988 INDUSTRIAL AND ENGINEERING CHE.\fISTRY VOL. 28, NO.

8
tial volume of the methane in the two-phase region is practi-
T ~ B L111.
E SPECIFIC
HE.4TS .4T CONSTLVT VOLUME O F AIIX- cally a constant and equal to the specific volume of methane
TURES O F M E T H A S E A S D CRUDE O I L
at the same temperature and pressure indicates that there is
Mass Per Cent Methane as Fol1oaa:-
're nip.
7-

0 1 414 2 367 4 323 5 106 6.06%

7
little t'ransfer of heavy components into the gas phase a t the
F. pressures and compositions investigated a t this temperature.
70 0 458a 0.465 0 469 0.491 0.495 0.476 S o 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
'70
0 512
0 526
0.518
0.532
0.531
0.547
0.569
0.589
0.575
0.595
0.562
0.583
Acknowledgment
a Specific heats reported for a specific volume of 0.035 cu. f t . per lb.

Financial assistance for t'his 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-
a t 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 TT-ith Literature Cited
composition for the two-phase portion of the system studied. Kralnes, H. M., and Gaddy, 1 . L., J . .Im. Chem. SOC.,53, 395
'
The points shown are not directly determined experimentally (1931).
but were read from smooth isothermal curves drawn through Sage, B. H., Backus, H. S.,and Lacey, W. N., IND.ENG.CHEX.,
the experimental points on the pressure-volume plane. The 27, 686 (1935).
(3) Sage, B. H., and Lacey, W.N., Ibid.,26, 103 (1934).
agreement of the data with a linear relation b e h e e n specific (4) Ibid.,27, 1484 (1935).
volume and composition is considered to be within the ab- Ibid., 28, 249 (1936).
solute accuracy of the measurements. Figure 8 is a similar Sage, B. H.. and Laces, V.N., Am. Petroleum Inst.. Production
diagram for the region near bubble point on a larger specific Bull. 216 (1935); Oil Weekly, 80, S o . 11, 31 (1936).
volume scale. The curvature of the isobars in the condensed (7) Sage, B. H., Lacey, W. S . , and Schaafsma, J. G., IND.ENG.
C H E U . , 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 BuZl. 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. ESG.
shown in Figure 9. The partial specific volume of the dis- C H E U . , 26, 1218 (1934).
solved methane increases somewhat as the concentration of
methane in the solution is increased. The fact that the par- RECEIVED
.Ipril 13, 1936

RESISTANCE OF SOLID SURFACES

TO WETTING BY WATER
S THE vaterproofing of light-weight
oven or knitted fabrics, it is generally
M Mellon Institute of Industrial Research, Pittsburgh, Pa.
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
will readily pass through if the pressure behind it is sufficient
to break the surface film across the openings. FTater will
penetrate, however, at a much lower pressure or even against
pressure, if it can spread over the surface of the threads from
one face of the cloth to the other. The waterproofing of open
fabrics, therefore, presents the problem of preventing this
spreading of water over the thread surfaces. The desired
effect is attained by depositing on the fabric some chemical
substance that has of itself this ability to resist wetting.
For practical reasons, preparations intended for use in
waterproofing open fabrics commonly consist of emulsions.
In these preparations the active water-repellent agent is
combined with other ingredients whose presence is required
to ensure the desired fluidity and stability in the emulsion,
to provide proper pH control, to increase the permanence
of the proofing effect, and to modify the appearance and feel
imparted to the finished fabric. These auxiliary constituents
may impair, or they may enhance, the effectiveness of the
proofing treatments. The complexity of the problem thus
presented makes it desirable to study carefully the rretting
characteristics of materials selected for this use.
ROBERT N. WENZEL
Alaiiy substances, some n idely different chemically, are
knowi and have been used as water-repelling agents. It is
obvious that they must possess this property in varying de-
gree. Yet no attempt to compare water-proofing agents on
the basis of a quantitative evaluation of this essential char-
acteristic appears t o have been macle. Moreover, few of the
experimental methods that have heretofore been applied in
the investigation of wetting problems are at all adaptable to
the study of the wetting of different solid substances by the
same liquid. The explanation probably lies in the fact that,
in most cases where wetting problems are of industrial im-
portance, the solid itself is not subject to modification or
control. Attention is therefore necessarily confined to the
liquid phase, its wetting power being altered either by the
use of liquids of different polarity or by the introduction of
surface-active solutes.
A survey of possible experimental procedures led finally
to the direct measurement of contact angles by the tilting
plate method as the most satisfactory for comparing a wide
variety of solid materials. When a suitable apparatus and
proper technic had been developed, this method was found
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. I t 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-
example, to the surface tension a direct measure of wettability, but that 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 lems involving the wetting of solid sur- crease which determines the
condition of the surface can be speed of wetting under the im-
simply and adequately explained
faces. I t has an important bearing on 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. Sow it
or rbsorting to the assumption of textile fabrics. should be apparent that, for
of surface contamination. It',s A convenient and dependable experi- identically the same increase in
only necessary to apply the fact the free liquid area at the upper
that, within a measured unit mental procedure for measuring the wet- 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 a t 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, 13, 14, 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 defme 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. I t 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, a t what of the physical condition of solid surfaces is likely t o 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 t o 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
or “actual surface” of a n interface and what might be called
its superficial or “geometric surface”; the latter is the surface
as measured in the plane of the interface. Where perfect
smoothness is an acceptable assumption, as a t liquid-liquid
or liquid-gas interfaces, actual surface and geometric surface
are identical, but at the surface of any real solid the actual
surface will be greater than the geometric surface because of
surface roughness. This surface ratio will be here termed the
“roughness factor” and designated by r:
actual surface
r = roughness factor =
geometric surface
By definition, surface tensions, like specific energy values,
are related to one unit of actual surface. But when water
spreads over the surface of a real solid, the forces that oppose
each other along a given length of the advancing periphery
of the wetted area are proportional in magnitude, not to
the surface tensions of the respective interfaces but to their
total energies per unit of geometric surface. This must be
true if surface tensions themselves are characteristic proper-
ties, unaltered by surface roughness. For if a solid, M , of
surface tension x and water-solid interfacial tension y presents
a surface so rough that its actual surface per unit geometric
surface is doubled, then its energy content per unit geometric
surface must also be doubled. T h a t surface can then be no
different in wetting characteristics from the smooth surface
of a solid, N , of surface tension 2x and water-solid interfacial
tension 2y. In the latter case the surface forces in vector
relation with the surface tension of the liquid a t the periphery
of the wetted area are equal to 22 and 2y; and so they must
be also for the roughened surface of solid M .
This point is illustrated in the diagrams. The upper left-
hand sketch of Figure 1 presents a plan view of the solid
surface. Line mn is a segment of the periphery of the wetted
area advancing from left to right. The solid surface is here
considered to be ideally smooth, and consequently the
energy cohtent of a measured unit area, abcd, will be exactly
the specific energy of the interface. Its values before and
after wetting are represented by force vectors SIand S12
which are considered to act on unit length ab of the periphery.
Their vector sum, S1 - Slz, defines the adhesion tension, A ,
its negative value indicating its direction and marking it as
a resistance to wetting.
The upper right-hand sketch of Figure 1 is the customary
diagram of the equilibrium relation between surface tension
Sz of the liquid, the contact angle 8, and adhesion tension A ,
as given in the equation ;
‘rn s, cose
FIGURE
1 . VECTOR
RELATIONS
OF SURFACE
FORCES
(Aboue) Solid surface smooth. (Below) Solid surface rough.
VOL. 28, NO. 8
A SI COS 8
I n this presentation the three forces, 81,S1s, and Sz,must all
be considered to act upon the same length of the intersection
of the boundary surfaces-that ip, between a and 6.
The lower diagrams of Figure 1 represent the way in
which the situation changes if the surface is roughened. The
specific interfacial energy a t the solid surface is concentrated
within a smaller measured area, efgh. The solid-liquid and
solid-air interfacial forces effective along the periphery from
a to b are therefore magnified by the same factor, r, by which
the surface contained within area abcd has been increased.
But the liquid-air interfacial force effective between a and b
remains, as before, the surface tension Sz. It must, therefore,
act a t a greater angle (as shown) if it is to balance the increased
resistance which the solid surface now opposes to the wetting
process.
By an exactly similar analysis, if the solid has a positive
wetting tendency and S I is therefore greater than S12,the
equilibrium contact angle, 8, would be less than go”, as would
also the angle 8’; but since 8’ has the greater cosine, it would
in this case be the smaller angle.
Effective Adhesion Tension
Apparently, then, the second equation of the familiar
expression,
A = S1 - S I 2 = 8, COS e
can apply only where all surfaces are perfectly smooth. For
any real solid the cosine of the equilibrium contact angle,
multiplied by the surface tension of the liquid, measures
not the adhesion tension A , but the product rA. We should
therefore write:
r A = r(S1 - S12)= S,cos e
This expression is of general validity because for smooth
surfaces, r is equal to 1.
The product rA may be termed the “effective adhesion
tension” ; it is the value always measured experimentally.
Unlike the adhesion tension, it does not have a fixed repro-
ducible value dependent solely upon the chemical composition
of the three contiguous phases. From factor r it derives a dis-
position to vary widely and to be extremely difficult to control.
Bartell and Smith (8), discussing the activation of carbons
by heat treatment, point out that the change in surface
energy and adhesion tension may result from (1) a difference
of crystal structure, (2) a difference in the amount of adsorbed
impurities, and (3) the formation of a highly roughened or
pitted surface. I n 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
(16, $0). 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
in determining wetting properties.
 INDUSTRIAL AND ENGINEERING CHEMISTRY 991
AUGUST, 1936

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. H e 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 cy, which corresponds to -cos 8 as
conventionally represented, the values of 8 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 FIGURE2. TILTISGPLATEAPPARATUS FOR COXTACT ANGLE
was found in the case of a limestone. A drop of high- MEASUREMENTS
aromatic tar was introduced under water onto a flat
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 wett,ed 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 mould be required to replace the limestone- to measure contact angles against cleavage surfaces of blende
mater interface by limestone-tar interface than could be and galena in studying the flotation of sulfide minerals.' 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, 11,22).
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
beharior 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
TABLEI. EFFECT OF DEGREE OF POLISH OF SOLID SURFACE ON plate is vertical, the water surface will curve down-
WETTING PROPERTIES OF TARIN THE PRESENCE OF WATER (27)
ward on either side of the plate. As the plate is
Cos a or tilted, the curvatures will change to maintain the
Nature of Solid Degree of Polish Tar -coss I 0
D~~~~~~ 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 .OO 138,2 and finally disappearing altogether. A t this point,
Ground surface High-aromatic 0.889 1.44 152.8 where the water surface is flat and horizontal right
Soottish whinstone High polish Low-aromatic
Fair polish
Ground surface
Low-aromatic
0.335
0.409
1.00
1.22 iyi:: up to the line of contact with the plate, the angle to
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.
1 It is interesting to note that Huntington reported widely different con-
Thus, if a wax of fair water-repellency exhibits a contact
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 t o 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 ENGINEERIXG-CHEMISTRY
The apparatus developed for the present use is shown in
Figure 2:
About half the length of a microscope slide, cut to 0.5-inch
width, is coated with the solid to be tested. The liquid is held in
a cell with ends and bottom of brass, the front and back sides con-
sisting of microscope slides joined in place with balsam cement.
The cell is supported on a mechanical stage that permits it to be
moved horizontally or raised and lowered smoothly and steadily.
A petrographic microscope is used in horizontal position, the
cell being independently supported between the microscope tube
and the revolving circular stage. The slide is clamped to the
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
sight. The edge of the plate is thus presented to the observer.
By revolving the microsco e stage, the plate is rotated about the
line of sight as a center. fts angular position at any time can be
read from the circular scale and vernier on the microscope stage.
The plate holder is provided with a screw adjustment for center-
ing the slide in the field.
VOL. 28, NO.8
of the water surface is an integrated effect apparent for a distance
of 1 cm. or more away from the plate.
For experimental work on finishes, this method has a
distinct advantage over hydrostatic pressure tests on proofed
pieces of standard fabric, because the numerical result
obtained is not descriptive of only the few least resistant
openings of the thousands included in the area under test.
When using fibrous materials on the plate, however, the sub-
merged area becomes wet through, more or less rapidly, and
while several measurements can usually be made a t a single
immersion, the readings cannot then be checked over the
same area without drying. With the bonded metal-paper
sheets, strips 10 to 15 centimeters long can be employed
and tested a t either end; also, the wet portions can be cut
away with metal shears to obtain further check readings.
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

FIQURE3. CHANGEOF CURVATURES

OF WATER
SURFACES
WITH ROTATION
OF PLATE TABLE11. COXT.4CT ANGLE MEASUREMENTS
ON PARAFFIN
WAX
It has been found satisfactory to use the microscope without Date Plate -Reading-. Differ-
0-
(0/2) rA =
either objective or eyepiece. Viewed in this manner, the appear-
ance of the meniscus and the way it changes as the plate is ro-
(1934) No. Temp. Left Right ence, D + 90 72 COS e
C. ------Degrees------ Dynes/cm .
tated are shown in Figure 3. With proper illumination, a fine June 1 1 .. 159.3 202.3 43.0 111.5
bright line appears near the bottom of the meniscus that is quite 159.0 204.3 45.3 112.6
sensitive to changes in the position of the plate. By adjusting 156.9 203.6 46.7 113.3
156.3 203.6 47.3 113.f
the forward edge of the plate to within 1 mm. of the cell wall, the Average 112.8 -27 0
water surface at that point is thrown upward and out of the way June 2 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. D
coating loosens and peels off when submerged in water, brass June 4 1 30 154.5 199.9 45.4 112.7
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 June 4 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- June 4 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 (f0). 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 111. CONTACT ANGLEMEASUREMENTS
ON WAXES AYD
of proofed textile fabric backed by a waterproof adhesive tspe WAXLIKEPRODUCTS
and mounted on metal plates. -Contact Angle--. Effective
Exact leveling of the apparatus is made unnecessary by taking 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 a C. -Deorees- Dunes/cm.
" ,
angle from the vertical, and this value plus 90' gives the contact Para5n wax, amorphous 31 108.7 111.8 110.2 -24.9
angle. Usually the operation is repeated a number of times for Ozokerite 29 110.1 109.9 110.0 -24.6
-28.4
each determination. Ozokerite: gdk!ed 29 113.3 113.0 113.2
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
-26.4
apparently what corresponds to a frictional resistance to move- Candelilla wax 29 110.2 112.8 111.5
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 (I),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- waxes:
25 112.1
mum contact angles, depending on the direction of rotation of 28 103.1
the cylinder, and observed that these angles were equidistant from 26 107.2
the value read with the cylinder stationary. Static readings, .. 119.1
however, are most unreliable. The liquid may rest at any angle .. 101.5
between two extremes (2). Moreover, in t,he study of water- ..
..
120.4
108.0
proofing we are interested in the total force resisting wetting; 28
26
131.4
124.4
and since this frictional force, if it may be called such, acts to as- I
J 28 129.9
sist the adhesion tension in opposing wetting, it is the maximum K 25 107.7
contact angle that becomes the important criterion. 26
28
123.6
108.0
As the water level is raised, minute surface irregularities on the 26 107.9
plate may cause the very tip of the water line to vibrate or ad- 26 112.6
vance with an irre ular motion. The individual threads of a 27 118.4
25 120.4
mounted piece of fa%ric have the same effect. This action does
not confuse the end point, however, because the main curvature
AUGUST, 1936 INDUSTRIAL ,4ND ENGINEERING CHEMISTRY 993
i
of the effective adhesion tension for waterproofing purposes,
the exact values of readings beyond 170' have very little VI. METALLIC
TABLE FROM CARBON
SOAPS ON PAPERSURFACE,
TETRACHLORIDE SOLUTION
significance.
-Contact Angle--.
Concn. of Initial .4fter
Experimental Results Soh. value ironing
Grams/liter -Degrees-
Table I1 gives data obtained with ordinary crystalline Mg stearate 4.8 128.4 164.3
paraffin wax and illustrates the degree of consistency in the Ca stearate 7.5 113.6 128.3
Ba stearate 2.4 118.9 150.2
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 a t different times P
on the same plate are likely to be in better agreement than
readings on duplicate plates. The results show that a \'IT.
TABLE bkALLIC SoaPs ON PaPER SURFACE,
ISOBUTYL
ALCOHOLSOLUTION
considerable variation in room temperature had no great Effective
effect on the readings -Contact Angle- Adhesion
Plate 1 Plate 2 Av. Tension
Table I11 presents the average readings on each of duplicate -Degrees- Dynes/cm.
plates of other waxes and waxlike products. In a few cases M g 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 Fax gave initial read- Th stearate 158.8 159.4 159.1 -67.2
Cd stearate 162.0 165.2 163.6 -69.1
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 a t 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 a t 125' C. I n 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 a t ethylene dichloride and one part carbon tetrachloride). These
115' and final values a t 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, a t 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
TIBLE Iv. CONT.iCT -4NGLE MEASUREMENTS ON MISCELLANEOCS are comparatively poor. In a similar test, using
MATERIaLS a solution containing 5.2 grams per liter in chlo-
--Contact A n g l e - 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-- Dunea/cm. nous chloride and sodium stearate (the latter
Cellulose acetate
Raw rubber
Acetone
(Molded strips)
Benzene
:::: :::;:::: :;A
59.5 5 5 . 5 57.5 38.7
made from a commercial triple-pressed distilled
stearic acid) was found sufficiently soluble in boil-
Synthetic resin (Coated paper) 86.2 4.8
G u m tragacanttt Hot nater 109.7 106:1 iOi:g -22. I ing isobutyl alcohol for coating on glass plates.
G u m arabic
copal Htohtywater
E l alcohol A:;!; l;f:: 1;:;; This coating gave initial values below 120' after
Gum guaiac E t h y l alcohol 64.3 67.4 65.8 -29.5 air-drying overnight, but the values increased
Gum kauri Isobutyl alcohol 87.0 79.1 83.3 8.4
Gum elemi Isobutyl alcohol 63.4 66.9 65.2 30,2 a.ftercontact with water, check readings near the
Rosin damma:
Gum E t h y l alcohol i!:: gi:: :;:; i;:: end of the plate being higher than readings taken
Ester gum Isobutyl alcohol 63.9 64.8 64.4 31.1 a t points where the surface had not been previ-
Stearyl alcohol None 49.2 51.0 50.1 46.2
134.4 131.9 133,I -49. 2 ously immersed. Values approximating 140'were
Stearone
Monohydroxystearone
Dihydroxystearone
Sone
None ;:::: :::;: ;:::; 1;::; thus obtained. Light ironing, without sufficient
Erucone
Stearone 90, rosin 10
None
None
115.4 114.8 115.1 -30.5
106.2 106.2 106.2 -20.1
heat to impair the coating, which had a tendency
Stearone 90,p a r a 5 n . 10 None 124.6 122.0 123.3 -39.5 to flake off on cooling, raised the contact angle
Stearone 90, synthetic wax 10
mixed ketones 10 Sone ;::,; i:;: E:: beyond 150'in every case, givingvaluesof 151.5',
Stearone 50, shellac wax 50 Xone 155.4 154.8 155.1 -65 3 152.4', and 159.0" on three different plates.
--_ _. The results of Table VI1 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
T ABL E V. METALLIC SOAPSON 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
Concn. of Contact No. of
Readings Av. values nearly as high, averaging 150.3', 159.4', and 151.2'
Soh Angle Averaged Deviation on three plates. But when molded into half-inch strips by
Groms/Ziter Degrees Degreea hydraulic pressure a t 5000 pounds per square inch (352 kg.
AI palmitate 25 154.8 14 1.1 per sq. cm.), it gave consistent readings averaging only 113.4'
A I stearate 25 157.6 6 3.9
Mg stearate
A I palmitate
5.6
2.5
140.6
148.8
6
6
0.9
1.8
where the plate was smooth, waxy, and transparent, and
-~ 119.2' where it was white, chalky, and opaque.
Rlost of the waxes gave the same values on glass whether
In the experiments of Table V, test cards, 10 X 2.5 inches deposited from a solvent or from t'he melted wax, but there
(25 X 6.4 cm.), were 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 on paper surfaces. Some examples are presented 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 wae 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
repellency imparted by dilute waterproofing baths to paper
TABLEVIII. EFFECTO F METHODO F PREPARINQ PLATES ON
CONT.4CT ANQLE MEASUREMENTSO F w.4XES 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
nally retested From CClr S o h .
the mechanical strength and uniformity of the fabric.
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 110 110.5 110.7 162.4
Spermaceti 110 113.8 149.6 repelling applications, as does any tendency of the deposit
Carnauba wax 125 129.2 l27:3 153.1 itself to give granular or microcrystalline, rather than smooth,
Synthetic wax A 112 116.6 164.9 158.0
Synthetjc 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 Coni-
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 hlellon
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 Ablett, R., Phil. Mag., 46,244 (1923).
Adam, N. K., “Physics and Cheniistry 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 Adam, N. K., and Jessop, G., J. Chem. Soc., 127, 1863 (1925).
resistance to the passage of water under pressure. This Baker, C. L., IND.ENQ.CHEM.,23, 1025 (1931).
difference is to be explained by effects on thread dimensions Barr, G., Dept. Sci. Ind. Research, 2nd Rept. of Fabrics Coordi-
nating Research Comm., 1930, 113-39.
and air porosity. Bartell, F. E., et al., Colloid Symposium Monographs, 5, 113
( 1 9 2 7 ) ; 10, 267 (1932); Ih-D. EXQ.CHEM., 19, 1277 (1927);
20,738 (1928); J . A m . Chem. Soc., 56, 2205 (1934); J.P h y s .
TABLEIX. CONTACT
ANGLE MEASUREMENTS
ox PROOFED Chem., 34, 1399 (1930).
FABRICS Bartell, F. E., and Hatch, G. B., Ibid., 39, 11 (1935).
Contact Angle Hydrostatic Pressure Bartell, F. E., and Smith, C. N., IND.ESG. CHEM.,21, 1102
Fabric Silk Rayon Silk Rayon (1929).
Openings/sq. om. 2700 1600 2700 1600
7- Degrees-- C m 01uater Bosanquet, C.H., and Hartley, H., Phil. Mag., 42,456 (1921).
Aqueous emulsion 167.8 169.0 17 5 9 5
Coffman, A. W., Chem. & Met. Eng., 3 9 , 1 4 4 (1932); U.S. Patent
Nonaqueous s o h . 169.3 ... 7.4 , . 1,862,332 (June 7, 1932).
English, L. L., Illinois State Nat. Hist. Survey, Bull. 17, .4rt.
5 (1928).
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 (6) but with cer- Green, E. L., J. Phys. Chem,., 33,921 (1929).
tain improvements in technic to be described in a later paper. Harkins, W. D., Colloid Sumposium Monographs, 6, 17 (1928).
Huntington, A. K., Trans. Faraday Soc., 1, 345 (1906).
Summary Kovalerski, I. I., Papier, 38, 139 (1935): Pulp & Paper Mag.
Can., 36, 547 (1935).
1. It is inherent in the fundamental theory of wetting Lee, A. R., J. Soc. Chem. I n d . , 55, 2 3 T (1936).
action that the wetting properties of a solid substance should Mack, C., IND.ENG.CHEM.,27, 1600 (1935).
Nuttall, W. H., J. Soc. Chem. Ind., 39, 67 (1920).
be directly proportional to the roughness of the surface wetted. 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- Stellwaag, F., 2. angew. Entomol., 10,163 (1924).
tered in experimental data, have usually been attributed to Sulman, H. L., Trans. Znst. Mining Met., 29,4 4 (1919).
some form of surface contamination. RECEIVED
3Iarch 27, 1936.