THE SPREADING OF LIQUIDS ON LOW ENERGY

SURFACES. I. POLYTETRAFLUOROETHYLENE 1

H. W. Fox and W. A. Zisman

Naval Research’Laboratory, Washington, D. C.
Received April 18, 1960; revised September 23, 1950

INTRODUCTION
When a drop of liquid on a solid surface does not spread but comes to
some equilibrium state, it exhibits a finite contact angle 6’ toward the
solid. Many authors have expressed this equilibrium by means of the
Young equation (1)
?‘SA = YSL + ?‘LA COS 0, PI

where YSA, ~sI,, and YLA are the free energies of the solid-air, solid-liquid,
and liquid-air interfaces, respectively. Bangham and Razouk (2) and
later Boyd and Livingston (3) have pointed out that Eq. [l] is incorrect
since ySA can be altered by adsorption of vapor on the solid. If the free
surface energy of a solid in a vacuum is 7~0; in saturated vapor, 7s~“; and
in vapor at pressure p, ysv; the correct statement of the Young equation
for a solid in saturated vapor is
ysvo = Y sL +’ yLvo cos eE. PI
In a vapor at partial pressure p, less than the saturation pressure, for
systems where 0 does not change with time,
ysv = ysL + yLv cos 8. 131
The correct form of the Young-Dupre relation for EVA, the work of
adhesion of the solid and the liquid, can, therefore, be derived from [3]
and the well-known Dupre relation
WA = YSO - YLV’ - YSL. c41
Eliminating ysL from [3] and [4] and noting that
YSO- YSV = r, c51
where r is the spreading pressure of the adsorbed vapor on the solid, then

WA = ?r + YLV 1 + E COS 8).

(

1 The opinions or asserti6ns contained in this paper are those of the authors and are
not to be construed as official or reflecting the views of the Navy Department.
514
 POLYTETRAFLUOROETHYLENE 515

For liquids of low vapor pressure, yLv and yLv* are essentially equal so
that [S] to a good approximation becomes
WA = r + yLV(1 + cos 0)

and for systems in saturated vapor

l/tTA = Ta + y-I,& + cos 6,). CSI
Doss and Rao (4) derived from Eq. [2] and an application of Lang-
muir’s principle of independent surface action, the following simple rela-
tion between the equilibrium Sontact angle 8B and G’,the fraction of the
solid furface covered with adsorbed molecules of the liquid:
cos 8, = 2a - 1. I31
Livingston (5) after discussing the derivation of Eq. [9] examined avail-
able data to check the theory and concluded that no reliable data were
available for which 0~ > 0 or u < 1.
In the past it has been difficult to measure WA for solid-liquid inter-
faces because most pure liquids spread on most clean solids. The excep-
tions to this in the literature have been limited largely to water or aqueous
solutions on hydrophobic surfaces and liquid metals on surfaces with
which they do not alloy. By “spreading” will be meant the indefinite
spreading of the bulk liquid, or a thin film but not a monolayer, i.e.,
Hardy’s “secondary spreading” (6) or Harkins’ “duplex spreading” (7).
A more recent development of interest here has been the discovery of
methods of modifying the wettability of solid surfaces by the adsorption
from solution of oleophobic monolayers of oriented polar compounds.
Many organic liquids as well as water will not spread on such surfaces
(8, 9). The wettability of platinum coated with such films has been dis-
cussed and analyzed in a later publication (10) where it is shown that an
oleophobic monolayer can reduce the free surface energy of a normally
high-energy surface to a point at which there will be no net energy de-
crease resulting from the spreading of the given fluid. In this case a drop
of liquid placed on the treated surface remains as a discrete droplet and
exhibits a finite contact angle. The study of the wetting of such low energy
surfaces is, however, limited to liquids which are not good solvents for the
monolayers..
The remarkable inertness of polytetrafluoroethylene (TFE) has been
described by Hanford and Joyce (11). Some preliminary observations by
US (12) indicated that many varieties of organic liquids do not spread on
TFE and that it is necessary to resort to liquids with surface tensions of
less than about 20 dynes/cm. at 20°C. before spreading is found. The
numerous new observations of this type given here have enabled us to
plot the contact angle as a function of molecular weight and related prop-
516 H. W. FOX AND W. A:ZISMAN

erties, as well as to calculate the adhesion tension, work of adhesion, and

the Doss and Rao surface condensation. In subsequent papers results will
be presented from the study of fhe wetting behavior of partially fluorin-
ated hydrocarbon solids and other low surface-energy solids.

MATERIALS AND EXPERIMENTAL PROCEDURES

The liquids used in this study tiere derived from various sources as
indicated in Tables I and II. The results obtained are in general insensitive
to small amounts of impurities, provided the impurities are of the same
molecular type and the same order of volatility as the nominal molecular
species. But it was of major concern to avoid the presence in nonpolar
liquids of small amounts of strongly adsorbable impurities such as highly
polar molecules. Such molecules tend to form oriented arrays, thereby
seriously modifying the underlying surfaces. To insure the absence of this
type of impurity, every liquid was passed through a column of an ap-
propriate adsorbent. The homologous series of n-alkanes was percolated
through successive layers of activated alumina and silica gel. The resulting
liquids (with the exception, of course, of the lowest members which nor-
mally have positive initial spreading coefficients) did not spread in a
hydrophil tray on ‘either acid or alkaline water. The di(n-alkyl)&thers
were similarly treated. Each of the homologous series of polymethylsi-
loxanes was percolated through Florisil until the equilibrium spreading
pressure was at a minimum (13). The alkyl benzenes were treated with
alumina, and the miscellaneous group of liquids were treated variously
with Florisil, alumina, and silica gel, always avoiding use of the latter
when the liquid contained ring structures. In some cases several percola-
tions were necessary, but in every instance but one the final percolate was
crystal clear and colorless, although some of the starting materials were
appreciably colored. Perchlorocyclopentadiene, never reported to be color-
less, was pale yellow after percolation. It was of considerable importance
too, that the high-boiling liquids contain no appreciable amounts of
volatile impurit,ies. Accordingly, such liquids -were stripped of volatiles
at 1OO’C. and about 5 mm. pressure using a countercurrent of CO2 to
carry off the vapor.
The surface tensions quoted in Tables I and II were taken from what
seemed the most reliable sources. Where such data were not available, the
surface tensions given were carefully measured in this laboratory using the
ring method, except in the case of the fluorocarbons. The Harkins and
Jordan correction tables for this method (14) are not extensive enough to
cover the unique combination of low surface tension and high density
characteristic of those materials if one uses rings of moderate size. The
surface tensions of the fluorocarbons were therefore measured by the
differential capillary rise method described by Sugden (15).
 POLYTETRAFLUOROETHYLENE 517

The TFE used in this study was obtained from the DuPont Company
as a uniformly white l-in. slab. Suitably small pieces (about 2.5 X 2.5
X 1 cm.) were cut from the slab and prepared as follows: A clean surface
free from gross irregularities was obtained by removing a layer 1 or 2 mm.
thick with a clean microtome. The resultant surface in general was dull
and showed knife marks. A glossy surface showing no knife marks was
obtained by taking advantage of the plastic properties of this polymer.
The piece was placed between two thick blocks of clean plate glass free
from scratches with the test surface against one of the blocks. This system
was then squeezed in a press at about 300 pounds per square inch
for 3 hr. during which period the press was heated to 150°C. and then
allowed to cool to 50°C. or less. This treatment produced surfaces which
showed, for a given liquid, relatively little variation in contact angle from
specimen to specimen. Considerable difficulty in achieving reproducibility
had been encountered in the early phases of this study because of differ-
ences in roughness of the TFE surfaces. The smoothed specimens were
then cleaned by boiling them in nitric-sulfuric acid (1: 2), and were rinsed
free of acid by boiling successively in three changes of freshly distilled
grease-free water. The few adhering droplets remaining after the last
rinse were earily shaken off, and the dry specimens while still hot were
placed in a covered dish to exclude dust but admit air, thus allowing the
specimen to come to equilibrium with its surroundings. It is of interest to
note that TFE which had been handled or allowed to stand uncovered for
a few days exhibited contact angles of 90” or less against water, whereas
freshly cleaned TFE gave a contact angle of 108-110” against water.
This value is the same as that frequently found in the literature as the
contact angle of water on paraffin.
All the measurements were made jn a constant-temperature room held
at 20.0 f O.l”C. and 50y0 relative humidity.
A number of contact angles were measured jn an atmosphere saturated
with the vapor of the liquid being measured. This was done by pouring a
few milliliters of the liquid into a cylindrical glass cell having fused win-
dows through which the specimen could be observed. The 50-ml. cell used
was made for a Cenco “photelometer” and its dimensions were such that
about one-half the specimen was immersed in the pool of liquid at the
bottom of the cell, the surface to be observed remaining about 1 cm. above
the liquid level. The cell was closed with a horizontal glass plate which
had in it a 5-mm. hole for insertion of the platinum wire carrying the
drops. The hole was covered while the specimen in the cell was allowed to
equilibrate with the vapor for at least 1 hr. Prior to placing the specimen
in the cell, all the components of the system were allowed to come to
thermal equilibrium with-the room, from 2 to 4 hr. generafly being suffi-
cient. The hole was then uncovered for the few seconds required to place
518 H. W. FOX AND W. A. ZISMAN

two drops of fluid on the surface of the specimen. The drops were observed
immediately and 1 hr. later. Only the few most volatile liquids showed a
change in drop size or in contact angle during the hour.
A single experiment was performed with hexadecane in vacuum. The
vacuum chamber had plane windows for observation, and manipulators
which could transfer a drop of liquid from a reservoir to the specimen
without breaking the vacuum. The experiment was done at a pressure of
less than 10m4 mm. of mercury. The drop when placed was observed im-
mediately and at 5-min. intervals thereafter.
The contact angles were conveniently measured with a refined version
of the contact angle goniometer described earlier (8), which gave a magni-
fied, high-contrast image of the drop profile. The main improvement in
the newer instrument was that provision had been made for raising and
lowering, and for tilting and translating the solid specimen positively. For
the vacuum experiment, it was necessary to mount the system so that the
goniometer telescope could be given the above degrees of freedom instead
of the specimen.
The general procedure was to place a drop of the fluid on the specimen
(in air or in the photelometer cell) by means of a flamed platinum wire,
taking considerable care that the drop be placed so as to insure an ad-
vancing contact angle. The drops could be varied in size with no observ-
able effect on the contact angle. Each reported value is an average of from
four to twelve separate determinations made on different specimens on
different days. With few exceptions the maximum deviation from the
mean encountered for a given system was f 2”. Most often, especially
for the high-boiling liquids, the maximum deviation from the mean was
f 1”.
Considerable difficulty, however, was encountered in obtaining
quantitative results with the few most volatile fluids, chiefly because of
two effects. There was a region of volatility (exemplified by the behavior
of heptane) in which the values tended to be low. The loss of material by
evaporation from the drop made its periphery recede, thus producing some
value of the contact angle less than the advancing angle. To overcome this
effect, the specimen was positioned in the field of the goniometer as pre-
cisely as possible so that a minimum of manipulation was necessary to
bring the drop into position for reading the angle. By this means a reading
could be taken within 5 sec. after placement of the drop. This procedure
minimized the effect, and the reported value is probably within a degree
or two of the true value. The other effect was noted for the two most
volatile materials (n-pentane and diisopropyl ether). Here the evapora-
tion was so rapid that no reliable value was possible in the open air. The
advancing edge of any spreading drop is in the form of a thin layer, a fact
which can easily be observed with any nonvolatile liquid. The very
 POLYTETRAFLUOROETHYLENE 519

volatile liquids evaporated so rapidly from the thin spreading edge that a
finite boundary of the drop was observed, superficially resembling the case
of a liquid which has a finite contact angle. The rapidly receding periphery
could be observed in profile through the goniometer telescope. The con-
tact angles observed under those conditions were invariably very small.

EXPERIMENTAL RESULTS
Tables I and II summarize the values of the surface tension at 20°C.
(yr,v), the average values of the measured contact angle (0), the calculated
values of the adhesion tension (yLv cos 0), and the Doss and Rao condensa-
tion (u) of all the liquids investigated. Homologous series of n-alkanes,
di(n-alkyl)ethers, n-alkylbenzenes, and polymethylsiloxanes are given in
Table I, while Table II includes a variety of liquids grouped as halogen-
ated compounds, esters, and miscellaneous liquids.
Several features of these tables are noteworthy. In three of the homol-
ogous series of Table I the adhesion tension is apparently constant over a
wide range of chain lengt,hs in a single series. But the n-alkylbenzenes
show a trend to increasing adhesion tension with decreasing surface ten-
sion, as do the liquids of Table II. The adhesion tensions of the hydrocar-
bon series and of the di(n-alkyl)ether series are close enough together so
that the average deviation in either sense may cover the differences.
For example, if the contact angles for the ethers and n-alkanes are plotted
together-against the number of carbon atoms, the points fall on the same

1.0
18 20 22 24 26 28
SURFACE
TENSION
AT20°C(D~NE~C~)
FIG 1. Surface tension vs. cosine 8 for the n-alkanes.
520 H. W. FOX AND W. A. ZISMAN
.
TABLE I
Surface Energy Relations of FOUT Homologous Series of Liquids and
Polytetrajhoroethylene at 20°C.
=

‘ hrc
Compound Ref. B YLV WO WA--w,
WA c
c If cpd YLY cos 9
YLV

ym?s/cm deg. pes/cm ~rgs/cm.! rgs/cm. W&WCTl&.!

n-Alkanes
Hexadecane @. 27.6 (19) 46 19.2 46.8 55.2 - 8.4 0.85
Tetradecane a 26.7 (19) 44 19.2 45.9 53.4 - 7.5 0.86
Dodecane a 25.4 (22) 42 18.9 44.3 50.8 - 6.5 0.87
Undecane, a 24.7 (22) 39 19.2 43.9 49.4 - 5.5 0.89
Decane a 23.9 (22) 35 19.6 43.5 47.8 - 4.3 0.91
Nonane b 22.9 19.4 42.3 45.8 - 3.5
(22) 32 0.92
Octane a 21.8 (22) 26 19.6 41.4 43.6 - 2.2 0.95
Heptane a 20.3 (22) 21 19.1 37.4 40.6 - 1.2 0.97
Hexane a 18.4 (19) 12 18.0 36.4 36.8 - 0.4 0.99
Pentane a 16.0 32.0 > 0.0
(22) Spread1 >32.0 1.0
Di(n-alkyl)ethers
Octyl B 27.7 (20) 49 18.2 45.9 55.4 - 9.5 0.83
Heptyl f 27.0 (20) 47 18.4 45.4 54.0 - 8.6 0.84
Amy1 a 24.9 (20) 40 19.1 44.0 49.8 - 5.4 0.88
Butyl a 22.8 (20) 31 19.5 42.3 45.6 - 3.3 0.93
Propyl a 20.5 19.4 41.0 - 1.1
(20) 19 39.9 0.97
Isopropyl a 17.8 (20) Spread; >35.6 35.6 > 0.0 1.0
n-Alkylbenzenes
Hexyl d 30.0 (25) 52 18.5 48.5 60.0 -10.5 0.81
Butyl 0 29.2 (25) 49 19.2 48.4 58.4 - 10.0 0.83
Propyl c 29.0 (25) 49 19.0 48.0 58.0 - 10.0 0.83
Ethyl c 29.0 ( (25) 48 19.4 48.4 58.0 - 9.6 0.84
Methyl E 28.5 (24) 43 20.9 49.4 57.0 - 7.6 0.87
Benzene c 28.9 (24) 46 20.1 49.0 57.8 - 8.8 0.85
Linear polymethyl-
siloxanes
Heptadecamer (13) 19.9 (13) 30 17.2 37.1 39.8 - 2.7 0.93
Dodecamer (13) 19.6 (13) 29 17.2 36.8 39.2 - 2.4 0.94
Nonamer (13) 19.2 (13) 26 17.3 36.5 38.4 - 1.9 0.95
Heptamer (13) 18.6 (13) 24 17.0 35.6 37.2 - 1.6 0.96
Hexamer (13) 18.5 (13) 19 17.5 36.0 36.9 - 0.9 0.97
Pentamer (13) 18.1 (13) 15 17.5 35.6 36.2 - 0.6 0.98
Tetramer (13) 17.6 (13) 8 17.4 35.0 35.2 - 0.2 0.99
Trimer (13) 17.0 (13) Spread; - >34.0 34.0 > 0.0 1.0
-
a Eastman “white label” grade.
b Kaiser Wilhelm Institut (“Reins? grade).
c American Petroleum Institute Spectrographic Standards (National Bureau- of
Standards).
d NDRC Preparation by Prof. Homer Adkins (University of Wisconsin).
8 Connecticut Hard Rubber Company.
f Wallace and Tiernan Company.
 POLYTETRAFLUOROETHYLENE 521

curve if the ether oxygen is counted as equivalent to a carbon atom in

making up the chain. The polymethylsiloxanes, on the other hand, give
significantly lower values when plotted on the same coordinates counting
each silicon and oxygen atom as equivalent to a carbon atom.
Among the liquids of Table II the adhesion tension varies with the
surface tension. When these liquids are arranged in order of decreasing
surface tension, they are in the order of increasing adhesion tension with
a few exceptions. Adhesion tensions of the liquids that spread are of course
indeterminate. Adhesion tensions of liquids whose surface tensions are
above about 55 dynes/cm. are negative since the contact angles were
greater than 90”.

SURFACE
TENSION
AT20°C(DYNES/CM)
FIG. 2. Surface tension vs. cosine0 for the di(n-alkyl)ethers.

When surface tension is plotted against cos 6 for the homologous series,
in each case except the n-alkylbenzenes, a straight line fits the points
better than the hyperbolas representing-the relation YLV cos 0 = constant
(Figs. l-3). Straight lines also give a good approximation of the relation-
ship between yLv and cos 0 for the halogenated and miscellaneous liquids
(Figs. 4 and 5). An insufficient spread in surface tension precludes drawing
such lines for the n-alkylbenzenes and the esters, so that these fluids have
been included in the plot of the miscellaneous group. The intercept of
each line of Figs. l-5 with the ordinate COB0 = 1.0 gives the surface ten-
sion of the liquid in the series which should just spread on TFE. The fact
that n-hexane gives a finite angle although its surface tension is less than
the value indicated by the intercept is anomalous and may be due to the
evaporation effects noted earlier. The two fluorinated liquids with surface
 TABLE II-Surface Energy Relations of Some Miscellaneous Liquids and Polytetrajluoroethylene at 20°C.
==I
Source Ref.
Compound of cpd. a WA w. WA--WC
YLV
__- -_- _- ---- ----_ --
deg. ergs/cm.~ wgs/cm.~ ergs/cm.=
Halogenated compounds
Methylene iodide 50.8 (26) 88 0.8 51.6 101.6 - 50.0 0.52
suna-Tetrabromoethane 49.7 (2’3 79 9.5 59.2 97.4 - 40.2 0.60
Aroclor 1242 (triohlorodiphenyl) 45.3 (23) 81 7.1 52.4 90.6 - 38.2 0.58
cr-Bromonaphthalene 44.6 (26) 73 13.0 57.6 89.2 - 31.6 0.65
Aroclor 1248 (tetrachlorodiphenyl) 44.2 (23) 78 9.2 53.4 88.4 - 35.0 0.60
Hexachloropropylene 38.1 (23) 65 16.1 54.2 75.2 - 22.0 0.71
Perchlorocyclopentadiene 37.5 (23) 67 14.7 52.2 75.0 - 22.8 0.70
sync-Tetrachloroethane 36.3 (26) 56 20.3 56.6 72.6 - 16.0 0.78
Hexachlorobutadiene 36.0 (23) 60 18.0 54.0 72.0 - 18.0 0.75
Tetrachloroethylene 31.7 (26) 49 20.8 52.5 63.4 - 10.9 0.83
Carbon tetrachloride 26.8 (26) 36 21.7 48.5 53.6 - 5.1 0.91
Polymonochlorotrifluoroethylene (86.9 cs.
at 100°F.) 25.1 (23) Spreads - >50.2 50.2 > 0.0 1.0
Perfluorinated aliphatic hydrocarbon 24.6 (23) <5 24.5 >49.1 49.2 :ca.) 0.0 >0.99
Perfluorotributylamine 16.2 (23) Spreads >32.4 32.4 > 0.0 1.0
Perfluorodibutylether 12.8 (23) Spreads >25.6 25.6 > 0.0 1.0
Esters
Tricresyl phosphate 40.9 (23) 75 10.6 51.5 81.8 - 30.3 0.63
Benzyl phenylundecanoate 37.7 (23) 67 14.9 52.6 75.4 - 22.8 0.70
Di-(2-etbylhexyl)phthalate 31.2 (23) 63 14.2 45.4 62.4 - 17.0 0.73
Di-(2-ethylhexyl)sebacate 31.1 (23) 62 ‘14.6 45.7 62.2 - 16.5 0.74
Pentaerythritol tetracaproate 30.4 (23) 64 13.3 43.7 60.8 - 17.1 0.72
1,6-Hexamethylene glycol di-a-ethylhex-
anoate 30.2 (23) 63 13.7 43.9 60.4 - 16.5 0.73
Di-(2-ethylhexyl)adipate 30.2 (23) 61 14.6 44.8 64.4 - 15.6 0.74
Tri-(2-ethylhexyl)tricarballylate 29.6 (23) 61 14.4 44.0 39.2 - 15.2 0.74
-
 TABLE II-Continued
--

Compound SOURZ Ref. e Yiv cos e WC WA-W, (I

of cpd. YLV WA
YLV
--
iynes/cm. deg. erQs/cm.= ergs/cm .2 el.QS/Gm.~
Miscellaneous liquids
Mercury 485. (1) 150 -420 65.0 970 -905 0.07
Water 72.8 (1) 108 - 22.5 50.3 145.6 - 95.3 0.35
Glycerol 63.4 (26) 100 - 11.0 52.4 126.8 - 74.4 0.41
Formamide 58.2 (26) 92 - 2.0 52.6 116.4 - 60.2 0.49
Ethylene glycol 47.7 (26) 90 0.0 47.7 95.4 - 47.7 0.50
tert-Butyl naphthalene 33.7 (23) 65 14.3 48.0 67.4 - 19.4 0.71
Carbon disulfide 31.4 (33 62 14.8 46.2 62.8 - 16.6 0.74
n-Heptylic acid 28.3 Gw 49 18.6 47.1 56.6 - 9.5 0.83
Polymethylphenylsiloxane (102 cs.) 26.1 (13) 55 15.0 41.1 52.2 - 11.1 0.79
Polymethylphenylsiloxane (dimer) 29.0 (23) 50 18.6 47.6 58.0 - 10.4 0.82
Polyethylsiloxane 23.3 (13) 43 17.0 40.3 46.6 - 6.3 0.87
Linear polymethylsiloxane (35 cs.) 19.9 (13) 38 15.7 35.6 39.8 - 4.2 0.89
Triptane 18.9 (24) <5 >37.7 37.8 (CCL) 0.0 >0.99
-
a Eastman “white label” grade. h Dow Corning Corp.
6 Eastman “technical” grade. i Monsanto Chemical Company.
c Eastman ‘Lpractical” grade. j Hooker Electrochemical Company.
d Preparation of this laboratory. k Sharples Chemicals Company.
e Commercial. C.P. grade. z Hercules Powder Company.
f U.S.P. grade. m E. I. DuPont de Nemours & Company.
g Minnesota Mining and Mfg. Co. (FCD-331, 49.0 cs. at 100°F.)
524 H. W. FOX AND W. A. ZISMAN

0.7-

.8-

I I I
17 18 19 20 21
SURFACE
TENSION
AT20°C(DYNES/GM)
Fra. 3. Surface tension vs. cosine0 for the linear polymethylsiloxanes.

tensions over 20 dynes/cm., one of which exhibited a low angle- and the
other of which spread, seem to be an exception to the rule for all the other
liquids. Properties other than the surface tension, such as molecular
weight, boiling point, and density, yield no new information when plotted
against 0 or cos 0.
An interesting example of the dependency of the contact angle on sur-
face tension is given by a group of six esters among the liquids of Table II.

“’ / I I I I I
20 25 30 35 40 45 50
SURFACE
TENSION
AT20°C(DYNES/CM)
FIG 4, Surface tension vs. cosine0 for the halocarbons.
 POLYTETRAFLUOROETHYLENE 525

I I I I I I
I0 20 30 40 50 60 70
SURFACE
TENSION
AT20WDYNEVtMl
FIG. 5. Surface tension vs. cosine 0 for some miscellaneous liquids.

Although di-, tri-, and tetraesters are represented in the group, the values
of the contact angles are found to lie between 61” and 64”, presumably be-
cause the spread in the values of the surface tensions is only I.6 dynes/cm.
The purpose of the single experiment in a vacuum was to show that
the non-wettability of TFE is not due to a film of trapped or adsorbed
air on the TFE surface. In t.his experiment the initial values of the contact
angles made by n-hexadecane on TFE ranged from 35” to 42”; moreover,
the contact angle decreased continuously with time. It was noted that
simultaneously the size of the drop decreased. The low values and the
continual decrease with time are undoubtedly due to evaporation of the

TABLE III
The Contact Angles of Volatile Liq,uids on Polytetrajiuoroethylene
in Air and in Air Saturated with the Liquid Vapor

Liquid 8, in air

Di(n-butyl)ether 34 34 0.93 0.93

n-Octane 26 26 0.95 0.95
n-Heptane 21 22 0.97 0.96
wHexane 12 (cu.) 7 0.99 1.0
n-Pentane (cu.) 0 Spreads 1.0 1.0

Silicone hexamer 19 22 0.97 0.96

Silicone pentamer 14 17 0.98 0.97
Silicone tetramer (cu.) 8 (cu.) 12 0.99 0.99
Silicone trimer Spreads Spreads 1.0 1.0
526 H. W. FOX AND W. A. ZISMAN

hexadecane, which at pressures of less than lo-* mm. is rapid enough to

produce values characteristic of some state intermediate between the
advancing and receding angle. Also, it should be pointed out that place-
ment of the drop cannot be done as carefully with the vacuum manipula-
tors as by hand in air, and that this also makes it difficult to insure the
formation of the advancing angle. This accounts for the spread in the
initial readings.
Another point of interest is the difference between the contact angles
on rough and smooth surfaces. It was found that increasing roughness

O-

-6O-
0 N-ALKANES
0 HALOGENATEO COMPOUNDS
-8O- 8 POLYMETHYLSlLOXANES
8 ESTERS
0 MISCELLANEOUS LIQUIDS
.\
I I I +,
20 40 60
SURFACE
TENSiON
AT,20°C(DYNES/CM)
FIG. 6. Spreading coefficient vs. surface tension of various
fluids on polytetrafluoroethylene.

would lower the contact angle. With liquids of low surface tension, a finite
angle would be observed on the smooth surface when the same liquid
would spread on the rough surface. This observation is consistent with
the conclusions from the work of Wenzel (16) and Cassie and Baxter (17)
on roughness for liquids having contact angles of less than 90”. .
Table III compares the contact angles of some of the volatile liquids
in air, and in air saturated with t.he vapor of the liquid in question. It was
intended by this means to arrive at an estimate of the importance here of
the PE term in Eq. [S] for the work of adhesion. As no difference was
 POLYTETRAFLUOROETHYLENE 527

found between 8 and BE for the less volatile liquids under both conditions,
it was concluded that the term TE was negligible for such liquids on TFE.
As before, measuring the most volatile materials gave considerable diffi-
culty, and the values are uncertain where the contact angle was very low.
Some facts do, however, emerge from these data. Except for hexane, the
value for which was a little uncertain both in air and in the saturated
atmosphere, the hydrocarbons and di-n-butylether show no significant
d%ference between the saturated and nonsaturated atmospheres. But
every one of the polymethylsiloxanes gave angles which were about 3”
higher in the saturated atmosphere than in air.

LINEAR POLYWETHYLSILOXANES
N-ALKYL BENZENES

SURFACE
TENSIONAT20'C (DYNES/GM)
FIG. 71 Spreading coefficient vs. surface tension of four homologous series
of fluids on polytetrafluoroethylene.

Since 1~~was found to be negligible even for materials as condensable

as heptane (but not for the polymethylsiloxanes), it can be concluded that
y1,~(1 + cos 0) is a good approximation for WA, the work of adhesion
between TFE and those liquids which do not wet it. WA, so calculated, is
given in Tables I and II and is remarkably constant considering the vari-
ation in YLV cos 0 of the liquids reported here. Even the liquids with nega-
tive values of YLV cos 0 have values of WA comparable to the others.
Tables I and II also include the values of W,, the work of cohesion (W, =
27~~) to permit the calculation of the spreading coefficient.
528 H. W. FOX AND W. A. ZISMAN

For all the liquids, the initial spreading coefficient WA 1 W, is

negative, of course, whenever 0 is not zero. If the liquids are arranged in
order of decreasing surface tension, with few exceptions they are also in
the order of increasing spreading coefficient. This relationship is shown
graphically in Fig. 6 where WA - W,‘is plotted against surface tension.
The ethers have been left out for the sake of clarity since the points nearly
coincide with those of the alkanes. Mercury is also omitted because the
compactness of the scale necessary to include it would hide the detailed
positions of the points given by all the other liquids. A portion of the same
plot is given in Fig. 7 on a magnified scale to show the details for the
members of the homologous series of n-alkanes, di(n-alkyl)ethers, poly-
methylsiloxanes, and n-alkylbenzenes.
DISCUSSION
From Figs. 1-4 it is obviously possible to estimate the surface tensions
of the liquids represented in these figures by observing the contact angle
against TFE. For the other liquids, a less accurate estimat,e can be made
from Fig. 5. The implication of the observed regularities is, of course, that
no other variables affecting spreading on TFE are present for the liquids
of this study other-than those in Eqs. [2] and [3]. ’
WA - W, can be calculated using the assumption made earlier that
aE = 0 and reduces to the simple relation
WA - w, = yI,v(cos e - 1). Cl01
If 6 can be expressed as a function of y, it would permit the derivation from
[lo] of the relations graphed in Figs. 6 and 7. Since cos 0 has been shown
to be a linear function of y, it becomes easy to find the required relations
by determining the equations of the straight lines cos 0 = ay +. c and
substituting in [lo]. Thus [lo] becomes
w&4 - WC = yL,v(ay + c - 1) = yIX(ay + b), Cl11
where c = b + 1. The coefficients a and b, so calculated, are given in
Table IV. The curves for WA - W, plotted against surface tension are
thus parabolic and cluster around the experimental curve for all the liquids
when superimposed on Fig. 6, as would be expected. When superimposed
on the magnified curves of Fig. 7, the calculated parabolas virtually coin-
TABLE IV
The Spreading as a Function
Coejkient of Surface Tension
in the Form WA - We = yL&-m f b)
Type liquid a v

n-Alkanes -0.034 0.62

Di(n-alkyl)ethers - 0.040 0.77
Polymethylsiloxanes -0.059 1.03
Halocarbons -0.031 0.64
Miscellaneous liquids -0.020 0.16
 POLYTETRAFLUOROETHYLENE 529

tide with the experimental curves. Extrapolation of the calculated parab-

olas to positive regions of WA - w, iS unwarranted Since g,?+presum-
ably exerts a significant influence when 0 approaches zero.
Equation [2] can be rearranged in the form
(-190 - YSL) - (YSO - YSV”) = “fLV’ COS OE.

Since YSO - ysvO = ?TEthe above equation can be written

YSO - ?‘SL = TE + “/LV’ COS OE. Cl21
The left hand side of [12] is the free energy of immersion of the solid in
the liquid, and [12] permits TE to be calculated from YLVO, 08 and a
measurement of the free energy of immersion. In the experiments de-
scribed here eE = 0, so that to a good approximation TE = 0 and YLVO=
y~v. Hence [12] can be written
YSO- ysL = yLv cos 8. ix31
For those liquids for which TE = 0 and yLv cos 0 is a constant, [13] shows
that the free energy of immersion is also constant. As yso is a constant of
the TFE, it follows that YSL must be nearly the same for all those liquids,
a remarkable result considering the variety of liquids for which the ad-
hesion tension was found to be between 18 and 20 dynes/cm.
There is apparently a range of “critical” surface tensions above which
no liquid studied here spreads on TFE and below which every liquid
spreads. This range has as a lower limit 17.5 dynes/cm. for t,he siloxanes
and 20.5 dynes/cm. for halogenated compounds. A parallel study made in
this laboratory (18) on the wetting of oleophobic monolayers on platinum
gave a value between 23.0 and 23.6 dynes/cm. for ~LV cos e for the n-al-
kanes and di(n-alkyl)ethers, while all the polymethylsiloxanes spread.
The critical surface tension below which all liquids spread on the mono-
layers was about 22 dynes/cm. Therefore, 23.0-23.6 ergs/cm.2 represents
the free energy of immersion in the n-alkanes, say, of a solid covered with
an exterior layer of methyl groups, whereas, 17.5-20.5 ergs/cm.2 repre-
sents that of a surface comprising perfluoromethylene and perfluoro-
methyl groups. The introduction of relatively small proportions of other
substituents into TFE was found to modify the wettability considerably,
and a study of the surfaces of modified polymers will be the subject of a
subsequent paper. Although it is st.imulating to try to relate the critical
surface tensions to the free energies of the solid-liquid interface and of the
solid surface itself, there is unfortunately no way of separating the two
energies by this method.
NO adequate explanation is at present available for the S-degree in-
creases in 0 given by each of the siloxanes in its saturated vapor. It would
be expected that with extensive adsorption of vapor the liquid droplets
would tend to give smaller angles against what must be films of their
530 H. W. FOX AND W. A. ZIS&AN

parent substance. That the reverse is true cannot be accounted for by

reduction of the apparent angle in air due to excessive volatility, because
the differences noted were the same.for three -adjacent members of the
homologous series with substantial differences in vapor pressure at 20°C.
The fraction (u) of the surface area covered with condensed molecules
from the liquid phase has been calculated using the Doss and Rao relation
[9], and the results are given in the last columns of Tables I, II, and III.
In general, the values of G are surprisingly large for most of the liquids;
for only a few like mercury and water is u less than 0.50. It is not evident
why such high-boiling liquids as Aroclor 1248, tricresyl phosphate, di-(2-
ethylhexyl)sebacate, and the polymethylphenylsiloxane [102 centistokes
(cs.) at 25”C.l should have values as large as 0.60, 0.63, 0.74, and 0.79,
respectively, nor why so many alkanes, dialkyl ethers, and polymethyl-
siloxanes should give finite contact angles while d is over 0.95. Since we
have shown that cos 0 is a linear function of yLv for each group of homolo-
gous liquids, and since the Doss and Rao relation gives cos 0, as a linear
function of c, it is evident that u can be expressed as a-linear function of
YLV. But from the physical definition of B it is unexpected to find large
values of u determined by y alone rather than by some expression con-
taining parameters determined by the specific attractions or energies of
the liquid-solid interface. It is therefore likely that u is not correctly given
by the simple theory of Doss and Rao.
The relative inertness of the TFE surface has been shown to result in
values of WA generally smaller than W, for the fluids used in this study,
so that the spreading coefficient is negative. Therefore most fluids do not
spread on TFE. This inertness of TFE surfaces is consistent with the
extraordinarily low surface tensions and high compressibilities of the per-
fluorinated hydrocarbon fluids. All these phenomena are apparently due
to the low intermolecular forces which are in turn a result of the large size
and.extreme electronegativity‘of the fluorine atoms. In practice the low
free energy of the surface of TFE has been reflected in the difficulty of
finding adhesives for this material as well as the difficulty encountered in
making TFE adhere to itself in the manufacture of solid TFE by sintering
the powder. Plasticization will probably depend on the use of a fluid with
a surface tension of around 20 dynes/cm. or less for nonfluorocarbon
liquids.
ACKNOWLEDGMENT
The authors wish to acknowledge the assistance of Mrs. Dorothy Wprkman who
measured many of the quoted surface tensions.

SUMMARY
1. Methods of preparing surfaces of polytetrafluoroethylene (TFE)
are described which permit obtaining reproducible and reliable measure-
 POLYTETRAFLUOROETHYLENE 531

ments of contact angles with liquids. Polytetrafluoroethylene is found to

be an ideal low energy surface for the study of the wetting relations of a
solid with a wide variety of organic and inorganic liquids.
2. It is shown that all but the lowest-boiling liquids studied do not
adsorb on TFE sufficiently from the vapor to produce a significant spread-
ing pressure. Hence the TE term in the expression for the work of adhesion
(WA) is negligible and WA = -y~v(1 + cos 0). The calculated values of
WA are found to be consistent and reasonable.
3. It is found that for each homologous series of liquids cos 0 is a linear
function of yLv. The constants of the resulting relations are given. From
this WA - W, can be expressed as a function of YLV alone.
4. The observations show that there is a critical surface tension (17.5-
20.5 dynes/cm.) below which liquids wet TFE.
5. It is concluded that the corrected Young-Dupr6 relation coupled
with the spreading coefficient permits a rational description of the results.
The Doss and Rao relation for the surface condensation leads to such
high values for high-boiling liquids as to make it unlikely that the theory
is correct.
REFERENCES
1. ADAM, N. K., The Physics and Chemistry of Surfaces. Oxford Univ. Press, 1941.
2. BANOHAM, D. H., AND RAZOUK, R. I., (a) Trans. Faraday Sot. 33, 1459, 1463 (1937);
(b) Proc. Faraday Sot. A166, 572 (1938).
3. BOYD, G. E., AND LIVINGSTON, H. K., J. Am. Chem. Sot. 64, 2383 (1942).
4. Doss, K. S., AND RAO, B. S., Proc. Indian Acud. Sci. 7A, 117 (1938).
5. LIVINQSTON, H. K., J. Phys. Chem. 48, 120 (1944).
6. HARDY, W. B., Proc. Roy. Sot. (London) A88, 313 (1933).
7. HARKINS, W. D., Chem. Revs. 29, 385 (1941).
8. BIGELOW, W. C., PICKETT, D. L., AND ZISMAN, W. A., J. Colloid Xci. 1, 513 (1946).
9. BIGELOW, W. C., GLASS, E., AND ZISMAN, W. A., J. Colloid Sci. 2, 563 (1947).
10. SHAFRIN, E. G., AND ZISMAN, W. A., J. Colloid Sci. 4, 571 (1949).
11. HANFORD, W. E., AND JOYCE, R. M., J. Am. Chem. Sot. 68, 2082 (1946). ’
12. Fox, H. W., AND ZISMAN, W. A., Rev. Sci. Instruments 19, 274 (1948).
13. Fox, H. W., TAYLOR, P. W., AND ZISMAN, W. A., Ind. Eng. Chem. 39, 1401 (1947).
14. HARKINS, W. D., AND JORDAN, H. F., J. Am. Chem. Sot. 52, 1751 (1930).
15. SUGDEN, S., The Parachor and Valency. A. A. Knopf, New York, 1930.
16. WENZEL, R. N., Ind. Eng. Chem. 28, 988 (1936).
17. CASSIE, A. B., AND BAXTER, S., Trans. Faraday Sot. 40, 546 (1944).
18. SHAFRIN, E. G., AND ZISMAN, W. A., Oleophobic Monolayers III: Wetting Effects
and Adhesional Energies, to be published.
19. VOGEL, A. I., J. Chem. Sot. (London) 1946, 133.
20. Ibid. 1948, 616.
21. Ibid. 1948, 607.
22. QUAYLE, 0. R., DAY, R. A., AND BROWN, G. M., J. Am. Chem. Sot. 66, 938 (1944).
23. This laboratory.
24. Doss, M. P., Physical Constants of the Principal Hydrocarbons, 4th Ed. The Texas
co., (1943).
25. QUAYLE, 0. R., Priqte communication.
26. Itiernutionul Critical Tables.