] EXPERIMENTAL

Wetting contact angle measurements were

For the solid-organic liquid drop-air system, carried out using the sessile drop method by
Eqs. [ 19 ] and [ 20 ] can be written in the forms the telescope-goniometer system, at 25×, for
d d PTFE, PE, PET, PMMA, and paraffin in a
3"oCOSOo = -3"0 + 2 ~1/-~-~ + 2V3"s3"
P op [21]
thermostated measuring chamber at 20
d d
43's3"o 43"~3"~ ___0.1 °C. The chamber was dried with molec-
3"ocos 0o = -3"0 + + 3"g + 3"g ular sieves (4 + 5 A) and then a beaker con-
[22] taining the liquid to be studied was placed in
it for 24 h. After this time a solid plate was
4AdAd
placed in the chamber, a drop of liquid (2 #1)
3"0cos Oo = 3"0 + 3"sdr s+r o3"~ ¢- 2 f~-~P
~3"op , [231
was settled, and the contact angle on both sides
Journal of Colloid and Interface Science, Vol. 127, No. 1, January 1989
 SURFACE FREE ENERGY
of the drop was read immediately. The mea-
surements were repeated several times by set-
fling other drops on the same plate. Next, a
new plate was placed in the chamber and the
above procedure was repeated. For a given
solid and liquid at least ten different plates
were used.
The PTFE plates (Z. A. Tarn6w, Poland)
used for the measurements were cut from a
large sheet and mechanically polished. Each
polished plate was cleaned by triple boiling in
HC1 solution (1:1) and triple boiling in doubly
distilled water. Final cleaning in doubly dis-
tilled water was performed in an ultrasonic
bath for 20 min; the plate was then dried by
hot blowing air.
The PE plates (Z. P. Ch. P[ock, Poland)
were cut from a large sheet and cleaned by the
procedure of Baszkin and Ter-Minassian-Sar-
aga (40). PE plates were dipped into CC14 for
15 min and then boiled in acetone for 5 h; the
last cleaning was performed in an ultrasonic
bath for 20 min.
The PET plates were cleaned in a detergent
solution and rinsed several times with doubly
distilled water and finally treated in an ultra-
sonic bath for 20 min.
The PMMA plates (Z. Ch. O~wiecim, Po-
land) were cut from a large sheet, one side of
which was covered with paper. The cleaning
procedure was the same as that in Good and
Koo's paper (41), and these plates were then
cleaned in an ultrasonic bath for 20 min.
Paraffin plates were obtained by overflowing
paper forms placed on a glass sheet. After stor-
age for 5 days, the plates were removed from
the glass and their surface was checked under
the microscope, and good plates were used for
measurements. The glass sheet on which paper
forms were placed was previously cleaned in
hot chromic acid and then dipped in HC1
(h 1), washed in doubly distilled water, and
dried at 105°C for 1 h.
For contact angle measurements the fol-
lowing liquids were used: benzene p.a. POCh
Gliwice (Poland), toluene p.a. POCh Gliwice
(Poland), p-xylene p.a. POCh Gliwice (Po-
land), m-xylene p.a. POCh Gliwice ( Poland ),
COMPONENTS 193
mesitylene pure Riedel d.H. (GBD), p-cy-
mene pure Riedel d.H. (GBD), ethylbenzene
p.a. POCh Gliwice (Poland), n-propylbenzene
pure Fluka AG (Switzerland), n-butylbenzene
pure Fluka AG (Switzerland), carbon tet-
rachloride p.a. POCh Gliwice (Poland),
bromoform p.a. POCh Gliwice (Poland),
diiodomethane pure Lachema Brno (Czecho-
slovakia), chloroform p.a. POCh Gliwice
(Poland), 1,1,2,2-tetrabromoethane pure
Aldrich-Europe (Belgium), 1,2,3-tribromo-
propane pure Reachim (USSR), dichloro-
methane pure Reachim (USSR), isoamyl
chloride pure Reachim (USSR), ethyl bromide
pure Reachim (USSR), tert.-butyl chloride
pure Sojuzchimexport Moscov (USSR), iso-
butylchloride pure Sojuzchimexport Moscov
(USSR), jodobenzene p.a. POCh Gliwice
(Poland), a-bromonaphthalene p.a. ZTChS
L6ci~ (Poland), a-chloronaphthalene p.a.
POCh Gliwice (Poland), bromobenzene p.a.
POCh Gliwice (Poland), chlorobenzene pure
Koch-Light Laboratories Ltd. (England), o-
nitrotoluene pure Fluka AG (Switzerland),
nitromethane pure Fluka AG (Switzerland),
nitrobenzene pure Reactivul Bucuresti (Ru-
mania), m-nitrotoluene pure Fluka AG
(Switzerland), isovaleronitrile pure Reachim
(USSR), butyronitrile pure Reachim (USSR),
carbon disulfide p.a. POCh Gliwice (Poland),
and phenylisothiocyanate pure Fluka AG
(Switzerland).
RESULTS AND DISCUSSION
Fowkes (2), as mentioned above, deter-
mined 3'~v to be equal to 21.8 m N / m , and
3'dwwas determined by Wu on basis of the har-
monic mean equation (9-13) to be equal to
22.13 mN/m. Good and Elbing (20) analyzed
interracial interactions at the water-organic
liquid interface for many liquids such as ali-
phatic and aromatic hydrocarbons, substituted
saturated and aromatic hydrocarbons and ni-
troaromatics, and phenylisothiocyanate, and
suggested that Fowkes' 3"°wvalue was about
10% higher than the true value of the disper-
sion component of the surface tension of water
Journal of Colloid and Interface Science, Vol. 127, No. 1, January 1989
194 JAIqCZUK AND BIALOPIOTROWICZ
and that it resulted from dispersion and dipole
induced-dipole interactions. Panzer (42) em-
ployed Beerbower's Eq. [43 ] and Hansen and
Beerbower's solubility parameters (44), and
calculated a dispersion component of water
surface tension that was equal to 10.8 m N /
m. From the data mentioned above it appears
that no agreement exists with regard to the
value of 3' dw.
Because we have assumed that the surface
free energy of a liquid and a solid is divided
into two components--dispersion and non-
dispersion (polar, see T h e o r y ) m a n d that in-
terfacial free energy can be determined by em-
ploying the geometric or harmonic mean of
these two components, we shall use 3"dw
= 21.8 m N / m (2) and 3"(v = 72.8 - 21.8
= 51.0 m N / m or 3"~v = 22.13 m N / m and
3"~v = 50.67 m N / m (9-13). The values of
3"dw = 21.8 and 22.13 m N / m are treated as
the given experimental constants, which were
calculated from the water-hydrocarbon sys-
tem (2). The3" $ and3" ~ values were calculated
from Eqs. [10] and [15] or Eqs. [10] and [16]
or Eqs. [ 10 ] and [ 17 ] in the same way and are
presented in Table I. For the calculations
mentioned above the values of 3"~v and 3"(v
and the values of 3"o and 3"wotaken from Good
and Elbing's paper (20) were used; these values
are listed in Table I. Given in columns 3 and
4 are the values of dispersion and polar com-
ponents of surface tension of organic liquids
calculated on the basis of the geometric mean
equation for 3"dw = 21,8 m N / m and 3"(v
= 51.0 m N / m (3"o(g-g),
d . 3"o(g-g)),
p columns 5
and 6 are values calculated on the basis of
the harmonic mean equation for 3"~v = 22.13
m N / m and 3"(v = 50.67 m N / m (3"O(h-h); d m N / m . In other cases the differences between
3"~)(h.h)) and in columns 7 and 8 are values
calculated on the basis of the harmonic and
geometric mean equations for 3"d = 22.13
m N / m and 3"(v = 50,67 m N / m (3"O(h-g); d be emphasized that, as mentioned above,
3"~(h-g))" It should be also emphasized that for
isoamylchloride, tert.-butylchloride, isobu-
tylchloride, nitromethane, isovaleronitrile, and
butyronitrile from Eqs. [ 10 ] and [ 16 ] exact
values of 3"O(h.h)
d and 3"O(h-h)P cannot be ob-
tained, and that for ethylbromide and dichlo-
Journal of Colloid and Interface Science, Vol. 127,No. 1, January1989
romethane two values of 3"d(h_h) and 3"O(h-h) v
fulfilling these equations exist. In the case of
isoamylchloride, isovaleronitrile, and butyro-
nitrile exact values of 3"aO(h_g)and 3" O(h-g) P can-
n o t be obtained from Eqs. [10] and [17]. The
data of the dispersion and nondispersion val-
ues (Table I) for the above liquids are the best
of possible approximations. From Table I it
appears that even for such liquids as benzene,
mesitylene, p-cymene, carbon tetrachloride,
and carbon disulfide having their dipole mo-
ment equal 0, 3"~) # 0. The reason that 3'~) ¢ 0
is probably the occurrence of nondispersion
interaction between water and the organic liq-
uids mentioned above. From Table I it also
appears that 3"o(g-s) d and 3"o(g-g)Pvalues (col-
umns 3 and 4) for many liquids are close to
d
3"O(h-g) and 3"~(h-g) (columns 7 and 8) but they
are higher than 3"O(h-h) d p
and 3"O(h-h), respec-
tively.
Comparing the values of the dispersion
components of organic liquid surface tension
calculated in this paper with those calculated
by Panzer (42), one can state that 3"o(g-g), d
d
3"O(h-h), d
and 3"O(h-g) ValUeS c a l c u l a t e d from
Eqs. [ 15 ], [ 16 ], and [ 17 ] for o-xylene, carbon
tetrachloride, bromoform, a-bromonaphthal-
ene, bromobenzene, and chlorobenzene differ
only slightly from those of Panzer (42),
d
3"o(P), for the same liquids. It is very charac-
teristic that 3"O(g-g) d d
and 3"O(h-g) values, ex-
cept for carbon tetrachloride, are higher, and
t h a t 3"d(h_h) v a l u e s a l e lower than3"do(p) values.
In the case of nitromethane, differences be-
tween 3"o(g-g)
d and 3"~o') and between 3" O(h-g) d
and 3"dotP)are greater than 2 m N / m and for
carbon disulfide differences are greater than 4
the dispersion components of liquid surface
tension calculated by us and those determined
by Panzer (42) are much larger. It should also
"~d(h_h) ValUeS for nitromethane and butyroni-
trile and 3"O(h-g) values for nitromethane are
only approximate values.
To compare the deviations of the dispersion
components of liquid surface tension for o-
xylene, carbon tetrachloride, bromoform,
 SURFACE FREE ENERGY COMPONENTS 195

TABLE I
Values of Liquid SurfaceTension (Column I),Their Dispersionand Nondispcrsion Components CalculatedUsing
the Geometric Mean, Eq. [15] (Columns 3 and 4), the Harmonic Mean, Eq. [16] (Columns 5 and 6),the Harmonic-
Geometric Mean, Eq. [17](Columns 7 and 8), and Water-Organic Liquid InterracialTension (Column 2)

Liquid 1 2 3 4 5 6 7 8

Water 72.80 -- 21.80 51.00 22.13 50.67 22.13 50.67

Benzene 28.88 33.90 27.08 1.80 22.27 6,61 27.09 1.79
Toluene 28.50 36.10 27.18 1.32 22.89 5.61 27.17 1.33
o-Xylene 30.10 36.10 28.73 1.37 24.43 5.67 28.70 1.40
m-Xylene 28.90 37.90 27.87 1.03 24.05 4.85 27.87 1.03
Mesitylene 28.80 38.70 27.90 0.90 24.28 4.52 27.89 0.91
p-Cymene 28.10 34.60 26.47 1.63 21.80 6.30 26.49 1.61
Ethylbenzene 29.20 38.40 28.25 0.95 24.53 4.67 28.24 0.96
n-Propylbenzene 28.99 39.60 28.21 0.78 24.81 4.18 28.21 0.78
n-Butylbenzene 29.23 41.40 28.68 0.55 25.75 3.48 28.67 0.56
Carbon tetrachloride 26.95 45.00 26.75 0.20 24.90 2.05 26.75 0.20
Bromoform 41.50 40.90 40.55 0.95 36.47 5.03 40.19 1.31
Diiodomethane 50.80 48.50 50.42 0.38 46.74 4.06 49.86 0.94
Chloroform 27.15 31.60 24.82 2.33 19.34 7.81 24:87 2.28
1,1,2,2-Tetrabromoethane 49.70 38.80 47.92 1.78 42.39 7.31 46.98 2.72
1,2,3-Tribromopropane 45.40 38.50 43.84 1.56 38.81 6.59 43.20 2.20
Dichloromethane 26.50 28.30 23.18 3.32 16.63 9.87 23.27 3.23
0.65 25.85
Isoamylchloride 23.50 15.40 11.85 11.65 7.25 16.25 9.75 13.75
Ethylbromide 24.20 31.20 21.78 2.42 15.73 8.47 21.86 2.34
0.13 24.07
tert-Butylchloride 19.60 23.75 14.05 5.55 6.00 13.60 13.57 6.03
lsobutylchloride 21.90 24.40 16.91 4.99 6.75 15.15 16.85 5.05
lodobenzene 39.70 41.80 38.94 0.76 35.27 4.43 38.68 1.02
ct-Bromonaphthalene 44.60 42.10 43.70 0.90 39.49 5.11 43.22 1.38
c~-Chloronaphthalene 41.80 40.70 40.81 0.99 36.65 5.15 40.42 1.38
Bromobenzene 36.50 38.10 35.29 1.21 31.11 5.39 35.09 1.41
Chlorobenzene 33.60 37.40 32.37 1.23 28.25 5.35 32.26 1.34
o-Nitrotoluene 41.50 27.20 37.01 4.49 30.68 10.82 36.45 5.05
Nitromethane 36.80 9.50 20.30 16.50 11.25 25.55 20.42 16.38
Nitrobenzene 43.90 25.70 38.56 5.34 31.94 11.96 37.81 6.09
m-Nitrotoluene 41.40 27.70 37.10 4.30 30.84 10.56 36.56 4.84
Isovaleronitrile 26.00 14.10 13.63 12.37 8.00 18.00 10.75 15.25
Butyronitrile 28.10 10.40 8.80 19.30 8.50 19.60 11.50 16.60
Carbon disulfide 32.30 48.40 32.23 0.07 31.00 1.30 32.21 0.09
Phenyl isothiocyanate 41.50 39.00 40.24 1.26 35.76 5.74 39.84 1.66

d i i o d o m e t h a n e , a - b r o m o n a p h t h a l e n e , bro- - 3'~(P)[ for each o f the liquids. All these

m o b e n z e n e , c h l o r o b e n z e n e , a n d c a r b o n di- A d
were s u m m e d , o b t a i n i n g ~ A~/o(g_g),
sulfide, calculated by using the g e o m e t r i c d d
A3'o(h_h}, a n d ~ A~'o(h_g). D i v i d i n g these
mean, harmonic mean, and harmonic-geo- s u m s by n, n u m b e r o f liquids, n = 8,
m e t r i c m e a n e q u a t i o n s with those calculated we o b t a i n Z A'yd(g-g)/n, Z A~'~(h-h)/n,
by P a n z e r ( 4 2 ) , we d e t e r m i n e d the values a n d Z A3'~(h-g)/n. T h e results are listed in
o f A'YO(g-g)
d d
= l"Yo(~-g) - - "Yd(P) l, i ~ { O ( h _ h )
d T a b l e II. F r o m Tab l e II it appears that a small
= I"gd(h_h)- '~d(p)I and d
A"/O(h-g) = I ' ~ /dO ( h - g ) m e a n deviation of3,d(h_~) from'y~(p) (42) an d
Journal of Colloid and Interface Science, Vol. 127, No. 1, January 1989
 196 JAlqCZUK AND BIALOPIOTROWICZ

TABLE II 61) and their dispersion and nondispersion

Average Deviations of the Dispersion Component of
Liquid SurfaceTensionCalculatedin this Paper(Eqs. [15],
[16], and [17]--see Table I) from Those Determinedby
Panzer (42), and Average Deviations of Contact Angles
Calculated in This Paper (Eqs. [21], [22], and [23], and
Eqs. [26], [27], and [28]) from the Measured Ones
Z ~'r~-~ ~ A~h_ ~
n n
n listed in Table V. Comparing the data in Ta-
=
Liquid 8 2.38 2.16
Solid n n n n
Paraffin 28 7.99 6.23
PTFE 28 1.54 6.06
PE 15 1.79 1.55
PET 13 1.97 1.95
PMMA 13 1.21 1.26
larger one of ~O(h-h)
d from ,yd(p) can be ob-
served. It is very interesting, however, that we
have obtained a few 3'd values for liquids sim-
ilar to Panzer's results (42), even though we
used "ydw= 21.8 m N / m (2) and 3~dw= 22.13
m N / m for our calculations, but not for Pan-
zer's dispersion component values of water
surface tension (10.8 m N / m (42)). It should
be noted that the dispersion component of
liquid surface tension obtained in another way
for water lies in the interval from 19.9 to 28.1
m N / m (20, 42, 45, 46-48), from 47.4 to 48.5
_+ 9 (2, 46) for diiodomethane, and from 34.6
to 47 _+ 7 m N / m (2, 46-48) for a-bromo-
naphthalene.
Unfortunately, we are not able to draw un-
ambiguous conclusions based only 3,d data
calculated from Eqs. [ 15 ], [ 16 ], and [ 17 ] since
there are only a few literature data concerning
this problem. Thus, to check the validity of
"rd and -},~)values (determined by us) in other
systems, we measured contact angles in par-
affin-liquid drop-air and polymeric solid-liq-
uid drop-air systems. We used the following
polymeric solids: PTFE, PE, PET, and
PMMA. These polymers were chosen taking
into account their different surface free energy
magnitudes (2-16, 30, 32, 39, 40, 42, 45, 49-
Journal of Colloid and Interface Science, Vol. 127, No. 1, January 1989
components (4, 13-16, 31, 39, 45, 56-61), as
well as the fact that for these polymers there
are a lot of liquids having 3'o >I 3's.
The results obtained for paraffin and PTFE
are listed in Table III and those for PE, PET,
and PMMA in Table IV. Our results are com-
>Z A ~ pared with some literature data (4, 30, 31, 42,
n
45-47, 51-72), the data (available for us) are
2.65
bles III, IV, and V leads us to the conclusion
that our values of 00(d) for the solids studied
coincide with the literature data. In the case
of a-bromonaphthalene our results are slightly
11.09 higher than those measured by others (30, 31,
3.62 42, 45, 46, 49, 62, 68, 69, 71, 72) except for
1.81 PTFE and paraffin. As regards other liquids
3.11 studied by us, very few literature data are
2.54 available. In the case of PTFE, our values of
0o(a) for benzene (45.6°), ethylbenzene
(44.6°), and carbon tetrachloride (33.0 ° ) are
in good agreement with those of Fox and Zis-
man (64, 67) (46 °, 48 °, and 36 °, respec-
tively). However, our values of 0o(a) on par-
affin for o-xylene (23.3 °), bromoform (45.9 °),
chlorobenzene (28.1 ° ), nitromethane (69.2 o ),
and butyronitrile (58.1 o), are higher than
those of Panzer (42) 12 °, 39 °, 51 °, and 29 °,
respectively. These divergences may be caused,
among other things, by the high solubility of
paraffin wax in some of the liquids studied.
For this reason the contact angle was measured
immediately after settling a drop of a given
liquid. From Table V it appears that differ-
ences exist for contact angle values measured
by various authors for the same systems. For
example, the contact angle values of diiodo-
methane on PET lie in the range from 23 to
38 ° (45, 66, 69), and a-bromonaphthalene
on PTFE from 60 to 76 ° (30, 45, 62, 63, 71),
and a-bromonaphthalene on PE from 14 to
36 ° (30, 45, 46, 62, 68).
Using the measured contact angle values
taken from Tables III and IV for water and
diiodomethane on paraffin, PTFE, PE,
PET, and PMMA, "Ys(z-g), d d
"YS(h-h), d
"YS(h-g),
P P n P
7S(g-S), 7S(h-h), a d 7S(h-8), the values of their
surface free energy were calculated from Eqs.
 SURFACE FREE ENERGY COMPONENTS 197

TABLE III

Contact Angle Values on PTFE and Paraffin Wax Measured and Calculated from Eq. [21] (Columns 2 and 6),
Eq. [22] (Columns 4 and 8), and Eq. [23] (Columns 3 and 7)

Teflon Paraffin

O0(d) 00(¢X1-$) O0(eXh-$) [~O(©Xb-h) ~13~d) ~O(¢XI-I) O0(¢Xh-$) O0(cXb~b)

Liquid 1 2 3 4 5 6 7 8

Water 111.0 111.0 110.8 110.2 110.6 110.9 109.0 108.3

Benzene 45.6 45.5 36.9 49.0 27.6 36.4 26.5 42.5
Toluene 43.1 43.7 34.3 45.4 27.5 33.6 22.6 38.0
38.7
o-Xylene 48.2 47.4 39.3 48.1 23.3 38.4 29.4 41.1
m-Xylene 42.7 44.0 34.7 43.7 18.0 33.9 23.0 35.8
Mesitylene 48.1 43.6 34.0 42.5 30.0 33.1 21.9 34.2
p-Cymene 44.5 43.4 34.0 47.0 30.5 33.5 22.3 40.2
42.1
Ethylbenzene 44.6 44.6 35.4 43.7 25.5 34.6 24.0 35,7
n-Propylbenzene 43.9 43.8 34.2 41.8 30.4 33.3 22.1 33,2
n-Butylbenzene 43.4 44.0 34.3 40.2 25.4 33.3 22.2 30,9
Carbon tetrachloride 33.2 37.2 23.6 28.2 16.1 22.7 -- 11,7
7.2 24.0
Bromoform 62.9 63.8 61.1 62.8 45.2 57.5 54.7 56,8
Diiodomethane 72.0 72.0 72.0 72.0 66.4 66.4 66.4 66,4
Chloroform 37.3 42.6 33.4 51.0 26.1 33.0 21.8 45,4
24.4 49,8
1,1,2,2-Tetrabromoethane 76.3 71.9 71.8 73.1 62.0 66.7 66.4 67.8
1,2,3-Tribromopropane 70.5 68.2 66.8 68.6 59.5 62.6 61.0 63.0
Dichloromethane 46.5 43.6 35.1 58.2 31.6 34.9 24,9 53.9
30,2 59.6
Isoamylchloride 63.1 64.5 78.8 92.1 60.5 61.3 76.9 90.8
82.9 97.1 87,5 103.7
Ethylbromide 37.3 34.3 22.1 52.0 24.3 21.3 -- 47.2
26.5 56.7 26.5 28,9 60.4
tert-Butylchloride 34.1 32.9 37.4 90.4 13.1 23.7 31,0 89.3
58.6 104.2 50.5 63,4 116.9
Isobutylchloride 37.0 37.2 33.1 91.3 22.0 28.2 24.2 90.1
45.8 101.6 42.7 49,5 103.8
Iodobenzene 64.2 61.6 58.1 59.9 43.5 54.9 51,4 53.5
a-Bromonaphthalene 66.0 67.0 65.2 66.4 41.2 61.0 59.2 60.6
c¢-Chloronaphthalene 64.4 64.2 61.5 63.3 44.4 57,9 55.2 57.3
Bromobenzene 58.1 57.9 53.3 56.9 32.1 50,9 46.0 50.5
Chlorobenzene 52.8 53.6 47.5 52.7 28.1 45,9 39.4 46.0
o-Nitrotoluene 64.2 67.1 64.7 69.4 59.4 62,1 59.0 64.6
Nitromethane 75.1 79.0 77.2 98.5 69.2 76.9 73.9 97.0
Nitrobenzene 69.4 70.0 68.3 72.5 49.2 65,4 62.9 67.8
m-Nitrotoluene 66.4 66.8 64.3 69.0 60.8 61,7 58.6 64.1
Isovaleronitrile 67.0 67.4 81.0 93.5 62.0 65,0 79.0 92.1
82.7 98.1
Butyronitrile 79.2 86.9 83.1 95.1 58.1 86,7 81.0 93.8
95.1
Carbon disulfide 51.7 50.1 42.1 41.9 42.2 40.5 32.6 32.2
Phenyl isothiocyanante 65.0 64.1 61.4 63.6 48,4 57.9 55.0 57.7

Note. The second value for a given liquid is calculated from Eqs. [26], [27], and [28] (see text).

Journal of Colloid andlnterface Science, Vol. 127, No. 1, January 1989

 198 SURFACE FREE ENERGY COMPONENTS

TABLE IV
Contact Angle Values on Polyethylene, Polyethylene Terephthalate, and Polymethyl Methacrylate
Measured and Calculated from Eqs. [21], [22], [23], [26], [27], and [28]

Polyethylene Polyethylene terephthalate Polymethyl methacrylate

00(d) 00(¢)~[-~ 00(¢Xh-g) 00[©Xh-h) 00(d) 00(©]~'-g) 00(¢)[h-g) 00(©Xh-h) 00(d) 00(¢)(g-g) 00(c)(h-g) 0(~c)(h-h)

Liquid 1 2 3 4 5 6 7 8 9 10 11 12

Water 96.1 96.1 96.1 96.1 76.5 76.5 76.5 76.5 73.8 73.8 73.8 73.8
Bromoform 36.7 38.9 36.7 36.4 21.4 17.2 17.0 20.2 19.0 1 8 . 6 18.6 21.9
Diiodomethane 52.8 52.8 52.8 52.8 40.8 40.8 40.8 40.8 36.5 36.5 36.5 36.5
1,1,2,2-Tetrabromoethane 50.9 51.4 51.4 51.4 37.8 35.0 35.0 31.9 30.3 2 9 . 6 29.6 26.0
1,2,3-Tribromopropane 43.1 45.6 44.6 44.6 26.1 25.6 24.9 20.5 18.9 17.3 16.8 16.6
Iodobenzene 33.1 35.0 32.2 31.8 19.2 18.7 18.6 22.6 19.4 2 0 . 3 20.6 24.5
a-Bromonaphthalene 41.1 44.3 43.0 42.7 22.7 25.6 24.8 22.1 1 8 . 0 17.5 18.6 21.4
a-Chloronaphthalene 36.3 39.4 37.4 37.1 18.5 17.0 16.7 19.8 19.0 18.3 18.3 21.4
Bromobenzene 21.8 26.4 22.0 22.0 14.8 16.4 16.9 19.6 16.7 18.5 19.7 22.5
Chlorobenzene 10.0 12.9 4.9 8.7 . . . . . . . .
o-Nitrotoluene 39.2 41.6 39.8 42.4 0.0 2.4 2.3 3.8 6.1 4.5 5.2 6.9
Nitromethane 55.0 54.9 56.0 75.9 30.0 31.9 36.6 55.8 28.7 32.0 37.3 56.8
Nitrobenzene 47.3 46.2 45.0 47.3 11.8 15.3 14.1 2.4 5.0 1.6 1.7 3.9
m-Nitrotoluene 40.8 41.2 39.4 41.8 0.0 3.0 2.9 3.8 7.0 5.0 5.6 7.1
Carbon disulfide 0.0 0.0 7.8 15.4 . . . . . . . .
Phenyl isothiocyanate 36.8 38.9 36.8 36.7 18.0 15.3 15.1 17.4 14.6 16.7 16.7 19.4

[25] a n d [18] o r Eqs. [19] a n d [22] o r Eqs. calculated values for w h i c h t h e s u m o f AOw
[20] a n d [ 2 3 ] , respectively. T h e o t h e r d a t a + A0o h a d a m i n i m u m value, where AOw
used for these calculations were as follows: = ]0w(c) - Ow(d)] a n d A 0 o = [0o(c) - Oo(d)[.
d
"gW(g-g) = 21.8 m N / m , "gw(g-g)
P = 51.0 m N / A similar a p p r o a c h was used in calculations
m ( 2 ) , "gotg-g)
d = 50.42 m N / m , a n d "gO(g-g)
P of'gd(h_h) for P T F E . Such a p r o c e d u r e for all
= 0.38 m N / m in Eqs. [25] a n d [18]; calculations a b o v e was n o t accidental. T h e
d
"gW(h-h), 22.13 r a N / m , "gW(h-h) P = 50.67 m N / m a i n feature o f the p r o c e d u r e is the conse-
m ( 9 ) , "gO(h-h)d" = 46.74 m N / m , a n d "gO(h-h)P q u e n t use o f t h e d a t a c a l c u l a t e d on the basis
=4.06 mN/m in Eqs. [19] a n d [ 2 2 ] ; o f the equations, the source o f w h i c h is the
d
"gW(h-g) = 22.13 mN/m,'g(V(h_g) = 50.67 m N / same theory. F o r example, i f we d e t e r m i n e the
d
m, "gO(h-g) = 49.86 m N / m , a n d "g~)(h-g) = 0.94 dispersion a n d p o l a r c o m p o n e n t s o f a given
m N / m in Eqs. [20] a n d [ 2 3 ] , a n d "gw = 72.8 organic liquid surface t e n s i o n f r o m a w a t e r -
m N / m ( 2 ) a n d "g~) = 50.8 m N / m were u e d organic liquid system using t h e g e o m e t r i c
in all equations. O n calculating it a p p e a r e d m e a n equation, we s h o u l d use these values in
t h a t for P T F E "gS(h-g) P < 0.01 m J / m 2 a n d further calculations o f c o n t a c t angle o n t h e
" gPS ( h - h ) < O a n d f o r p a r a f f i n "gS(g-g)
P was slightly solid surface s t u d i e d for which dispersion a n d
higher t h a n O, a n d "g~(h-h) a n d "gS(h-g) P < 0. n o n d i s p e r s i o n c o m p o n e n t s o f surface free en-
Since it is recognized that surface free energy ergy are also d e t e r m i n e d f r o m s o l i d - w a t e r
o f paraffin is d u e to dispersion i n t e r m o l e c u l a r d r o p - a i r a n d s o l i d - d i i o d o m e t h a n e d r o p - a i r
interactions only, we r e p e a t e d l y calculated its systems o n the basis o f t h e g e o m e t r i c m e a n
surface free energy a s s u m i n g "g vS(g-g), "g pS(h-h), equation.
a n d "gS(h-g)
p equal zero. As "gS(g-g), d d
"gS(h-h), and T h e values o f "gS(g-g), d d
"gS(h-h), d
"gS(h-g),
P P P
"gd(h_g) values were t a k e n for paraffin, such "gS(g-g), "gS(h-h), a n d "gS(h-g) c a l c u l a t e d in t h e

Journal of Colloid and Interface Science, Vol. 127, No. 1, January 1989
 SURFACE FREE ENERGY COMPONENTS 199

TABLE V

Literature Data of Contact Angles on Paraffin Wax, PTFE, Polyethylene, Polyethylene

Terephthalate, and Polymethyl Methacrylate

Polyethylene Polymethyl
Liquid Paraffin Polytetrafluoroethylene Polyethylene terephthalate methacrylate

Water 108 (4); 110-108 (31); 116 (30); 106-112 (31); 95 (31); 93.9 (32); 71 (45); 81 (69) 80 (4); 74 (31);
106 (42); 110 (45); 112 (45); 108 (62); 95 (45); 103 71 (42); 74
108-111 (64); 105 112.3 (63) (46); 94 (62); (45); 76
(65); 110-111 (67) 95 (68) (46); 85
(64); 80
(68); 78
(70); 71 (71)
Benzene 46 (62)
Ethylbenzene 48 (67)
Carbon tetra 24 (42) 36 (62); 36 (67)
chloride
o-Xylene 12 (42)
Bromoform 39 (42) 4 (42)
Diiodomethane 66 (4); 61 (45) 77 (4); 85 (45); 76 (46); 52 (4); 46 (31); 23 (45); 38 (69) 41 (4); 28-34
88 (62); 63.4-102.7 51.9 (32); 46 (31); 31.5
(63) (42); 50 (46); (42); 34
52 (62); 47 (45); 34 (68)
(68)
a-Bromonaph- 38 (45); 47 (64) 72 (30); 76 (45); 73 15 (30); 33 (45); 7 (45); 15 (69) 14 (30); 3 (42);
thalene (62); 76.5-96.1 (63) 14 (46); 35 11 (45); 7
(62); 36 (68) (47); 15
(68); 17
(71); 16 (72)
Chlorobenzene 20 (42)
o-Nitrotoluene
Nitromethane 51 (42) 14 (42)
Nitrobenzene 45 (42) 1 (42)
Butyronitrile 29 (42)

Note. Reference numbers appear in parentheses.

above way are presented in Table VI along with the literature data (2-16, 30, 32, 39, 40,
with literature data for dispersion and polar 45, 49-72) (Table VI), we conclude that our
components of surface free energy for the results are in the range of these data. It is very
above solids. From Table VI it appears that interesting that for PE and PET the 3'S(h-h)Val-
for all solids studied 3's(g-g) < '~S(h-g) < "~S(h-h), ues are very close to surface tension values of
for PET and PMMA "YS(h-h) d < d
~/S(h-g) the same melted polymers measured by Wu
< d P P P
7 S(g-g) a n d "/S(g-g) < "YS(h-g) < "YS(h-h), a n d (12, 13, 16) (34.1-35.7 mJ/m 2 and 44.4-44.6
for PE 'S{S(h-h)
d d
< ')/Stg-g) d
< "~S(h-g) P
and 3'sth-g) m J/m 2), and for PTFE the 3's(g-~)value (21.77
<( P P
'~S(g-g) < "~S(h-h). It should be emphasized mJ/m 2) is nearly indentical to the surface
that for PE, PET, and PMMA, differences be- tension of a fluorocarbon oil C21F44 ( 2 1 . 5 m N /
tween 3's<g-g)and ~/S(h-g)and ~S(h-h) are rather m) that has been directly measured by Dettre
small and do not exceed 2 mJ/m 2; however, and Johnson (58).
larger differences are encountered between the Using our 3,sa, -rsp, 3'~, and 3,p (Tables I
dispersion and polar components of those sol- and VI), we have calculated from Eqs. [21 ],
ids. Comparing our results of the dispersion [22], and [23] the contact angles (Oo(c)) for
and polar components of surface free energy the paraffin-organic liquid drop-air and poly-
of paraffin and the polymeric solids studied mer-organic liquid drop-air systems. From

Journal of Colloid and Interface Science, Vol. 127, No. 1, January 1989
 b~
TABLE VI
Dispersion and Polar Component Values of Surface Free Energy of Paraffin, PTFE, Polyethylene, Polyethylene Terephthalate, and Polymethyl Methacrylate
Calculated from Eqs. [18], [19], [20], [22], [23] and [25], and Literature Data of These Components

Literature data

Solid 7~ "f~h-s) "Y.~h-h) "YP

S(g-g) 'YPS(h-g) 'YPS(h-h) 'YS(g-g) "~S(hl) 'YS(h-h) ,yd ~'~PS '~S or 'Yc

Paraffin 25.09 27.64 28.71 0.00 0.00 0.00 25.09 27.64 28.71 31.0 (14); 32.0 (14); 31.0 (14); 32.0 (14); 25.5 (42); 25.5
25.5 (42); 25.5 (45); 15-22 (55); 23.7 (56)
(45); 15-22 (55);
23.7 (56)
Polytetrafluoro- 21.72 24.96 25.81 0.05 0.00 0.00 21.77 24.96 25.81 19.5 (2); 18.6 (4); 0.5 (4); 1.5 (4); 19.4 (4); 14 (4); 19.3 (8); 21.4 (8);
ethylene 12.5 (4); 20.5 2.0 (13); 1.0 14.3 (8); 22.5 (13); 22.6 (14); Z,
(3
(13); 15-28 (30); (30); 1.7 (31); 16-29 (30); 19 (31); 19.6 (53); N
17.3 (31); 21 0 (53) 18.5 (55); 15.6-19.1 (56); 21.5
(45); 19.7 (49); (57); 21.5 (58); 22.5 (58); 22.5 >,
22.5 (50); 24.0- (59); 23.9 (61); 19.6 (73) Z
27.1 (51); 25
(53) >
Polyethylene 32.10 33.32 30.46 0.72 0.69 3.70 32.82 34.01 34.16 34.21 (4); 35 (2); 3.4 (1); 1.1 (4); 0 37.6 (1); 33.1 (4); 33.2 (4); 35.6 S"0
32 (4); 33.2 (4); (4); 2.21 (5); (8); 36.1 (13); 35.9 (14); 35.7
35.3 (13); 22-33 0.8 (13); 0.97 (16); 23-33 (30); 31 (55); 32.6 ,--t
(30); 33.15 (32); (28); 0-1 (30); (55); 36.1 (56); 36.1 (59); 34.7 ©
36 (45); 24.2 0.01 (53) (61); 34.0 (72)
(51); 24 (53); 42
(54)
Polyethylene 37.02 36.69 32.96 5.33 5.90 11.25 42.35 42.59 44.21 36.5 (1); 44 (2); 13 (1); 3.5 (4); 49.5 (1); 47 (3); 41.3 (4); 43.8 (8);
terephthalate 37.8 (4); 43.2 (4); 4.1 (4); 9.3 42.1 (13); 44 (14); 44.6 (16);
32.8 (13); 43 (13); 4.4 (53) 54.4 (53); 43 (55); 41.3 (56);
(45); 50 (53) 42.1 (59); 44 (73)
Polymethyl 38.95 38.26 34.55 5.95 6.76 12.13 44.90 45.02 46.68 35.9 (4); 31.3 (13); 4.3 (4); 10.1 (13); 40.2 (4); 41.2 (13); 42.5 (14); 41.4
methacrylate 14-34 (30); 33 9-14 (30); (16); 23-48 (30); 45.4 (31); 94.1
(31); 41 (45); 12.4 (31); 3.1 (53); 39 (55); 41.2 (59)
55.9 (51); 91 (53)
(53); 69 (54)

Note. Reference numbers appear in parentheses. ~ "!

 SURFACE FREE ENERGY COMPONENTS
these equations we calculated 0o(c) for PTFE
and paraffin for all liquids listed in Table I,
while for PE, PET, and PMMA, 0ot~) only for
such liquids for which the surface tension was
higher or only slightly lower than their surface
free energy were calculated. For the latter liq-
uids (for which 3"s > 3'0) 0o(~) values were
also calculated from Eqs. [26], [27], and [28]
assuming that 3"s - 7re = 3"o (29).
--3"S "~- 2,/V3' d.
S')' 0d + 2~-7s3"o
P p
cos Oo =
3"0
-3"s + ( 4 3"s3"o/3"s
d d d
+ 3"~)
4 P P P
+ ( 3"s3"o/3"s + 3"~)
COS 0 0 =
3'o
cos 0o
-3's + (43"s3"o/3's
d d d + 3"~) + 2f~s3,o
P p
3"O
In Eqs. [21] and [26] 3" 0O(g-g), 3" O(g-g),
p polymers the calculated (00(c)(g-g)) and mea-
d P
3's(g-g), and 3"s(g-g) values, and in Eqs. [22]
and [27], 3" dO(h-h), 3" PO(h-h), 3" S(h-h),
d and
P difference between 0o(~)(g-g)and 00(d) does not
"Ys(h-h) v a l u e s , and in Eqs. [23] and [28],
d P d P
3"O(h-g), 3"O(h-g), 3"S(h-g), and 3"S(h_g) values
were used. The values of 0o(¢) calculated from
the above equations are presented in Tables
III and IV.
In Table III, the 0o(e) values calculated from
Eq. [21], denoted as 0o(c)(g-g), are listed in
columns 2 and 6.0o(¢)values calculated from
Eq. [23] for all liquids tested and from Eq.
[28] for isoamylchloride, ethylbromide, tert-
butylchloride, and isobutylchloride for PTFE
and paraffin, and chloroform, dichlorometh-
ane, and isovaleronitrile for paraffin, denoted
as 00(c)(h_g), are given columns 3 and 7. 0o(c)
values calculated from Eq. [22 ] for all liquids
tested and from Eq. [ 27 ] for isoamylchloride,
ethylbromide, tert.-butylchloride for PTFE,
and toluene, p-cymene, carbon tetrachloride,
chloroform, isovaleronitrile, butyronitrile for
paraffin, denoted as 0 o(~)(h-h), are listed in col-
umns 4 and 8.
Table IV lists 0ot¢)(g-g), 00(c)(h-h), and
00(c)(h-g) values calculated from Eq. [ 21 ] (col-
201
umn 2), Eq. [22] (column 4), and Eq. [23]
(column 3), respectively, for PE for all liquids
listed in Table IV, except chlorobenzene
and carbon disulfide, values of which were
calculated from Eqs. [ 26 ], [27 ], and [ 28 ],
respectively. In the case of PET the values of
0o(c)(g-g), 00(c)(h-h) and 00(c)(h_g ) w e r e calcu-
lated from Eqs. [21 ], [22], and [23], respec-
tively, only for diiodomethane, water, 1,1,2,2-
tetrabromoethane, 1,2,3-tribromopropane,
[26] and a-bromonaphthalene, and for nitroben-
zene from Eqs. [21] and [22]. The remaining
liquids were calculated from Eqs. [ 26 ], [ 27 ],
and [ 28 ]. For P M M A the values of 0O(c)(g-g),
00(c)(h-h), and 00(c)(h_g ) were calculated from
[27]
Eqs. [ 21 ], [ 22 ], and [ 23 ] only for water, diio-
domethane, 1,1,2,2-tetrabromoethane; the
other liquids were calculated from Eqs.
[ 26 ], [ 27 ], and [ 28 ] (1,2,3-tribromopropane
00(c)(g_g) and 00(c)(h-g ) were calculated from
Eqs. [21] and [23]).
[281
From Tables III and IV one can see that for
sured (0O(d)) contact angle values are in a good
agreement. For nearly 50% of the systems the
exceed 1o. Only for the systems PTFE-chlo-
roform and butyronitrile, and PMMA-nitro-
methane and nitrotoluene are the differences
between 0o(c)(g-g) and 00(d) greater than 5°;
00(o)(h-h) values for polymers are slightly more
different from 0Old) than is 0o~c)(g-g)from 00(d).
However, neglecting the polymer-isoamyl-
chloride, tert.-butylchloride, isobutylchlo-
ride, nitromethane, isovaleronitrile, and bu-
tyronitrile systems, the differences between
00(c)(h-h) and 00(d) are not so large so as to
state that there is no agreement between the
calculated and measured contact angles.
For calculations of 3'O(h-g)a p
and 3"Orb-g),
00(~)(h-g) values were obtained, while for PTFE
they are less convergent from the measured
ones. For the other polymers the differences
between 0o(c)(h-g) and 00(d) are, for many sys-
tems, smaller, neglecting the systems including
the liquids for which3, dO(h_g) and3, ~(h-g) values
were determined approximately.
In the case of the paraffin-organic liquid
Journal of Colloid and Interface Science, Vol. 127, No. 1, January 1989
202 JAiqCZUK AND BIALOPIOTROWICZ
drop-air system, the convergence of the mea-
sured and calculated contact angle values is
"weaker." For this system, except for water,
ethyl bromide, and carbon disulfide, the values
of 00(d) are less than those of 0o(c)(g_g), while
00(c)(h_h) values are greater than the mea-
sured ones, except for carbon disulfide. Only
0o(c) (h-g) values agree better with 00(d) for
many systems. For the same paraffin-organic
liquid drop-air systems, the differences be-
tween the measured and calculated contact
angles are larger than 10°. We think the main
cause of these differences is the high solubility
of paraffin in some of the liquids studied (as
mentioned above). The effect of solubility of
paraffin in a given liquid on contact angle was
observed during measurements. For these liq-
uids, for which the ability of paraffin solution
was low, we observed small changes of contact
angle with time and we observed good agree-
ment between the particular series of contact
angle measurements for a given system and
smaller differences between 00(d) and 0O(c) for
the same system.
To compare the deviation of the calculated
contact angles from the measured ones, in Ta-
ble II we listed the average deviation of the
calculated contact angle from the measured
ones, denoted as Y~AOotg_g)/n, ~, AOo(h-h)/n,
and Z AOo(h_g)/n, where n is the number of
elements taken into account during sum-
marion, and Z A0o(g_g), ~ A00(h-h), and
Z A0o (h-g) are the sum of the differences be-
tween 0O(c)(g-g) and 00(d)(~ A0o(g-.), where
A00 (g-g) : [OO(c)(g-g) -- 00(d)[); 00(c)(h-h)
and 00(d) (Z A00(h-h), where A00(h_h)
= ] O 0 ( c ) ( h _ h ) - O0(d)[) ; and O0(c)(h-g)and
O0(d) ( ~ A00(h_g), where A0O(h_g) = [Oo(~)(h_g)
- O0(d)1). However, in the summations of AOo
those systems were neglected that included the
liquids for which T ~ and 3'~ values were cal-
culated approximately. If, for example, even
one value of TO(g-g),
d d
TO(h-h), d
o r To(h-g)
was calculated approximately then AOo(g_g),
A00(h-h), nor A00(h_g)was taken into account.
From Table 1I it can be seen that the average
deviation of 0o(c)(g-g) from 0o(0) for polymers
Journal of Colloid andlnterface Science, Vol.127,No. l, January1989
does not exceed 2 °. For PE and PET the av-
erage deviation of 00(c)(h-8) from Oo(a) is
smallest among all average deviations of 0otc)
from 00(d); however, the average deviation of
00(c)(h-g) from Oo(a) for PTFE is largest and
is equal to 6.06 ° . The average deviation
of 00(c)(h-h) from 00(d) is smallest for PE
and largest for PTFE. For all polymers
Z AOo(h_h)/n > Z AOo(g_g)/n. In the case of
paraffin, the average deviation of 0o(o from
00(d) is larger than that for polymers, and the
average deviation of 0Otc)(h-s) from 00(d) is
equal to 6.23 ° and that Of0otc)(h-h)from 00(d)
is as high as 11.09 °. Thus, on the basis of Table
II, one may state that for the studied polymeric
solids good agreement exists between the
measured and calculated contact angles.
However, in the ease of paraffin as appears
from Table III, agreement also exists between
these contact angles for some liquids which do
not attack the surface of paraffin.
Agreement between many measured and
calculated contact angle values, primarily on
polymers, suggests that values of T~, Tg,
~ds, a n Jo 3'sP are characteristic constants for both
solids and liquids, which, determined for one
system, maintain their magnitude in other
systems. On this basis, however, it cannot be
stated for certain that the dispersion compo-
nent of surface free energy results from Lon-
don forces only, and that the nondispersion
component results directly from the action of
non-London forces. Rather, it may be as-
sumed that the dispersion component of sur-
face free energy of a liquid and a solid includes
the part due to dipole induced-dipole inter-
action (20), and the polar component is the
result of specific and nonspecific forces.
Agreement between 0O(c) and 60(d) values
also suggests that the geometric mean and
harmonic mean for nondispersion interfacial
interactions work well at least in the systems
studied here. We think, however, that there
are no theoretical reasons for pair-wise sum-
marion of hydrogen bonding; we think that
hydrogen bonding has an influence on another
kind of polar interaction, and it seems that the
 SURFACE FREE ENERGY COMPONENTS
existing m o d e l s o f interfacial i n t e r a c t i o n s
p r o b a b l y fail in this case. N o t a s u m m a t i o n o f
interactions of complex molecules but a kind
o f association o f m o l e c u l e s f o r m e d b y h y d r o -
gen b o n d i n g m i g h t be useful.
O n the basis o f the p r e s e n t studies a n d cal-
culations, it c a n b e a s s u m e d t h a t division o f
surface free energy o f liquids a n d solids i n t o
c o m p o n e n t s m a y be useful to d e t e r m i n e the
surface p r o p e r t i e s o f m a n y solids ( a t least ap-
p r o x i m a t e l y ) , since there is n o reliable m e t h o d
for d e t e r m i n i n g the surface free energy o f
m a n y solids. H o w e v e r , w h e n it is t a k e n into
a c c o u n t t h a t t h e d e t e r m i n e d values o f 3"~ a n d
3'~, e m p l o y i n g the geometric m e a n , h a r m o n i c
m e a n , or h a r m o n i c - g e o m e t r i c m e a n equation,
can be u s e d for calculations o f 3"~ a n d 3"~
c o m p o n e n t s , we shall e m p l o y t h e s a m e k i n d
o f t h e m e a n as in d e t e r m i n a t i o n o f 3"~
a n d 3"~.
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