1534 J. J. BIKERMAN Vol.

62

value. However, it has been reported by Smith14
that the width of such crystallites are from 360 to
390 A. The 400 A. length, therefore, does not
seem to be unreasonable. (2) Again, if the present
values of y and B are not far from reality the chains
in the amorphous phase of polyethylene are highly
oriented. Their configurations are much more ex-
tended than the random coil configuration. Thus
the specific volume of the amorphous phase niay be
quite different from the value extrapolated from the
liquid state. This fact also supports the view on
the growth of spherulites that the formation of a
nucleus is induced by the growth of the first crystal-
lite. (3) Equation 3 indicates that for polydis-
persed polymers the degree of crystallinity depends
on the number average molecular weight. The
number average molecular weights of commercial
polyethylenes usually vary within a very narrow
range.16 As a result, the crystallinity is not greatly
affected by the molecular weight based on viscosity
measurements.
Acknowledgment.-The authors are indebted t o
counted in the term dXu,etc. I n order to count each
type of undesirable configurations only once we ar-
rived a t the present form of equation 7. To evalu-
ate c $ ~ , one has to count the configurations contain-
ing groupings of different numbers of x, -x steps,
such as “x, -x”, “x, -x, x”, etc., separately. Let
qhXdenotes the number of configurations containing
the largest grouping of x and -x steps. Then
,
The first part of 41%is the permutation within the x
step grouping and the second part is the permuta-
tion outside this grouping. For the number of con-
figurations & containing the next largest grouping
of x and -x steps, the expression is
n,+ n-. - l)!
[ ( ( n , - l)!n-.!
+ (n, + n-. - l)!
9% = n,! (n-z - l)!l
I

Dr. H. W. McCormick of the Physical Research The first bracket again is the permutation within
Laboratory for his assistance in the centrifugation the x step grouping. The first term in the second
of polymer samples. bracket is the permutation outside the x grouping
and the second term which represents the config-
Appendix urations with another x step adjacent to the x
The Evaluation of Q’.-In the derivation of grouping is subtracted from the first term. Thus
equation 7, c $ ~4,~, , and c $ have ~ the sum of all these @qx, dzX. . . . terms corre-
~ ~ ~ already been c $ is
counted once in the term qjX; similarly 4xyzhas been sponding to all possible numbers of x step groupings.
(14) D. C. Smith, “Molecular Structure of Marlex Polymers,”
All the other 4 terms have to be evaluated similarly.
presented a t ACS meeting, Dallas, 1956. It is quite obvious then when y becomes large 8’ is
(15) H. Smith, J . Poly. Sei., 21, 563 (1956). impossible to evaluate numerically.

USE OF HYSTERESIS OF WETTING FOR MEASURING SURFACE TENSION1

BY J. J. BIKERMAN
Department of Civil and Sanitary Engineering, Massachusetts Institute of Technology, Cambridge 39, Mass.
Recewed June 16, 1968

The hysteresis of wetting observed when a artially wetted vertical slide is moved in and out of a liquid can be used to
calculate the surface tension of the liquid. !&e vertical displacement of the liquid surface h2 - h1 = (2y/gp)’/e(M2:/a -
M l ’ / g ) , if A f 2 = 1-( 1 - F22/L2y2)‘/zand Ilfl = 1 - (I - F12/L2y2)’/2; F , and F2 are the capillary forces on the slide a t
the two positions of the surface, L is the length of the 3-phase boundary, -1 is surface tension, g is acceleration due to gravity,
and p the density of the liquid. The method was tested successfully on water and mercury and is suitable for the latter
liquid.

I. Introduction 11. Theory

I n the course of a study of the hysteresis of wet- A vertical plate suspended in a liquid surface
ting it was noticed that the surface tension y of the (see the continuous curve in Fig. 1) is subject to
liquid can be calculated from the hysteresis data. capillary force3 ~

As a new method of measuring y , the procedure F, = L ~ C O S ~ ~ (1)

seems t o be advantageous for mercury only. Solids
which give a zero contact angle with mercury are
soluble in the latter and thus are apt to contaminate
it (alt,hough the contamination may be insignifi-
cant in favorable instances2); thus the easier
methods of measuring y cannot be used with safety,
and those that can are not more convenient than
the present one. At any rate it has a theoretical
significance and thus deserves a description.
(1) Presented a t the 134th National Meeting, American Chemical
L is the perimeter of the plate (that is the length
of the 3-phase boundary line) and is the contact
angle. If now the level of the liquid be raised t o
the position indicated by the dashes while, be-
cause of the hysteresis of wetting, the 3-phase line
retains its position, the contact angle increases
to e2 and the capillary force diminishes t o
F~ = L~ e2
COS (2)
From F1 and Fz, y can be calculated without meas- ,

Society, Chicago, September, 1958. uring el and e2.

(2) E. A. Owen and A . P. Dufton, I’roc. Pliys. Soc. ( T m d o h ) , 38, (3) E.Q.,J. J. Bikerman, “Suiface Chemistry.” 2nd edition, Aca.
204 (1920). deniic Press, Inc., New York, N. Y . , 1958, p. 9.
Dec., 1958 MEASUREMENT TENSION
OF SURFACE BY HYSTERESIS
OF WETTING 1535

Figure 2 represents the vertical cross-section of

a meniscus at a vertical plane wall (shaded) for
el > 90". The equation of the curve is simply
I
r l R = hgp (3)
if R is the radius of curvature a t a point h cm.
below the Rat portion of the meniscus, g is ac-
celeration due t o gravity, and p is the density of
the liquid minus the density of air. As Fig. 2 Fig. 1.-Vertical cross-section of a meniscus a t a vertical
shows, R d8=ds; ds is the length of the surface plate (shaded). Because of the hysteresis of wetting, the
curve between 8 and 8+d8, and 8 is the variable 3-phase line does not move when the liquid surface is raised
angle between this curve and the vertical. On the from the continuous to the discontinuous curve; el is the
initial and e2 is the resulting contact angle.
other hand, ds = -dh/cos 8, see insert in Fig. 2.
Hence, R = -dh/cos 8 de. Setting this into 3, we
obtain
-y cos e dB = g p h dh (4)
and after integration between 8 = O1 and 8 = go",
that is also between h = hl and h = 0
y (1 - sin e,) = .3gphI2 (5 )
Thus, hl = ( 2 y / g p ) ' / 2 ( 1 - sin O1)'/2. But sin
el = (1 - cos2 8 , ) ' / 2 and cos 8, = F1/Lr from equa-
tion l. Hence

Analogously

and

Fig. 2.-Sketch for calculating the relation between the

Equation 8 rather t,haii equation 6 or 7 must be contact angle (e,) a t a vertical wall (shaded) and the vertical
distance of the 3-phase line from the flat portion of the
used to calculate y because neither 121 nor hz is meniscus.
measured in the method presented here, but only
the difference h2 - hl. Since equation 8 does not of the top plate when screw 5 was turned. The pitch of the
make clear how y varies with the measurable screw was 0.0635 cm. When assembled, screw 5 was in
sleeve 3, and the top plate was resting on cylinder 7.
quantities, the approximation The value of hz - hl was not exactly equal to the displace-
ment shown by scale 4 because of the change in the volume
(9) of the meniscus, caused by this displacement. The correc-
tion term evidently was Ah = ( F s - F 1 ) / g p A cm., A being
is helpful4; the coefficient k , a pure number, varies the area of the vessel; it had to be added to tne difference
between the readings on scale 4. In our experiments, A
only from 1.00 t o 1.25 when F / L y increases from was 60 cm.2 or 19.0 cm.,2 and Ah ranged between 0.001 and
zero t o 0.80 or 8 varies between 37 and 143". 0.003 cm.
The absence of any measurable shift of the 3-phase line
111. Experiments is best proved by measuring F Iand FZat different displace-
The vertical plate was suspended from the beam of an ments of plate 8. Thus, if displacements of 0.06 and 0.09
analytical balance, whose pans previously were removed, and cm. give identical values for y, there certainly was no move-
equilibrated with a weight at the other end of the beam. ment of the air-liquid-solid boundary during the experiment.
Then a dish filled with liquid was raised until the liquid When the displacements were greater (e.g., over 0.18 cm.),
touched the lower edge of the plate. An additional weight the calculated value of y usually was too small, undoubtedly
W1 now was needed to maintain the horizontal position of because the 3-phase boundary did not remain stationary.
the beam; this weight was reckoned positive if added to the A considerable error can be introduced by suspending the
equilibrating load, and negative if hanged a t the side of the slide on a thin thread or a fine hook. The extension of the
plate. Next the liquid level was raised by a definite length, thread or the hook depends on the load; if the latter varies
equal to h2 - hl of equation 8, and again the weight (W2)by the value Fz - F1, the extension also changes, thus
needed for balance was determined. affectingthe true value of h2 - hl. As, in the present series
A convenient device for raising the dish is illustrated in of experiments, h2 - hl was less than 0.1 cm., the change of
Fig. 3. It consists of three separate parts shown one above 0.001 cm. in the thresd or hook length would cause an error
the other in the sketch. The bottom plate (1) carries two of more than 2% in y, see equation 9.
slender columns (2, 2) and a threaded sleeve (3) with a The values of F1 and Fz to be put into (8) or (9) also were
scale (4). The middle part is a screw ( 5 ) provided with a a little different from the weights Wl and W Zneeded for
pointer (6). The top part (8) is a thick plate in which 3 equilibrium. This was caused by buoyancy. The buov-
cylindrical indentations were drilled, one for the screw and ancy correction of Fl was always small and estimated from
two for the guiding columns ( 2 , 2 ) which prevented rotation the downward displacement of platform 8, Fig. 3, required
to withdraw the slide from the liquid. The additional
(4) NOTEADDED IN THE PRooF.-According t o J. Guastslla, J . correction for F2 was gpzua(h2 - hl), if w and 6 are the width
k -
Chim. p h y s . , 51. 688 (1051), B diffrretitisl forni of eqiintiort (9). \\,it11
1 , was derived by It. Mrttaloii, "TIiBsr de Doctorst," Lpon, lYd8.
nnd the thicliness of the slide; for instance, 8'2 - F, was
snittller than W z - W1by 980.4 X 2.5 X 0.005 X 0.067
1536 J. J. BIKERMAN
7-
.4
-2
I I , 1 ' I
Fig. 3.-Instrument used to raise the liquid level by small
measurable increments. See the text for the meaning of the
numbers.
g. cm./sec.a when the slide wa8 2.5 cm. wide and 0.005
cm. thick, and water was raised 0.067 cm.
Although the balance was sensitive to 0.0001 g., readings
could be made to the nearest milligram only because of the
powerful dumping of the system, made clear by equations I
and 2.
To satisfy the requirement for a sturdy suspension and to
have only a small buoyancy correction, the following form of
the vertical plate was selected. A piece (for instance 2.5
X 1.3 X 0.005 cm.) of a thin metal foil was introduced
between the bottom edges of two parallel beryllium-copper
plates (of about 10 X 5 X 0.03 cm.) so that the major part
of the foil (e.g., 2.5 cm. wide and 0.8 cm. in height) remained
outside, and the 3 metal members were glued or soldered
together. Then a hole was drilled near the top edge of the
Be-Cu plates; it served to suspend the plates directly on a
hook of the balance.
A typical experiment with water may now be described.
A strip of silver foil was coated with a polystyrene. Its L
was 5.00 qm. and the buoyancy correction was, as calculated
in a prevlous F g r a p h . 1.3 mg./mm. immersion. After
the contact wit water at 21 O and a relative humidity of 50%
the additional weight W 1was +0.075 g. (and Fl was +0,076
g.); the ositive sign means that the plate was pulled into
wat,er. &hen the dish was raised 0.0635 cm., W Zwas
Vol. 62
-0.015 g. ( L e . , FZ was -0.013 g.); water tended to expel
the plate. The value of hz - hl was 0.635 + (0.076
0.013)/1.00 X 60 = 0.0650 cm.; 1.00 is the density of water
+
and 60 cm.2 was the area of the dish. With these values,
equation 9 affords y = 73.5 g. sec.-Z. The considerable
error presumably was caused by the low precision of the
values of Fl and F z which, as mentioned above, could be
measured only to the nearest 0.001 g.
From the many measurements performed on mercury
menisci it appears that the surface tension of a mercury pool
kept in a closed balance box in air rapidly decreases. The
value of y calculated from the two first measurements on a
particular pool was greater than those derived from the
subsequent readings; and when the greater (absolute)
value of F was determined first, the calculated y was greater
.
than when the measurement of the smaller force preceded
that of the larger one. The following description of a t'ypical
experiment will make these statements clearer.
An aluminum foil, 0.0052 cm. thick and with a perimeter
L of 6.10 em., was brought in contact with mercury in a
dish of 60 cm.2 area a t 24.6-24.7' and a relative humidity
of approximately 30%. The W1was -0.800 g. When the
dish was raised 0.0635 cm., the needed weight increased to
- 1.723 g. The dish was lowered to the initial position and
IB1 was found to be -0 791 g. After another ascent-
descent-ascent the weight was -1.677 + -0.774 +
-1.652 g. Thus the difference W1 - W Zwas 0.923, 0.886
and 0.878 for the three successive pairs of values. When
another sample of mercury was taken from the same bottle
but the slide a t once immersed in it for approximately 0.1
em., the first weight (W,) was -1.721 g.; after lowering the
dish by 0.0635 cm. the weight (W1) was -0.780 g.; thus
the difference Wl - W zwas 0.941 g., that is eater than the
-
greatest value of W1 W zobserved when %?was measured
before W Z .
The above description is summarized in the table in which
arrows indicate the sequence of measurements.
-Wl and -W2 values in g. wt.
-Wi 0.800 0.791
L i" L ;.774L
-Wz 1.723 1.677 1.652 1.721
Vi - W2 0.923 0.886 0.878 0.941
Taking, in this experiment, W1 to be the average of the
two earliest data, that is, equal to -0.790, and analogously
Wzto be -l/2(1.723 + 1.721) = -1.722g.andcorrectingfor
buoyancy, we obtain F1 = -0.780 g. wt. and Fz = -1.696
g. wt. The distance hz - hl was 0.646 cm. Equation 6
then gives y = 464 g , sec. a. This is a reasonable value.
As would be expected, the y of mercury depended on acci;
dental surface contamination more than on the bulk purity of
the sample. There was no definite difference between the y-
values of purest commercial mercury straight from the bottle
and of mercury purified only by spraying through dilute
nitric acid; however, a thorough drying of the latter sample
proved necessary. They was independent of the material of
the slide (aluminum, silver coated with silver sulfide, metal
coated with polystyrene or with polyethylene).
Acknowledgment.-The financial assistance of
the Lord Manufacturing Company of Erie, Penn-
sylvania, is gratefully acknowledged.