March 1950 INDUSTRIAL AND ENGINEERING CHEMISTRY 471

LITERATURE CITED
represent the over-all process has been written. The hydro-
carbon effluent when charging a straight chain C4 hydrocarbon
always contained butenes and butadiene, suggesting that these
materials may be intermediates in the reaction. The somewhat
higher yields from butenes than from butane would tend to
confirm this. However, these yield data are complicated,
especially in fixed bed operation, by the heat effects resulting
from the highly exothermic nature of the reactions.
ACKNOWLEDGMENT
The authors wish to express their appreciation to J. T. Clarke,
C. H. Cuinane, and B. R. Stanerson for their contributions to the
experimental work and to members of the Analytical and Testing
Department of the Beacon Laboratories for carrying out much of
the analytical work involved.
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(1) Auwers, K. V., and Kohlhaas, W., J. prakt. Chem., 108, 321-31
(1924).
(2) Fawcett, F. S., J. Am. Chem. Soc., 68, 1420-2 (1946).
(3) Fawcett, F. S., and Rasmussen, . E., Ibid., 67, 1705-9 (1945).
(4) Lowry, T., and Nasini, A., Proc. Boy. Soc. (London), A123,
686-91 (1929).
(5) Meyer, V., and Kreis, H., Ber., 17, 1558-63 (1884).
(6) Morton, A. A., ‘‘The Chemistry of Heterocyclic Compounds,”
p. 40, New York, McGraw-Hill Book Co., Inc., 1946.
(7) Rasmussen, . E., Hansford, R. C., and Sachanen, A. N., Ind.
Eng. Chem., 38, 376-82 (1946).
(8) Shepard, A. F., Henne, A., and Midgley, T., J. Am. Chem. Soc.
56, 1355-6 (1934).
(9) Steinkopf, W., ‘‘Die Chemie des Thiophenes,” p. 115, Dresden u.,
Leipzig, Theodor Steinkopff, 1941 (J. W. Edwards, Ann
Arbor, Mich., 1944).
Received August 31,1949.

Diffusion Coefficients in
Multicomponent Gas Mixtures
D. F. FAIRBANKS1 AND C. R. WILKE
University of California, Berkeley, Calif.

An experimental study has been made of the diffusion where D'a is some proper effective diffusion coefficient for com-
of vapors into multicomponent gases by vaporization of ponent A, which will be a function of the gas composition. In
liquids in a long tube under conditions such that the this case p( is the sum of the partial pressure of all gases other
theory of diffusion in the semi-infinite column is appli- than A.
cable. The results have verified the relation: On the basis of the theories of Maxwell (6) and Stefan (8, 9),
Wilke (10) has derived an expression given in Equation 3 for the
effective diffusion coefficient and discussed its general use in dif-
ye + yc + yc + ,
fusion calculations.
, ,
···

d7b dZc d7d

where D'A is the effective diffusion coefficient of gas A D’a _1 ~

VA
(3)
with respect to the total gas mixture; DAB, DAC, Dad, M- -L M. 4_ _L
Dab Dac Dad
etc., are the respective binary diffusion coefficients; and
yA, yB, yc, etc., are the mole fractions of the components
where yA, yB, y0, etc., are the mole fractions of components A, B,
in the mixture.
C, etc., and DAB, DAC, etc., are the respective .binary diffusion
coefficients of component A with respect to each component of
A
binary system the rate of unidirectional diffusion of a gas,
INA, through second stagnant
a gas, B, may be expressed by the
the mixture.
The present paper reports the experimental verification of
equation Equation 3 under conditions approximating those assumed in its
—DabP dpA
Na (1) derivation—namely, the diffusion of one gas into a mixture of
RTPi dx stagnant gases.
where Na = rate of diffusion of A, gram moles per second-sq.
cm. THEORY
Dab = diffusion coefficient, sq. cm. per second
P = total pressure, atmospheres On the basis of experimental convenience an apparatus was
R =
gas constant, cc.-atmospheres per gram mole-” K. construeted to operate on the principle of diffusion in the semi-
T =
temperature, K.
”
infinite column. In this method a suitable liquid is allowed to
Pa =
partial pressure of component A, atmospheres
X = distance in direction of diffusion, cm. evaporate upward into the gas mixture from the bottom of a long
Vi =
pressure of nondiffusing gas B, atmospheres glass tube under conditions such that a negligible quantity of
For diffusion of A into a multicomponent mixture of stagnant vapor reaches the upper end of the tube during the time of the
experiment. This method has been suggested by Arnold (2),
gases it is convenient to express the rate of diffusion by an equa- who has integrated the differential equations applicable to this
tion analogous to Equation 1: case for diffusion in binary systems. These binary equations may
,r -D'jjP dp A be extended to multicomponent systems if the diffusing gas, A,
(2)
_

A
is maintained at concentrations sufficiently low that the average
' ' '

RTn dx
1
Present address, Department of Chemical Engineering, Massachusetts diffusion coefficient given by Equation 3 remains essentially con-
Institute of Technology, Cambridge, Mass. stant during the diffusion process. This is accomplished in prac-
472 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 42, No. 3

The general procedure in the application of this theory to the

Table I. Function Fv (£) determination of the diffusion coefficient is to measure the volume
Vapor Vapor of gas, V, displaced from the top of the tube as a function of time,
Mole Mole . According to Equation 5 a plot of V vs. 1/2 should be a
Fraction, Fraction,
y* Fv y* Fv straight line of slope (dV/de1/2) which may be determined from
0 1 0.50 0.6215 the best line through the plot of the experimental data. This
0.05 0.9635 0.55 0.6810
0.10 0.9268 0.60 0.5398 formulation for the slope is convenient from the experimental
0.15 0.8900 0.65 0.4976
0.20 0.8527 0.70 0.4540 standpoint, because only the time must be referred to a zero value
0.25 0.8152 0.75 0.4088 and the volume measurements may be started at a later and more
0.30 0.7774 0.80 0.3616
0.35 0.7391 0.85 0.3112 convenient period of the experiment. Equation 5 may be solved
0.40 0.7004 0.90 0.2546 for the diffusion coefficient:
0.45 0.6613 0.95 0.1893
1 0

7
/ dv
y
\del/2)Fv
n
D (9)
4 (y*)2 ai
tice by using liquids of relatively low vapor pressure. Arnold’s
APPARATUS AND PROCEDURE
development will be reviewed briefly, in so far as it is applicable
to the present work. isschematic diagram of the apparatus. A gas mix-
Figure 1 a

Consider a vapor, A, diffusing at constant temperature and ture of the desired composition was prepared prior to each ex-
pressure from a liquid surface into a mixture of gases in a long periment in an external mixer (not shown) connected directly
cylindrical tube. The gas space will be assumed initially free of to the diffusion tube.
vapor, and the tube will be assumed of infinite length. As vapori-
zation proceeds gas is withdrawn from the upper end of the tube Diffusion Tube. The diffusion tube was a vertical borosilicate
at a measured rate to maintain the condition of constant pres-
sure. For this unsteady state process the following equation is glass tube with an average internal diameter of 1.043 cm. and a
length of about 200 cm. Liquid entered the tube at the bottom,
applicable: the inflow being induced by an initial difference in the liquid level
between the two sides of the U-shaped injector section. The high
dhM . 1
(í>Va\
1 dlM f4) side of the U was connected to the top of the diffusion column;
dx2 Ll -

y* \ i>x / J cte DÁ M as the liquid entered the bottom of the column, an equal volume of
gas left it at the top, and there was, therefore, no sudden change
where x distance in direction of diffusion, cm. (measured
—
of pressure in the system at the onset of the experimental run.
from liquid-gas interface) After the liquid was in, stopcocks were shut, isolating the column
mole fraction of A at distance x
= from the U.
Ua
mole fraction of A at interface (x 0), determined
Barostat. The barostat was a mercurial manometer in a U-
y* = —

by liquid vapor pressure shaped tube, and its purpose was to indicate the difference in
(dyA/dx)o mole fraction gradient at x
= 0 = pressure between the gas in the diffusion system and a near-
effective diffusion coefficient for gas A, sq. cm. per vacuum maintained in the barostat’s upper chamber.
D'a · =

second As the liquid in the diffusion tube evaporated, the slow increase
=
time, seconds of pressure inside the system caused the mercury surface in the up-
per vacuum chamber of the barostat to rise. A sharp-pointed
The boundary conditions for integration are as follows: tungsten wire was sealed into this upper chamber, and electrical
connections were made so that the wire and the mercury surface

y =
y* at x = 0 for all values of

y = 0 at = 0 for all values of x except zero

Integration of Equation 4 with these boundary conditions gives

the relation:
4 BMW (5)
Fv

where V —
volume of vapor formed in time , ce.
= time of diffusion, seconds
a = cross section of tube perpendicular to direction of
diffusion, sq. cm.
Fv = factor correcting for deviation from Fick’s law
The correction factor, Fv, is defined as follows:

Va
Fv =
(6)
\/
where is defined by the expressions

I = —

Va
+ Vir 2 (1 + erf ) (7)

_2_ n xl dx
erf e (8)
VVo
Arnold has solved Equations 6 to 8 numerically for F„ for
various conditions of vaporization and absorption. Values of
Fv are given in Table I for the present case of vaporization with
zero initial vapor concentration in the tube. Because Fv is a
function of y* only, it is constant for any one experiment.
March 1950 INDUSTRIAL AND ENGINEERING CHEMISTRY 473

would form the contact points of a switch which, in turn, con-
trolled a vacuum-tube relay. The relay was constructed after a
plan given by Serf ass (7). The relay operated an indicator light,
and, thus, tibe making and breaking of contact at the mercury
surface were made detectable. No arcing was observable in the
upper chamber, and the arrangement was found to be very sensi-
tive in indicating the attainment of the desired pressure.
and minimize temperature differences between jacketed and un-
jacketed portions of the equipment.
Preparation of Apparatus for Operation. Before each
run the apparatus was carefully brought to temperature, evacu-
ated, and checked for leaks. The gas mixture was then admitted
to the apparatus from the mixing section. The procedure of al-
ternate evacuation and filling was repeated several times to sweep
the apparatus free of residual gases from the preceding experi-
ment. After final introduction of the gas, stopcocks were closed
to isolate the main diffusion section from the U-shaped liquid in-
jection tube, and the injection tube was filled with the liquid to
be evaporated. After a few minutes’ preheating by means of a
portable water bath brought up around the injection tube, the
liquid was ready for injection into the diffusion tube.
Materials. The source and purity of all gases and liquids
used in the experiments are summarized in Table II.

Table II. Specification of Materials

Boiling
Substance Source Point, °C. Remarks
Hydrogen Electrolytic, Univ. 99.9% hydrogen
of Calif. Chemis-
try Dept.
Argon Linde Air .Products 99.0% A, 1.0%
Co.
Air Atmospheric Dried over P2O5
before use
Figure 2. Volume-Time Data for Typical Run Toluene Eastman Kodak Co. 110.5 Accepted b.p.
110.62° C.(1)
Ethyl pro- Eastman Kodak Co. 98.7- Accepted b.p.
pionate 99.3 99.0° C. (S)
Capillary Volumeter. The volumeter was a vertical cali-
brated capillary tube which had a nominal internal diameter of 1
mm. It was connected at the top to the top of the diffusion tube
and at the bottom through a stopcock to a mercury reservoir in a RESULTS
leveling bulb.
At the start of an experimental run, the capillary was filled with For each run, volumes of gas evolved from the top of the tube
mercury. As described above, the vaporization of the liquid were plotted against the square root of time on rectangular co-
caused the pressure in the apparatus to increase until, finally, the ordinates. Figure 2 shows a typical plot, in this case for the dif-
mercury in the barostat came in contact with the tungsten wire. fusion of ethyl propionate into a mixture of 20% air-80 % hydro-
The time of the contacting was recorded along with the accom-
panying level of mercury in the volumeter. Then, by releasing gen. From the slope of the best straight line through the data the
some mercury from the volumeter, gas could be withdrawn from diffusion coefficient was calculated by Equation 9.
the diffusion tube, lowering the pressure there and breaking the The vapor pressure of ethyl propionate was calculated by inter-
barostat contact. The vaporization of the liquid continued, and
the pressure of the gas again increased until contact was again polation of data from the International Critical Tables (3), and
made. Once more the time and the volumeter scale reading were the vapor pressure of toluene was calculated from data published
noted. The process was repeated until all the mercury had been by the National Bureau of Standards (1).
emptied from the volumeter. For purposes of comparison the diffusion coefficients were con-
verted from their values at room temperature and prevailing
With the aid of the volumeter calibration the volume corre- barometric pressure to the standard diffusion coefficient used in
sponding to each scale reading could be calculated. Thus a series the International Critical Tables (4) defined by the relation:
of data giving the increase of vapor volume with time was ob-
tained. Zero volume was arbitrary, only the change in volume
being obtained. Zero time was the moment that the liquid en-
tered the diffusion tube. The volume-time data formed the basis
for the calculation of the diffusion coefficient.
Temperature Control. It was necessary to keep the diffusion
tube at constant temperature to avoid thermally induced con-
vection currents and volume fluctuations.

To obtain close control the diffusion tube was encased in a wa-

ter jacket through which about 2 liters per minute of water were
pumped from a 50-liter constant temperature bath. The tem-
perature of the water bath was maintained within ±0.010 C. by a
sensitive mercury-expansion switch which controlled an electrical
heating unit immersed in the bath. The bath was stirred continu-
ously and was well insulated. Corrections to the observed gas
volumes were made for slight fluctuations in the water bath tem-
perature.
In order to observe the temperature of the evaporating liquid
and detect any evaporative cooling effects, a fine-wire Chromel-
Alumel thermocouple was sealed through the wall near the bottom
of the diffusion tube, and was placed so that the surface of the
liquid was about 1 mm. above the thermocouple junction.
The apparatus was housed in a windowless, tightly shut, sub-
terranean room to obtain freedom from drafts and room tempera-
ture fluctuations. Corrections were made for the effects of small
variations in room temperature on the unjacketed tubing in the
varostat and volumeter. Experiments were conducted at ap- Figure 3. Diffusion of Ethyl Propionate into Hydrogen-
proximately room temperature to facilitate temperature control Air Mixtures
474 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 42, No. 3

DISCUSSION

The present experimental technique gives values of D which

are self-consistent and reproducible. Furthermore, the straight-
line relation obtained in all the runs in the plot of V vs. 91/2 is in
agreement with the theory and supports the validity of the
method.
It is of interest to compare the results obtained for the binary
systems with the corresponding results of other investigators.
For diffusion of ethyl propionate into air Winkleman (4) obtained
data giving D0 = 0.0653 sq. cm. per second compared to an
average value of 0.069 sq. cm. per second for the present work.
Mack (5) has measured the diffusion of toluene into air, leading
to a value of D0 =0.071 sq. cm. per second as opposed to the
value of 0.081 sq. cm. per second for the present work.
A possible explanation for the lower diffusivities reported by
these investigators may be advanced on the basis of the dif-
MOLE % OF ARGON IN GAS MIXTURE ferent experimental techniques employed. Both Winkleman and
of Toluene Mack employed the steady-state evaporation of the correspond-
Figure 4. Diffusion into Hydrogen-Argon
Mixtures ing liquid in a tube. Because of the greater rate of diffusion em-
ployed in these steady-state methods, as opposed to the present
unsteady-state method, significant evaporative cooling of the
where D is the diffusion coefficient determined at T° K. and P liquid may have occurred. The effect of evaporative cooling is to
mm., D0 is the standard diffusion coefficient, T0 is the standard lower the reported value of the diffusion coefficient througli use of
temperature, 273.10 K., and P„ is the standard pressure, 760 mm. an erroneously high vapor pressure in the calculations. Mack’s
method further involved adsorption of
the vapors in charcoal at the end of the
diffusion tube opposite the liquid, and as-
Table III. Experimental Data and Calculated Results sumed that the adsorbed vapors exerted
Pressure ^V
no appreciable vapor pressure over the
Gas Composition, Temp,, Mm. d0U2 D, Sq. Do, Sq.
Liquid Run Volume % 0
c. Hg Cc./Sec.V2 Cm./Sec. Cm./Sec. charcoal. Any error in this assumption
Ethyl pro- 34 100% air 27.9 763.0 0.0162 0.085 0.070 due to excessive vapor adsorption would
pionate 35 100% air 27.9 751.7 0.0162 0.086 0.071
36 100% air 27.8 755.2 0.0161 0.082 0.067 lead to an erroneously low value for the
44 80% air, 20% Hi 28.0 760.7 0.0174 0.098 0.081 diffusion coefficient.
47 75.6% air, 24.4% H. 29.0 759.8 0.0179 0.103 0.085
42 50.6% air, 49.4% Hi 27.9 758.1 0.0209 0.140 0.115 When the present method is used,
45 20.0% air, 80.0% He 27.9 761.2 0.0276 0.247 0.204
46 8.6% air, 91.4% Hi 27.9 760.1 0.0308 0.307 0.252 errors due to an initial disturbance of the
39 100% H2 27.9 753.7 0.0358 0.410 0.334
40 100% H2 27.9 755.4 0.0364 0.414 0.339 gas in the diffusion tube accompanying
41 100% H, 27.8 756.2 0.0340 0.374 0.306 injection of the liquid or any other dis-
Toluene 25 100% air 27.7 758.2 0.0132 0.098 0.081 turbance such as thermal convection cur-
26 100% air 27.7 760.2 0.0131 0.098 0.081
27 100% air 27.7 758.2 0.0133 0.099 0.082 rents, room vibrations, etc., would lead
49 100% A 28.1 756.8 0.0127 0.087 0.071 to high values for the diffusion coefficient.
50 51.4% A, 48.6% H, 28.1 756.4 0.0166 0.148 0.121
51 31.0% A, 69.0% Hi 28.0 756.8 0.0194 0.204 0.167 In view of these possible sources of error,
52 16.5% A, 83.5% Hi 28.0 757.1 0.0229 0.286 0.234
53 100% Hi 28.0 758.8 0.0324 0.571 0.469 the agreement between the results of the
54 33.3% air, 34,2% A,
32.5% , 28.1 759.4 0.0159 0.136 0.112 present study and those of the investiga-
tors noted above is believed to be satis-
factory. Although further study is de-
sirable to reconcile the differences in
The essential results of the experiments are tabulated in Table results between these experimental techniques, this was not given
III. Values of D0 for diffusion of ethyl propionate into hydrogen- further attention in the present work, because the primary ob-
air mixtures are plotted as a function of gas composition in jective was to study the mixture properties with respect to dif-
Figure 3. The data for diffusion of toluene into hydrogen-argon fusion. The data are believed to approximate the absolute values
mixtures are shown in Figure 4. The solid curves in Figures 3 and of the diffusion coefficient sufficiently closely, and to be suffi-
4 are calculated from Equation 3, based on the terminal points of ciently reproducible and internally self-consistent to constitute a
the curves corresponding to the respective binary diffusivities. valid experimental verification of Equation 3 for the effective
The agreement between Equation 3 and the experimental points diffusion coefficient in multicomponent mixtures.
is believed to be satisfactory, and constitutes experimental verifi-
NOMENCLATURE
cation of Equation 3 and the theory leading to its derivation.
The dotted lines in Figures 3 and are 4 the results obtained as- a —
cross-sectional area perpendicular to direction of diffusion,
sq. cm.
suming the binary diffusivities to be additive on a mole fraction D = diffusion coefficient, sq. cm. per second
basis, and illustrate the serious error that may be involved in the D' = effective diffusion coefficient with respect to a multicompo-
employment of this relationship. nent mixture, sq. cm. per second
standard diffusion coefficient at 273.1° K., 760 mm., sq.
Equation 3 is further verified for a four-component system D0 =

cm. per second

(run 54 in Table III) for diffusion of toluene into an air-argon- Fv = correction factor for deviation from Fick’s law
hydrogen mixture composed of approximately one third of each N = rate of diffusion, moles per second-sq. cm.
gas. The experimental value of D0 is 0.112 sq. cm. per second p partial pressure, atmospheres
—

compared to a value of 0.104 sq. cm. per second calculated by

P = total pressure, atmospheres
R =
gas constant, cc. atmosphere per gram mole-° K.
Equation 3. Again, the simple additive relation on a mole frac- T =
temperature, K.
°

tion basis seriously

is in error, giving a value for D„ of 0.203 sq. V =
volume, cc.
cm. per second. x =
distance in direction of diffusion, cm.
March 1950 INDUSTRIAL
y =
mole fraction
y* =
equilibrium vapor mole fraction at gas-liquid interface
ß =
time, seconds
=
parameter defined by Equation 7, a function of y*
Subscripts
A. B, C, etc. components A, B,
=
C, etc., of gas mixture
i stagnant gas or gases
=
o —
gas-liquid interface or standard temperature and pressure
LITERATURE CITED
(1) American Petroleum Institute Research Project 44, Table 5K,
Washington, D. C., National Bureau of Standards, 1945.
Low Temperature Stiffening
of Elastomers
S. D. GEHMAN, P. J. JONES, C.
The Goodyear Tire and Rubber Company, Akron 16, Ohio
The generally observed stiffening of elastomers
temperatures may be supplemented by the occurrence of
crystallization if the elastomers have sufficient regularity
of molecular structure and other conditions are favorable.
To study these effects, observations of the progressive stiff-
enings of elastomer compounds at low temperatures were
made by measurements of the relative torsional modulus
of test strips mounted in racks which were stored at low
temperature. The periods of observation extended over 30
to 60 days with temperatures in the range from —59° to
18° C. A correlation was found between density changes
—
due to crystallization as determined dilatometrically and
torsional stiffness changes. Factors studied in addition to
EXTENDING the low temperature range for useful applica-
INtions of elastomers, other
the phenomena of spontaneous stiffening
must taken into account.
due to crystallization or causes be
Crystallization, accompanied by progressive stiffening, sometimes
occurs over a long period of time. In general, this may be ex-
pected in the case of elastomers which have sufficient regularity
of molecular structure to show the more familiar phenomenon of
crystallization upon stretching. Because such elastomers include
some of the most useful types of rubber, it is important to under-
stand under what conditions spontaneous crystallization at low
temperatures is to be anticipated.
Work reported from the National Bureau of Standards (10,11),
dealing principally with the crystallization and melting of un-
vulcanized Hevea rubber, furnishes a useful background for the
crystallization phenomena with vulcanizates. Observations of
the progressive low temperature stiffening of a class of technical
vulcanizates have been published by Gregory, Pockel, and Stiff
(7). Forman (6) investigated the comparative cold hardening
of neoprene, GR-S, and Hevea vulcanizates over a period of
time at low temperatures. Conant and Liska (S) observed
progressive stiffening with plasticized butadiene-acrylonitrile
vulcanizates, which was attributed to low temperature incom-
patibility or crystallization of the plasticizer. Forman reported
similar effects for plasticized compounds of Neoprene Type FR.
Beatty and Davies (2) studied effects of time, temperature, and
stress on the behavior of rubber at low temperatures.
The present work comprises a description of what appears to
be an improved technique for securing extensive data on the
progressive stiffening of elastomers, a survey of the effects of
AND ENGINEERING CHEMISTRY 475
(2) Arnold, J. H., Trans. Am. Inst. Chem. Engrs., 40, 361 (1944).
(3) International Critical Tables, Vol. Ill, New York, McGraw-
Hill Book Co., 1929.
(4) Ibid., Vol. V.
(5) Mack, J. Am. Chem. Soc., 47, 2473 (1925).
(6) Maxwell, J. C., “Scientific Papers,” Vol. 2, p. 57, Cambridge,
England, Cambridge University Press, 1890.
(7) Serf ass, E. J., Ind. Eng. Chem., Anal. Ed., 13, 262-3 (1941).
(8) Stefan, Sitzber. Akad. Wise. Wien, 63 (2), 63 (1871).
(9) Ibid., 65 (2), 323 (1872).
(10) Wilke, C. R., Chem. Eng. Prog., 46, 95-104 (1950).
Received July 5, 1949.
S. WILKINSON, JR., AND D. E. WOODFORD
at low temperature included compounding variables such as cure
and plasticizer content. Some data were obtained to show
the acceleration of crystallization due to compressive stress.
Progressive stiffening due to crystallization was observed
for vulcanizates of Hevea, Neoprene Type GN, and Butyl
rubber as well as for an 85-15 butadiene-styrene redox-type
copolymer. The results were interpreted in accordance
with concepts of crystal nucleation and growth with
necessary modifications due to the molecular structure of
elastomers. Although the phenomenon of spontaneous
crystallization of elastomers was found to be complicated
by many factors, a useful degree of generality appears in
some of the results.
temperature and other significant variables on the crystallization
of typical vulcanizates of technically important elastomers, and a
discussion of the results in order to reach an understanding of
their significance in terms of general principles applicable to
crystallization and the molecular structure of elastomers.
EXPERIMENTAL METHOD
A method of measuring the torsional stiffness of rubber samples
previously described (1, 6) has been adapted for securing data on
the stiffening due to prolonged exposures to low temperature.
Figure 1 is a photograph of the assembled apparatus. The test
strips were mounted in supplementary racks as shown in Figure 2.
Ten of these racks were available for the investigation, so that
fifty samples could be run concurrently.
The torsional stiffness of each test piece was measured at room
temperature and at the storage temperature. The racks were
then stored in constant temperature cold boxes or cold rooms at
the desired temperatures. It was found advantageous to invert
glass beakers over the racks to minimize the chances of any tem-
perature variation of the samples due to opening a cold box during
the course of the tests. The racks were removed at suitable inter-
vals and the test pieces were measured without changing their
temperature, by transferring the rack to be measured into the ap-
propriately precooled insulated cylinder of the apparatus and
carrying the rack to the measuring stand where the storage tem-
perature was maintained. After measurement, the rack was re-
moved from the insulated cylinder in the cold box, if it was desired
to continue the test.
In the presentation of the results, the ratio of the torsional
modulus measured at various time intervals to the original