J Therm Anal Calorim
DOI 10.1007/s10973-014-3781-8
Plasticizer loading in acoustic encapsulants
Impact on dynamic mechanical properties
Matthew Rice
Received: 19 July 2013 / Accepted: 18 March 2014
Ó Akadémiai Kiadó, Budapest, Hungary 2014
Abstract Acoustically transparent elastomers are the
windows through which the United States Navy views the
ocean. For acoustic clarity and sensitivity, it is important
that the elastomer operates well outside damping condi-
tions as dictated by the temperatures and frequencies of
interest. Damping behavior is characterized by a peak in
the loss tangent. However, the temperature and frequency
location of this peak can shift in response to absorbed
plasticizing fluids. This material characteristic is under
investigation using dynamic mechanical analysis (DMA) to
assess its dependence on the plasticizer and polyurethane
component chemistry. In this first stage of the research, a
temperature range from -100 to 100 °C and samples sat-
urated with fluid were explored by DMA to determine the
limiting behavior of the samples, enabling more detailed
investigation in future work. Association of absorbed
plasticizers with polyurethane components by polarity was
demonstrated in the results by the shifting of the appro-
priate hard and soft block loss tangent peak.
Keywords DMA
Polyurethane
Plasticizer
Acoustic

Diffusion
Damping
Abbreviations
DMA Dynamic mechanical analyzer
PTFE Polytetrafluoroethylene
Originally presented at the 2012 North American Thermal Analysis
Society Conference, Orlando, FL.
M. Rice (&)
Devices, Sensors, and Materials Research and Development
Branch, Sensors and Sonar Systems Department, Naval
Undersea Warfare Center, Division Newport, 1176 Howell
Street, Newport, RI 02841, USA
e-mail: matthew.a.rice@navy.mil
DOP Dioctyl phthalate
DOTP Dioctyl terephthalate
TBTO Tributyltin oxide
DCOIT 4,5-Dichloro-2-n-octyl-4-isothiazolin-3-one
Introduction
The U.S. Navy uses rubbers and polyurethanes to create
acoustic windows, to encapsulate transducers to protect
them from the ocean environment, and to serve as an
acoustic medium in sonar arrays.
The dynamic mechanical behaviors of these materials
change when they absorb plasticizers such as transducer fill
fluids (e.g., castor oil, hydrocarbon distillates and syn-
thetics, silicone fluids). Material change can also occur
from intentional additives, such as the anti-biofouling
compounds tributyltin oxide (TBTO) and 4,5-dichloro-2-n-
octyl-4-isothiazolin-3-one (DCOIT), as the navy seeks to
improve its current acoustic materials and introduce new
composites. The resulting change can lead to signal loss
and degraded acoustic and mechanical performance of the
elastomers.
The most significant change for sonar purposes is the
value of the loss tangent (tan delta), which is an indication
of the mechanical damping character of the material. Sig-
nificant acoustic damping losses can occur at conforma-
tional disorder transition temperatures, such as the glass–
rubber transition. The temperatures of these transitions are
frequency dependent [1, 2], and can shift to lower values as
a result of plasticization by fluids and additives [3, 4].
Due to their chemical nature, polyurethanes tend to
exhibit diblock morphology. This refers to the association
123
 M. Rice

of chemical components to ‘‘soft block’’ and ‘‘hard block’’
phases [5, 6]. The soft block phase constitutes the majority
of the materials, consisting of large molecular mass
polymer. Interspersed within this phase are hard block
regions, consisting of groupings of the polar compounds
of the polyurethane (isocyanate, chain extender alcohol/
amine). Both the hard block and soft block phases can
exhibit an associated conformational disorder transition
temperature. The influence of a plasticizer on shifting
these transitions will depend on its polarity match with the
associated phase.
Prior investigations into the dynamic mechanical proper-
ties of polyurethanes have focused on their relationship with
the internal molecular structure of the polymer [7, 8]. The
changes in these properties due to plasticizers are of naval
interest under the following situations: when the material
encounters in-service conditions, and when the material is
improved by additives. To this end, the work presented is
focused on the shift in transition temperatures of two well-
understood acoustic polyurethanes in response to the
absorption of plasticizing fluids. The author hopes in future
work to study the dependence of the degree of shift with the
amount of plasticizer loading using theoretical models.
Experimental
Polyurethane samples described previously were immersed
in the plasticizer of interest at *23 °C after initial mass
was measured using a microbalance. Control samples were
maintained in similar containers, but were not immersed in
fluid. On a periodic basis, samples were removed from the
fluid, blotted with paper towels, and weighed to track the
uptake of fluid by the polyurethane. Once samples were
saturated, the next phase of the measurement process
proceeded with dynamic mechanical analysis. Using the
methods of Crank and Aminabhavi et al. [9, 10], diffusion
coefficients for the fluid through the polyurethane could be
estimated from this mass uptake data.
Dynamic mechanical analysis
The second phase of the work was to record the transition
temperatures of the loaded polyurethane samples using a
TA Instruments 2980 DMA with the single cantilever
clamp configuration. Samples were oscillated at 50-lm
amplitude at a 1-Hz frequency while the temperature was
linearly increased 2 °C min-1 from -100 to 100 °C. Cold
nitrogen vapors generated from liquid nitrogen were used
for cooling. Initial and final sample masses were taken to
determine the amount of entrained fluid that may have
volatilized during the heating process.

Materials Results and discussion

The polyurethanes used in this effort were ConathaneÒ EN-
7 by Cytec Industries, Inc. and NUWC XP-1, an in-house
formulation. The plasticizers used in this effort were sonar
transducer fluid (castor oil, per MIL-T-17128C), Isopar-L
isoparaffinic hydrocarbon from ExxonMobil, distilled
water, and dioctyl phthalate (DOP) (C99 %) and dioctyl
terephthalate (DOTP) (C98 %) both from Sigma-Aldrich.
Plasticizer absorption
Saturation values and diffusivities for the plasticizers in the
two polyurethanes are shown in Table 1. Significant
absorption to *50 % by mass of the phthalate fluids by
Table 1 Saturation and diffusivity of plasticizers in polyurethanes

Preparation of polyurethane samples Samples Saturation/mass% Diffusivity/cm2 s-1

EN-7 polyurethane
Polyurethanes were mixed according to manufacturer’s Water –a –a
recommendations, degassed under vacuum, and injection- Isopar-L 27.9 4.7E-8
potted into metal molds to create 0.5 in. 9 1.6 i-
DOP 52.2 1.6E-9
n. 9 0.0625 in. samples of mass 0.7–0.8 g each. Spray
DOTP 51.6 1.9E-9
PTFE mold release was used to facilitate sample removal.
Castor oil –b –b
EN-7 was cured overnight (C16 h) at *23 °C followed by
XP-1 polyurethane
3 h at 80 °C. XP-1 was cured overnight (C16 h) at 60 °C.
Water 2.1 5.5E-8
Isopar-L 8.4 1.2E-8
Methods
DOP 27.6 1.7E-9
DOTP 17.2 1.8E-9
Plasticizer absorption
Castor oil –b –b
a
The first phase of the work was to prepare sets of poly- Inconclusive results due to measurement error
b
urethane samples, each loaded with a different plasticizer. Saturation limit not yet reached at time of writing

123
Plasticizer loading in acoustic encapsulants

1 Air Table 2 Primary transition temperature (as determined by peak of

DMA/tan delta (young s) /E /E

0.9 Isopar-L loss tangent) of plasticizer-saturated polyurethanes and relative tem-

DOP perature shift from control sample
0.8
DOTP Samples Transition temperature/°C Temperature shift/°C
0.7
0.6 EN-7 polyurethane
0.5 Air (control) -58 0
0.4 Water –a –a
0.3 Isopar-L -77 -19
0.2 DOP -55 3
DOTP -56 2
0.1
XP-1 polyurethane
0
–100 –80 –60 –40 –20 0 20 40 60 80 100 Air (control) -26 0
Temperature/°C Water -25 1
Isopar-L -32 -6
Fig. 1 Overlay of DMA curves of plasticizer-laden EN-7 DOP -40 -14
polyurethane
DOTP -35 -9
a
1 Air Inconclusive results due to measurement error
Water
0.9
DMA/tan delta (young s) /E /E

Isopar-L
0.8 DOP Table 3 Secondary transition temperature (as determined by peak of
DOTP loss tangent) of plasticizer-saturated polyurethanes and relative tem-
0.7
perature shift from control sample
0.6
Samples Transition Temperature
0.5
temperature/°C shift/°C
0.4
0.3 EN-7 polyurethane
50 60 70 80 90 100 Air (control) 49 0
0.2
Water –a –a
0.1
Isopar-L (low peak) 19 -30
0
Isopar-L (high peak) 54 5
–100 –80 –60 –40 –20 0 20 40 60 80 100 b
Temperature/°C DOP – –b
b
DOTP – –b
Fig. 2 Overlay of DMA curves of plasticizer-laden XP-1 XP-1 polyurethane
polyurethane
Air (control) 86 0
Water 54 -32
EN-7 was observed, accompanied by swelling of the sam- Isopar-L 53 -33
ple. The recorded fluid uptake profile will enable future DOP 78 -8
samples to be created at specific degrees of loading. Mea- DOTP 96 10
surement error prevented the analysis of water in EN-7. a
Inconclusive results due to measurement error
At the time of this writing, castor oil had not yet reached b
No discernible peak found
saturation in either EN-7 or XP-1.
the equipment to maintain oscillation control. As a result,
Dynamic mechanical analysis data above 20 °C for DOP/EN-7 and 40 °C for DOTP/EN-
7 are suspect. This behavior will be re-examined in future
The DMA curves of EN-7 and XP-1 polyurethanes satu- work using a sample configuration more appropriate for
rated with the plasticizing fluids are shown in Figs. 1 and 2, these low modulus conditions such as shear or dual-canti-
respectively. Transition temperatures associated with the lever clamps.
primary and secondary loss tangent peaks and their tem- The results indicate that water reduces the temperature
perature shifts from control samples are listed in Tables 2 of the high-temperature peak in XP-1 and does not shift the
and 3, respectively. low-temperature peak, confirming the significance of
High uptakes of the phthalate fluids by EN-7 depressed polarity. The nonpolar fluid Isopar-L is shown to reduce the
the stiffness of the polyurethane such that it was too low for temperature of the low-temperature peak of both

123

polyurethanes as expected. The unanticipated splitting of
the high-temperature peak in EN-7 by Isopar-L is either an
artifact due to solvent volatility, or it is associated with the
increased free volume of the nonpolar components of the
curative and isocyanate compounds, while the associations
between the polar components remain unaffected. The
depression of the analogous peak in XP-1 suggests signif-
icant steric hindrance by nonpolar components of the
curative and isocyanate compounds around more weakly
associated polar components.
Both phthalate fluids reduce the temperature of the low-
temperature peak in XP-1, but do not shift the analogous
peak in EN-7. This indicates a resistance to dissociation of
the EN-7 base component by the phthalate fluids. The
associated increase in loss tangent is due to significant
viscous response by the high entrainment of the fluid. The
high-temperature peak in XP-1 is reduced in temperature
by DOP and increased by DOTP, albeit a *5 °C shift in
both cases. This behavior will also be re-examined in
future work using shear or dual-cantilever clamps.
Conclusions
Polyurethane samples of EN-7 and XP-1 were successfully
loaded with plasticizing fluids and characterized by
dynamic mechanical analysis, with few exceptions. Room-
temperature (*23 °C) saturation values and estimated
diffusion coefficients were determined for the different
plasticizing fluids in the different polyurethanes. Fluid
uptake data will enable efficient sample preparation for
future work aimed at extrapolation of behavior over a
greater range of frequencies via the time–temperature
superposition method.
The anticipated shifts seen in the conformational dis-
order transition temperatures of the polyurethanes due to
123
M. Rice
absorbed plasticizers were in alignment with the polarity of
the plasticizers and the polyurethane diblock morphologi-
cal chemistry. The unexpected behavior of a split loss
tangent peak in EN-7 polyurethane by Isopar-L fluid is
explained either by an artifact due to solvent volatilization
or by the existence of significant nonpolar character in the
EN-7 hard block phase.
Acknowledgements The author wishes to thank Dr. Thomas S.
Ramotowski for his mentoring and guidance. This work was sup-
ported by the In-house Laboratory Independent Research (ILIR)
program of the Office of Naval Research, and by the New Profes-
sional Development Program (NPDP) of the Naval Undersea Warfare
Center division Newport, Rhode Island.
References
1. Menard KP. Dynamic mechanical analysis: a practical introduc-
tion. Boca Raton: CRC Press LLC; 1999.
2. Menczel JD, Prime RB. Thermal analysis of polymers: funda-
mentals and applications. Hoboken: Wiley; 2009.
3. Perfetti G, Alphazan T, Wildeboer WJ, Meesters GMH. Thermo-
physical characterization of PharmacoatÒ 603, PharmacoatÒ 615
and MowiolÒ 4-98. J Therm Anal Calorim. 2012;109:203–15.
4. Amim J Jr, Blachechen LS, Petri DFS. Effect of sorbitan-based
surfactants on glass transition temperature of cellulose esters.
J Therm Anal Calorim. 2012;107:1259–65.
5. Szycher M. Handbook of polyurethanes. Boca Raton: CRC Press
LLC; 1999.
6. Capps RN, Elastomeric materials for acoustical applications.
Orlando: Naval Research Laboratory Underwater Sound Refer-
ence Detachment; September 15, 1989.
7. Lee JD et al., High strength polymers. Carderock: NSWCCD;
2001–2003. ILIR-733.
8. Thompson CM, Heimer WL II. Relationship between acoustic
properties and structure of polyurethanes. J Acoust Soc Am.
1985;77:1229–38.
9. Crank J. The mathematics of diffusion. London: Oxford Uni-
versity Press; 1956.
10. Aminabhavi TM, Thomas RW, Cassidy PE. Predicting water
diffusivity in elastomers. Polym Eng Sci. 1984;24:1417–20.