988 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 28, NO.

tial volume of the methane in the tivo-phase region is practi-

Table III. Specific Heats at Constant Volume of Mix-
tures of Methane and Crude Oil
cally a constant and equal to the specific volume of methane
at the same temperature and pressure indicates that there is
Mass P er Cent M ethane as Follows:
little transfer of heavy components into the gas phase at the
—
—

0 1.414 2.367 4.323 5.106 6.062

pressures and compositions investigated at this temperature.
0
F.
70 0.458a 0.465 0.469 0.491 0.495 0.476 No plots of the thermodynamic properties were made since
100 0.472 0.478 0.485 0.510 0.515 0.498
130 0.485 0.492 0.500 0.530 0.535 0.519 they are similar in appearance to diagrams for other mixtures
160 0.499 0.505 0.516 0.549 0.555 0,540 published earlier (5, 6).
190 0.512 0.518 0.531 0.569 0.575 0.562
220 0.526 0.532 0.547 0.589 0.595 0.583
a
Specific heats reported for a specific volume of 0.035 cu. ft. per lb. Acknowledgment
Financial assistance for this work was given by the Ameri-
can Petroleum Institute. The Union Oil Company of Cali-
marked, indicating an approach to the critical composition fornia furnished the analysis of the crude oil with the excep-
at these temperatures. The change in specific gravity with tion of the molecular weight determinations. J. E. Sher-
equilibrium pressure for a temperature of 160° F. is depicted borne and W. R. Mendenhall carried out several of the labora-
in Figure 6; the curve for pure methane, near the bottom, was
tory measurements.
obtained by interpolation of published compressibility data
(1). Figure 7 shows the variation in specific volume with Literature Cited
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composition for the two-phase portion of the system studied. (1) Kvalnes, . M., and Gaddv, V. L., J. Am. Chem. Soc., 53, 39S
The points shown are not directly determined experimentally (1931).
but were read from smooth isothermal curves drawn through (2) Sage, B. H., Backus, H. S., and Lacev, W. ’., Ind. Eng. Chem.,
the experimental points on the pressure-volume plane. The 27, 686 (1935).
(3) Sage, B. H., and Lacey, W. N., Ibid., 26, 103 (19.34).
agreement of the data with a linear relation between specific (4) Ibid., 27, 1484 (1935).
volume and composition is considered to be within the ab- (5) Ibid., 28, 249 (1936).
solute accuracy of the measurements. Figure 8 is a similar (6) Sage, B. H., and Lacey, W. N., Am. Petroleum Inst., Production
Bull. 216 (1935); Oil Weekly, 80, No. 11, 31 (1936).
diagram for the region near bubble point on a larger specific
(7) Sage, B. H., Lacey, W. N., and Schaafsma, J. G., Ind. Eng.
volume scale. The curvature of the isobars in the condensed Chem., 26, 874 (1934).
region is in contrast to the straight lines in the two-phase re- (8) Sage, B. H., Mendenhall, W. R., and Lacey, W. N., Am. Petro-
gion. The partial specific volumes, Vp, under constant pres- leum Inst., Production Bull. 216 (1935); Oil Weekly, 80, No. 13,
sure conditions, of methane in these mixtures at 160° F. is 30 (1936).
(9) Sage, B. H., Schaafsma, J. G., and Lacey, W. N., Ind. Eng.
shown in Figure 9. The partial specific volume of the dis-
Chem., 26, 1218 (1934).
solved methane increases somewhat as the concentration of
methane in the solution is increased. The fact that the par- Received April 13, 1936,

RESISTANCE OF SOLID SURFACES

TO WETTING BY WATER
ROBERT N. WENZEL

®
THE
waterproofing of light-weight
I knitted fabrics, it is generally
woven or Mellon Institute of Industrial Research, Pittsburgh, Pa.
1 essential to preserve the air porosity of the
material. The waterproofness that can be effected is therefore
definitely limited by the size of the openings, because water Many substances, some widely different chemically, are
will readily pass through if the pressure behind it is sufficient known and have been used as water-repelling agents. It is
to break the surface film across the openings. Water will obvious that they must possess this property in varying de-
penetrate, however, at a much lower pressure or even against gree. Yet no attempt to compare water-proofing agents on
pressure, if it can spread over the surface of the threads from the basis of a quantitative evaluation of this essential char-
one face of the cloth to the other. The waterproofing of open acteristic appears to have been made. Moreover, few of the
fabrics, therefore, presents the problem of preventing this experimental methods that have heretofore been applied in
spreading of water over the thread surfaces. The desired the investigation of wetting problems are at all adaptable to
effect is attained by depositing on the fabric some chemical the study of the wetting of different solid substances by the
substance that has of itself this ability to resist wetting. same liquid. The explanation probably lies in the fact that,
For practical reasons, preparations intended for use in in most cases where wetting problems are of industrial im-
waterproofing open fabrics commonly consist of emulsions. portance, the solid itself is not subject to modification or
In these preparations the active water-repellent agent is control. Attention is therefore necessarily confined to the
combined with other ingredients whose presence is required liquid phase, its wetting power being altered either by the
to ensure the desired fluidity and stability in the emulsion, use of liquids of different polarity or by the introduction of
to provide proper pH control, to increase the permanence surface-active solutes.
of the proofing effect, and to modify the appearance and feel A survey of possible experimental procedures led finally
imparted to the finished fabric. These auxiliary' constituents to the direct measurement of contact angles by the tilting
may impair, or they may enhance, the effectiveness of the plate method as the most satisfactory for comparing a wide
proofing treatments. The complexity of the problem thus variety of solid materials. When a suitable apparatus and
presented makes it desirable to study carefully the wetting proper technic had been developed, this method was found
characteristics of materials selected for this use. to be rapid and precise, and to afford results reproducible
AUGUST, 1936 INDUSTRIAL AND ENGINEERING CHEMISTRY 989

with a considerable degree of for the dry area around it.

accuracy anywhere within the Either value may be the greater,
Because of their recognized practical but suppose that in this case the
entire range of practically sig-
nificant values. Measurements importance, wetting phenomena have wetted area has the lower spe-
then soon revealed the fact that, been receiving more and more attention cific energy and that therefore
for certain materials, the method in textile technology. In this paper the the drop tends to spread spon-
of producing the surface—that author discusses critically the application taneously. Assume that it has
is, its physical condition—had a not reached equilibrium, that its
much more pronounced effect
of wetting theory to the study of water-
shape is, say, approximately
on its water repellency than was repelling agents. It is shown that, con- hemispherical. Spreading will
to be explained on the basis of trary to the usual assumption, the adhe- then take place, and, as it does,
any conception of wetting resist- sion tension, as defined in terms of char- both the wetted area under the
ance as a fixed property of chemi- acteristic interfacial tension values, is not drop and the free liquid surface
cal substances, comparable, for over it will be thereby in-
a direct measure of wettability, but that
example, to the surface tension creased. The former involves a
values in terms of which it is the latter depends also definitely on the release of energy, the latter a
usually expressed. physical condition of the surface wetted. consumption of energy. The
It is suggested that the ob- This fact must be recognized in all prob- difference is the net energy de-
served effect of the physical crease which determines the
lems involving the wetting of solid sur-
condition of the surface can be speed of wetting under the im-
faces. It has an important bearing on
simply and adequately explained posed conditions and is thus a
without denying the specific the effectiveness of water-repelling ma- measure of the wetting charac-
character of interfacial tensions terials deposited on the fibrous surfaces teristics of the solid. Now it
or resorting to the assumption of textile fabrics. should be apparent that, for
of surface contamination. It 4s A convenient and dependable experi- identically the same increase in
only necessary to apply the fact mental procedure for measuring the wet-
the free liquid area at the upper
that, within a measured unit surface of the drop, a greater
area on a rough surface, there is ting of different solids by the same liquid amount of actual surface is
actually more surface, and in is described, and measurements on a com- wetted under it if the surface
that sense therefore a greater prehensive list of water-repelling sub- of the solid is rough than if it
intensity of surface energy, than stances are presented. It is shown how is smooth. Consequently, for
in the same measured unit area the process involving the rough
on a smooth surface. That this
this method can be used to evaluate the
surface, there is a greater net
simple fact, while it can have no surface effect of aqueous waterproofing energy decrease to induce spread-
effect upon the specific surface emulsions as well as nonaqueous water- ing, and the rough surface is
energy values, does necessarily proofing solutions. wetted the more rapidly.
involve a proportional change The same reasoning applies
in the wetting characteristics for a water-repellent surface,
of the solid, will appear from the in which case the dry interface
following brief consideration of the fundamental principles of has the lower specific energy. The drop will then spon-
wetting action. taneously assume a more spherical form. Again, for an
identical change in the shape of the drop, and therefore in the
Theory of Wetting Action at Solid Surfaces area and total energy content of the free liquid surface, there
The physico-chemical principles underlying wetting action will be more actual surface involved in the change at the
are to be found in standard texts (2, 12, 20) and have been solid-liquid interface if the surface is rough than if it is
recently reviewed in papers dealing with scientific and tech- smooth. The net energy decrease will thus be greater for
nical problems in many different fields (4-7, 11, IS, Ilf, the rougher surface. Here the process considered is the
16-19, 21, 22). reverse of wetting, and the rough solid is therefore the more
Whenever a process involves the wetting of a solid by a strongly water-repellent.
liquid, three different interfacial boundary surfaces—in the In either case the effect of a roughened surface is to magnify
present instance, solid-liquid, solid-air, and liquid-air—are the wetting properties of the solid. A solid substance with a
involved. Wetting replaces an area of the solid-air interface positive wetting tendency will wet the more readily, the
by an equal area of solid-liquid interface and is generally also rougher its surface. If the smooth surface is water-repelling,
accompanied by an extension of the liquid-air interface. the roughened surface will be more strongly so.
These surface relations vary with the conditions of the Because forces are more easily visualized than energy
problem and may change progressively as wetting proceeds. values, it is conventional, in the analysis of wetting problems,
As each interface has its own specific surface energy content, to define force concepts (the interfacial surface tensions) as
wetting, with its accompanying change in the extent of each numerically equal to the characteristic interfacial specific
interface, results in a net decrease or increase in total surface energy values, and to deal with these forces as vector quanti-
energy. Wetting is thus a thermodynamic process, and the ties constant in magnitude and variable in direction. It is
magnitude of the free energy change involved determines in this translation from energies to forces that the importance
whether or not wetting will proceed spontaneously, at what of the physical condition of solid surfaces is likely to be ob-
rate and how far it can progress against the external forces scured. For when energy values, in dyne centimeters per
that may be brought into play to resist it, or, alternately, how square centimeter, are replaced by forces expressed in dynes
large an external force may be needed to overcome the per centimeter length, it becomes important to bear in mind
initial resistance to wetting. the fact that the ends of this centimeter length are actually a
Consider a drop of water resting on a horizontal solid sur- centimeter apart in space only if the surface involved is per-
face. The specific energy content of the solid interface will, fectly smooth.
in general, be different for the wetted area under the drop than We must, then, recognize a distinction between the total
990 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 28, NO. 8

or “actual surface” of an interface and what might be called A =

Si cos
its superficial or “geometric surface”; the latter is the surface
In this presentation the three forces, Si, Sn, and S2, must all
as measured in the plane of the interface. Where perfect be considered to act upon the same length of the intersection
smoothness is an acceptable assumption, as at liquid-liquid
of the boundary surfaces—that is, between a and b.
or liquid-gas interfaces, actual surface and geometric surface
The lower diagrams of Figure 1 represent the way in
are identical, but at the surface of any real solid the actual
which the situation changes if the surface is roughened. The
surface will be greater than the geometric surface because of
surface roughness. This surface ratio will be here termed the specific interfacial energy at the solid surface is concentrated
within a smaller measured area, efgh. The solid-liquid and
“roughness factor” and designated by r: solid-air interfacial forces effective along the periphery from
actual surface a to 6 are therefore magnified by the same factor, r, by which
r =
roughness factor the surface contained within area abed has been increased.
geometric surface
But the liquid-air interfacial force effective between a and b
By definition, surface tensions, like specific energy values,
are related to one unit of actual surface. But when water remains, as before, the surface tension S2. It must, therefore,
act at a greater angle (as shown) if it is to balance the increased
spreads over the surface of a real solid, the forces that oppose resistance which the solid surface now opposes to the wetting
each other along a given length of the advancing periphery
of the wetted area are proportional in magnitude, not to process.
the surface tensions of the respective interfaces but to their By an exactly similar analysis, if the solid has a positive
total energies per unit of geometric surface. This must be wetting tendency and Si is therefore greater than S]2, the
true if surface tensions themselves are characteristic proper- equilibrium contact angle, , would be less than 90°, as would
also the angle '; but since ’ has the greater cosine, it would
ties, unaltered by surface roughness. For if a solid, M, of in this case be the smaller angle.
surface tension x and water-solid interfacial tension y presents
a surface so rough that its actual surface per unit geometric Effective Adhesion Tension
surface is doubled, then its energy content per unit geometric
surface must also be doubled. That surface can then be no Apparently, then, the second equation of the familiar
different in wetting characteristics from the smooth surface expression,
of a solid, N, of surface tension 2x and water-solid interfacial A =
Si —

iSi2 =
S2 cos

tension 2y. In the latter case the surface forces in vector can apply only w’here all surfaces are perfectly smooth. For
relation with the surface tension of the liquid at the periphery any real solid the cosine of the equilibrium contact angle,
of the wetted area are equal to 2x and 2y; and so they must
multiplied by the surface tension of the liquid, measures
be also for the roughened surface of solid M. not the adhesion tension A, but the product rA. We should
This point is illustrated in the diagrams. The upper left- therefore write:
hand sketch of Figure 1 presents a plan view of the solid
rA r(Si
=
Sn) S¡ cos
—
=

surface. Line mn is a segment of the periphery of the wetted

area advancing from left to right. The solid surface is here This expression is of general validity because for smooth
considered to be ideally smooth, and consequently the surfaces, r is equal to 1.
energy content of a measured unit area, abed, will be exactly The product rA may be termed the “effective adhesion
the specific energy of the interface. Its values before and tension”; it is the value always measured experimentally.
after wetting are represented by force vectors Si and Sn Unlike the adhesion tension, it does not have a fixed repro-
which are considered to act on unit length ab of the periphery. ducible value dependent solely upon the chemical composition
Their vector sum, Si —

Sn, defines the adhesion tension, A, of the three contiguous phases. From factor r it derives a dis-
its negative value indicating its direction and marking it as position to vary widely and to be extremely difficult to control.
a resistance to wetting. Bartell and Smith (8), discussing the activation of carbons
The upper right-hand sketch of Figure 1 is the customary by heat treatment, point out that the change in surface
diagram of the equilibrium relation between surface tension energy and adhesion tension may result from (1) a difference
Si of the liquid, the contact angle , and adhesion tension A, of crystal structure, (2) a difference in the amount of adsorbed
as given in the equation: impurities, and (3) the formation of a highly roughened or
pitted surface. In the revised formulation here proposed,
a change in crystal structure is probably to be considered a
change in A itself, a new form of matter having appeared.
At the same time, it is to be recognized that, for a single
crystal, the surface energy will be different on different faces
(Iff, 20). Adsorbed impurities must reduce the total exposed
surface and effect a corresponding change in surface energy,
modified by the energy contributed by the exposed surface of
the impurity. Regarding the effect of a roughened surface
Bartell and Smith say: “It is conceivable that the interfacial
tension of a highly pitted or highly roughened surface would
be slightly different from that of a plane surface of the same
solid.” More recently, however, Bartell and Hatch (7) pref-
ace a report on the wetting characteristics of galena with
this statement: “Recent work has shown that the free sur-
face energy of a solid, hence its wetting characteristics, may
be altered much more easily than had previously been sup-
posed.” The experience accumulated in the course of the
present research, extending over the past two years, amply
supports the opinion of these investigators that the exact
surface condition of the solid is a highly important factor
(Above) Solid surface smooth. (Below} Solid surface rough. in determining wetting properties.
AUGUST, 1936 INDUSTRIAL AND ENGINEERING CHEMISTRY 991

Data recently published by Lee (17) on adhesion

in relation to bituminous road materials are worthy
of note in this connection. Lee placed drops of road
tars on highly polished glass and stone surfaces un-
der water and calculated interfacial tensions and
contact angles from the dimensions of the drops
after long immersion. He found that differences
due to various degrees of roughness of the solid sur-
face were much greater than any differences due to
the nature of the materials.
Lee’s data on the effect of the degree of polish of
the solid surface are reproduced in Table I. From
his values of cos a, which corresponds to —cos as
conventionally represented, the values of and of r

given in the table were calculated, r being taken as

1.0 for the highly polished surface. Values of r for
the roughened surfaces vary from 1.22. for a fair
polish, to as high as 2.24.
Concerning these measurements Lee says;
These results show that the binder has much more
difficulty in wetting a rough stone surface which is al-
ready in contact with water than in wetting a smooth
surface. In addition to the frictional effect of the
rough surface, water is presumably entrapped in the
minute crevices of a rough surface and prevents the
tar from wetting the solid. A striking example of this
was found in the case of a limestone. A drop of high- Figure 2. Tilting Plate Apparatus for Contact Angle
aromatic tar was introduced under water onto a flat Measurements
surface of this material having a ground finish. After
remaining in position for a day, no contact had taken place be- angle to 147° and greatly improve the effectiveness of this
tween the limestone and the tar, and, on tilting the stone, the
wax as a water-repelling agent.
drop traveled across the surface of the stone without leaving a
stain. Highly polished limestone, however, was wetted as easily Factor r further accounts for the fact that many substances
as granite. show excellent water-repelling properties on textile fibers
when they are but slightly effective on smooth surfaces. It
The value of cos a that Lee gives for this high-aromatic therefore widens the field of choice for textile proofing com-
tar on highly polished limestone under water is 0.835. It pounds. It means also that the success of a spotproofing
requires a roughness factor of only 1.2 to increase this value treatment is determined by the physical characteristics of the
to unity. The interfacial contact angle would thus reach total deposit, as actually laid down on the fabric, quite as
180°. For any roughness factor beyond this, the effective much as by its chemical composition.
adhesion tension would have a negative value, a resistance
to wetting, greater than the whole of the tar-water interfacial Experimental Procedure
tension. Stated otherwise, in order to effect the smallest The tilting plate method of measuring contact angles was
conceivable area of contact between the ball of tar and the apparently first described by Huntington (15) who used it
solid, more energy would be required to replace the limestone- to measure contact angles against cleavage surfaces of blende
water interface by limestone-tar interface than could be and galena in studying the flotation of sulfide minerals.1 In
recovered from the tar-water interface destroyed. Unless different forms it has since been employed by a number of
sufficient additional energy could be derived from the investigators (3, 9, 11, 13, 21, 22).
weight of the drop or were otherwise applied, wetting could The principle of the method may be stated briefly. If a
not occur. Factor r thus offers a simple explanation of the flat plate is dipped into a liquid, the surface of the liquid as
behavior observed by Lee. The cushioning of the drop by it approaches the plate will curve upward or downward to
a film of water then appears as a consequence of the increased establish the angle of contact required by the several inter-
resistance to wetting, rather than as its cause. facial surface tensions. If the liquid is water and the plate
is coated with a water-repellent substance, the con-
tact angle will be greater than 90° and, when the
Table I. Effect of Degree of Polish of Solid Surface on
Wetting Properties of Tar in the Presence of Water (17) plate is vertical, the water surface will curve down-
ward on either side of the plate. As the plate is
Nature of Solid Degree of Polish Tar Cos —
r 6 tilted, the curvatures will change to maintain the
Degrees contact angle, the curvature of the water surface on
Plate glass High polish Low-aromatic 0.289 1.00 106.8 the under side of the plate becoming less and less
Ground surface Low-aromatic 0.647 2.24 130.3
Plate glass High polish High-aromatic 0.617 1.00 138.2 and finally disappearing altogether. At this point,
Ground surface High-aromatic 0.889 1.44 152.8 where the water surface is flat and horizontal right
Scottish whinstone High polish Low-aromatic 0.335 1.00 109.6
Fair polish Low-aromatic 0.409 1.22 114.2 up to the line of contact with the plate, the angle to
Ground surface Low-aromatic 0.573 1.71 125.0 which the plate is tilted measures the contact angle.
If the plate is tilted beyond this position, the water
surface on the under side of the plate takes the
The influence of a distinct crystal habit in a waxlike material opposite curvature, rising as it meets the plate.
on the excellence of its waterproofing effect is exactly similar.
It is interesting to note that Huntington reported widely different con-
Thus, if a wax of fair water-repellency exhibits a contact
1

tact angles for the same mineral, depending on the direction of cleavage, a
angle of 115° when the measurement is made on a perfectly result ascribable to different intensities of surface energy on different planes
smooth surface, a roughness factor of 2.0 would increase the of the crystal lattice.
992 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 28, NO. 8
The apparatus developed for the present use is shown in of the water surface is an integrated effect apparent for a distance
of 1 cm. or more away from the plate.
Figure 2:
About half the length of a microscope slide, cut to 0.5-inch For experimental work on finishes, this method has a
width, is coated with the solid to be tested. The liquid is held in distinct advantage over hydrostatic pressure tests on proofed
a cell with ends and bottom of brass, the front and back sides con-
pieces of standard fabric, because the numerical result
sisting of microscope slides joined in place with balsam cement. obtained is not descriptive of only the few least resistant
The cell is supported on a mechanical stage that permits it to be
moved horizontally or raised and lowered smoothly and steadily. openings of the thousands included in the area under test.
A petrographic microscope is used in horizontal position, the When using fibrous materials on the plate, however, the sub-
cell being independently supported between the microscope tube
and the revolving circular stage. The slide is clamped to the merged area becomes wet through, more or less rapidly, and
while several measurements can usually be made at a single
revolving stage in such position that the coated end dips into the
water in the cell and its plane surfaces are parallel to the line of immersion, the readings cannot then be checked over the
sight. The edge of the plate is thus presented to the observer. same area without drying. With the bonded metal-paper
By revolving the microscope stage, the plate is rotated about the sheets, strips 10 to 15 centimeters long can be employed
line of sight as a center. Its angular position at any time can be
read from the circular scale and vernier on the microscope stage. and tested at either end; also, the wet portions can be cut
The plate holder is provided with a screw adjustment for center- away with metal shears to obtain further check readings.
ing the slide in the field. The method gives results accurate to within a few degrees.
It can be used to measure angles up to and slightly beyond
170°, but it is difficult to take readings that close to the
horizontal. Bearing in mind that the water repellency is
proportional not to the contact angle but to its cosine, and
further that 180° corresponds to the maximum useful value

Figure 3. Change of Curvatures of Water

Surfaces with Rotation of Plate Table II. Contact Angle Measurements on Paraffin
Wax
It has been found satisfactory to use the microscope without Date Plate Differ-
-

tA -
either objective or eyepiece. Viewed in this manner, the appear- /—Heading— (D/2)
(1934) No. Temp. Left Right + 90 72 cos 9
ance of the meniscus and the way it changes as the plate is ro- 0
c. -Degrees- Dynes/cm
tated are shown in Figure 3. With proper illumination, a fine 1 159.3 202.3 43.0 111.5
bright line appears near the bottom of the meniscus that is quite 159.0
156.9
204.3
203.6
45.3
46.7
112.6
113.3
sensitive to changes in the position of the plate. By adjusting 156.3 203.6 47.3 113. t
the forward edge of the plate to within 1 mm. of the cell wall, the 112.8 -27.9
Average
water surface at that point is thrown upward and out of the way 1 19 155.7 201.4 45.7 112.8
so as not to interfere with observation of the meniscus beyond. 156.5 202.7 46.2 113.1
The plates may be coated by dipping into the melted sample at 156.4 201.4 45.0 112.5
a suitably elevated temperature or by any other convenient 155.5 201.6 46.1 113.0
means. In cases where the solid will not adhere to glass, or the Average 112.8 -27.9
30 154.5 199.9 45.4 112.7
coating loosens and peels off when submerged in water, brass
1
154,3 201.8 47.5 113.5
strips of similar dimensions have been used. If necessary, several 154.6 201.3 46.7 113.4
small holes can be drilled through the metal near the bottom 153.7 199.9 46.1 113.1
edge and others well above the water level so that the coatings on Average 113.2 -28.4
the opposite faces of the plate will be tied together by the coating 2 30 159.5 197.7 38.2 109.1
material itself and thus securely anchored to the plate. If suf- 159.5 199.5 40.0 110.0
159.6 197.6 38.0 109.0
ficiently rigid, a plate molded of the material to be tested can be 158.0 198.4 40.4 110.1
used. Tests on emulsions, to be applied from dilute baths, have Average 109.5 -24.0
been made possible by using half-inch strips cut from sheets fabri- 3 30.5 157.3 198.9 41.6 110.8
cated by bonding heavy steel-plate paper of pure rag stock to 159.0 197.0 38.0 109.0
both sides of a 28-gage steel sheet by means of a metallic adhe- 156.3 197.4 41.1 110.6
157.7 198.0 40.3 110.2
sive {10). These sheets can be dipped, run through squeeze rolls, Average 110.2 -24.9
and ironed dry exactly as a textile fabric would be; but being
rigid, they can be used for the contact angle measurements.
Finally, if desired, measurements can be made directly on strips Table III. Contact Angle Measurements on Waxes and
of proofed textile fabric backed by a waterproof adhesive tape Waxlike Products
and mounted on metal plates.
Exact leveling of the apparatus is made unnecessary by taking /-Contact Angle--~ Effective
Plate Plate Adhesion
two successive readings, the plate tilting in the one case to the Temp. 1 2 Average Tension
left, in the other to the right. Half the difference then gives the e
C. -— -Degrees- Dynes/cm.
angle from the vertical, and this value plus 90° gives the contact Paraffin wax, amorphous 31 108.7 111.8 110.2 -24.9
angle. Usually the operation is repeated a number of times for Ozokerite, yellow 29 110.1
113.3
109.9
113.0
110.0
113.2
-24.6
-28.4
each determination. Ozokerite, bleached 29
Bees wax 30 106.8 108.3 107.6 -21.8
For concordant results, all settings must be made while the cell Carnauba wax, crude 28 123.7 122.0 122.8 -39.0
is very slowly raised. This procedure is essential, for there is Carnauba wax, refined 27 124.8 125.8 125.3 -41.6
Candelilla wax 110.2 112.8 111.5 -26.4
apparently what corresponds to a frictional resistance to move-
29
Spermaceti 26 111.9 108.4 110.2 -24.9
ment of the liquid-air interface across the surface of the solid. Japan wax 27 102.7 103.1 102.9 -16.1
Thus Ablett {1), who used a horizontal cylinder coated with paraf- Montan wax, crude 140.0 139.6 139.8 -55.0
fin and dipping into water, found definite maximum and mini- Commercial synthetic waxes:
112.3 112.2 -27.2
A 25 112.1
mum contact angles, depending on the direction of rotation of B 28 103.1 101.6 102.4 -15.5
the cylinder, and observed that these angles were equidistant from C 26 107.2 107.6 107.4 -21.5
the value read with the cylinder stationary. Static readings, D 119.1 121.1 120.1 -36.1
-16.7
E 101.5 105.4 103.4
however, are most unreliable. The liquid may rest at any angle F 120.4 118.2 119.3 -25.2
between two extremes {2). Moreover, in the study of water- G 108.0 108.6 108.3 -22.1
proofing we are interested in the total force resisting wetting; H
I
28
26
131.4
124.4
131.4
122.6
131.4
123.5
-47.6
-39.7
and since this frictional force, if it may be called such, acts to as- J 28 129.9 130.8 130.4 -46.7
sist the adhesion tension in opposing wetting, it is the maximum K 25 107.7 106.8 107.2 -21.3
contact angle that becomes the important criterion. L 26 123.6 124.2
107.6
123.9
107.8
-40.2
-22.0
M 28 108.0
As the water level is raised, minute surface irregularities on the N 26 107.9 105.8 106.8 -20.8
plate may cause the very tip of the water line to vibrate or ad- O 26 112.5 112.6 112.6 -27.7
vance with an irregular motion. The individual threads of a P 27 118.4 118.5 118.4
120.6
-34.2
-36.7
25 120.4 120.9
mounted piece of fabric have the same effect. This action does Q
not confuse the end point, however, because the main curvature
AUGUST, 1936 INDUSTRIAL AND ENGINEERING CHEMISTRY 993

of the effective adhesion tension for waterproofing purposes,

the exact values of readings beyond 170° have very little Table VI. Metallic Soaps on Paper Surface, from Carbon
Tetrachloride Solution
significance. z-Contact Angle-->
Concn. of Initial After
Experimental Results Soln. ironing
Grams/liter --D egrees
Table II gives data obtained with ordinary crystalline 4.8 128.4 164.3
Mg stearate
paraffin wax and illustrates the degree of consistency in the Ca stearate 7.5
2.4
113.6
118.9
128.3
150.2
Ba stearate
contact angle readings. The plates were of glass or metal Th stearate 4.0 108.4 147.4
and were coated by dipping. Readings taken at different times
on the same plate are likely to be in better agreement than
Table VII. Metallic Soaps on Paper Surface, from Hot
readings on duplicate plates. The results also show that a Isobutyl Alcohol Solution
considerable variation in room temperature had no great Effective
effect on the readings z-Contact Angle-- Adhesion
Plate 1 Plate 2 Av. Tension
Table III presents the average readings on each of duplicate Degrees-< Dynes/cm.
plates of other waxes and waxlike products. In a few cases Mg stearate 145..9 140..6 143.,2 -57. .6
Sn stearate 151..6 149 1 150..4 -62 .6
initial transient readings were obtained, higher than the Ba stearate 152..5
.

157. 2 154..8 -65 .2

final constant values. Thus Japan wax gave initial read- Th stearate 158..8 159. 4 159. 1
163 6
-67 .2
-69. 1
Cd stearate 162..0 165. 2
ings of 107° to 111° C., which dropped to relatively con- Zn stearate 162. 9 170. 1 166. 5 -70. ,0
A1 stearate 169. 4 170 .8 170. 1 -70. 9
stant values at 103° and to still lower values around 99.5°
after soaking the slides for 15 minutes in water. Carnauba
wax gave initial transient values around 130° and constant
values at 125° C. In the case of the wax listed as commercial of the metallic soaps in chlorasol (a mixture of three parts
synthetic wax K, which gave initial transient readings at ethylene dichloride and one part carbon tetrachloride). These
115° and final values at 107° C., the change was due to solu- cards were then air-dried overnight, cut into strips, and tested
tion of the sample or some constituent thereof in the water, at a number of different points. The number of areas tested
inasmuch as the same plate again gave high initial readings and the extent of variation of the readings are indicated.
on changing the water in the cell. The two more dilute solutions were applied five times with
Measurements recorded on gums and certain other materials intermediate air-drying.
are summarized in Table IV. As indicated, some of these With carbon tetrachloride as the solvent, the initial values
materials were deposited from solvents. obtained were lower but were increased in every case by
pressing under a hot iron. The data are shown
in Table VI. Results here for calcium stearate
Table IV. Contact Angle Measurements on Miscellaneous are comparatively poor. In a similar test, using
Materials a solution containing 5.2 grams per liter in chlo-
z—Contact Angle—< Effective rasol, calcium stearate gave final values of 147.1°
Plate Plate Aver- Adhesion
Solvent 1 2 age Tension and 147.9°. Tin stearate prepared from stan-
•Degrees- Dynes/cm. nous chloride and sodium stearate (the latter
Cellulose acetate (Molded strips) 64.0 64.8 64.4 31.1
Cellulose acetate Acetone 63.8 63.7 63.8 31.8 made from a commercial triple-pressed distilled
Raw rubber Benzene 59.5 55.5 57.5 38.7 stearic acid) was found sufficiently soluble in boil-
Synthetic resin (Coated paper) 86.2 4.8
Gum tragacanta Hot water 109.7 1Ó6.1 107.9 -22.1 ing isobutyl alcohol for coating on glass plates.
Gum arabio Hot water 97.4 100.1 98.8 -11.0
Gum copal Ethyl alcohol 103.6 106.0 104.8 -18.4 This coating gave initial values below 120° after
Gum guaiac
Gum kauri
Ethyl alcohol
Isobut.vl alcohol
64.3
87.0
67.4
79.1
65.8
83.3
-29.5
8.4 air-drying overnight, but the values increased
Gum elemi Isobutvl alcohol 63.4 66.9 65.2 30.2 after contact with water, check readings near the
Gum dammar Carbon tetrachloride 58.2 62.8 60.5 35.4
Rosin Ethyl alcohol 64.4 69.1 66.8 28.4 end of the plate being higher than readings taken
Ester gum Isobutyl alcohol 63.9 64.8 64.4 31.1 at points where the surface had not been previ-
Stearyl alcohol 49.2 51.0 50.1 46.2 °
Stearone 134.4 131.9 133.1 -49.2 ously immersed. Values approximating 140 were
Monohydroxystearone 119.4 119.0 119.2 -35.1
thus without sufficient
Dihydroxystearone 113.8 113.6 113.7 -28.9 obtained. Light ironing,
Erucone 115.4 114.8 115.1 -30.5 heat to impair the coating, which had a tendency
Stearone 90, rosin 10 106.2 106.2 106.2 -20.1
Stearone 90, paraffin 10 124.6 122.0 123.3 -39.5 to flake off on cooling, raised the contact angle
Stearone 90, synthetic wax 10 145.8 144.3 145.0 -59.0
Stearone 90, mixed ketones 10 138.7 141.5 140.1 -55.2 beyond 150° in every case, giving values of 151.5°,
Stearone 50, shellac wax 50 None 155.4 154.8 155.1 -65.3
152.4°, and 159.0° on three different plates.
The results of Table VII were obtained by
dipping the paper-surfaced plates into solutions
The most varied results were obtained with metallic soaps. in hot isobutyl alcohol and drying in a desiccator overnight
This fact will be apparent on inspection of Tables V, VI, and before testing. Subsequent pressing with a hot iron gave no
VII, which give the results found on metal-bonded paper improvement in these results.
surfaces. Of particular interest are a number of different values ob-
tained for aluminum stearate. Deposited from solution on
Table V. Metallic Soaps on Paper Surface, from Chlora- paper surfaces, it afforded results shown in Tables V and VII,
sol Solution varying rather widely. Similarly deposited on glass, it gave
No. of values nearly as high, averaging 150.3°, 159.4°, and 151.2°
Concn. of Contact Readings Av.
Soln. Angle Averaged Deviation on three plates. But when molded into half-inch strips by
Grams/liter
A1 palmitate 25
Degrees
154.8 14
Degrees
1.1
hydraulic pressure at 5000 pounds per square inch (352 kg.
A1stearate 25 157.6 6 3.9 persq. cm.), it gave consistent readings averaging only 113.4°
Mg stearate 5.6 140.6 6 0.9 where the plate was smooth, waxy, and transparent, and
A1 palmitate 2.5 148.8 6 1.8
119.2° where it was white, chalky, and opaque.
Most of the waxes gave the same values on glass wiiether
In the experiments of Table V, test cards, 10 X 2.5 inches deposited from a solvent or from the melted wax, but there
(25 X 6.4 cm.), w^ere treated on squeeze rolls with solutions were a few· notable exceptions. All gave high values when
994 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 28. NO. 8

deposited paper surfaces. Some examples are presented

on 2. An improved apparatus for comparing the wetting
in Table VIII. Residual traces of nonaqueous solvents were characteristics of solid surfaces is described. The method
eliminated as a cause of this behavior by the fact that it was applies the tilting plate principle for the direct measurement
also observed with ether after long aeration and with absolute of contact angles. This method is capable of accurate and
alcohol. Those waxes that gave higher values on glass, when reproducible results provided the readings are taken dynami-
deposited from a solvent, reverted to the lower values if the cally. It should have a wide range of applicability.
plates were placed in an oven for a few minutes to fuse the 3. Contact angle measurements on a number of waxes,
coating. There was no appreciable alteration in the ap- metallic soaps, gums, and certain related compounds are
pearance of the deposit. reported.
4. A technic has been devised for comparing the water
Table VIII. Effect of Method of Preparing Plates on repellency imparted by dilute waterproofing baths to paper
Contact Angle Measurements of Waxes and textile surfaces. For this purpose, contact angle measure-
From Melted Sample ments have the advantage that they are not influenced by
Origi- Same plate the mechanical strength and uniformity of the fabric.
nally retested From CCh Soln.
reptd. after 6 mo. On glass On paper 5. The large amount of surface per unit area of fibrous
Beeswax 108 113.6 125.0 155.2 materials plays a prominent part in the effectiveness of water-
Paraffin 110 110.5 110.7 152.4
Spermaceti 110 113.8 149.6 repelling applications, as does any tendency of the deposit
Carnauba wax 125 129.2 127.3 153.1
Synthetic wax A 112 116.6 164.9 158.0 itself to give granular or microcrystalline, rather than smooth,
Synthetic wax H 131 129.8 131.6 150.4 coatings.
Synthetic wax P 118 123.8 136.2 149.2
Acknowledgment
The research described in this contribution was conducted
The advantages and limitations of contact angle measure- on Mellon Institute’s Industrial Fellowship on Textile Finish-
ments are well illustrated by the comparison, given in Table
ing, which is sustained by the Onyx Oil & Chemical Com-
IX, of contact angle and hydrostatic pressure test results pany, Jersey City, N. J. The author is grateful to this donor
obtained on two different fabrics proofed by identically the for cooperation during the investigation and also for permis-
same treatment and on the same fabric proofed by different sion to publish this paper.
treatments. The contact angle measurements show that the The bonded metal sheets used in the experiments were
two fabrics, after being treated with the same aqueous water-
supplied through the courtesy of A. W. Coffman of Mellon
proofing emulsion, have equally repellent thread surfaces. Institute.
This result is not shown by the hydrostatic pressure method
because of the difference in the construction of the fabrics. Literature Cited
The second preparation applied to the same silk fabric is a (1) Ablett, R., Phil. Mag., 46, 244 (1923).
(2) Adam, N. K., “Physics and Chemistry of Surfaces,” Oxford
nonaqueous solution of waxes capable of proofing the thread Univ. Press, 1930.
surfaces equally well, but it is seen to impart much less (3) Adam, N. K., and Jessop, G., J. Chem. Soc., 127, 1863 (1925).
resistance to the passage of water under pressure. This (4) Baker, C. L., Ind. Eng. Chem., 23, 1025 (1931).
difference is to be explained by effects on thread dimensions (5) Barr, G., Dept. Sci. Ind. Research, 2nd Rept. of Fabrics Coordi-
and air porosity. nating Research Comm., 1930, 113-39.
(6) Bartell, F. E., et al., Colloid Symposium Monographs, 5, 113
(1927); 10,267 (1932); Ind. Eng. Chem., 19, 1277 (1927);
20, 738 (1928); J. Am. Chem. Soc., 56, 2205 (1934); J. Phys.
Table IX. Contact Angle Measurements on Proofed
Chem., 34, 1399 (1930).
Fabrics
(7) Bartell, F. E., and Hatch, G. B., Ibid., 39, 11 (1935).
Contact Angle Hydrostatic Pressure (8) Bartell, F. E., and Smith, C. N., Ind. Eng. Chem., 21, 1102
Fabric Silk Rayon Silk Rayon
Openings/sq. cm. 2700 1600 2700 1600 (1929).
-
Degrees--·. Cm. of water (9) Bosanquet, C. H., and Hartley, H., Phil. Mag., 42, 456 (1921).
Aqueous emulsion 167.8 169.0 17.5 9.5 (10) Coffman, A. W., Chem. & Met. Eng., 39,144 (1932); U. S. Patent
Nonaqueous soln. 169.3 7.4 1,862,332 (June 7, 1932).
(11) English, L. L., Illinois State Nat. Hist. Survey, Bull. 17, Art.
5 (1928).
(12) Freundlich, H., “Colloid and Capillary Chemistry,” tr. by
The hydrostatic pressure tests of Table IX were obtained H. S. Hatfield, London, Methuen & Co., 1926.
with an apparatus essentially that of Barr (5) but with cer- (13) Green, E. L„ J. Phys. Chem.., 33, 921 (1929).
tain improvements in technic to be described in a later paper. (14) Harkins, W. D., Colloid Symposium Monographs, 6, 17 (1928).
(15) Huntington, A. K., Trans. Faraday Soc., 1, 345 (1906).
Summary (16) Kovalevski, I. I., Papier, 38, 139 (1935): Pulp & Paper Mag.
Can., 36, 547 (1935).
1. It is inherent in the fundamental theory of wetting (17) Lee, A. R., J. Soc. Chem. Ind., 55, 23T (1936).
action that the wetting properties of a solid substance should (18) Mack, C., Ind. Eng. Chem., 27, 1500 (1935).
be directly proportional to the roughness of the surface wetted. (19) Nuttall, W. H„ J. Soc. Chem. Ind., 39, 67 (1920).
(20) Rideal, E. K., “Introduction to Surface Chemistry,” 2nd ed.,
This fact does not appear to have been clearly recognized. London, Cambridge Univ. Press, 1930.
Variations in the wetting properties of a solid, when encoun- (21) Stellwaag, F., Z. angew. Entomol., 10, 163 (1924).
tered in experimental data, have usually been attributed to (22) Sulman, H. L., Trans. Inst. Mining Met., 29, 44 (1919).
some form of surface contamination. Received March 27, 1936.