Mass Transfer (Absorption) Coefficients

Prediction from Data on Heat Transfer and Fluid Friction

T. H. CHILTONAND A. P. COLBURN,E. I. d u Pont de Nemours & Company, Wilmington, Del.

N T H E design of apparatus One of the authors previously suggested that a t r a n s f e r per unit of surface
involving diffusional proc- set of curves proposed .for estimating heat trans- area :
esses, s u c h a s dehumidi-
fication or partial condensation,
fer coeficients, by means of a “heat transfer
evaporation of a liquid into a factor,” (h/cG)( c ~ / k ) ~ could
‘ ~ , also be used for
gas, drying of solids in the initial estimating coeficients for transfer of material
state, absorption of a gas by a by diffusion. It is shown in the present paper
l i q u i d , and rectification, it is that these curves predict aalues of mass transfer The function of the dimen-
n e c e s s a r y to have a means of sionless group ( c p / k ) w a s n o t
estimating the rate of transfer of
coeflcients in close agreement with data for flow included in the original Reynolds
the diffusing component per unit inside of tubes taken f r o m the work of Greene- analogy, although it was recog-
of size of the apparatus con- Walt, that of Sherwood and Gilliland, and some nized by Reynolds himself that
sidered. Relatively few experi- unpublished data of the authors; data for jlow some function of the ratio of vis-
mental data have been obtained across a single tube from the work of Lorisch; and cosity to thermal conductivity
for the vazious types of appara- should b e i n t r o d u c e d . T h e
tus and conditions encountered;
data for jlow over plane surfaces from the work power function employed in the
and owing to the difficulties inci- of Thiesenhusen. equations given is derived from
dent to such studies, the relia- numerous correlations of data on
bility of the results is often open to question. There has, heat transfer in turbulent flow, where it serves to relate these
therefore, been a great need for a convenient method of apply- factors as single-valued functions of the Reynolds number,
ing the well-substantiated correlations from the analogous independent of the properties of the fluid.
processes of fluid friction and heat transfer to test the diffu- As shown in the previous paper ( 2 ) ,Equation 1 (the modi-
sion data available and to permit predictions to be made fied Reynolds analogy) holds for fully turbulent flow inside
where there are no applicable data. It is the purpose of this tubes, and for flow parallel to plane surfaces, but does not
paper to describe such a method and by it to compare apply to streamline tubes or flow across tubes and tube banks.
representative experimental data on diffusional processes with Hence, as indicated in Equations 2 and 3, different symbols
results of fluid friction and heat transfer studies. have been used to represent the friction and heat transfer
The method proposed has its basis in the Reynolds analogy factors.
between heat transfer and fluid friction. Stated in words, Processes in which material is transferred by diffusion are
this analogy postulates that “the ratio of the momentum closely related to heat transfer, since the latter can be con-
lost by skin friction between two sections a differential dis- sidered merely as the diffusion of hot molecules into a region
tance apart to the total momentum of the fluid will be the of cold ones and a corresponding diffusion of cold molecules
same as the ratio of the heat actually supplied by the surface in the reverse direction. Since the mechanism is so similar,
to that which would have been supplied if the whole of the it would be expected that a relationship could be obtained
fluid had been carried up to the surface.” The development for diffusional processes entirely analogous to that for heat
of the present form of the resulting equations has been treated transfer. The diffusional process most nearly similar is rec-
in some detail in a previous paper ( 2 ) . o,
As applied to heat transfer, the equa-
tion reads:
APg
&)
S
= (e)(&> s cp 2’3

(1)
T h e q u a n t i t y o n the left of the OO1

equation has long been found to be a

function of the R e y n o l d s n u m b e r ,
dup/p, and has often been represented
by the symbol, 1/2f. This function
can be expressed not only in terms of
overall pressure drop and ratio of cross
section to surface area, but also in
terms of skin friction per unit surface
area, as: IO im lox) man

-&)
APg 8 R
=2=5f
1
(2) FIGURE PROCESSES
1. TRANSFER IN CONDUITS
- 11 -
Similarly, for heat transfer the ratios Heat transfer: j =
cG
‘’
(s)*’a -
frP
Atm 4L
d (CC) */’

can be expressed not only in terms of transfer: 3 p Kp,l

(G/Mn)
(p%) ‘/a E PEILE
Apm
EC L)(
Po 4L
‘ pkd
l/a

the temperature change but also in

terms of the iilm coefficient of heat Friction: 1/zj
GZ P * GZ 4L
1183
 1184 INDUSTRIAL AND EKGINEERING CHEMISTRY
tification, in which the total number of moles of material
passing through the apparatus remains constant, and dif-
fusion occurs in both directions. For this process the rate
of material transfer, w, can be expressed either in terms of
the change in partial pressure of one of the diffusing compo-
nents or in terms of a mass transfer coefficient, K , in moles
per unit time per unit area per unit partial pressure differ-
ence, as follows:
Rearrangement of the terms of this equation leads to an
(4)
expression involving the ratio of the change in partial pres-
0 0 ,m Im) vlm
FIGURE
2. TRANSFER
PROCESSES ACROSS ST.4GGERED TUBEB A N K S
mres to the mean difference in partial pressures between the
gas mixture and the surface, analogous t o that relating tem-
perature change and temperature difference. An extension
of the Reynolds analogy leads to the expectation that this
ratio
will be the same function of Reynolds number as the corre-
sponding heat transfer factor, and will equal the friction factor
under the same conditions as it does. It is therefore desig-
nated by the same symbol, j, as the heat transfer factor de-
fined by Equation 3.
In Equation 5 a function of the ratio of viscosity to diffu-
sivity has been inserted exactly analogous to that employed
on the (cpllc) group in defining the heat transfer factor. The
latter function has been shown ( 2 ) to give a satisfactory
correlation of heat transfer data over a range of ( c p l k ) values
from 0.7 to 1000; and since it has been shown further that
the Prandtl equation, involving a different function of
( c p i k ) , is not so satisfactory for high values of this group,
the power function of ( p / p k d ) included in the above equa-
tions is now preferred to the theoretical equation proposed
several years ago by one of the present authors ( 1 ) for corre-
lating diffusional data. It is possible that the correct value
of the exponent may not be the same as on the (cp,lk) group
for heat transfer, but it will be necessary to have data cover-
ing a wide range of ( p / p k d ) values to justify any considerable
change in this function.
Vol. 26, No. 11
In other processes, such as absorption, stripping, evapora-
tion of a liquid into a gas, or condensation of a vapor from a
mixture with inert gas, the total number of moles does change
as the gar mixture passes through the apparatus, and also
the diffusion is chiefly, if not wholly, in one direction. The
differential rate of material transfer can then be expressed :
dw = d ( L’
Mmn
= K)
ApdA
stant and making use of the relation M
G, = s(
Carrying out the differentiation, considering S and II con-
,)%n leads
t o the equation:
where p , = n - p
(G,/Mi) = moIar mass velocity of the inert gas
The corresponding mass transfer factor for
this case then becomes:
The quantity pot has been included on both
sides of this equation, since K varies inversely
with pQf, as follows from the Stefan diffusion
equation; and the same function of ( p / p k d ) is
included ar in Equation 5.
When the diffusing vapor is relatively dilute
mcu
throughout the apparatus, and in some other
cases, average values may be used for pa), pol
K , and G, and Equation 8 may be integrated
to give:
()(E)( ;)( 2)’
7 ’3 =
&) &) 2 /3
=3 (9)
When the diffusing component changes greatly in partial
pressure through the apparatus, p,/ will change considerably,
and also G, .V,,,,and sometimes (,u/pkd)2’3, so that K is not
a constant. Furthermore, the true mean driving force,
Ap,, is not in general equal to the logarithmic mean of the
terminal driving forces. In such cases, K , Ap, and w must
be computed at several intermediate values of composition;
then from a plot of l / ( K A p )vs. w, the required surface area is
obtained by a graphical integration, according to the equation:
Or instead of calculating values of K , the integration can
almost as well be made in terms of partial pressures, as shown
by the 1a.t term in Equation 10, since generally varies so
slightly with velocity that an average value can be used sat-
isfactorily.
When, however, the diffusing component is so dilute that
pol, G, and K can be considered substantially constant, and
when the solute follows Henry’s law, or the solution exerts a
negligible vapor pressure over the working range, then the
driving force is equal to the logarithmic mean of the terminal
values, and the required surface area is simply:
It should be emphasized that these equations apply only
to diffusion into or out of the fluid undergoing relative mo-
November, 1934 IN DUSTR IA L AN D E N GI NEER IN G CH EM ISTR Y 1185

evaporation of water into air flowing countercurrent to it in a

falling film tower 1.04 inches in diameter, 67 inches long.
To insure that there would be no water-film resistance to
heat transfer, the inlet water temperature was adjusted ap-
proximately to the vet-bulb temperature of the inlet air so
that the heat for vaporization mould come from the air
stream. Under these conditions the mater temperature did
not change appreciably in passing down the tower, and the
logarithmic mean values of Ap, and At, could be used.
The data are given in Table I and are plotted in Figure 4.
FIGURE3. TRAUSFER PAR~LLE
PROCESSES TOL The velocity employed is the velocity relative to the wall of
PLANE SURF4CES
the tube. 90 consideration was given t o the relative ve-
Friction 1/91 = %
G2 locity with respect to the falling water film; the latter was
Heat tranefer I =
CG
‘’
(dZi3
Xasa transfer j =
(‘Y
( GK/p. qMf m )
~

pkd

’tion, and do not, for example, allow for any liquor-film re-
sistance. 2 5 IOOca

In the previous paper, friction and heat tranqfer factors Y

were determined and compared by means of most of the re-
liable heat transfer data and pressure drop correlations for
three important cases: (1) flow inside of conduits, (2) flow
across single cylinders and tube banks, (3) flow parallel t o
plane surfaces. Plots of curves which were found best to
represent the existing data are given by Figurec, 1, 2, and 3,
respectively, for the cases mentioned.
It was suggested that the j factors from these same curves
could be used to predict mass transfer coefficients by employ-
ing Equations 5 and 9, which are analogous to the corre-
sponding heat transfer equation (Equation 3). Certain
further modifications are necessary in using these charts over
the whole range-for example, in allowing for the effect of
free convection. For flow inside tuber in the viscous re-
gion-i. e., a t Reynolds numbers less than 2300-4 was
found in the heat transfer correlations ( 2 ) that the effect of
..
free convection was amroximated bv the function:
FIGURE3 . V4PORIZ\CIO\ OF LIQ~JIDS IV 4
FALLIYGT O ~ FFILW
~ R ( D 4 ~ 4O F SHERWOOD
4 x 1GILLIL~RD)
estimated to be about 1.5 feet per second, uhereas the gas
velocity ranged much higher. It will be seen that the heat
transfer factors lie generally somewhat above the line, while
those for mass transfer are in substantial agreement with it.
In all of these graphs the line drawn is that taken from the
appropriate general curve, Figure 1, 2 , or 3, whereas the
points represent experimental data.
Extensive data on the evaporation of several liquids into
an air stream in a falling film tower of about the same size
(1.05 inches diameter, 41 .O inches long) have been recently
published by Gilliland and Sherwood ( 5 ) . Their data for
the turbulent region (again on the hacis of velocity relative
to the tube wall) were represented by the equation:

This equation, transformed to the type of coordinates em-

FIGURE4. HE.4T k N D h1.4SS
TRANSFERFACTORS FOR l r A -
PORIZATION OF W A T E R
FALLINGFILMTOWER (DATA
OF AUTHORS)
For mass transfer, the vis-
cosity ratio can be neglected
as being generally equal to
unity. The a p p r o p r i a t e
Grashof group, however, is
a function of density differ-
ence caused by concentra-
IN A tion drop instead of a tem-
perature drop 13); thus :
ployed in the present paper, is represented by the line marked
‘[Sherwood and Gillilsnd” on Figure 5. This line represents
j as defined by ~ (ggml(
$d)
0.66
, while the definition for the
“predicted” line is given by Equation 9. The difference be-
tween the 0.56 and the 0.67 powers of the group (p/Pkd) is,

Gr.lf = (d3p2g A M Ap/pZM,JI) (14)

4.v = (1 + 0.15 G T M ~ ” ) ~ (1 5)

Otherwise it is suggested that the lines given for viscous

flow can be used with the same provisos as for heat transfer-
namely, that the mean partial pressure difference is the arith-
metic mean, and that, for constant equilibrium pressures, DG
5 tow0

asymptotic values of j will be reached a t corresponding values P

Of ( L ; d ) / ( p pkd)’I3. FIGURE6. ABSORPTIONOF WATER BY SULFURIC
ACIDIN A FALLTNG
FILMTOWER( n A T . 4 O F GREENE-
DATA
C O M P A R I S O S I\ ITH E X P E R I M E N T A L WALT)

As mentioned above, the data that can be used to check the
application of these predicted curves to mass transfer proc-
esses are relatively few. An attempt has been made t o cover
those which were regarded as most reliable and n-hich were
reported in sufficient detail.
In an investigation carried out by the authors, both heat
transfer and mass transfer factors were determined for the
for the mixtures considered, less than 10 per cent. If the
original data were correlated by the use of ( p / p k d ) *’3 instead
of the 0.56 power, the result would be to bring the data for
vaporization of water slightly nearer the predicted line, and
those for organic liquids slightly farther away.
The agreement of the viscous flow data of Gilliland and
Sherwood with the “theoretical equation for rodlike flow”
1186 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 26, No. 11
TABLEI. HEATAND MASS TRANSFER FACTORS
FOR VAPORIZATION
OF FLOW
OVER PLANESURFACES
WATERINTO AIR IN A FALLING
FILMTOWER(DATAOF THE AUTHORS)
(Total pressure taken as 1 atm.: p = 0.042 lb./(hr.)(ft.): (cp/k)z’a = 0.83: There have been a number of attempts to
( p / p k d ) z ’ 8 = 0.71) measure the rate of evaporization of liquids
Kun No. 1 2
Air velocity, ft./sec. 3.1 6.0 8.3
3
8.3
4
13.9
5 from flat surfaces, especially the evaporation
Water rate, lb./(hr.)(ft. perimeter) 252 254 254 254 254 of water from pans and from natural reser-
Entering air temp., O C . :
Dry bulb 19.6 19.8 2.0 20.2 20.3 voirs. Since there is no movement of the liquid
Wet. bulb
Exit air temp., O C.:
6.7 6.7 6.7 6.7 6.7 (as there is in a falling film tower), there may
Dry bulb 12.0 12.2 12.0 12.2 12.3 be an appreciable resistance to heat transfer
Wet bulb from the body of the liquid through the quies-
Partial pressure of water vapor, atm.: 10.4 10.2 9.8 9.7 9.6
Inlet air
Outlet air
0.0015
0.0115
0.0015
0.0109
0.0015
0.0106
0.0015
0.0102
0.0015
0.0100
cent film a t the surface in supplying the heat
Entering water temp., e C. 10.5 10.6 10.3 10.2 10.2 of vaporization unless the heat is supplied by
Vapor pressure of inlet water, atm.
Exit water temp., O C .
0.0125
11.0
0.0126
11.0
0.0124
10.8
0.0123
10.6
0.0123
10.5
the gas stream itself. rn the experimentsof
Vapor pressure of outlet water, atm. 0.0129 0.0129 0.0128 0.0126 0.0125 T h i e s e n h u s e n (9) this effect was circum-
--t Pd /IA)t /mA P ~
(P! 2.35 1.87 1.76 1.66 1.58
(ti 1.90 1.82 1.83 1.67 1.69 vented by an ingenious thermocouple just a t
j mass
3, heat transfer
transfer
Reynolds number
:::::;::::::i5
1710
::::ti$ :::::!:
3320 4600 6130 7450
the liquid surface, so that the interface tem-
perature and the corresponding vapor pressure
could be measured, and the mass transfer
and thereby with the empirical heat transfer correlations of coefficient could be determined unaffected by the liquid film
McAdams (8) is considered as affording the same kind of resistance.
basis for the predicted j values for mass transfer a t Reynolds
numbers lower than 2300 as do the data on heat transfer,
after allowing for the effect of natural convection (g).
Data of Greenewalt (6) on the countercurrent absorption
of water vapor from air by 72 per cent sulfuric acid in a
falling film tower, 2 inches in diameter and 27 inches long,
having a Venturi gas entrance, have been plotted on Figure 6.
For all except the 1o.west velocities (where the gas velocity
was lower than the liquid surface velocity) there is good am
Im,
I
2
I I I I IIII I I I ill^
5 0003 2 5 1ooooo
agreement between the observed mass transfer factors and 2.”
the appropriate line from Figure 1. The line used for com- FIGURE8. EVAPORATION
OF WATER FROM PLANE
parison in the viscous region is that chosen for a value SURFACES
(DATAOF THIESENHUSEN)
of [ ( L / d ) / 4 ~=] 10; the value of L/d in the tower used was
13.5 and the value of @M is estimated as being between 1 and 3. Thiesenhusen’s apparatus consisted of an electrically
heated circular vessel a t the bottom of a small wind tunnel,
FLOW
ACROSS TUBES 2.16 X 5.3 inches; the rate of evaporation was measured
a t three air velocities, 1.64, 3.28, and 4.92 feet per second,
Diffusional data for flow a t right angles to tubes are and a t several water temperatures from 52’ to 83” C. The
relatively few. LorisCh (7) obtained a few Points for flow diameter of the circular dish was 5.0 inches, but the average
across tube banks but did not report his original data. The length, called for in the calculation of the Reynolds number,
original data of Lorisch (7) on absorption Of water from a , taken 8s ( ~ / 4 )x 5.0 inches = 3.95 inches. The
L G / ~ was
stream of air flowing &Crossa single cylinder, which he average values of the j factors a t the several temperatures a t
using for the reverse purpose of estimating heat transfer CO- each of the three air velocities used are represented on Figure 8.
efficients, are given h a form such that they may be trans- Individual values varied by a maximum of about 20 per
posed fairly readily to the authors’ coordinates; they are cent, It was shorn in the previous paper (2) that for flow
shown in Figure 7. I n these experiments moist air Was blown over plane surfaces, the heat transfer factors checked closely
across a stick of fused caustic soda, 0.396 inch in diameter, with friction factors, not only in the turbulent but in t h e
5.23 inches long, and the gain in weight of the Caustic gave viscous region as well, The same agreement in the viscous
the amount of water absorbed. The experimental values region is shorn by these vaporization data.
are seen from Figure 7 to lie some 20 to 25 per cent higher
than the line representing heat transfer factors for flow at CONCLUSION
r i g h t angles to-
single cylinders As illustrated by these typical correlations, it is believed
f r o m Figure 2, that mass transfer factors can be estimated with a sufficient
and this is within degree of certainty for design calculations, by analogy with
the limits of de- heat transfer processes, not only for flow inside tubes, but also
v i a t i o n of t h e for flow across tubes and tube banks and flow over plane sur-
heat transfer faces. Such factors, defined by Equation 8, permit predic-
d a t a o n which tions of performance of falling film absorption columns; and
this c u r v e was by the use of Equation 5 the efficiency of wetted wall columns
b a s e d . It i s for distillation can be estimated in advance. The authors
t h e r e f o r e be- hope to present further papers giving a comparison between
FIGURE 7. ABSORPTION OF WATERFROM
lieved t h a t t h e AIR FLOWING ACROSS A SINGLE CYLINDER such predicted values and those actually realized, and out-
previously o b - (DATAOF LORISCH) lining the adaptation of similar methods of correlation to the
performance of packed absorption and distillation columns.
tained lines for
heat transfer factors for flow across both single cylinders and NOMENCLATURE
tube banks will give fairly reliable values for mass transfer
coefficients. An example of the use of these curves in pre- Any set of self consistent units may be used; those of the,
dicting dehumidification coefficients is given in a contemporary foot-pound-hour-” C. system are given for illustration; totaL
paper (4). and partial pressures are, however, expressed in atmospheres..
November, 1534 INDUSTRIAL AND ENGINEEKING CHEMISTRY 1187
A = surface area, sq. ft. U = linear velocity, ft./hr.
G = mass velocity, lb./(hr.)(sq. ft.) W = rate of material transfer, lb. moles/hr.
G , = max. mass velocity (through min. cross section) 11 = total pressure, atm.
G r = Grashof group, ( d 3 p 2 pAt g / p 2 ) P = coefficient of expansion, 1 / O C.
GTM = Grashof group for mass transfer, ( d a p a A M A g / p * M , I I ) P = viscosity, lb./(hr,)(ft.); pr = film viscosity; pa = vis-
K = molar mass transfer coefficient, Ib. moles/$r.) (sq. ft.) cosity in main body of fluid
(atm.) P = density, lb./cu. ft.
L = length, ft. d = free convection factor for heat transfer = (pLg/p,)
M , = mean mol. weight (1 + 0.015 Gr1’3)*
A M = difference in mol. weights between inert and diffusing
components
d .?4 = free convection factor for mass transfer = (1 + 0.015
G%M1’3)3
N = number of rows of tubes
A P = pressure drop, lb./sq. ft.
R = frictional resistance per unit surface area, force units CITED
LITERATURE
Re = Reynolds number, dG/p (1) Colburn, A. P., IND. Ero. CHEM.,22, 967-70 (1930).
s = cross-sectional area, sq. ft. (2) Colburn, A. P., Trans. Am. Inst. Chern. Engrs., 29, 174-209
c = sp. heat at constant pressure, P. c. u./(lb.)(” C.) (1933).
d = diam., or equivalent diam., ft. (3) Colburn, A. P., and Hougen, 0. A., Bull. Uniu. Wis. Eng. E&.
d, = outside t’ubediam., ft. Sta. Ser. No. 70, esp. p. 54 (1930).
d, = min. clearance between tubes, ft.
(4) Colburn, A. P., and Hougen, 0. A., IND.ENQ.CHEM.,26, 1178
f = friction factor (Equation 2) (1934).
9 = acceleration of gravity, 4.18 X 108 ft./(hr.)(hr.) (5) Gilliland, E. R., and Sherwood, T. K., Ibid., 26, 516-23 (1934).
h = film coefficient of heat transfer, P. c. u./(hr.)(sq.ft.)(” C.)
j = heat transfer or mass transfer factor (Equations 3, 5, 9) (6) Greenewalt, C. H., Ibid., 18, 1291-5 (1926).
(7) Lorisch, W., Forschungsarbeiten, Heft 322, 46-68 (1929).
k = thermal conductivity, P. c.u./(hr.)(sq. ft.)(”C./ft.)
k d = diffusion coefficient, sq. ft./hr.
(8) Mc;idams, W. H., “Heat Transmission,” pp. 207-9, McGraw-
Hill Book Co., Kew York, 1933.
P = partial pressure of diffusing component, atm. (9) Thiesenhusen, H., Gesundh.-Ing., 53, 113-19 (1930).
Po = partial pressure of inert component, atm.
Par = log. mean partial pressure of inert component in ‘(film,”
atm. RZICEWED September 15, 1934. Presented as part of the Symposium on Dif-
A p = difference between p and the equilibrium partial pres- fusional Processes before the Division of Industrial and Engineering Chem-
sure at the surface; A p , = mean difference istry a t the 88th Meeting of the American Chemical Society, Cleveland,
t = temp., C. O Ohio, September 10 t o 14, 1934. This paper is Contribution 145 from the
Af = temp. difference, usually log. mean, O C. Experimental Station of E. I. du Pont de Nemours & Company.

Surface Energy Relationships between

Pigment Materials and Rubber
A. DEPEWAND M. K. EASLEY,
HARLAN American Zinc Sales Company, Columbus, Ohio
whether the composition of the

A BOUT fifteen years ago

SchiPPel (9) found that
compounded rubber be-
came less dense on stretching,
Microscopical observations hazre been made to
determine the adhesion of rubber to pigment mate-
rials. The bond between carbon and rubber is
relatively very strong in comparison with that of
Pigment affected the bond* En-
dres (6) studied the vacuoles
that f o r m w h e n pigmented
and that t h e d e n s i t y c h a n g e r u b b e r is s t r a i n e d , a n d h e
varied g r e a t l y w i t h the corn- zinc oxide, while other pigment materials give pointed out that agglomerates
pound. His data showed that intermediate results. Overcure lowers the adhe- acted as large particles in some
when rubber was stretched: sion, and particle shape influences the separa- and broke up in O t h e r
cases w h e n t h e r u b b e r was
(1) The volume increase was tion. Separation OCCUrS at partick Sizes which stretched, very large
especially large with coarse
merits and approached zero wKf;
fine pigments were incorporated in
are Coarser than those found in mnmercial pig-
ments, indicating that the breaking of rubber
vacuum pockets. H e found
no evidence that the s u r f a c e
rubber. occurs within itself rather than at pigment-rubber of nonreactive Pigments affected
(2) W i t h pigments of t h e t h e a d h e s i o n of r u b b e r t o
very finest kind, the volume in- interfaces. pigments and he believed that
crease was greater than would be
expected from the general rela- “rubber adhered t o r e a c t i v e
tionship of size to volume increase. pigments such as zinc oxide very tenaciously.”
(3) The volume increase increased as the pigment concentra- w ~ along
~ anGentirely ~ different
~ path, Bartell and his
tion increased; the volume increase was especially large for
heavily compounded stocks. co-workers studied the adhesion of materials to liquids by
measuring displacement pressures. By this method Bartell
Schippel concluded that the volume increase was due to and Osterhof (2) showed that carbon was wet extremely well
the pulling away of the rubber from the pigment particles, by organic liquids, such as benzene, but poorly by water,
and he verified this conclusion by observing that vacuum whereas silica was wet well by water but poorly by benzene.
pockets developed when rubber containing coarse material They predicted that lines could be drawn relating the wetting
was stretched. I n the case of the very h e pigments, un- of other materials by liquids if the adhesion tension to one of
mixed groups of pigment behaved as coarse particles. them was known. They did not have finely divided solid
Green (6) further confirmed Schippel’s explanation by ex- materials that covered the wetting range satisfactorily to
tending the microscopic observation to pigment-size particles prove their contention. However, Bartell and Walton (3)
and photographing the vacuum pockets that developed. found that antimony sulfide behaved similarly to carbon,
This work, however, did not give any information as to and that the surface of the antimony sulfide particles could be