Dynamic Bulk Modulus of

Various Elastomers
J. BURNS, Florida Institute of Technology,Melbourne, Florida 32901
and P. S. DUBBELDAY and R. Y. TING, Naval Research
Laboratory, Underwater Sound Reference Detachment,
Orlando, Florida 32856-8337

Synopsis
The dynamic bulk modulus of elasticity has been measured for 14 different rubbery elastomers:.
three natural rubbers, five neoprene, three polyurethanes, and one each of butyl, nitrile, and
butadiene types. The measurements ranged in temperature from - 10 to +4O"C, a t frequencies
from 5 to 3000 Hz, but mostly in the range 100-1000 Hz, at 2.5 MPa pressure. Values of the real
(storage) part of the modulus fell within 35% of the mean value of 2.9 GPa for all elastomers,
whereas loss moduli were a few percent of the storage moduli. Master curves were obtained for
two neoprenes, a polyurethane, and a butyl rubber. These were fitted by hyperbolic functions
with four adjustable parameters. Effects of room-temperature aging in artificial sea water were
also studied. Aging versus time profiles fell into two distinct forms. Natural rubbers were least
stable, neoprenes were intermediate, and urethanes proved most stable in bulk modulus.

INTRODUCTION
The bulk modulus bears a different relation to the structure of an elastomer
than do other elastic moduli. The bulk modulus is associated with short range
and local structure and is only indirectly determined by longer-range polymer
chain mechanics that are of central importance in determining tensile and
shear properties. From a structural standpoint, the bulk modulus may be
considered to play a role that is complementary to the roles of shear and
tensile moduli.
Despite the importance of the bulk modulus as a complement to the other
elastic properties, it has been the least studied of the elastic properties of
elastomeric solids. This is partly because of the practical difficulty in measur-
ing this modulus with high accuracy, although the measurement appears
simple enough in principle.
It is alternatively possible in principle to calculate the bulk modulus K
from knowledge of two other elastic moduli such as Young's modulus E and
the shear modulus G. For isotropic solids, standard elasticity theory shows
that K is proportional to (3G - E ) - ' ; but for rubbery elastomers which have
Poisson's ratios near 0.5, the factor 3G - E is nearly zero. This magnifies
small errors in either G or E , giving large errors in K . Therefore, determina-
tion of the bulk modulus by calculation from shear and Young's moduli has
not proved very useful.
There are two principal experimental methods for measuring the dynamic
bulk modulus as functions of temperature and frequency in elastomers. In the
impedance tube method [l] the speed of a longitudinal acoustic plane wave in

Journal of Polymer Science: Part B: Polymer Physics, Vol. 28, 1187-1205 (1990)
0 1990 John Wiley & Sons, Inc. CCC 0887-6266/90/0701187-19$04.00
1188 BURNS, DUBBELDAY, AND TING

the material is measured. This sound speed plus the density of the solid yields
the plane-wave (or dilatational) modulus M , which is related to the bulk
modulus and the shear modulus by the simple relation M = K + 4G/3. In
most rubbery elastomers G is less than 0.5%of M , so K equals M to a good
approximation. There are technical difficulties in making accurate measure-
ments of the plane-wave speed, mostly connected with edge effects when the
acoustic wavelength is not negligibly small compared with the dimensions of
the sample. The method is therefore most useful a t relatively high frequencies,
above about 10 kHz.
At lower frequencies a second method using an acoustic coupler is more
useful. This technique was first developed a t the National Bureau of Stan-
dards by McKinney, Edelman, and Marvin [2]. The method employs a
heavy-wall, steel pressure vessel in which there is a cavity containing the
sample, two piezoelectric transducers, and a filling fluid. It is necessary that
the sample be subjected to pure compression without any significant pressure
gradient, so the method works only for wavelengths much longer than sample
dimensions, usually a t low audio frequencies from a few hertz to a few
kilohertz.
Both the impedance tube (plane-wave modulus) and acoustic coupler meth-
ods have been used in this laboratory to measure the dynamic bulk modulus,
but the coupler has generally given the more accurate results to be reported
here.

ANALYSIS AND EXPERIMENT

The coupler used a t NRL-USRD for the present investigation is similar to
one described in detail by Bobber [3] for use in calibrating hydrophones. For
the present application, the same kind of heavy steel chamber was used,
except that only two ports were required, one for a driver-transducer and one
for a receiver. Reciprocity of the two transducers is not required. To make this
point clear and to show the approximations made in the basic equations, the
main line of the derivation of the equation relating the bulk modulus to the
parameters of the coupler and its contents will be given, following closely
the analysis of McKinney, Edelman, and Marvin [2].
The sum of the changes of volume A Y of all the items inside the coupler
equals the change of volume of the cavity A K , or

AK = C~v,.
i

I t is essential to assume that the pressure changes A P throughout the cavity

are uniform; i.e., A P must be the same everywhere in the cavity during the
pressure cycle produced by the driver which acts as a volume expander. This
sets an upper limit to the frequency that may be employed in a given
chamber. Dividing Eq. (1) by A P ,

-=c-
AK
AP
Av,
AP
 DYNAMIC BULK MODULUS OF ELASTOMERS 1189

For the passive material, i.e., everything in the chamber including the cham-
ber itself but excluding the transducers, one may set

where K is the bulk modulus, and P is the compressibility. For active

materials, specifically the piezoelectric transducers in the chamber, one may
write in the linear region in which they operate,

E = a P + bu
and
I = CP+ du, (4)

where E is the voltage across the transducer, I is the current through the
transducer, u is the volume velocity, P is the pressure in the cavity and a , b,
c, and d are properties of the transducer material, These relations are applied
to the driver and receiver in the coupler, indicated by indices 1 and 2,
respectively. By algebraic manipulation, the electrical parameters of the two
transducers may be related to the respective material parameters of the driver
and receiver. It is not necessary in this manipulation to assume reciprocity of
either transducer. The ratio of driver to receiver voltages is given for the open
receiver-circuit case by

where C is the total compliance of all the passive materials in the coupler
minus the chamber compliance.
T o calibrate the chamber, one measures the above voltage ratio R o when
the chamber is filled with a fluid of known compressibility Po and again when
the coupler contains a metal of known volume vb and known (small) com-
pressibility P b . In this case, the voltage ratio is Rb. Measuring the voltage
ratio R , with an elastomer sample of volume V , in the coupler, the compress-
ibility P, of the sample may be calculated from the following expression which
is easily derived from eq. (5). It gives the sample compressibility in terms of
measured voltage ratios for the coupler containing, variously, metal (brass in
this work), the unknown sample, and oil (only). The relation is

All of the R ratios in this expression are complex numbers, as eq. (5)
suggests. I n general, /I,will be a complex number whose real part gives the
storage compressibility of the sample and whose imaginary part gives the loss
compressibility. Both Po and Pb are, for all practical purposes, real because
1190 BURNS, DUBBELDAY, AND TING

the fluids used in these measurements and the metal calibration materials
(brass in the present case) have very low losses, well below the limit of
detection of our apparatus. Since the brass sample is virtually incompressible
in comparison with the oil, this calibration procedure actually compares the
compliance of the oil displaced by the brass with the compliance of the
elastomer sample. The term p,/& amounts to a small correction for
the compliance of the brass, but typically this correction is of the order of 1%.
The oil used as a filling fluid in most of our work has been purified Baker
DB Grade castor oil. This oil is commonly used as a coupling fluid in
hydrophones, and its sound speed has been carefully measured over the range
of pressures and temperatures of interest by Timme [4]. These sound speed
values together with densities from measurements by Stallard (given in
Timme's paper) yield bulk modulus values for castor oil with overall accura-
cies of about 2%.
The usefulness of castor oil a t low temperatures is unfortunately limited by
its high viscosity and by what appears to be a physical change (possibly gel
formation) a t about -18°C. The onset of this change is already apparent in
calibration data at temperatures as high as O'C, and it has not proved
possible to use this oil much below this temperature. Another fluid, di-2 ethyl
hexyl sebacate, was tried since this fluid was used by McKinney and Belcher
[5]. The compressibility of this oil is accurately known, and its viscosity is
much lower than that of castor oil. Unfortunately, we found that the sebacate
oil reacts with a number of elastomers of interest in this work, and this
reactivity ruled out its use. A fully fluorinated, low-viscosity, polymeric
hydrocarbon fluid, Fluorinert 43, produced commercially as an inert cleaning
material for the integrated circuit industry, has been found to be a satisfac-
tory substitute for castor oil. Fluorinert 43 has been used successfully in a
second coupler of simple cylindrical shape having a somewhat longer chamber
but in other respects similar to the original rectangular coupler. In order to
minimize absorption of air and particularly water vapor which proved to be a
problem with castor oil, the cylindrical coupler has a means to store the oil
under vacuum when it is not in the chamber. It is particularly gratifying to
note that both couplers with different chamber shapes and sizes, different
filling fluids, and different sets of transducers gave results that agree to within
2%, a limit set by the accuracy of the compressibility data for the filling fluids.
The choice of suitable transducers is crucial for good accuracy and high
precision of the measurements. Long-term transducer stability is important
for maintenance of calibration. It is also important that the transducers come
rapidly to thermal and electrical equilibrium after changes in temperature or
pressure. After some not very satisfactory experience with other transducers,
we arrived a t a suitable design using stacks of thin disks of samarium-mod-
ified lead titanate 1.90 cm in diameter by 0.16 cm thick, four disks to a stack.
The disks were made by the Edo Western Corporation. They have silvered
faces for electrical contact. Thin metal foils were placed between the disks to
provide external electrical leads, and the stack was cemented together with
epoxy. The complete stack was mounted, also with epoxy, to electrical
feedthroughs passing through the chamber walls, and the transducers were
surrounded by electrically grounded mesh screens for protection against
 DYNAMIC BULK MODULUS OF ELASTOMERS 1191

SAMPLE? f OIL

V
TRANSDUCERS
COUPLER

COMPUTER
(CONTROL - OSCILLATOR
-
REFERENCE FREQUENCY LOCK-IN
AND ANALYZER
1LDATA STORAGE) I I I

1
DIGITAL
VOLTM€ER

DIGITAL
VOLTMETER -

Fig. 1. Electrical arrangement.

accidental contact with the sample. The disks on each stack were connected in
parallel electrically, giving a total capacitance of about 1300 pF. The stack
resonance frequency was quite high, about 145 kHz. For comparison, the
lowest chamber resonance of the rectangular coupler occurred a t about 8.3
kHz with no sample in the chamber. This resonance did not appreciably affect
measurements a t frequencies below 3 kHz.
Figure 1 shows schematically the principle of the coupler and the electrical
arrangement used.
Originally, no computer control was employed. All data were plotted in
analog form and manually reduced using eq. (6). In this arrangement, a
Wavetek 185 sweep-frequency generator delivered a constant voltage sine
wave of slowly increasing frequency to the driver transducer. The output
voltage from the receiver transducer was fed into a Princeton Applied Re-
search PAR 5204 lock-in amplifier synchronized with the Wavetek frequency.
The PAR outputs (in-phase and quadrature) were recorded in separate runs
by a Hewlett-Packard HP7015B X-Y recorder whose x axis was driven by a
voltage proportional to the Wavetek frequency. In this way plots were made
of output voltage versus frequency. The input voltage to the driver transducer
was held constant, allowing output voltages to be converted to voltage ratios
R for use in eq. (6). In-phase voltage ratios determined the real or storage part
of the bulk modulus K‘, whereas the quadrature voltages gave the loss
modulus K”. With this system it was possible to achieve accuracies of about
f8% for K’ and f30% for K ” . Unfortunately, this was not good enough to
observe fine details precisely enough to permit construction of master curves,
although major features of the bulk modulus could be determined.
1192 BURNS, DUBBELDAY, AND TING

Later refinements to improve the accuracy included substitution of a more

stable frequency synthesizer (Rockland Model 5100), digital voltmeters replac-
ing the plotter, improved thermal control of the coupler, and replacement of
the original transducers by the modified lead titanate disk types described
above. The system was placed under computer control to take and record data
automatically. Altogether, these changes reduced the experimental uncer-
tainty to about k 1%for K’ and about 8% for K ” . This level of precision
was adequate to permit determination of the WLF frequency-temperature
shift factors, aT [6], giving the complete forms of both K’ and K” as
functions of frequency and temperature.

RESULTS
Results of our measurements fell into two categories: (1)relatively low-pre-
cision bulk moduli of a wide variety of rubbery elastomers, and (2) high-preci-
sion data on four elastomers from which master curves were obtained. The
low-precision results were obtained with the early manually controlled analog
version of the coupler and associated electronics. The uncertainties in K”
values from these measurements were too large to permit more than rough
quantitative conclusions about the relative magnitudes of K’ and K”. It was
found that the loss tangent (tan6 = K”/K’) was small for all elastomers
tested. Small, in this case, means less than about 0.05 over the range of
variables employed, and usually tan6 was appreciably less than 0.05. The
later high-precision measurements confirmed these findings quantitatively
and, in fact, showed that all of the four samples yielding master curves had
maximum loss tangents less than 0.01.
The first group of results included data from 13 different kinds of elas-
tomers in six different chemical groups: three natural rubbers, five neoprenes,
two polyurethanes, and one representative sample each of polybutadiene,
butyl, and nitrile rubbers. Formulations and cure conditions of these elas-
tomers are listed in Appendix B. The temperatures ranged from 0°C to 30°C
and frequencies from 100 Hz to 3 kHz. The pressure was 2.5 MPa, although
pressure dependence was investigated briefly up to 25 MPa, establishing the
fact that while the bulk modulus increased with pressure, as it should, there
was no significant pressure dependence below about 5 MPa in these samples,
within the uncertainty of the first group of measurements.
Figure 2 shows the results of measurements of K’ a t 10°C over the
frequency range 100 Hz to 1 kHz. The modulus varied approximately linearly
with frequency in this range; for convenience, this frequency range has been
condensed in the figure where the height of each bar represents the linear
variation of K’ with frequency over the stated range.
One data set in Figure 2 for a neoprene (type 5109) shows the full range of
K’ taken from a master curve for this material obtained from the later
high-precision data. It displays the general scale of the range of variations to
be found for the bulk modulus in these elastomers.
A significant point to note from Figure 2 is that for all samples represented,
K‘ varies relatively little from one type of elastomer to another among the 13
types shown. The modulus K‘ for all of these samples varies less than +35%
 DYNAMIC BULK MODULUS OF ELASTOMERS 1193

NATURAL RUBBER NEOPRENES URETHANES MIX.

Fig. 2. Storage modulus K' for various types of elastomers. Bars give ranges of K' values in
10' Pa at 10°C for frequencies of 100-3000 Hz.

from the mean value of 2.9 GPa. It should also be noted that this is a value
typical of a wide range of organic liquids, a fact that is consistent with
interpretation of the bulk modulus as arising primarily from localized short-
range processes of the kind that are believed to dominate in liquids. In other
words, it appears that rubbery elastomers behave elastically in compression
very much like liquids. Another feature to support this contention is the
relatively small magnitude of the loss moduli of these elastomers. In all cases
K" was less than 5% of K ', and in most cases values of K" were less than 2%
of K ' , as borne out by the high-precision results. Again, small losses are
typical of liquids. This contrasts markedly with the relatively high losses in
shear and tension exhibited by these same samples. For example, the same
B252 butyl rubber formulation used in our bulk modulus gave a ratio G"/G'
as large as unity in shear measurements made in this laboratory by Capps and
Thompson [7].
Data taken with the improved experimental apparatus were, in most cases,
not taken on exactly the same specimens used in the earlier, low-precision
measurements but, instead, were new specimens made from the same rubber
formulations and having the same curing and molding schedules as the earlier
samples. Tests for reproducibility of results with samples made to the same
specifications showed that with care K' could be reproduced to within 2%.
Although later, high-precision results did not cover as wide a variety of
elastomers, they did, however, have low enough experimental uncertainties to
permit us to determine the WLF temperature-frequency shift factors aT for
four different elastomers: two neoprenes, a butyl, and a urethane rubber. The
shift factors then made it possible to construct master curves for these four
elastomers showing the entire functional dependence of the bulk modulus
upon temperature and frequency.
These master curves were fitted to hyperbolic functions, which permitted
the complete dynamic bulk modulus to be characterized by just four parame-
ters for a given reference temperature.
1194 BURNS, DUBBELDAY, AND TING

MASTER CURVES
The temperature-frequency shift method is widely used in elastomer work
and is described in detail in both the original literature by Williams, Landel,
and Ferry [6] and in Ferry’s book [S]. For practical reasons, experimental data
generally can only be obtained over a limited range of frequencies and
temperatures. The WLF method provides a way to combine pieces of data
taken at different temperatures, each covering a limited frequency range.
These constant-temperature segments of data are first plotted as functions of
frequency on a logarithmic scale and are then shifted along the log-frequency
scale until they form a smooth sigmoidal curve.
T o do this accurately, it is necessary for there to be considerable overlap in
K’ between adjacent segments of the data that are to be fitted together by
shifts along the logarithmic frequency abscissa. Generally this overlap is
obtained by taking K’ versus frequency data either over a wide frequency
range or, more often, a t small temperature increments.
The log-frequency shifts required to perform this transformation must
themselves form a smooth curve when plotted against temperature measured
from some arbitrarily chosen reference value. Generally, a reference tempera-
ture about 50°C above the glass transition temperature has been found
empirically to give the best results, according to Ferry [8]. The WLF shift
method has been shown by Cohen and Turnbull [9] and Bueche [lo] to have a
theoretical basis in the free volume theory of viscoelasticity.

3.4

-30 -25 -20 -15 -10 -5 0 5 10 15 20 25 D

X (- In f/fm)

Fig. 3. Master curves showing K’ and K “ for 5109s neoprene. The full line K‘ curve was
calculated from a best fit of experimental data to Eq. (7). Experimental points are shown for
temperatures a t 5°C intervals from 0 to 30°C. In the interest of clarity, only data points a t 250
Hz are shown. The experimental points were plotted after being smoothed by linear regression of
[-In( K’/Z’)]-*. They show a standard deviation from the calculated curve of 0.005 GPa and a
relative deviation of about 0.2%. The corresponding unsmoothed raw data points have a standard
deviation of 0.011 GPa, or about 0.4%.
 DYNAMIC BULK MODULUS OF ELASTOMERS 1195

The use of hyperbolic fitting functions for K‘ and K ” has been proposed by
Burns and Dubbelday [ll] and also by Burns, Dubbelday, and Ting [12] by
analogy with Fuoss and Kirkwood’s work on dielectric properties of polymers
[13]. The hyperbolic tangent function has a suitable sigmoidal shape and can
be fitted quite well to experimental values of K ‘ ( x ) , where x = In( f/f,) +
cl(T - T,)/(c, + T - T,), with f, being the frequency at which the K’
curve has an inflection point at temperature T,. A parameter a is employed in
the hyperbolic functions. It is conveniently referred to as the “spread factor”
because it serves to spread the hyperbolic tangent function out along the x
axis. In a similar manner, the loss modulus K ” can be fitted to a hyperbolic
secant curve with the same spread factor. This function is suitably bell-shaped
and has a maximum at the same abscissa point as the inflection of the K’
curve.
Figure 3 shows a master curve for a typical type 5109s neoprene elastomer.
This curve was constructed by fitting the experimental data to a hyperbolic
tangent function of the logarithm of frequency [Eq. (7)] by the procedure
described in Appendix A. The reference temperature for this plot is 14”C, the
best-fit value of T,, where the inflection occurs in the K ’ ( x ) curve (see
Appendix A). Note that the very wide span of frequency covered in Figure 3 is
purely formal and not intended to imply that in reality the master curves can
be extrapolated so far. Other effects would be expected to enter at very low
and very high frequencies, effectively limiting the range over which the
hyperbolic function representation is applicable.
The fitting functions are of the form

AK
K’ = K,’ + -[1 + tanh( a x ) ] (7)
2

where K,’ is the limiting value of the storage modulus at low frequencies, x is
the argument defined above, A K is the difference between limiting values of
K’ at high and low frequencies, and a [0 I a I 13 is the empirical spread
factor. These parameters are shown graphically in Appendix A.
The spread factor was introduced by Fuoss and Kirkwood [13] in connec-
tion with dielectric losses in polymers and was shown by them to be a measure
of the distribution of dielectric relaxation times. A broader relaxation time
distribution gives a smaller value of a. The value a = 1 corresponds to a
single relaxation time, whereas a = 0 gives a uniformly broad distribution of
relaxation times. Actual values of a found for the elastomers measured in this
work were quite small, ranging from 0.035 to 0.060. These low values point to
broad distributions of compressional relaxation times in these elastomeric
materials.
The fitting functions used in eqs. (7) and (8) are modified from those of
Fuoss and Kirkwood, who actually proposed only the sech(ax) function for
the dielectric loss and did not suggest a corresponding hyperbolic function for
the real part of the dielectric constant. In our case, the storage modulus
function tanh(ax) was suggested by the form of the single relaxation time
1196 BURNS, DUBBELDAY, AND TING
TABLE I
Master Curve Parameters for Four Elastomers

5109 Neoprene 2.61 0.75 0.060 25.0 0.023 15.0 38

5109s Neoprene 2.83 0.47 0.044 14.0 0.0104 11.3 25
B252 Butyl 2.26 0.80 0.035 22.0 0.0138 18.9 36
PR1562 Urethane 2.16 0.53 0.046 17.5 0.0122 16.1 34

functions for K' and K" (Perepechko [14], Bueche [lo]). The factor a
multiplying K" in eq. (8) normalizes the loss modulus, making the total loss,
integrated over all frequencies, independent of the spread factor; otherwise
the loss would increase indefinitely and unphysically as the relaxation time
spectrum broadens toward the limit a = 0.
Equations (7) and (8) require only four parameters to fully specify the
complex bulk modulus K' + iK". These parameters are K & A K , a , and f,
the position of the inflection of K' for a given reference temperature. Alterna-
tively, the temperature T, at which K" peaks for a given reference frequency
could be used inasmuch as temperature and frequency are interrelated
(Appendix A).
In order to obtain a good fit to eqs. (7) and (8) it is necessary for the data to
cover a sufficient range of frequency and/or temperature for a good portion of
the master curve to be represented. In particular, the region near x , needs to
be covered t o get a good value of a,and then some data need to extend to near
either the high or low frequency limit (or the equivalent temperatures) so A K
can be properly determined. Curve fitting when these criteria are not met does
not give reliable values for some of the parameters.
Four of the 14 elastomers studied in this investigation met the above
criteria well enough to permit reasonably good curve fitting. The parameters
of the resulting master curves are given in Table I.
The two neoprene (polychloroprene) samples are interesting in that they
have the same basic formulation, but the 5109 material is the more heavily
filled with carbon black of the two, containing 25.7% carbon black by weight
as compared with 20.3% for the 5109s material. Information on the formula-
tions of these and some of the other elastomers measured is given in Appen-
dix B.
The more heavily filled 5109 is slightly softer than 5109S, although the
difference is only a few percent. The spread factor a is higher for 5109,
indicating that the more heavily filled material has a somewhat narrower
distribution of relaxation times. Unpublished data obtained by R. N. Capps in
this laboratory also show that Young's modulus is higher by about a factor of
3 in the more heavily filled 5109 as compared with 5109s. This is a much more
pronounced effect of filler than is observed for the bulk modulus.
The peak amplitude of the loss modulus is proportional to a A K , and this
product is about twice as large for 5109 as it is for the more lightly filled
5109s. This is as expected since, in general, fillers increase mechanical losses.
 DYNAMIC BULK MODULUS OF ELASTOMERS 1197

Peak loss values for the other materials in Table I show that butyl rubber and
polyurethane have about the same maximum loss values as the more lightly
filled 5109s neoprene. The interesting thing is that the loss peak values show
so little variation among different types of elastomers in Table I.
The last two columns in Table I give the WLF shift parameters c1 and c2
for the four elastomers. Note that c1 is here given for the shift factor uT
defined as the natural log of the frequency shift as used in Appendix A rather
than in terms of the common log, as is conventional. The tabulated values
should be multiplied by 0.4343 for comparison with conventional values in
Ferry’s book and elsewhere. All four elastomers in the table have shift
parameters that lie within about 20% of the average values 15 and 33,
respectively. In the free volume theory the product of the two shift parame-
ters is proportional to the critical free volume that must exist for transport to
occur. Of the four samples above, only 5109s has a substantially different c1c2
product than the others, its value being about half that of the other three.
The reason for this is not known, since the connection between values of the
shift parameters and structural or chemical properties of the elastomer are
not well understood, particularly in the case of the bulk modulus.
The utility of master curves for compactly presenting information about
elastic moduli is well recognized. Such curves are particularly useful when
they can be fitted to a simple function with a small number of parameters, as
in the present case. These parameters then suffice t o characterize the entire
dynamic modulus as functions of both temperature and frequency. It should
be pointed out, however, that the parameters a, A K , K;, and T, used in
Table I to specify the master curves do not constitute the whole story. It is
also necessary to know the parameters that characterize the temperature-
frequency transformation. These are found from the WLF shift method, and
there are three such parameters: the two constants, c1 and c2, of the WLF
equation (see Appendix A or Ferry [S]) and a reference temperature To which
may be chosen arbitrarily but which should be approximately 50°C above the
glass-transition temperature. In our treatment T,,, was chosen as the reference
temperature To.Thus there are really six parameters to be determined in all:
four from the hyperbolic function fit and three from the WLF shifts, but one
of the latter, To,is arbitrarily chosen to be T,.

AGING EFFECTS
Few, if any, studies of the effects of aging upon the bulk modulus of
elastomers have been reported. Since the effects are small, it is necessary to be
able to measure K with a precision of the order of 1 or 2% to reliably detect
changes caused by aging a t room temperature in the elastomers studied in this
work.
Aging, as the term is used here, refers to slow changes in a material which
affect its elastic properties, in this study bulk modulus. These effects take
place on time scales of weeks, months, and even years and fall into two general
categories: chemical and physical. Chemical aging refers to slow changes in
chemical bonding within a material which affect the dynamics of polymer
chains within the material; e.g., continuing addition or breaking of cross
1198 BURNS, DUBBELDAY, AND TING

linkages. Physical aging refers to slow structural changes that do not involve
the formation or breaking of molecular bonds as, for example, slow thermal
relaxation of hindered rotation of some molecular groups which allow the
structure t o rearrange into a lower energy configuration. There is a connection
between physical aging, creep, and slow annealing. As defined here, both
chemical and physical aging should be more or less strongly temperature
dependent.
A third type of aging might be defined as involving absorption of gas or
liquid from the surface into the volume of the material; i.e., a kind of impurity
transport into the material. This diffusion of impurities into a sample could
lead to chemical and/or physical aging effects, the latter including the effect
upon chain dynamics of the presence of impurities. In general, it is difficult in
practice to avoid diffusion of impurities into or out of a sample when it is aged
in air or water, so aging usually includes some unavoidable impurity transport
effects. In the present investigation it was an objective to study aging under
exposure t o artificial sea water, so it was possible to have both water and salt
transport into the samples as well as some leaching of material out of the
samples. No attempts were made to relate aging to material transport of this
kind, but both water absorption and leaching are believed to be small
second-order effects.
Most of the aging studies were begun with the early, analog version of the
apparatus, and the samples being aged were later measured with the improved
coupler system. Thus the precision of the early measurements on long-aged
samples is not as good as more recent measurements on the same samples aged
for shorter times. Some types of rubber were restudied with the later appara-
tus, beginning the aging process again on freshly prepared samples. This
afforded some comparison with earlier data.
Results are shown in Figure 4 as aging profiles in which the relative changes
in K ’ are plotted as functions of aging time in months. The sparse data points
have been connected by smooth curves which are to be regarded as merely
schematic, showing general trends of the aging process.
The aging profiles fall into two distinct groups. The first, typified by the
natural rubbers, is characterized by a small (about 5%)decrease in K‘ over the
first 3 months followed by a rapid rise to about 25% above the baseline value,
whereupon the bulk modulus stabilizes a t the higher value and undergoes
little further change. The second form of aging profile shows a rapid dip in K ’
over the first few months, generally of about 5-lo%, followed by a rise to a
relatively stable value near the baseline K’ a t 12 months and beyond. This
stable value does not differ by more than a few percent from the initial value
of the modulus. All of the neoprenes exhibited the latter profile, and all of the
natural rubbers showed the first type of profile. However, of the two ure-
thanes, one aged like a natural rubber and one like a neoprene.
Aging effects appear to be much less pronounced in the bulk modulus than
in shear or Young’s modulus. This is not surprising, for the latter moduli
should be more sensitive to chemical aging which affects long-range configu-
rations of the polymer chains. The bulk modulus on the other hand, being the
result of a short-range, liquidlike mechanism would be expected to be a more
stable property, less affected by aging.
 1.4 - -
-
-
w
so.9 - sx
dO.8 - -
0.7 - - -
-
g 0.6 - -
p 5 - - -
K
NATURAL RUBBERS: NEOPRENES POLWRWES:
0- M-165-4 0 BC-165-2
- o - URALm 3140
x , n - AA-1 65-6 1 A BC-165-3
- c5 n BG-165-1
0- 334-270 0 5109-S
- o PR1526
--
0 5109
-
I I I I I I I I I I I I I I I I I ] I I I I I I I I I

Fig. 4. Aging profiles for various rubbers aged at room temperature in artificial sea water: relative age-induced
changes in K ' as functions of aging time.
1200 BURNS, DUBBELDAY, AND TING

CONCLUSIONS
Results of our measurements on a variety of different types of rubbery
elastomers show relatively narrow ranges of values for both the storage bulk
modulus and the loss modulus as functions of frequency and temperature, and
the bulk moduli of these materials show little dependence upon chemical
composition of the elastomers. This is in marked contrast to the wide varia-
tions observed in shear and tensile properties of elastomers with different
chemical compositions and preparation. The close similarity in bulk modulus
values of a wide variety of materials found in this work is a significant result,
The values of both K’ and K” are comparable to those of organic liquids, and
the resemblance is consistent with a similarity in the mechanisms believed to
be responsible for the compressibilities of both classes of materials. The bulk
modulus in an elastomer appears to be associated with local short-range
molecular interactions of the same kind as predicted by free volume theories
of liquids. Values of the storage bulk modulus K‘ are close to 3 GPa,
regardless of elastomer type among these types studied.
The losses in these materials are also small, around 1 or 2% of the average
K’ values. These also contrast markedly with values of shear and Young’s
modulus for such materials where storage modulus values are typically more
than two orders of magnitude smaller than K‘ and where loss modulus values
are much larger relative to the storage moduli. Typically the dependence of
the losses of shear and Young’s modulus upon chemical formulation of the
elastomer is much more pronounced, as well.
The experimental bulk moduli were well fitted by simple hyperbolic func-
tions containing a small number of adjustable parameters. One of these
parameters controls the spread of the functions on a log-frequency scale, and
this spread factor is believed to be a measure of the breadth of the distribu-
tion of relaxation times in the elastomers in much the same way that it serves
in the dielectric case [13]. All samples fitted in this way showed evidence of
very broad relaxation time distributions. Such broad distributions are to be
expected from free volume theories of amorphous materials where there does
not seem to be any single dominant mechanism possessing a well-defined
relaxation time or closely grouped set of relaxation times.
Data on the effects of aging in artificial sea water a t room temperature
showed two principal types of changes in bulk modulus with aging time. The
natural rubbers exhibited an increase of K’ after a few months, reaching
stable values about 25% higher than the initial bulk modulus. The neoprenes,
on the other hand, showed an a rapid early dip in K’ of about 5-lo%,
followed by a rise to a stable value within a few percent of the initial value. It
may be that this initial softening of the neoprenes is related to the effects of
water absorption, although the present study did not test this hypothesis.

We gratefully acknowledge the assistance of L. C. Colquit, M. E. Browder, C. W. Ramzy, J. G.

Wilson, J. Morales, and V. V. Apostolico in various phases of the lengthy measurement program.

APPENDIX A
The method used in this work to smooth the data and to construct master
curves does not follow the conventional frequency-shift procedure described
 DYNAMIC BULK MODULUS OF ELASTOMERS 1201

T1
-- - - - - ---
- -2.5-_
T4
T5
2-

T6
k
--L5.L ----
T7
- - -- - - - -
T8

T9
T10
K’ =STORAGE
T15 M 0 0UL U S
0.5 -

I I I I
0
fl f2 -3 -2 -1 0 1 2
LOG (f/fm)
Fig. A.l. Hypothetical case showing the overlap needed for application of the conventional
frequency-shift procedure. Horizontal translations of the line segments to form a smoothly fitting
single curve yield the master curve. The WLF shift function uT is determined by the frequency
shifts required to perform these translations. The procedure is usually carried out graphically.

by Ferry [8]. Our data consists of segments of K’( f ) a t various temperatures

that often do not possess the overlap required for application of the usual
shift method. A favorable case with adequate overlap is illustrated in Figure
A.l, where it can be seen that horizontal shifts of the segments overlap,
providing a means of smoothly joining the segments together to form a
smooth curve.
Since our data do not meet the overlap criterion for direct application of
the frequency-shift method, we proceed instead by using an expression for the
functional temperature dependence of K’( T ) that is derivable from the Rouse
theory for the temperature dependence of elastic moduli given by Ferry
[8; Chap. lo]. This equation is

[-In( K ’ / T ) ] -’= a + bT (A.1)

in which T is the absolute temperature.

Equation (A.1) permits one to smooth data taken a t a single frequency but
a t different temperatures using linear regression. The particular choice of
frequency does not affect the result, so it may be chosen to lie in a region
where the data is smooth and f a r from any system resonances. In our case
convenient frequencies lay between 0.1 and 1.0 kHz, and 200 Hz was usually
chosen, with K ’ values measured a t 5°C intervals between - 5°C and + 40°C.
Experimentally K‘( f ) was found to vary linearly with frequency between
0.1 and 1.0 kHz to a very good approximation, so once the constants a and b
1202 BURNS, DUBBELDAY, AND TING

were found by regression, eq. (A.l) could be used to interpolate between the
5°C temperature intervals of the experimental data to provide data segments
with the overlap needed to construct the master curve by the usual
frequency-shift method.
However, master curves may alternatively be constructed from the slopes of
the short K’( f ) segments; differentiating eq. (7) one has
dK’ AK
- - - a -sech2 ax
d3c 2
This has the advantage of eliminating the graphical “eyeball” method of
fitting the segments together.
The variable x in eqs. (7) and (8) is a function of frequency, but it is also a
function of temperature because frequency and temperature are interrelated
through the Boltzmann time-temperature superposition principle, which is
one of the fundamental tenets of linear viscoelasticity theory (see, for exam-
ple, Ferry [8; p. 171 or Bueche [lo; p. 1731). The definition of x and of uT
leads to the relation between x and T ,

c ~ ( T -Tm)
x( f = f,) = -In(+.) =
c2 + ( T - T,) .

Here T, is a reference temperature at which x = 0 and uT = 1.

Equation (A.3) is of the familiar form of the temperature dependence of the
WLF shift factor (Ferry [8]). Thus, fitting experimental slopes of K’( f ) to eq.
(A.2) determines the shift parameters c1 and c2 through eq. (A.3), from which
the master curves can be found by substitution into eqs. (7) and (8).
Altogether there are six parameters appearing either explicitly or implicitly
in eqs. (7) and (8). Three of these, a, AK, K,’ (or K L ) serve to position the
master curves on the K’-x axes. The other three, cl, c2, and the reference
temperature, T, in this case, fix the temperature-frequency shift function in
accordance with the Boltzmann superposition principle. The K’( T ) data can
be fitted directly to eq. (7) with x replaced by eq. (A.3). However, this is a
six-parameter fit, and it does not appear to be robust enough for general use.
We have devised a two-step approach that reduces the number of parameters
to be determined in each fit to a more tractable number by making use of the
slopes, dK ’/&.
Evaluating eq. (A.2) at f = f, gives

At a convenient frequency within the range of the experimental data, values

of the slopes of the segments of K ’ ( T ) can be fitted to eq. (A.4) to find the
four parameters A = a A K / 2 , cl, c2, and T,. In favorable cases this actually
becomes a three-parameter fit because in such cases T, can be determined
from the condition that T = T, at the maximum of eq. (A.4). In such cases
when the data covers the region around the maximum of eq. (A.4), for
temperatures not too far from T,, c2 in the denominator will be much larger
 DYNAMIC BULK MODULUS OF ELASTOMERS 1203

than ( T - Tm), reducing the argument of the sech function to acl(T - T,)/c,
which can be written simply B(T - Tm). Now the fit involves only two
parameters explicitly, the constants A and B, and generally gives a robust fit.
Even with the slope method, the fit may not be satisfactory for data f a r from
the inflection region of K ’ (or the maximum of K”) for the same reason that
the conventional shift method is not satisfactory for such data.
With A and B determined from the slopes, the K’ data can be fitted to eq.
(7) to find the two remaining parameters, a and K,’. In cases where the slopes
require a three parameter fit, both c1 and c2 will be determined, leaving the
K ’ fit to eq. (7) to evaluate a and K,’ as before.
Because of the complex manner in which the parameters are found, it is
difficult to assess the uncertainties in the final results. This is a common
problem with the usual frequency-shift procedure as well. Much depends upon
where the data lies on the master curve; if it lies in the region of the inflection
point, the curve fit will be relatively robust, and the parameters will be
relatively well determined. If, however, the data are far from the inflection
region, then the fits will not be very precise, and the uncertainties in the
parameters will be relatively large. These remarks hold equally well for the
conventional WLF master curve construction, and our method appears to give
comparable accuracy. One measure of uncertainty in the results is the close-
ness with which the experimental data match the hyperbolic master curves in
eqs. (7) and (8). Figure 3 indicates that in the case of 5109s neoprene the fit is
quite good, within perhaps 2%. This was a favorable case, however, and in
general the uncertainty will be appreciably larger. The data are repeatable on
the same sample to within a few tenths of a percent. They are repeatable on
different samples of the same formulation, prepared in the same way, to

FREQUENCY (kHz)

Fig. A.2. Typical data on the bulk modulus, K ’ , as a function of frequency for 5109s neoprene
at two temperatures.
1204 BURNS, DUBBELDAY, AND TING

within 1%.The accuracy of the bulk modulus of the fluid medium, castor oil,
is about 2%, according to T i m e [4], and this is believed to represent the
accuracy of our later measurements, although the precision is considerably
better than this. Figure A.2 illustrates a typical set of unsmoothed data points
in the frequency range 100-1000 Hz a t two different temperatures, 5 and
15°C.

APPENDIX B
Formulations of Some Elastomers

Type designation Ingredient Parts by weight

Natural rubbers
334-270 SMR-5 Natural rubber 100
Carbon black 20
Zinc oxide 5
Octamine, antioxidant 2
Sulfur 1.5
Altax, accelerator 1
Thionex, accelerator 0.3
Stearic acid 1
Plasticizer 3
Cure 15 min at 300°F
AA-165-4 AA-165-6
AA-165-4 and AA-165-6 Smoked sheet rubber 100 100
Stearic acid 1 1
Protox 166 5 5
Carbon black 40 65
Octamine 2 2
Circo LP oil 3 3
Sulfur 1.5 1.5
Altax 1 1
Unads 0.3 0.3
Cure 15 min a t 280°F
Neoprenes
5109 5109s
5109and5109S Neoprene GRT 100 100
Carbon black 40 33
Red lead 15 15
Octamine 2 2
Stearic acid 1 1
TE-70 processing aid 2 2
Alax 1.5 1.5
Cure Min./Temp. (OF) 25,' 320 30/ 310
BC-165-2 BC-165-3
BC-165-2 and BC-165-3 Neoprene WRT 100 100
Stearic acid 1 1
Octamine 2 2
Carbon black 20 45
Circo LP oil 15 15
Red lead dispersion 15 15
Sulfur 1 1
Unads 1 1
Cure 45 min at 310°F.
 DYNAMIC BULK MODULUS OF ELASTOMERS 1205

(Continued )

Type designation Ingredient Parts by weight

Polyurethane
BG-165-1 Millathane E-34 100
Cadmium stearate 0.5
Caytur 4 1
Sulfur 1.5
Thermax 2
Captax 2
Altax 4
Califlux 510 10
Cure: 15 min at 310'F
Butyl Rubber
B-252 Butyl 150 100
Carbon black 50
Zinc oxide 5
Red lead 10
Circo LP oil 5
Dibenzo GMF 3
AA-1177-20 Wax 6
Cure 40 min at 307'F.

Note: for more detailed information and sources of ingredients listed, see R. N.
Capps, and C. M. Thompson, Handbook of Sonar Passive Materials, Naval
Research Laboratory, Washington, D.C., 1981, NRL Memorandum Report 4311.
Some of the elastomers listed in the present paper such as Uralite 3140 and PR
1526 are proprietary formulations.

References
1. R. N. Capps, J . Acoust. SOC.Am., 73, 2000 (1983).
2. J. E. McKinney, S. Edelman, and R. S. Marvin, J . Appl. Phys., 27, 425 (1956).
3. R. J. Bobber, Underwater Electroacoustic Measurements, U S . Government Printing Office,
Washington, D.C., 1970.
4. R. W. T i m e , J . Acoust. SOC.Am., 52, 989 (1972).
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Received May 2, 1988

Accepted January 17,1989