International Journal of Adhesion and Adhesives 87 (2018) 64–72

Contents lists available at ScienceDirect

International Journal of Adhesion and Adhesives

journal homepage: www.elsevier.com/locate/ijadhadh

Thermomechanical behavior of aerospace-grade RTV (silicone adhesive)☆☆,☆ T

Todd M. Mower
M.I.T. Lincoln Laboratory, Lexington, MA 02420, USA

ARTICLE INFO ABSTRACT

Keywords: Measurements of mechanical properties of the commercial polysiloxane RTV 566 were conducted over a range of
Polyphenylmethylsiloxane temperatures, with particular focus on characterizing isothermal behavior at reduced temperatures to reveal
Low-temperature testing possible evidence of crystallization in this material. Conventional testing was performed using typical tem-
Thermal expansion perature sweeps to measure elastic flexural and tensile moduli, and thermal expansion coefficients with and
Elastic modulus
without volumetric constraint. The glass transition temperature was determined to be about −115 °C.
Shrinkage
Crystallization
Measurements of the tensile moduli of RTV 566 specimens were also conducted under isothermal conditions
at reduced temperatures. After exposure to temperatures below −75 °C for several hours, tensile moduli rose by
as much as a factor of 40. Volumetric shrinkage of 0.35% was demonstrated after 50 h under isothermal con-
dition at −80 °C. These measurements demonstrate previously unpublished manifestations of crystallization
occurring in this material, which is based upon a polydimethylsiloxane with phenyl substituents for some of the
methyl groups.

1. Introduction applications destined for deployment in space, chiefly because of its

1.1. Motivation
During environmental testing of a telescope lens assembly built at
MIT Lincoln Laboratory, the focus continued to shift after thermal
equilibrium had been established at cold temperatures (−75 °C and
−85 °C). This shift steadily developed increasing magnitude and sta-
bilized after several days, and could be accounted for by neither ther-
moelastic mismatches nor viscoelastic behavior of the materials used in
the assembly. While considering other possible causes for the behavior
of the lens assembly, crystallization of the silicone adhesive used to
mount the lenses was suspected. Because very few studies of crystal-
lization in silicone materials (typically polydimethylsiloxane, PDMS)
have been published in the open literature, the investigation reported
here was undertaken.
Room temperature vulcanizing (RTV) adhesives have been available
and in use for many decades. One very prominent RTV developed by
General Electric over fifty years ago is based up PDMS, with phenyl
substituting for some of the methyl groups in the chemical configura-
tion; this adhesive is marketed as RTV 566 and is classified as a poly-
phenylmethylsiloxane [1]. This material has been used in many
low-outgassing behavior (meeting NASA requirements, as specified in
ASTM E595), low glass transition temperature (Tg), and enhanced
thermal conductivity. Despite widespread use of RTV 566 throughout
the aerospace and optical communities, very little data concerning its
thermomechanical behavior have been published in open literature.
Moreover, measurements of its mechanical properties have typically
been conducted under ambient conditions or using linear ramps in
temperature. A primary goal of this study was to explore the tem-
perature and strain conditions that might induce crystallization in RTV
566.
Compliant adhesives are very often used to bond brittle elements,
such as glass lenses, to stiff metal structures. Examples of the prominent
use of RTV 566 within the aerospace community abound. In NASA's
Geostationary Operational Environmental Satellite (GOES), RTV 566
was used to bond the glass secondary mirror into a supporting structure
made with Invar [2]. In the Geoscience Laser Altimeter System (built at
NASA's Goddard Space Science Facility), RTV 566 was used to bond
optic mount shims in the Laser Select Mechanism. The Jet Propulsion
Laboratory has also used RTV 566 in critical assemblies built for NASA,
including the Mars Exploration Rover (MER)/Mars Science Laboratory
(MSL) and JUNO flight projects [3]. Within the Fermi Large Area

☆☆
The author has no financial interest in this work or any other conflicts of interest.
☆
Distribution Statement A. Approved for public release: distribution unlimited. This material is based upon work supported by the National Aeronautics and Space
Administration under Air Force Contract No. FA8702-15-D-0001. Any opinions, findings, conclusions or recommendations expressed in this material are those of the
author(s) and do not necessarily reflect the views of the National Aeronautics and Space Administration.
E-mail address: mower@ll.mit.edu.

https://doi.org/10.1016/j.ijadhadh.2018.08.009
Accepted 7 August 2018
Available online 23 August 2018
0143-7496/ © 2018 The Author. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
T.M. Mower
Telescope (formerly GLAST), a photomultiplier tube was bonded to an
aluminum housing using RTV 566. The European Space Agency has also
used RTV 566 in assembly of some of its space systems—for example
with mounting beamsplitters used for interferometers [4].
1.2. Background: crystallization in polysiloxanes
Crystallization in polysiloxanes has been demonstrated through a
few limited studies over the past sixty years, and typically occurs during
cooling but it can occur during heating, after supercooling [5]. Crys-
tallization is an exothermic process, usually with an associated volu-
metric decrease and mechanical stiffness increase. It is seldom nu-
cleated during brief-duration cooling (as in typical testing of
mechanical properties), but either slow cooling or prolonged exposure
to cold can trigger crystallization.
Though crystallization in polysiloxanes is not widely recognized
within the wide community that uses it in mechanical applications
(even those subjected to low temperatures) several incidental ob-
servations of such behavior have been made. While studying gas per-
meability characteristics of silicone rubber, Zhang stated that “standard
silicone rubber (VMQ) tends to crystallize at −50 °C” [6]. Rey et al.
performed DSC measurements showing crystallization of RTV 141 at
−83 °C [7]. Using an interferometer to measure volumetric changes, in
1950 Weir, Lesser, and Wood observed behavior they ascribed to
crystallization occurring between −60 ° and −67 °C in Dow-Corning
Silastic X-6160 and in General Electric 9979G silicone rubbers, and
between −75 ° and −85 °C in Silastic 250 [8]. Their measurements
demonstrated that, for these materials, volume change varied from
approximately 3 to 7% during crystallization. Electron micrographs of
replicas of crystallites formed in PDMS at −110 °C were produced by
Marei et al. in 1970 [9]. More recently, direct scanning electron mi-
crographs of crystals formed in PDMS at −70 °C were produced by
Sundararajan [10].
Extensive characterization of the low-temperature mechanical and
thermal behavior of a polysiloxane used in components included in
nuclear weapons was performed by The Los Alamos National
Laboratory (LANL) [11]. The material (DC745U, produced by Dow
Corning), consists of dimethyl, methyl-phenyl, and methyl-vinyl si-
loxane repeat units [12]. Chemical analysis and additional thermal/
mechanical tests were performed by Lawrence Livermore National La-
boratory (LLNL) [13]. Results from differential scanning calorimetry
(DSC) tests conducted by LANL on DC745U indicate it has a glass
transition temperature (Tg) of about −122 °C. During increasing tem-
perature ramps, an endothermic peak at −55 °C occurred, which is
associated with the melting of crystallites. A subsequent cooling at 5 °C/
min revealed a crystallization temperature of about −61 °C. Mechan-
ical testing showed an increase in shear modulus by as much as two
orders of magnitude, with a strong dependence on temperature. This
particular polysiloxane experiences crystallization at approximately
−50° after a dwell time of about two hours. At colder temperatures,
crystallization begins to take place much more rapidly.
Exploration of potential crystallization in several silicones at low
temperatures was performed by The Aerospace Corp in 1977 [14] as
part of an investigation to determine the root cause of failure of a diode
crystal used in a “GPS solar array” bonded with a polysiloxane (RTV DC
6-1104). The diode crystal had routinely survived quench-cooling to
−195 °C, well below the glass transition temperature of the RTV.
However, when the assembly was cooled slowly (10 °C/min), the diode
crystal cracked. DSC measurements performed at this rate showed that
“substantial crystallization occurred in the vicinity of −58 °C.” Several
other commercial polysiloxanes were included in the Aerospace study,
including RTV 560, 566, and 567; DSC measurements of those materials
indicated no crystallization occurred at the cooling rates used.
65
International Journal of Adhesion and Adhesives 87 (2018) 64–72
1.3. Scope of the present work
This study was performed to carefully characterize the thermo-
mechanical behavior of RTV 566 at reduced temperatures, because al-
though it is used extensively in aerospace applications, little informa-
tion about its behavior has been published. Thermal expansion of this
material was measured over the range from +40 to −60 °C, demon-
strating the sensitivity of such measurements to the influence of multi-
axial constraint in such elastomeric materials. Measurements of the
elastic modulus of RTV 566 in both bending and tensile deformation
modes were conducted over the temperature range from +40 to
−115 °C. Creep and relaxation measurements were also made, de-
monstrating the importance of these viscoelastic behaviors particularly
at reduced temperature (−80 °C). A primary focus of this investigation
was to reveal whether changes in the mechanical behavior of RTV 566
evolve while it is subjected to cold temperatures for extended periods.
To that end, measurements of the tensile modulus were performed
under isothermal conditions at temperatures as low as −85 °C, for
durations sometimes exceeding 60 h. Volumetric contraction under si-
milar isothermal conditions was measured, providing additional evi-
dence that this PDMS material experiences crystallization when held at
cold temperatures for long periods.
2. Characterization of RTV 566 “conventional” behavior
2.1. Thermal expansion
2.1.1. Methods
Specimens of RTV 566 material were prepared according to proce-
dures recommended by the manufacturer (Momentive Corp.). A precise
ratio of 1 part curing agent (alkyl tin carboxylate]) to 1000 parts by
weight resin was mixed thoroughly (using a FlackTek speedmixer and
techniques to introduce the catalyst to the resin), degassed and cast into
sheets with thicknesses ranging from 1 to 3 mm. These sheets of ma-
terial were cured at room temperature (~23 °C) for several weeks be-
fore testing.
Thermal expansion of RTV 566 material was measured using a TA
Instruments Q400 thermomechanical analyzer (TMA). Note that this
study did not explore variation in thermal expansion as a function of
material batches and thermal history, though such effects have been
observed previously. Initial thermal expansion measurements were
conducted in “penetration mode,” using specimens with thickness of
1.7 mm and lateral dimensions of approximately 5 ×5 mm. For these
measurements, a contact force of 0.05 N was applied with the probe. The
specimen temperature was held constant at −80 °C for 15 min at the
beginning of each test, and was then ramped up at 1 °C/min to 80 °C.
2.1.2. Measurements
A typical plot showing measured specimen dimension change is
shown in Fig. 1a, along with the computed coefficient of thermal ex-
pansion (CTE, alpha). In penetration mode, the apparent CTE of this
material at room temperature is about 400 E-6/ °C. As a consequence of
the very high bulk modulus of this material (nearly incompressible), the
expansion coefficient is influenced strongly by constraint from material
surrounding the contact area, hence measurements were also per-
formed in a tensile mode to create a geometry with much less con-
straint. Specimens with approximate dimensions of
0.35 × 3.5 × 13 mm were loaded in tension with 0.02 N force. The
resulting CTE exhibited with the 50× lower geometric “constraint
factor” is much lower (about 220 E-6/ °C at room temperature) as seen
in Fig. 1b. This result will be discussed more fully in a subsequent
section of this report. Note that the negative slope of the expansion
measured in penetration mode (compression) may be the result of
competing creep strain.
T.M. Mower International Journal of Adhesion and Adhesives 87 (2018) 64–72

Fig. 1. Thermal expansion measurements of RTV 566 in (a) penetration mode and (b) tensile mode, demonstrating effect of constraint due to highly incompressible
nature of this elastomer.

2.2. Complex modulus

2.2.1. Methods
Mechanical stiffness of RTV 566 materials was measured under a
variety of conditions, using two different TA Instruments dynamic
mechanical analyzers (DMAs): a Q800 instrument, which was used to
subject specimens to double-cantilever bending, and an RSA G2, which
was operated in tensile mode. The same lot of material used to measure
CTE was used for these initial mechanical measurements. In the canti-
lever bending tests, specimens with width of 12.5 mm, thickness of
approximately 3 mm, and length of 35 mm were deflected with an
amplitude of 200 µm at an oscillation frequency of 1 Hz. In tensile tests,
specimens with thickness of 1.8 mm, width of 3.8 mm, and length of
20 mm were subjected to strain amplitude of 0.05%, oscillating at 1 Hz.
Temperature sweeps for both types of measurements were executed at a
linear rate of 1 °C/min. Fig. 3. Effect of vacuum bakeout (two days at 65°C) on elastic modulus as
determined by DMA in cantilever bending mode.

2.2.2. Measurements
Mechanical stiffness data measured with the dynamic mechanical
analyzers using standard temperature sweeps are plotted in Fig. 2. The
bending results show a peak in the “tan delta” (ratio of loss modulus to
storage modulus) at about −108 °C, which is one indication of the glass
transition temperature of polymer materials. (The peak of tan delta is
often as much as 10 °C higher than the peak of the loss modulus.) At
temperatures below Tg, the storage modulus (elastic, or real part of
complex modulus) rises so rapidly with decreasing temperatures that
with both instruments, the force limit was reached and the runs ter-
minated. Results from the tensile measurements show peaks in the loss
modulus at about −115 °C, providing a reliable indication of the Tg.
Influence of the effect of vacuum baking upon the elastic modulus of
RTV 566 was explored using cantilever bending. The data plotted in
Fig. 3 show that vacuum bake-out appears to raise the elastic modulus
by 10 to 20%.
2.3. Creep and relaxation
2.3.1. Methods
Although polysiloxane (RTV 566) can endure extremely high strains
and can be considered to be a “hyperelastic” material, it is a polymer
and thus exhibits viscoelastic characteristics as well. The tensile mod-
ulus is not a constant value when under continuous strain, but rather
relaxes over time at characteristic rates dependent upon temperature
and, to a lesser extent, strain. Similarly, the polymer material experi-
ences creep strain while under constant load. These effects could

Fig. 2. Dynamic mechanical analyzer measurements of the behavior of RTV 566 in (a) cantilever bending mode and (b) tensile deformation.

66
T.M. Mower
Fig. 4. (a) Dynamic mechanical analyzer (Q800) used to measure creep behavior (b) of RTV 566 under tensile stress of 0.5 MPa, at constant temperature of −80 °C.
influence measurements of modulus conducted over an extended period
of time, so testing to indicate their potential effects was conducted.
Sheets of RTV 566 material prepared using methods described be-
fore were cut into specimens with dimensions of 19.5 × 3.7 × 1.8 mm,
to be measured in tensile mode in a Q800 DMA, as shown in Fig. 4a. For
creep testing, stress of approximately 0.5 MPa was applied during iso-
thermal conditions at −80 °C. Relaxation tests were performed in a
similar manner, under isothermal conditions with temperatures ranging
from +40 to −80 °C, while under constant tensile strain of 25%.
2.3.2. Measurements
During creep testing at −80 °C, RTV 566 exhibited non-linear be-
havior immediately, with strain rising quickly and becoming linear with
time as shown in Fig. 4b. The creep strain continued to increase line-
arly, until after 4 h under load the strain reached a value of 19%,
showing no indication of diminishment in the creep rate. Relaxation
behavior of RTV 566 is quite dependent upon temperature, as shown in
the data plotted in Fig. 5. At room temperature, the modulus drops by
about 5% when subjected to a constant strain of 25% for 1 h, and
thereafter remains nearly constant. At reduced temperatures, the tensile
modulus relaxes much more rapidly. For example, at −80 °C, modulus
relaxation of over 12% occurs during the first 20 min; thereafter, the
rate of relaxation becomes linear without reaching a plateau.
3. Low temperature, extended duration behavior
3.1. Tensile modulus
3.1.1. Methods
Measurements of the tensile modulus of RTV 566 were conducted
under isothermal conditions (“soak”) at reduced temperature for
Fig. 5. (a) Relaxation modulus of RTV 566, under tensile strain of 25% at constant temperature of −80 °C. (b) Comparison of stress relaxation rates as a function of
temperature.
67
International Journal of Adhesion and Adhesives 87 (2018) 64–72
extended durations to explore the possible evolution of crystallization
phenomena. A dynamic mechanical analyzer (TA Instruments RSA G2)
was connected to a continuous supply of liquid nitrogen to make such
operation possible, and provisions were made to reduce formation of
frost and ice within the equipment. A nearly-sealed plastic bag housed
the entire instrument and was filled continuously with dry nitrogen gas
supplied at 70 °C, as shown in Fig. 6.
Each measurement began by cooling specimens at a rate of 1 °C/min
from 40 °C to the designated cold temperature, followed by soaking for
24 to 72 h. The modulus was measured by fluctuating the tensile strain
at a frequency of 1 Hz, with a peak amplitude of 0.5%. During testing,
specimens were subjected to a superimposed, constant axial strain
ranging from 0 to 25%. Specimen gage length was 20 mm, with typical
specimen width of 4 mm and thickness of 1.8 mm. A video camera
within the environmental chamber indicated that little or no frost
formed on specimens during testing.
3.1.2. Measurements
The first specimens tested in the RSA were cut from a sheet fabri-
cated using RTV 566 material mixed in our laboratory and cured at
room temperature for several weeks. Shown in Fig. 7 are data recorded
while measuring the tensile modulus of a specimen of this material.
During the ramp down in temperature from +40 °C to −85 °C, the
tensile modulus increased from about 9 to 15 MPa. Note that this spe-
cimen was subjected to a superimposed, constant tensile strain of 25%,
which elevates the measured modulus, relative to the behavior mea-
sured while under little strain (about 5 MPa at room temperature).
While held at a constant temperature of −85 °C, an increase in the
elastic modulus began to occur after about 1 h. After soaking for 6 h at
this temperature, a fairly rapid rise in modulus occurred such that after
24 h, the modulus reached 175 MPa. Thereafter, the modulus increased
T.M. Mower
Fig. 6. RSA G2 enclosed in sealed bag continuously backfilled with heated, dry nitrogen gas to prevent buildup of frost during extended duration, low-temperature
testing.
Fig. 7. Elastic tensile modulus of RTV 566 while under constant superimposed
axial strain of 25% and soaked at −85 °C. Specimen material mixed and im-
mediately cured in our laboratory.
at a slower rate and did not reach a plateau with a steady-state value.
This growth in modulus appears to be a physical manifestation of the
polysiloxane material experiencing a very slow crystallization process.
While the test specimen was in a state exhibiting high modulus,
distinct fluctuations in the force measured by the instrument evolved
and continued to exist while the specimen was in the changed state.
When observed initially, repeated tests were performed to ensure spe-
cimens were securely clamped in the grips. Special wave washers were
installed beneath the clamp screws, to provide continued clamping
force when the specimen thickness shrank, but fluctuations in the
measured load continued to be exhibited. A plausible explanation for
this phenomenon is that the evolving material microstructure experi-
enced slipping between lamellar crystallites and polymer chain seg-
ments as the crystallization process progressed. We note that to confirm
the temporal change in measured modulus was not an artifact of the
cold instrument, tests were performed with no specimen installed; those
measurements demonstrated a “noise floor” that was four to five orders
of magnitude below the forces generated while specimens were tested.
Influence of temperature and applied strain were initially explored
with our lab-mixed RTV 566, as indicated by the data shown in Fig. 8.
We observe that the initial value of the elastic tensile moduli for ma-
terials stretched only 15% are much closer to the nominal, room-tem-
perature value (~ 5 MPa). When soaked at −75 °C, the material showed
no modulus increase (crystallization) within 36 h while subjected to
15% axial strain. Increasing the strain to 25% did cause the measured
68
International Journal of Adhesion and Adhesives 87 (2018) 64–72
Fig. 8. Elastic tensile modulus of RTV 566 material mixed and immediately
cured in our laboratory, under constant superimposed, axial strain at indicated
temperatures.
modulus to begin to increase while under isothermal conditions at
−75 °C. Decreasing the soak temperatures to −80 and −85 °C sig-
nificantly accelerated the onset of modulus increase and caused higher
magnitudes of modulus to be reached, so that by 48 h, over 200 MPa
was reached for specimens soaked at −85 °C while stretched 25%.
Use of adhesive resins mixed with curing agents and frozen before
curing by commercial firms is becoming increasingly prevalent. We
therefore included in this study a batch of specimens fabricated with
RTV 566 resin that had been mixed with curing agent, frozen im-
mediately and stored at −80 °C. The first specimen fabricated from this
material, when tested isothermally (at −80 °C), displayed such rapid
rise in elastic modulus that we tested multiple specimens from material
mixed in our laboratory to confirm that instrumentation and data
processing were accurate. The resulting data shown in Fig. 9 clearly
demonstrate excellent repeatability of those measurements and a pro-
nounced difference in crystallization behavior of RTV 566 material that
was mixed and immediately cured, versus a different batch of material
that was premixed and frozen in the uncured state for approximately
ten weeks. Further investigation of this difference in behavior is illu-
strated in Fig. 10, which indicates that under similar conditions of
applied strain amplitude, material that had been frozen in the uncured
state consistently experienced earlier and more significant increases in
the elastic moduli than did material that was cured immediately after
mixing. We note here that other differences may exist between mate-
rials mixed and cured in our lab and materials generated using
T.M. Mower
Fig. 9. Isothermal modulus comparison between premixed, frozen RTV 566 and
four specimens prepared from resin mixed and cured immediately.
Fig. 10. Measured tensile moduli of RTV 566 at soak temperature of −80 °C,
under differing levels of applied axial strain. Comparison between two different
batches of material, one fabricated from pre-mixed, frozen resin and one from
resin mixed and cured immediately.
commercially mixed, frozen resin. Exploration of such possible batch-
to-batch differences is beyond the scope of this study.
Several measurements were conducted to demonstrate a melting ef-
fect, wherein the warming material might reach a temperature that
caused crystallites to melt suddenly, revealed by a rapid drop in the
modulus. Shown in Fig. 11 are two plots from tests that applied slow
(0.5 °C/min) increases in temperature after exposure to cold tempera-
tures for long periods that caused elevation of tensile modulus (crystal-
lization). In each case, the modulus decreased slowly with increasing
temperature, and no sharp transition was observed. When the tempera-
ture reached approximately −58 °C, the modulus returned very near to
the value exhibited by the materials prior to their crystallization.
Fig. 11. Heating of crystallized RTV 566 material at 0.5 °C/min, after crystallization at −85 °C (left) and −80 °C (right), revealing no indication of sharp melting
transition, with return to initial modulus (melting completed) by −58 °C.
69
International Journal of Adhesion and Adhesives 87 (2018) 64–72
Fig. 12. Shrinkage of RTV 566 measured in TMA under isothermal condition at
−80 °C.
3.2. Shrinkage associated with crystallization
Because the occurrence of volumetric shrinkage during crystal-
lization of polymers has been well established (for example, by Gent in
natural rubber [15] and polybutadiene [16], and by Treloar in raw
rubber [17]), the possibility of shrinkage occurring during crystal-
lization of RTV 566 was explored using our TMA. To inhibit formation
of frost within the instrument, it was enclosed in a nearly sealed bag,
continuously filled with dry nitrogen gas. Thin specimens of RTV ma-
terial (length ~ 12 mm) were subjected to tension with a very low force
(0.01 N, producing stress ~ 11 kPa) to reduce the influence of creep on
the measured strain. Temperature was ramped down at 1 °C/min to
−80 °C, where it was held constant for extended periods.
An example of measured linear dimension change is shown in
Fig. 12. These data indicate the initial thermal contraction of the ma-
terial, followed by a dwell period with no change in dimension. After
15 h at −80 °C, the material commenced contracting at a rate which
declined with time. Isothermal shrinkage culminated after 50 h, when
this specimen demonstrated shrinkage of about 0.35%, following the
shrinkage associated with the initial thermal contraction. Isothermal
shrinkage (associated with crystallization) measured similarly with
other specimens ranged between 0.35 and 0.40%.
4. Discussion
4.1. Behavior indicated by conventional testing
4.1.1. Thermal expansion
When thermal expansion of RTV 566 is measured in penetration
mode (Fig. 1a) with specimens having lateral dimensions much greater
than the probe diameter, apparently very high values of CTE are
T.M. Mower
generated. This results from the nearly incompressible behavior of the
material creating lateral constraint upon the volume of material be-
neath the probe, resulting in expanding material being forced to move
upwards— contributing more to the linear thermal expansion measured
in the vertical direction. The extent to which this behavior occurs with
specimens having finite dimensions is characterized by the “shape
factor,” which is the ratio of the area of unloaded faces of components
to their loaded areas. Influence of the shape factor upon the effective
material properties of rubber materials has been analyzed and in-
vestigated quite thoroughly [18,19].
Our measurements (Fig. 1b) with thin strips of RTV 566 in tensile
mode exhibit a linear CTE of about 220 µ/°C, much lower than the ef-
fective CTE when measured in penetration mode with surrounding
material creating constraint. Note that confined compression mea-
surements we made recently at room temperature reveal a bulk mod-
ulus of approximately 75 MPa during initial, trivial loading and rise to
over 1 GPa when under high (7 MPa) hydrostatic pressure. Invoking the
idealized equations of linear elasticity, calculated values of the Poisson
ratio range from about 0.493 under light loading, to 0.4994 when under
high pressure. Though these values do indicate that RTV 566 is, in fact,
quite nearly incompressible, it should be realized that the elastic rela-
tions used are strictly appropriate only for small strains, and further-
more, break down when the Poisson ratio approaches a value of 0.50.
4.1.2. Elastic modulus
The data presented in Fig. 3 indicate RTV 566 has a room-tem-
perature flexural modulus of about 4 MPa. With decreasing tempera-
ture, the modulus increases linearly until about −60 °C, where the
modulus is approximately 8 MPa. Those data also reveal a small (20%)
increase in modulus resulting from exposures to vacuum bakeout, a
procedure used frequently to reduce offgassing of components destined
for service in space environments.
As the temperature of RTV 566 is reduced further, the glass tran-
sition region is approached, which involves an increase in the elastic
modulus by more than two and a half orders of magnitude. Although
some interpretations of Tg utilize the peak in the tan delta curve (which
is about −106 °C in the data shown in Fig. 2), a more widely used
approach is to identify the peak of the loss modulus as Tg, which from
these measurements appears to be about −114 °C. (Note that peaks in
tan delta often are as much as 15 °C above the peak loss modulus.) The
modulus continues to increase with decreasing temperature, causing
the instrument to terminate the measurements shown in Fig. 2 when the
force limit was reached.
4.2. Low-temperature isothermal behavior
4.2.1. Modulus increase
Measurements of RTV 566 in tensile mode (Figs. 7–10) under iso-
thermal conditions at reduced temperatures present a time-dependent
growth of the elastic modulus that is consistent with the progression of
crystallization in polymers, which has historically been monitored most
frequently with measurement of density change [17] or volumetric
shrinkage [15,16]. In all of our testing at temperatures of −80 °C and
below, an initial static period was followed by a rise in the elastic
modulus that accelerated until the fastest rate of modulus increase was
established, producing a linear rise in stiffness with time. The rates of
modulus increase then slowed steadily, indicating that an asymptote
would be reached at times greater than testing constraints allowed. This
process parallels the description provided by Billmeyer, explaining that
“….crystallization in polymers involves the steps of (primary) nucleation
and relatively rapid spherulite growth, followed by a slow, kinetically diffi-
cult improvement in crystal perfection [20].”
The length of the initial dwell period during isothermal conditions,
where no increase in modulus occurred, was quite sensitive to both
temperature and applied, superimposed constant strain. Onset of
modulus increase occurred more rapidly with increasing strain
70
International Journal of Adhesion and Adhesives 87 (2018) 64–72
amplitude, which is consistent with the conformational change required
to organize crystallites into lamellar groups. With increased externally
applied strains, some straightening of random, coiled polymer chain
segments occurs, helping to overcome resistance to restructuring
caused by the existence of molecular crosslinking. Influence of me-
chanical strains upon morphology of polymer crystallization has been
revealed comprehensively through X-ray diffraction studies [21–23]
that demonstrate crystallites show a preferred orientation in the di-
rection of the largest strains, and the amount of crystallization increases
rapidly with increased extension [17].
Lower isothermal (soak) temperatures resulted in earlier onset and
greater rates of modulus increase, as well as higher apparent asymptotic
values of modulus being attained. The data in Fig. 8 show no increase in
tensile modulus when RTV 566 was soaked at −75 °C while under
strain of 15%. Increasing the applied stretching to 25% resulted in a
very slow rise in modulus, suggesting that crystallization can be sti-
mulated at −75 °C with application of sufficient strain. At lower tem-
peratures, modulus increase (crystallization) transpired much more
readily. Data presented in Fig. 8 show that crystallization occurs at
−80 °C with just 5% applied strain, developing much more rapidly and
to a greater extent with higher applied strains. At −85 °C, the process of
crystallization in RTV 566 begins soon after reaching isothermal con-
ditions. While at −85 °C and 25% strain, the tensile modulus reached
210 MPa after 48 h. Note that this temperature is approximately 30 °C
above the glass transition temperature of RTV 566.
Unlike glass transition phenomena, crystallization in polymers is a
very time-dependent process. Rates of crystallization in polymers have
been well characterized, finding that, in general, “as the temperature is
lowered, the rate increases, goes through a maximum, and then de-
creases as the mobility of the molecules decreases and crystallization
becomes diffusion controlled [21].” Bukhina and Kurlyand state that
the maximum rate of crystallization in polydimethylsiloxane (PDMS) is
thought to occur at a temperature of −80 °C, “but a high rate of crys-
tallization in this temperature range hampers the exact determination
of (the maximum rate temperature) so the available literature data are
not unequivocal [24].”
While the Tg of PDMS is reported as −126 °C (e.g. [5,14]), our
modulus measurements indicate Tg of RTV 566 is about 11 °C higher.
This is consistent with assertions that “the presence of phenyl sub-
stituents (in the polymer chain) results in an increase of Tg [24]” and
the only description of the chemistry provided by the manufacturer of
RTV 566 (“silanol-stopped, phenyl-containing, silicone polymer”). Ad-
dition of a variety of functional groups into PDMS can inhibit its crys-
tallization due to the disruption of symmetry along the polymer back-
bone, but substituents with phenyl have been most effective in this
regard [25]. Although the presence of phenyl groups in RTV 566 delays
its ability to undergo crystallization, causing the lack of its observation
in earlier studies [14], our data demonstrate that the presence of phenyl
in RTV 566 does not prevent its crystallization when exposed to low
enough temperatures for extended durations.
The melting temperature of crystallites formed in RTV 566 was in-
vestigated by continuing to measure the tensile behavior while slowly
heating material from a crystallized state. The data shown in Fig. 11
indicate a continuous, slow process of modulus reduction while heating,
with melting apparently completed upon reaching −58 °C. This gradual
progression could be due either to discrete, sequential melting of in-
dividual crystallites or a systemic, global softening of all crystallites
simultaneously. While the latter process would have been enabled by
the uniform sample temperature created by the slow warming condi-
tions, it is possible that, just like the crystallization process, melting is a
localized phenomenon involving individual crystallites. In contrast,
Verzino and Fillers observed distinct melting in several crystallized
polysiloxanes at narrowly defined temperatures, using DSC. More re-
cently, melting of crystallized PDMS (silanol-terminated, with Tg
~ −127 °C) was shown by Lund et al. (also using DSC) to occur across a
broad temperature range of −55 to −35 °C [26]. Melting across such
T.M. Mower
wide temperature range is similar to what we have demonstrated with
RTV 566, which is also “silanol stopped.”
The question may arise whether the mechanical properties of RTV
566 that has experienced crystallization become restored after re-
turning to the amorphous state. To address this question, measurement
of the tensile modulus as a function of temperature was performed on
two specimens after they had been crystallized extensively at −85 °C.
In both cases, the resulting data closely match the measurements of
virgin material, as plotted in Fig. 2. Thus, it appears that the amorphous
polymer regains its original physical properties after being temporarily
transformed to a crystalline state.
4.2.2. Possible effects of freezing uncured resin
Tensile modulus measurements plotted in Figs. 9, 10 indicate that
RTV 566 material that is premixed and frozen in the uncured state, then
cured after an extended period of time has a greater capacity to undergo
crystallization than does material that is mixed and immediately cured.
A plausible explanation for this behavior is that storing the mixed, but
uncured resin at cold temperature (−80 °C) prior to curing somehow
reduces the catalyst's ability to promote crosslinking of the polymer
chains. Lower crosslink density would permit conformational changes
to occur more readily because polymer chains would more easily uncoil
and slip past each other, with fewer side groups bonded. This mobility
enables the folding of chains into lamella (often strain assisted) that
provide the necessary precursors for formation of crystallites during the
crystallization process [27].
Potential degradation of the efficacy of condensation curing agents
caused by cold storage of mixed but uncured silicone resins appears to
be a topic that has not been addressed in the open literature. It is,
however, common practice to keep reactive components separate so
that partial crosslinking does not occur. Although low-temperature
storage will certainly retard reaction rates, it is likely that some che-
mical reaction is still occurring at temperatures near −80 °C. Any lo-
calized, partial crosslinking may consume some nearby reactive end-
groups and thus form isolated, non-reactive nodules. These nodules can
later disrupt the normal crosslinking process when the resin is returned
to room temperature.
Additional differences may exist between the RTV 566 materials
produced with resin mixed and frozen by a vendor and materials mixed
and immediately cured in our own lab. Possible batch-to-batch varia-
tions may have existed in the chemical composition of the different
resin sources, as well as the possible inhibition of curing mechanisms
caused by freezing mixed but uncured resin. It is beyond the scope of
this study to perform comprehensive studies to explore the effects of
batch-to-batch variations upon thermomechanical properties of RTV
566 in either the amorphous or partially crystallized states.
4.2.3. Shrinkage
Monitoring of crystallization in polymers has historically been
performed indirectly using measurements of density change or heat
capacity. Direct evidence of formation of spherullites has been obtained
with polysiloxanes having chemical composition and molecular struc-
tures that enable crystallization at warm temperatures (from ambient to
over 100 °C) using optical [28] or electron microscopy [29]. Char-
acterization of strain-induced crystallization in natural rubber has been
performed widely using X-ray diffraction [23], but at ambient tem-
peratures or above. Since the aforementioned analytical techniques are
not feasible at low temperatures for the extended periods needed to
promote crystallization in RTV 566, we sought further evidence of this
behavior by measuring material shrinkage.
Change in length of RTV 566 specimens was measured with the
TMA at a temperature of −80 °C,1 while under an applied tensile stress
of about 11 kPa. The data shown in Fig. 12 indicate that shrinkage
1 2
This is the low-temperature limit of the instrument.
71
International Journal of Adhesion and Adhesives 87 (2018) 64–72
under these conditions reached a stable value of 0.35% after 50 h. The
time-dependency of the isothermal contraction is closely analogous to
change in modulus measured under similar conditions (low strain at
−80 °C), including: the dwell period wherein little change occurs, the
varying rate of property change, and the time required for a stable state
to develop.
Gent reported volumetric shrinkage during crystallization of natural
rubber and polybutadiene rubber to be about 2.3% and 3.4%, respec-
tively. Volumetric contraction of raw rubber, reported by Treloar,
reached a maximum of approximately 2% after 300 h at 0 °C while
being stretched 25% No published data for shrinkage of PDMS asso-
ciated with crystallization is seemingly available. The lower value of
shrinkage reported here may be simply attributed to the different
chemical composition and configuration of PDMS, as well as the pre-
sence of a small fraction of iron oxide filler2 in RTV 566.
5. Conclusions
Despite widespread use in many optical instruments of the poly-
siloxane, elastomeric adhesive material marketed under the tradename
RTV 566, very little data concerning its thermomechanical behavior
have been published in open literature. Reported here are some results
from extensive characterization of the mechanical behavior of RTV 566
performed at temperatures ranging from ambient to −120 °C. In ad-
dition to conventional testing using temperature sweeps, the present
investigation sought evidence that RTV 566 experiences a change in
structure, from an amorphous state to a crystalline nature, when ex-
posed to cold temperatures for prolonged periods.
Measurements with a dynamic mechanical analyzer demonstrated
that RTV 566 has an elastic flexural modulus of approximately 4 MPa at
room temperature. The modulus rises linearly with reducing tempera-
ture, nearly doubling as the temperature reaches −60 °C. As tempera-
ture is reduced below −85 °C, the modulus rises very rapidly as the
glass transition region is encountered, with Tg shown to be about
−114 °C. Tensile relaxation measurements with a DMA demonstrated
the viscoelastic behavior of RTV 566, with the rate of relaxation in-
creasing with reductions in temperature. This is consistent with the rise
in the loss modulus (and tan delta) at lower temperatures. Thermal
expansion measurements in a TMA illustrated the effect that volumetric
constraint can have on nearly incompressible elastomeric materials:
slender specimens in tension exhibited a CTE of approximately 220 µ/
°C, but when short and wide specimens were tested in penetration
mode, the apparent CTE value was much higher.
Data produced by this study present manifestations of crystal-
lization occurring in RTV 566 under isothermal conditions at reduced
temperatures for long periods of time. Some principal supporting evi-
dence includes these observations:
• During isothermal measurements at temperatures of −80 °C and
below, after a quiescent dwell period, the elastic modulus increased
with accelerating rates until nearly asymptotic levels were attained.
This process is consistent with published descriptions of crystal-
lization in polymers, involving nucleation and rapid growth of
spherulites followed by culmination of the changes.
• Increase in the tensile elastic modulus can be as great as a factor of
40 (from about 5 MPa to over 200 MPa) when the material is ex-
posed to −85 °C for 48 h, while subjected to a constant, super-
imposed axial strain of 25%. This is not a glass transition phenom-
enon, as this testing temperature is approximately 30 °C above the
Tg for this material.
• Isothermal increase in the elastic modulus of RTV 566 is sensitive to
the level of applied mechanical strain, which is consistent with
molecular orientation providing favorable nucleation sites that
Added by the manufacturer.
T.M. Mower
accelerate the initiation and growth process of crystallization.
• Linear shrinkage in RTV 566 was observed during isothermal con-
ditions at −80 °C in a TMA; with multiple tests, shrinkage of ap-
proximately 0.35% was measured.
Acknowledgements
This material is based upon work supported by the National
Aeronautics and Space Administration under Air Force Contract No.
FA8702-15-D-0001. Any opinions, findings, conclusions or re-
commendations expressed in this material are those of the author(s)
and do not necessarily reflect the views of the National Aeronautics and
Space Administration. Discussions with Dr. Ethan Parsons and John
Wellman of MIT Lincoln Lab, concerning behavior of elastomers, are
much appreciated.
Data availability
The raw/processed data required to reproduce these findings can
not be shared at this time due to sponsor limitations and security re-
strictions imposed by the U.S. government.
References
[1] Salama AM, Rowe WM, Yasui RK. Stress analysis and design of silicon solar cell
arrays and related material properties, NASA Technical Report TR-32-1552.
Pasadena, CA: Jet Propulsion Laboratory; 1972.
[2] Yoder PR. Mounting optics in optical instruments. 2nd ed. 359. Bellingham, WA:
SPIE; 2008.
[3] Ramesham R. Reliability and qualification of hardware to enhance the mission as-
surance of JPL/NASA projects, In: Proceedings of the 40th international conference
on environmental systems, AIAA; 2010.
[4] Va Veggel AA, Nijmeijer H. Stable mounting of beamsplitters for an interferometer.
Precis Eng 2009;33:7–17.
[5] Dupont A. Characterization of silicones, in Silicones in industrial applications
(Chapter 2). In: JaegerGleriaeditors. Inorganic polymers. NY: Nova Science; 2007.
[6] Zhang H. The permeability characteristics of silicone rubber, 2006. In: Proceedings
of SAMPE Fall technical conference, “Global advances in materials and process
engineering”, coatings and sealants section, November 6 – 9, Dallas, TX; 2006.
[7] Rey T, et al. Effects of temperature on the mechanical behavior of filled and unfilled
silicone rubbers. In: Proceedings of the 8th European conference on constitutive
72
International Journal of Adhesion and Adhesives 87 (2018) 64–72
models for rubbers, Jun, Spain, 2013; 511-514.
[8] Weir CE, Leser WH, Wood LA. Crystallization and second-order transitions in sili-
cone rubbers, NBS Research Paper RP2084 (44), U. S. Department of Commerce;
1950.
[9] Marei AI, et al. The strength and supermolecular structure of siloxane elastomers.
Polym Sci U S S R 1969;9(11):2162–70.
[10] Sundararajan PR. Crystalline morphology of poly(dimethysiloxane). Polymer
2002;43:1691–3.
[11] Ortiz-Acosta D. Low temperature studies on DC745U pressure pads, Report LA-UR-
13-25885. Los Alomos, NM: Los Alamos National Laboratory; 2013.
[12] Ortiz-Acosta D. Historical material analysis of DC745U pressure pads, Report LA-
UR-12-23612. Los Alomos, NM: Los Alamos National Laboratory; 2012.
[13] Maxwell RS, et al. Baseline and lifetime assessments for DC745U elastomeric
components, Report UCRL-TR208929. CA: Lawrence Livermore National
Laboratory; 2005.
[14] Verzino WJ, Fillers RW. Low-temperature differential scanning calorimetry of
polysiloxanes, Report SAM SO-TR-78-107. El Segundo, CA: The Aerospace
Corporation; 1978.
[15] Gent AN. Crystallization in natural rubber. IV. Temperature dependence. J Polym
Sci 1955(XVIJI):321–4.
[16] Gent AN, Zhang L-Q. Zhang, Strain-Induced crystallization and strength of elasto-
mers. I. cis-1,4-Polybutadiene. J Polym Sci: Part B: Polym Phys 2001;39:811–7.
[17] Treloar LRG. The physics of rubber elasticity. 3rd ed. 22. USA: Oxford University
Press; 1975.
[18] Kelly JM, Lai J-W. The use of tests on high-shape-factor bearings to estimate the
bulk modulus of natural rubber. Seism Isol Prot Syst 2011;2(1):21–33.
[19] Horton JM, Tupholme GE, Gover MJC. Axial loading of bonded rubber blocks. Trans
ASME 2002;69:836–43.
[20] Billmeyer FW. Textbook of polymer science. 3rd ed. 283. NY: Wiley; 1984.
[21] Tosaka M. Strain-induced crystallization of crosslinked natural rubber as revealed
by X-ray diffraction using synchrotron radiation. Polym J 2007;39:1207–20.
[22] Huneau B. Strain-induced crystallization of natural rubber: a review of X-ray dif-
fraction investigations. Rubber Chem Technol 2011;84(3):425–52.
[23] Nie Y, et al. Features of strain-induced crystallization of natural rubber revealed by
experiments and simulations. Polym J 2017;49:309–17.
[24] Bukhina MF, Kurlyand SK. Low-temperature behavior of elastomers. Netherlands:
VSP; 2007.
[25] Zlatanic A, et al. Suppression of crystallization in polydimethylsiloxanes and chain
branching in their phenyl-containing copolymers. Macromolecules
2017;50:3532–43.
[26] Lund R, et al. Dynamical and structural aspects of the cold crystallization of poly
(dimethylsiloxane) (PDMS). Macromolecules 2008;41:1364–76.
[27] Nitta KH. On the orientation-induced crystallization of polymers. Polymers
2016;8(6):229–41.
[28] Magill JH. Crystallization of Poly (tetramethyl-p-silphenylene)-siloxane (TMPS)
polymers, Part 2. J Polym Sci 1967;5:89–99.
[29] Haller MN, Magill JH. Morphology of polysiloxanes crystallized from the melt. J
Appl Phys 1969;40:4262–5.