March 1950 INDUSTRIAL AND ENGINEERING CHEMISTRY
LITERATURE CITED
represent the over-all process has been written. The hydro-
carbon effluent when charging a straight chain C d 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. Culnane, 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
i
the analytical work involved.
Diffusion Coefficients in
Multicomponent Gas Mixtures
D. F. FAIRBANKS AND C. R. WILKE
University of Callfornia, Berkeley, Calif.
A n experimental study has been made of the diffusion
of vapors into multicomponent gases by vaporization of
iiquids in a long tube under conditions such that the
theory of diffusion in the semi-infinite column is appli-
cable. The results have verified the relation:
D‘A =
1 - yA
YB + y c f Y D + * * *
DAB DAC DAD
where D‘A is the effective diffusion coefficient of gas A
with respect to the total gas mixture; DAB,DAG,DAD,
etc., are the respective binary diffusion coefficients: and
yA, ye, ye, etc,, are the mole fractions of the components
in the mixture.
’
I N A binary system the rate of unidirectional diffusion of a gas,
A , through a second stagnant gas, B , may be expressed by the
equation
where N A = rate of diffusion of A , gram moles per second-sq.
cm.
DAB = diffusion coefficient, sq. cm. per second
P = total pressure, atmospheres
R = gas constant, cc.-atmospheres per gram mole-” K.
T = temperature, OK.
PA = partial pressure of component A , atmospheres
X = distance in direction of diffusion, cm.
pi = pressure of nondiffusing gas B, atmospheres
For diffusion of A into a multicomponent mixture of stagnant
gases it is convenient to express the rat,e of diffusion by an equa-
tion analogous to Equation l :
Present addresa, Department of Chemical Engineering, Massachusetts
InaCitute of Technology, Cambridge, Mass.
471
(1) Auwers, K. V., and KohIhaas, 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, H. E., Ibid., 67,1705-9 (1945).
(4) Lowry, T.,and Nasini, A,, Proc. Roy. SOC.(London), A123,
686-91 (1929).
(5) Meyer, V.,and Kreis, H., Bey., 17,1558-63 (1884).
(6) Morton, A. A., “The Chemistry of Heterocyclic Compounds,”
p. 40,New York, McGraw-Hill Rook Co., Inc., 1946.
(7) Rasmussen, H. E., Hansford, R. C., and Sachanen, A. N., IND.
ENO.CHEM.,38,376-82 (1946).
(8) Shepard, A. F., Henne, A., and Midgley, T., J . Am. Chem. SOC.
56, 1365-6 (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.
where 0;is some proper effective diffusion coefficient for com-
ponent A , which will be a function of the gas composition. In
this case p i is the sum of the partial pressure of all gases other
than A .
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-
fusion calculations.
D‘A = 1- YA
(3)
ya+yc + E + . . . .
DAB DAC DAD
where yB, ye, etc., are the mole fractions of components A , B,
C, etc., and DAB, DAC,etc., are the respective binary diffusion
coefficients of component A with respect to each component of
the mixture.
The present paper reports the experimental verification of
Equation 3 under conditions approximating those assumed in its
derivation-namely, the diffusion of one gas into a mixture of
stagnant gases.
THEORY
On the basis of experimental convenience an apparatus was
construeted to operate on the principle of diffusion in the semi-
infinite column. I n this method a suitable liquid is allowed to
evaporate upward into the gas mixture from the bottom of a long
glass tube under conditions such that a negligible quantity of
vapor reaches the upper end of the tube during the time of the
experiment. This method has been suggested by Arnold ( d ) ,
who has integrated the differential equations applicable to this
case for diffusion in binary systems. These binary equations may
be extended to multicomponent systems if the diffusing gas, A ,
is maintained a t concentrations sufficiently low that the average
diffusion coefficient given by Equation 3 remains essentially con-
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 F, (2)
I. FUNCTION 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 6. According to Equation 5 a plot of V zs. should be a
Fraction, Fraction,
II* R Y* R straight line of slope (d‘V/d61’2jvc-hich 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 standpoint, because only the time must be referred to a zero value
0.20 0.8527 0.70 0.4540
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 0.7381 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

tice by using liquids of relatively low vapor pressure. Arnold’s

development will be reviewed briefly, in so far as it is applicable
to the present work.
Consider a vapor, A, diffusing at constant temperature and
pressure from a liquid surface into a mixture of gases in a long
cylindrical tube. The gas space will be assumed initially free of
vapor, and the tube will be assumed of infinite length. As vapori-
zation proceeds gas is withdrawn from the upper end of the tube
at a measured rate to maintain the condition of constant pres-
sure. For this unsteady state process the following equation is
applicable :
(4)
where z = distance in direction of diffusion, cm. (measured
from liquid-gas interface)
YA = mole fraction of A at distance z
y
: = mole fraction of A at interface ( 5 = 0), determined
by liquid vapor pressure
( ~ Y A / ~ z ) ,= mole fraction gradient a t z = 0
D; . = effective diffusion coefficient for gas A , sq. cm. per
second
e = time, seconds
The boundary conditions for integration are as follows:
y = g* at z = 0 for all values of 6
APPARATUS AND PROCEDURE
Figure 1 is a schematic diagram of the apparatus. A gas mix-
ture of the desired composition was prepared prior to each ex-
periment in an external mixer (not shown) connected directly
to the diffusion tube.
DIFFUSIOW TUBE. The diffusion tube was a vertical borosilicate
glass tube with an average internal diameter of 1.043 em. and a
length of about 200 cm. Liquid entered the tube a t the bottom,
the inflow being induced by an initial difference in the liquid level
between the two sides of the U-shaped injector section. The high
side of the U was connected t o the top of the diffusion column;
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
of pressure in the system at the onset of the experimental run.
After the liquid was in, stopcocks were shut, isolating the column
from the U.
BAROSTAT.The barostat mas a mercurial manometer in a U-
shaped tube, and its purpose was to indicate the difference in
pressure between the gas in the diffusion system and a near-
vacuum maintained in the barostat’s upper chamber.
As the liquid in the diffusion tube evaporated, the slow increase
of pressure inside the system caused the mercury surface in the up-
per vacuum chamber of the barostat to rise. A sharp-pointed
tungsten wire was sealed into this upper chamber, and electrical
connections were made so that the wire and the mercury surface

y = 0 at 6 = 0 for all values of z except zero

Integration of Equation 4 with these boundary conditions gives

the relation:

where V = volume of vapor formed in time 6, CG.

6 = time of diffusion, seconds
a = cross section of tube perpendicular to direction of
diffusion, sq. cm.
F , = factor correcting for deviation from Fick’s law
The correction factor, F,, is defined as follows:
2
:
Y
F, = ~

z/F 9
where 4 is defined by the expressions

Arnold has solved Equations 6 to 8 numerically for F , for

various conditions of vaporization and absorption. Values of
F, are given in Table I for the present case of vaporization with
zero initial vapor concentration in the tube. Because F , is a
function of y* only, it is constant for any one experiment. Figure 1. Schematic Diagram of Apparatus.
March 1950 INDUSTRIAL AND ENGINEERING CHEMISTRY 473
would form the contact points of a switch which, in turn, con- and minimize temperature differences between jacketed and un-
trolled a vacuum-tube relay. The relay was constructed after a jacketed portions of the equipment.
plan given by Serfass ( 7 ) . The relay operated an indicator light, PREPARATION OF APPARATUS FOR OPERATION.Before each
and, thus, the making and breaking of contact a t the mercury run the apparatus was carefully brought to temperature, evacu-
surface were made detectable. No arcing was observable in the ated, and checked for leaks. The gas mixture was then admitted
upper chamber, and the arrangement was found to be very sensi- to the apparatus from the mixing section. The procedure of al-
tive in indicating the attainment of the desired pressure. 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
V . 0 , I I I I I I I 4 I I to isolate the main diffusion section from the U-shaped liquid in-
jection tube, and the injection tube was filled with the liquid to
0.7 be evaporated. After a few minutes' preheating by means of a
portable water bath brought up around the injection tube, the
0.6
liquid was ready for injection into the diffusion tube.

u 0.
MATERIALS.The source and purity of all gases and liquids
8
U'
used in the experiments are summarized in Table 11.
10.4
3
>o 0.3
TABLE11. SPECIFICATION
OF MATERIALS
0.2 Boiling
Substance Source Point, O C . Remarks
0.1 Hydrogen Electrolytic Univ.
of Calif. 'Chemis-
.. 99.9% hydrogen
try Dept.
0 Argon Linde Air Products .. 99.0% A, 1.0%
0 10 PO 30 40 50 Go.
TIME, SEC. 'I2 Air Atmospheric .. $"z
Dried over PnOs
before m e
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 99.00 c. (5)
CAPILLARY VOLUMETER.The volumeter was a vertical cali-
brated capillary tube which had a nominal internal diameter of 1
mm. It was connected a t the top to the top of the diffusion tube
and at the bottom through a stopcock to a mercury reservoir in a RESULTS
develing 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 polation of data from the International Critical Tables (S), and
the pressure of the gas again increased until contact was again
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 a t 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.I t was necessary to keep the diffusion 0.35 I I I I I I I I I
tube a t constant temperature to avoid thermally induced con-
vection currents and volume fluctuations.
0.30
To obtain close control the diffusion tube was encased in a wa-
ter jacket through which about 2 liters per minute of water were 0.25
pumped from a 50-liter constant temperature bath. The tem-
perature of the water bath was maintained within 10.01 C. by a
sensitive mercury-expansion switch which controlled an electrical 0.90
heating unit immersed in the bath. The bath was stirred continu- d
ously and was well insulated. Corrections to the observed gas 0.1 5
volumes were made for slight fluctuations in the water bath tem-
perature.
I n order to observe the temperature of the evaporating liquid 0.10
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-
0*05
01
t I I I I I I I I
1I.
0 20 40 60 80 100
ture fluctuations. Corrections were made for the effects of small M O L E % OF A I R IN G A S M I X T U R E
variations in room temperature on the unjacketed tubing in the
varostat and volumeter. Experiments were conducted a t ap- Figure 3. Diffusion of Ethyl Propionate into Hydrogen-
proximately room temperature t,o facilitate temperature control Air Mixtures
474 INDUSTRIAL A N D ENGINEERING CHEMISTRY Vol. 42, No. 3
0.5 f I 1 I I I I DISCUSSION

1
The present experimental techniqoe gives values of D which
are self-consistent and reproducible. Furthermore, the straipht-
line relation obtained in all the runs in the plot of V us. is in
agreement with the theory and supports the validity of the
method.
It is of interest to compare the iesults obtained for the binary
'\ - systems with the corresponding results of other investigators.
0.2 -
\
- For diffusion of ethyl propionate into air Winkleman (4) obtained
data giving D o = 0.0653 sy ciii. per second compared to an
- \
'\
- average value of 0.069 sq. cin. per second for the present \\orl<.
'\ Mack ( 5 ) has measured the diffusion of toluene into air, leading
0.1 - '\ -
\ to a value of I), = 0.071 sq em. pel second as opposed to the
- - value of 0.081 sq. cin. pel second for the present work.
0 . I I I I I I 1 I A possible explanation for the loir el diffusir rties repoi teci by
0 PO 40 60 80 100 these investigators may be aclvniiced 011 the basis of the dif-
MOLE 70 OF A R G O N IN G A S MIXTURE ferent experimental techniques employed. Both Winkleiiiari and
Figure of Toluene into Hydrogen-Argoll
Mack einployed the steady-state evaporation of tile correspond-
Mixtures ing liquid in a tube. Because of the greater rate of diffusion ein-
ployed in these steady-state methods, as opposed to the present
unsteady-state method, sigiiiticaiit evaporative cooling of the
where D is the diffusion coefficient determined a t !Po K. and P liquid may have occurred. The effect of evaporative cooling is to
mm., Dois the standard diffusion coefficient, To is the standard lower the reported value of the diffusion coefficient through use of
temperature, 273.1 ' K., and Pois the standard pressure, 760 inni. an erroneously high vapor pressure in the calculations. Mack's
method further involved adsorption of
tlie v q m s in charcoal at the erid of the
diffusion tube opposite the liquid, and as-
TABLE1x1. EXPERIMENTAL DATA AND CALCCL.4TED 1tEsULTS sunied that the adsorbed vapors exerted
Gas Composition, Temp.,
Pressure,
Mm.
dV
D ,Sq. D O , Sq. no appreciable vapor pressure over the
Liquid Run Volume % C. Hg Cc./Sec.l/* Cm./Sec. Cm./Sec. charcoal. Any error in this assumption
Ethyl pro- 34 27.9 763,O 0.0162 0.085 0.070 due to ewessive vapor adsorption would
pionate 35 27.9 751.7 0.0162 0 086 0.071
36 27.8 755,2 0.0161 0.082 0.067 lead to an erroneously low value for the
44 28.0 760.7 0,0174 0.098 0.081 diffusion coefficient.
47 29.0 759.8 0.0179 0.103 0.086
42 27.9 758.1 0.0209 0.140 0.115 When the present method is used,
45 27.9 761.2 0.0276 0,247 0,204
46
~~ 27.9 760.1 0.0308 0.307 0.252 errors due to an initial disturbance of the
39 27.9 753.7 0.0358 0.410 0.334
40 27.9 755.4 0.0364 0.414 0,339 gas in the diffusion tube accompanying
41 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% sir 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 roefficient.
50 5 1 . 4 7 A 4 8 . 6 % IIr 28.1 756.4 0.0166 0.148 0.121
51 3 1 . 0 d A: 6 9 . 0 % H? 28.0 756.8 0.0194 0.204 0.167 In view of these possible sources of error.
52 1 6 . 5 % A , 8 3 . 5 % Hz 28.0 757.1 0.0229 0.286 0.234
63 1 0 0 ~ oHs 28.0 758.8 0,0324 0.571 0.469 the agreement between the results of tlie
54 3 3 . 3 % air, 3 4 , 2 % A , present,study and those of the investiga-
3 2 . 5 % HI 28.1 759.4 0.0159 0.136 0.112
t'ors noted above is believed to be satis-
factorv. illthough further study is dc-
I

sirable to reconcile the differences in

The essential results of the experiments are tabulated in Table i esults between these experimental techniques, this was not given

111. Values of Do for diffusion of ethyl propionate into hydrogen-
air mixtures are plotted as a function of gas composition in
Figure 3. The data for diffusion of toluene into hydrogen-argon
mixtures are shown in Figure 4. The solid curves in Figures 3 and
4 are calculated from Equation 3, based on the terminal points of
the curves corresponding to the respective binary diffusivities.
The agreement between Equation 3 and the experimental points
is believed to be satisfactory, and constitutes experimental verifi-
cation of Equation 3 and the theory leading to its derivation.
The dotted lines in Figures 3 and 4 are the results obtained as-
suming the binary diffusivities to be additive on a mole fraction
basis, and illustrate the serious error that may be involved in the
employment of this relationship.
Equation 3 is further verified for a four-component system
(run 54 in Table 111) for diffusion of toluene into an air-argon-
hydrogen mixture composed of approximately one third of each
gas. The experimental value of Dois 0.112 sq. cm. per second
compared to a value of 0.104 sq. cm. per second calculated by
Equation 3. Again, the simple additive relation on a mole frac-
tion basis is seriously in error, giving a value for D oof 0.203 sq.
cm. per second.
further attention in the present work, because the primary ob-
jective was to study the mixture properties with respect to dif-
fusion. The data are believed to approximate the absolute values
of the diffusion coefficient sufficiently closely, and to be suffi-
ciently reproducible and internally self-consistent to constitute a
valid experimental verification of Equation 3 for the effecti\ e
diffusion coefficient in multiromponent mixtures.
NOMENCLATURE
a = cross-sectional area perpendicular to direction of diffusion,
sq. cm.
I) = diffusion coefficient, sq. cm. per second
D' = effective diffusion coefficient with respect to a multicompo-
nent mixture, sq. cm. per second
I), = standard diffusion coefficient a t 273.1' K., 760 mm., sq.
cm. per second
F , = correction factor for deviation from Fick's law
1v = rate of diffusion, moles per second-sq. cm.
p = partial pressure, atmospheres
P = total pressure, atmospheres
R = gas constant, c,c. atmosphere per gram mole-" K .
T = temperature, K.
V = volume. cc.
5 = distancl? in direction of diffusion, cm.
March 1950 INDUSTRIAL A N D ENGINEERING CHEMISTRY
y = mole fraction
y * = equilibrium vapor mole fraction at gas-liquid interface
e = 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. S. WILKINSON, JR., AND D. E. WOODFORD
The Goodyear Tire and Rubber Company, Akron 16, Ohio
T h e generally observed Stiffening of elastomers at low
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
I N EXTENDING the low temperaturerange for useful applica-
tions of elastomers, the phenomena of spontaneous stiffening
due to crystallization or other causes must be taken into account.
Crystallization, accompanied by progressive stzening, 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 a t low temperatures. Conant and Liska (3) 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 (8) studied effects of time, temperature, and
stress on the behavior of rubber a t 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
475
(2) Arnold, J. H., Trans. Am. Inst. Chem. Engrs., 40, 361 (1944).
(3) International Critical Tables, Vol. 111, 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) Serfass, E. J., IND.ENG.CHEM., ANAL.ED., 13,262-3 (1941).
(8) Stefan, Sitzber. Akad. Wiss. 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.
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 a t 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 a t 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