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1
COMPOSITES 2001 Convention and Trade Show
Composites Fabricators Association
October 3-6, 2001
Tampa, FL USA
Use Of Dynamic Mechanical Analysis in
Thermoset Resin Development (For
Composites Applications)
by
Steven Nahm, Ph.D.,
SMITH Fibercast, a Varco Company1
Abstract
DMA is compared to DSC as a method of thermal
analysis and materials characterization. The basic
instrument parameters are briefly described, as
well as their influence on the data collected. The
glass transition temperature, Tg, in polymers can be
defined in several ways from DMA data. These are
compared with Tg assignments made from DSC and
in relation to the heat deflection temperature.
DMA samples are much larger than those used in
DSC, making their measured properties more rep-
resentative of the bulk properties in heterogeneous
materials. Examples of evaluating solid and liquid
samples of thermoset resins are illustrated. The
relationship between resin cure conditions, the de-
gree of cure and ultimate cure, as measured by Tg,
is related through first principles to molecular mo-
tions in adhesive and structural laminate resins.
Finally, a novel technique is described which can
be used to assess the effects of resin structural
changes on adhesive performance.
What Is DMA And How Do I Use It
A Brief Description of the Methodology
Dynamic Mechanical Analysis is a test methodol-
ogy that can evaluate the mechanical properties of mate-
rials as a function of temperature and frequency. As
most commonly employed, the DMA sample is vibrated
through small amplitudes to characterize its mechanical
response as a function of temperature.
Polymeric materials are called viscoelastic because
they exhibit the properties of both liquids and solids.
The type of behavior that dominates depends on both the
rate and the temperature at which the distortion occurs.
A classic example of rate dependent behavior is Silly
Putty, a novelty from childhood. If you pull on it
slowly, it stretches and flows like a liquid, but if you pull
on it fast, it breaks like a brittle solid. Similarly, Tup-
perware is tough at room temperature, but it will break
if you drop it on the floor when you take it out of the
freezer.
With DMA, a periodic force (stress) is applied to
the sample, and the resultant distortion (strain) is meas-
ured. Flexural, tensile, or compressive deformations re-
sult in modulus properties, identified by the E symbol, or
by G in shear. The more delayed the response, the more
viscous the material, while less delayed responses are
characteristic of more elastic materials. Viscous materi-
als have high damping (loss modulus, E” or G”) which
tends towards soft and rubbery behavior, while elastic
materials typically have high stiffness (storage modulus,
E’ or G’) which tends to translate as hardness and brittle
behavior. The ideal polymer for any given application
will have a blend of these characteristics resulting in the
optimal properties required. Another term often seen in
relation to DMA is tan δ (delta), defined as the ratio of
G”/G’ or E”/E’.
In a typical oscillatory DMA experiment, the sam-
ple is vibrated at a fixed rate starting at a low tempera-
ture, and is heated at a controlled rate to an elevated final
temperature. At the low temperature, like the frozen
Tupperware example, the sample is stiff, hard and brit-
tle. As the sample warms up, it softens and finally be-
comes rubbery. The change between brittle and rubbery
behavior is called the glass transition, and the tempera-
ture range over which it occurs is known as the glass
transition temperature, Tg. The value of Tg depends on
both the polymer and on how the experiment is con-
ducted.
The next few sections discuss how the various ex-
perimental parameters can effect the results obtained
from DMA experiments. After that, some examples of
how we have used DMA techniques in resin develop-
ment are discussed.
Comparison with DSC
Most people who work with thermoset resins have
at least some familiarity with a thermal analysis tech-
nique known as DSC – Differential Scanning Calorime-
try. DSC measures differences in heat capacity, Cp, be-
tween a sample and a reference as a function of tem-
perature. While this is a very sensitive technique,
changes in Cp are small when a sample is heated through
the Tg, especially when compared to changes in the me-
chanical properties measured by DMA. Differences in
the measured signal strength below and above the Tg can
be as much as about 1000 times larger in DMA than in
DSC2. This makes DMA the preferred technique for
measuring Tgs of highly filled materials, such as com-
posites.
DSC samples are very small, about 10 mg, the size
of a small water drop (10 mm3). In contrast, DMA sam-
ples are substantially larger. Generally, the sample must

be a regular rectangular prism about the size of the part
of the key that goes into the lock (3 cm long, 1 cm wide,
and 2 mm thick).
The much larger DMA sample may better represent
bulk material properties than the small DSC sample, es-
pecially in heavily filled materials like composites.
However, it requires careful preparation to make sure all
the edges are straight and parallel if the modulus values
calculated by the instrument’s software are to be mean-
ingful. If sample Tg and approximate modulus values are
all that matters, then a less than perfectly shaped sample
will work.
Since the sample temperature effects its response,
and plastics have low thermal conductivities, the heating
rate for DMA must be slower than for DSC to ensure that
the larger sample is all at the same temperature during
measurement. In a DSC experiment, heating rates as
high as 40°C per minute might be used (ASTM D-3418
recommends 10°C/min), but heating rates less than 5°C
per minute are generally recommended in DMA experi-
ments (ASTM E-1640-94).
Sample Preparation
Preparing “perfect” solid samples can present some
challenges, especially if the equipment available for
shaping them is limited. The type of test will influence
the shape and size of the sample required, based on the
type of fixture used to hold it. For cantilever beam, 3-
point bending and tensile experiments, a regular rectan-
gular prism with straight parallel sides and smooth flat
surfaces is required. Reproducibility in modulus values
from sample to sample will depend critically on the
“goodness” of sample geometry attainable. For com-
pression, expansion, and penetration testing, a minimum
thickness of a few millimeters is required, but shape is
less important than the parallelism obtained between the
top and bottom surfaces of the sample.
For liquid thermoset samples that will be cured in
the instrument, the most important consideration is that
you do not glue the clamp jaws together during the ex-
periment. Commercial DMAs have ovens that will get
hot enough to burn off most resins from the clamps, but
this takes time, and we like to avoid it. In general, liquid
samples must be supported, loss of volatile components
must be minimized, and sample size and geometry
should conform as well as possible to the requirements
for a solid sample in the chosen test clamp. We make
disposable fixtures based on U-shaped wires (such as
half a large paperclip), or a piece of aluminum window
screen to support our liquid samples. The supports are
wrapped in ordinary aluminum foil to prevent loss of
volatiles. These fixtures work well in our DMA using
the single or dual cantilever beam test modes.
2
Defining Tg
We intuitively recognize the significance of the
glass transition, Tg, but there are many ways to define it
from a single DMA experiment. Figure 1 shows the re-
sults from a typical DMA experiment. There are 3
curves plotted: G’ or storage modulus (stiffness), G” or
loss modulus (damping), and tan δ or the phase angle
(G”/G’ ratio; the response delay). The easiest definitions
of Tg are the temperatures of the peak maxima in either
the G” (339°F) or tan δ curves (349°F), as these are
completely unique and unambiguous points. Alternate,
less unique, values are based on the G’ plot, and require
construction of lines tangent to the curve. Variability
can occur in these values, based on the points selected
for the tangents to intersect the curve.
For our applications, the most relevant assignment
of Tg is based on the onset point of the step change in the
storage modulus curve (293°F), defined by the intersec-
tion of two tangents as shown in Figure 1. This value
approximates the upper use temperature for the material,
where its mechanical properties start to fall off drasti-
cally. The G’ step change inflection or midpoint is also
used (335°F), and is generally similar to the G”max. To
avoid drawing tangents for the midpoint Tg, the tem-
perature of the peak maximum of the first derivative of
the G’ curve can be used; it is also called the inflection
point Tg of the G’ curve. Since there are so many ways
to define Tg, and they can all give different values from
the same experimental data, it is necessary to report
which definition was used to assign a Tg value deter-
mined by DMA.
The peak maxima of the G” or tan δ curves result
in higher assigned values for Tg than the onset value
from the G’ curve. These apparently higher values may
give a false sense of security in relation to the resin Tg as
measured by DSC. We have found that the G’ onset Tg
is generally more similar to the value we measure by
DSC. This, and its relation to mechanical strength, is
why we favor Tg defined as the onset value for the step
change in the G’ curve, and in particular, when the Tg is
determined from a real part.
Heat distortion temperature (HDT) and deflection
temperature under load (DTUL) values have been used
for many years as practical indicators for upper use tem-
peratures for polymeric materials. Their relation to Tg
depends on the polymer3 and cure conditions, but they
are generally similar to Tg. Furthermore, HDT (and
DTUL) may vary substantially for materials based on a
single polymer depending on the filler type, fiber orien-
tation and length, and loading as well. In the past, HDT
and DTUL samples had to be prepared separately, and
generally could not be made from real parts. Therefore,
their value for characterizing the upper use temperature
of the real parts was limited. A recent publication out-
lines a procedure using DMA to determine HDTs3 from
real parts.

Effect of Frequency
As illustrated by the Silly Putty example, the rate
at which the sample is distorted can have a dramatic ef-
fect on the way the material behaves, and fails. The time
frame of the applied distortion is the frequency of the
stress. High frequency stress gives higher apparent stiff-
ness (flexural or storage modulus) and Tg values, while
low frequency distortions will give lower apparent values
for the same material measured under otherwise identi-
cal conditions. Impact testing is an example of a high
frequency distortion with which we are all familiar.
HDT/DTUL, creep and compression set testing are ex-
amples of low frequency distortions.
Figure 2 illustrates the substantial effect frequency
can have when measuring mechanical properties. For
this vinyl ester resin example, frequencies from 0.10 to
100 Hz were used. Onset Tg values range over 20°F, and
differences in the storage modulus vary with tempera-
ture. Frequency response differences in viscoelastic
materials are largest near the Tg, where the balance be-
tween elastic and viscous behavior is changing rapidly.
Far from the Tg, where the elastic or viscous character of
the resin dominates, differences are smaller and rela-
tively insensitive to temperature changes. When report-
ing a Tg value determined by DMA, it is necessary to re-
port the frequency at which the measurements were
made. The differential response of viscoelastic materials
to frequency can be used to predict long term material
properties. The relationship between frequency and
temperature is known as the TTS (Time - Temperature
Superposition) Principle4.
Effect of Heating Rate
Ideal DSC samples are thin giving them large sur-
face area to volume ratios. Heat transfer from the pan
surfaces to (or from) the sample is fast through direct
contact (conduction) from (or to) a large heat sink.
These factors contribute to minimizing thermal gradients
throughout the sample volume in spite of the fast heating
rates commonly employed in DSC. However, differ-
ences are still present in the measured Tg values (and
sensitivity) in DSC which are influenced by heating
rate2, where higher heating rates lead to higher apparent
Tg values.
On the other hand, DMA samples are much larger,
have much smaller surface area to volume ratios, and
heat transfer to the samples occurs by both convection
through air and conduction through contact with the fix-
ture clamps. Diffusion of heat through the thicker DMA
samples is inhibited by the low thermal conductivities of
polymers. To help ensure that DMA samples are at a
uniform temperature throughout their entire volume, they
must be heated at much slower rates than for DSC. In
addition, a longer soak time at the starting temperature is
recommended to ensure that all samples start the experi-
ment at the same uniform initial temperature
3
In Figure 3, the effect of heating rate on the Tg of a
polycarbonate sample is illustrated. The fundamental ba-
sis for the Tg is independent of heating rate, but, as in
DSC, the apparent Tg is higher for faster heating rates.
Faster heating rates produce larger temperature differ-
ences between the sample and the air (the sample is actu-
ally cooler than the air). They also produce steeper tem-
perature gradients within the sample due to the differ-
ences in heat transfer by conduction (clamps) and con-
vection (air). Therefore, when reporting a Tg value de-
termined by DMA, it is necessary to report the heating
rate at which the measurements were made.5
Because of the slow heating rates required in DMA,
the cure state of thermoset samples can change substan-
tially during measurement, so it is a good practice to de-
termine the Tg of a sample twice. Reporting both the “as
received” and “second heat” values is typical. This may
be important for quality assurance/quality control
(QA/QC) reasons, comparing the part as made for sale
with the application specifications and its fitness for use.
For a partially cured sample, there will be a differ-
ence in Tg values between the “first heat” (Tg1) and
“second heat” (Tg2) determinations, while for a fully
cured sample, there is little difference. The difference
between Tg2 and Tg1, or ∆Tg, can be used to quantitate
the degree of resin cure6. For some partially cured sam-
ples, especially if badly undercured, as shown in Figure
4, an increase and decrease in storage modulus, G’,
looking like a second Tg, can appear in the first heating
cycle. This is an artifact caused by additional curing
taking place during the first measurement cycle and is
not a valid Tg.
Effect of Amplitude
There are two principal considerations for selecting
the test amplitude. The first is that testing must be con-
ducted within the linear portion of the classic
stress/strain curve (low forces, small displacements) to
avoid irreversible damage to the sample, which would
change the G’ and G” values measured. The second,
which is especially valid for stiff composite samples, is
based on instrument limitations, where high amplitudes
may not be accessible due to the high forces required to
attain them. This is particularly true in compression and
tensile testing modes. As a corollary, instrument limita-
tions can introduce noise in the signals when driving soft
samples at low amplitudes with low forces. The attain-
able upper and recommended lower limits vary by in-
strument manufacturer.
Selecting Test Conditions
In general, a 3-point bend fixture is a bad choice for
testing a composite above its Tg because the sample may
not be stiff enough to provide the restoring force this test
mode requires. A compression fixture is a bad choice for
composites below their Tg because they are too stiff for
the low forces available in commercial DMA machines

to compress. However, there may be cases where these
limitations can be ignored or exploited. For example, we
have used compression to test samples collected by cus-
tomers which were too small for a cantilever beam, and
have used 3-point bending to test adhesive joints to fail-
ure (see the example discussed in Figure 10). Single or
dual cantilever beam testing are good general purpose
modes because they can evaluate both very stiff and very
soft samples. For screening studies, a frequency of 1 Hz,
an amplitude between 10 µm and 100 µm, and a heating
rate between 2°C/min and 5°C/min is a good starting
point.
The temperature range over which a material is
evaluated depends on the purpose of the test. In general,
the range should be large enough to include both the
highest and lowest temperatures the product would be
expected to see in use. This should especially include
any conversion operations, like an oven cure after paint-
ing. In addition, uncontrolled winter and summer stor-
age and shipping temperatures can be extreme. This
alone suggests that the minimum temperature range over
which a candidate material should be tested for a prod-
uct designed for use under “ambient“ conditions should
be between about -30°C (-22°F) and +85°C (+185°F).
For routine QA/QC testing, the sample evaluated
must be representative of the “real” part, in both compo-
sition (filler type and amount) and cure (catalyst type and
level used, cure cycle time and temperature). This means
that neither mold flashing nor adhesive squeeze-out from
a joint are likely to be acceptable for judging part fitness
for use. Nevertheless, you can take some shortcuts, since
you know what you are looking for and what to expect.
For example, you might be able to heat the sample faster,
or prepare your sample a little less rigorously, as long as
you have proven by previous experiments that the as-
sumptions you make when taking these shortcuts are
valid.
Some Real World Applications
In regard to the composites we manufacture for cor-
rosion applications (storage tanks, piping and connec-
tors), we use the expression “ambient cure” when we
mean a cure initiated without adding external heat. We
employ some resins that can exhibit substantial exo-
therms, depending on the cure package, part thickness,
mold temperature, and maybe even the weather. The
cure of such resins in thick sections is certainly not iso-
thermal. On the other hand, an elevated temperature cure
of a thin part may be considered isothermal if the heat
sink character of the mold is such that it cools the part
during the exotherm.
Watching an Adhesive Cure
A number of simple tests can describe the gel time
and basic cure behavior of thermoset resins. However,
even by measuring hardness vs time, it would be difficult
4
to quantitate either the degree of cure or the rate of prop-
erty development in a resin after the gel point. This is
because hardness is measured at room temperature, nor-
mally well below resin Tg, where hardness is not very
sensitive to the degree of cure. Furthermore, especially
in highly filled systems like glass fiber reinforced com-
posites, the reinforcement can have a substantial effect
on the measured hardness, independent of resin cure
state, leading to false conclusions.
The current example illustrates the utility of DMA
methodology, combining a long isothermal cure segment
with measurement of the “as made” and post cured Tg, to
compare the effects of the initial cure conditions on ini-
tial and ultimate properties. In Figure 5, the cure re-
sponse of a vinyl ester adhesive resin is compared under
two different isothermal conditions (75°F and 90°F)
which might be encountered during the field fabrication
of adhesive joints. The liquid adhesive resin samples
were supported on a piece of aluminum window screen
(wrapped in aluminum foil to reduce styrene losses) in
the single cantilever beam mode.
As expected, the open time is longer for the cooler
sample (90 vs 49 minutes), and once cure begins,
strength development is slower. The open time is given
by the indicated step change (onset) tangents in the stor-
age modulus (G’) curve, and the slope gives the rate of
cure. Gel time is assigned as the peak maximum in the
loss modulus (G”) curve. Note that the adhesive samples
continued to cure well after gellation, as indicated by the
continued increase in their storage moduli over the 8
hours of this part of the test.
After isothermal curing in the DMA, the samples
were rapidly cooled to –40°F and then heated at 5°C/min
to measure their “as made” Tgs. Figure 6 shows that af-
ter 8 hours, the 75°F-cured sample had a Tg1 of 106°F,
while the 90°F-cured sample had a Tg1 of 125°F. Above
about 175°F, both samples show signs of further curing.
After post curing in the DMA, the Tg2 value for both
samples was near 190°F.
These results lead to two very important conclusions:
• After a resin gels, it gets hard on a molecular level,
retarding further cure at that temperature. This
limits the Tg (and strength) the resin can achieve,
and makes post curing critical when high tempera-
ture performance is required.
• No resin will attain a Tg substantially higher than
the highest temperature experienced during cure
(including exotherm and post cure).
Three important corollaries follow from this:
• Resins with high exotherms during cure (in thick
sections) can achieve high Tgs under “ambient” con-
ditions.

• When a thin layer of a “hot” resin is cured adjacent
to a large heat sink (an adhesive in a joint), it will
not have a high exotherm, and therefore will not
reach a high Tg.
• Different locations in the same part can vary in cure
state based on their heat history (laminate thick-
ness), especially if the part is not post cured.
Curing an Epoxy Prepreg
Another example helps drive home the importance
of matching the cure conditions to the resin (and ulti-
mately with the application), and the value of DMA in
helping to achieve this match. Figure 7 compares three
samples of a commercial epoxy prepreg, cured under dif-
ferent conditions. After determining Tg1, the samples
were post cured (10 minutes at 400°F) as part of the
DMA method, and then Tg2 was determined, Figure 8.
As expected, the Tg1 values are lower than Tg2, and none
of the Tg1s are much different from the initial cure tem-
peratures; Table I summarizes the data. The surprise
comes when we compare the Tg2 values. The Tg2 for
Sample #1, initially cured at the lower temperature for
the shortest time, is higher than Tg2 for Sample #2, cured
longer at the same temperature. Sample #3, initially
cured at a higher temperature has an even lower Tg2 after
the same post cure treatment (see Table I).
Partially cured thermoset resins are often referred to
as “B-staged”, where the “A-stage” is prior to reaction,
and “C-stage” is fully cured. There are some advantages
to B-staging resins, for example the manufacture of a
prepreg in one location, and its use to make a finished
product in another. However, these results make it ap-
parent that there are different degrees of B-staging. A
prepreg is manufactured as a “soft” B-stage, whereas
these samples cured at 200°F or 255°F might be termed
“hard” B-staging. The caveat here is that the softer the
B-stage, the more fully the epoxy resin will cure under
otherwise identical post cure conditions. Or said differ-
ently, if an epoxy resin is cured all at once instead of in
stages, it will cure further, achieving higher performance
capabilities. Why is this?
The basis for these differences in cure behavior can
be found in the way polymers move. Because molecules
repel each other when they get too close, there is always
some empty space between them. This empty space is
called free volume. As liquids, small molecules can eas-
ily exchange places with nearest neighbors because the
holes between them are similar in size to the molecules
themselves. More importantly, they are not constrained
by being part of a larger structure. On the other hand,
polymers are much larger than the empty spaces around
them, and therefore cannot move as a single unit. So
polymer molecules move in smaller units, called seg-
ments, which don’t require as large a free volume. How-
ever, in addition to a nearby space to move into, the
segments require other parts of the molecule farther
5
away to have moved a little bit first, to provide “slack” in
the chain. Eventually, this cooperative or correlated
movement can result in diffusion of whole molecules
through the bulk material (in the melt), but more often,
only results in different degrees of entanglement.
Molecules in a “soft” B-stage network have high
mobility because they have a lower molecular weight
and there are few crosslinks. Such networks also have
higher concentrations of reactive groups, more free vol-
ume, and a lower Tg than one at a “hard” B-stage. These
features enable the reactive groups to move with fewer
constraints, more like small molecules, and to more eas-
ily find a reaction partner with which to form new
crosslinks. The harder the B-stage, the more fully
formed the network is. This means larger molecular
segments must move to enable the remaining reactive
groups to get close enough together to form new
crosslinks. This requires an increase in correlated mo-
lecular motions to further increase crosslinking (counter
entropic). Thus, as the network becomes more
crosslinked, it becomes progressively more difficult to
crosslink it further7.
There are two take-home lessons here:
• The curing process should be matched to the resin to
get all the performance possible from the resin. If
your process allows it, cure the resin all the way in
one heating operation. Otherwise, cure the resin as
little as practical in your process and then post cure
to get higher performance (Tg).
• Second, the resin should be matched to the curing
process to get the all the process can deliver. If
there are temperature or cycle time constraints in the
process that prevent the resin from reaching its po-
tential, consider a (cheaper) resin that can be fully
cured by the process. Just because you are buying a
high Tg resin, does not mean you will get a high Tg
when you are finished. Find out from the resin sup-
plier how to get the high Tg, and then test your proc-
ess to make sure you do.
Adhesive Development
A recent project involved development of an im-
proved vinyl ester adhesive. An adhesive joint between
a pipe and a fitting must perform for years under a wide
range of temperatures and pressures (not to mention
chemical environments). The upper use temperature tar-
get for the new adhesive was above the Tg typical for this
type of resin, and it still had to function at normal tem-
peratures as well. Increasing the Tg by changing the
resin type could result in a brittle adhesive with a differ-
ent chemical resistance profile. We wanted the new ad-
hesive to handle the same chemical services, but at
higher temperatures, without becoming brittle at normal
temperatures.

We devised a DMA method to screen resin candi-
dates for both Tg and strength above Tg based on a con-
stant applied force and controlled temperature ramp.
Most of us are familiar with heat deflection temperature
(HDT) and deflection temperature under load (DTUL)
testing. A sample of specified dimensions is placed in a
3-point bending fixture, a fixed force is applied, and the
sample is heated at a specified rate until a predetermined
amount of deflection is reached. The temperature at
which this occurs is called the HDT or DTUL. This type
of nonisothermal and controlled force method is well
suited to DMA techniques.
We catalyzed the various resin candidates, and
made lap joints with controlled bond line thickness. The
resins were cured at room temperature overnight, fol-
lowed by a 2 hr post cure at 200°F. The samples were
then placed in the DMA and a constant force was applied
at right angles to the overlapped joint area while they
were being heated at 2°C/min until failure (see Figure
9a). This is really a compression test method (until the
joint fails), and we followed the progress of each run by
watching probe displacement.
In preliminary work, we determined that using our
machine’s maximum load of 18N, about 16 psi over the
joint area, would cause joint failures with the current ad-
hesive at temperatures near 300°F. Interestingly, even at
this high a compressive load, we can still see the effects
of variations in the coefficient of thermal expansion
(CTE) with temperature8, as well as other mechanical
effects. This allowed us to assign a Tg, and observe bond
line thickness changes, both of which are related to resin
composition. Dimension changes in Figure 10 are re-
ported relative to the probe’s starting position and the
direction in which it applies the force. Thus, under com-
pression, probe displacement is positive, and negative
during expansion.
Several different responses to this test method are
illustrated in Figure 10. The negative slope at the begin-
ning of the test means the samples were expanding, ex-
pected behavior during heating. We defined the Tg as-
signed by this method as the intersection of two tangents
drawn as for an onset Tg in the storage modulus (G’)
curve in an oscillatory DMA test (see Figure 1). Heating
through the Tg softens the sample, allowing it to be com-
pressed, resulting in a positive slope. The height of this
part of the curve is related to resin compressibility under
the test conditions, see Curve 1. Resin expansion con-
tinues at temperatures above the maximum compression
point, where the CTE again overcomes the applied com-
pressive force. Irregularities in these portions of the
curves are due to adhesive or cohesive damage within the
bonded area leading to joint failure. When the joints fail,
there is a steep rise in the slope, truncated in this figure.
In duplicate tests, we observed joint failure temperature
(JFT) variability of 25 - 50°F for each resin. This sug-
gests the JFTs are not entirely characteristic of the resins,
but more a function of the substrate surfaces and the fin-
6
ished joint profiles used in this study. Table II summa-
rizes the results illustrated in Figure 10.
Curve 1 is the unmodified control resin, and has the
largest amount of compressibility. The other samples are
modified versions of the same base resin, which result in
different network structures and enhanced crosslinking.
In the glassy state, below their respective Tgs, the sam-
ples exhibit nearly identical CTEs, as well they should,
since they are all closely related formulations. The dif-
ferent effects on the network structures by the modifica-
tions are only apparent above the resins’ Tgs. The re-
duction in compressibility is evidence of enhanced
crosslinking obtained by the modifications.
The modification in Curve 2 is quite interesting. It
may have formed a second phase with a higher Tg, or un-
dergone further crosslinking (above about 175°F, where
compression is temporarily prevented) during the test.
The Tg of the new network is reached around 193°F (ar-
row), and compression resumes. What makes this modi-
fication so interesting is that even in the absence of the
additional curing, it reduced resin compressibility near
the first Tg without the expected increase in Tg. The
modification in Curve 3 behaved more as expected, re-
sulting in both an increased Tg and reduced compressi-
bility, the result of a more tightly crosslinked network.
The modification in Curve 4 further increased resin Tg
and reduced compressibility. It also provided a remark-
able improvement in adhesion to the steel substrates, as
we were unable to break joints made with this resin up to
the temperature limit of the test (250°C).
Conclusions
We have compared DMA techniques with the more
familiar DSC analysis, and shown that DMA is a power-
ful tool that can provide information not available from
DSC. The major instrument parameters of frequency,
heating rate and amplitude, their influence on the out-
come of an analysis, and their selection, have been dis-
cussed. Definitions of the glass transition in polymers,
and its assignment from DMA data, have been covered.
DMA samples are substantially larger than those
used in DSC. Solid samples require some care to prepare
for obtaining comparable modulus values from duplicate
samples, but very useful qualitative and quantitative data
can still be collected from samples that are less than per-
fect, especially when prepared from real parts. Using
inexpensive and easy-to-make disposable fixtures for
liquid samples can provide important data relating to the
curing behavior of thermoset resins and part manufac-
turing processes.
Building on this background, several examples
were used to illustrate the application of this methodol-
ogy to real world resin development problems. In one
example, the effect of cure temperature demonstrated
how the data could be used to estimate the open time for
an adhesive, it’s rate and level of property development,
 7
and the effect of post cure. Other data have illustrated
the relationship of cure temperature to Tg1 and the ulti-
mate Tg of a resin, which was related to first principles.
Finally, a novel technique used to assess the effects of
resin structural changes on adhesive performance was
described.
 8

Figure 1. S om e definitions of glass transition tem perature (Tg) from DMA

21000 1400
Loss Modulus, G", Peak Maximum tan delta, P eak Maximum
Tg = 339 F Tg = 349 F
! !
! " #
! 0.12 1200
18000 !
!
# "
!
" #
! # " 0.10 1000
Storage Modulus (MPa)

Storage Modulus, G', Onset

Loss M odulus (M Pa)

15000 " #
Tg = 293 F
!# "

Tan Delta
"
0.08 800
#

12000 ! "
#
" #
0.06 600
!
Storage Modulus, G', Inflection P oint # "
Tg = 335 F " #
9000
!
# " 0.04 400
" #
!
# "
6000 "
! # 0.02 200
" # "
" " "
" "
# # #
# # #
3000 0
0 100 200 300 400 500
Temperature (°F) Universal V2.5H TA Instrum ents

Figure 2. Effect of frequency on Tg assignment from DMA data.

10000

100 Hz
Tg = 232 F
9000

8000
0.10 Hz
Storage Modulus (MPa)

Tg = 212 F
7000

6000

5000

4000

3000

2000
120 160 200 240 280 320 360 400
Temperature (°F) Universal V2.5H TA Instruments
 9

Figure 3. Effect of heating rate on assigned polycarbonate Tg.

2500 600
313.38°F
$ %
! $
! $ $
! $ 310.24°F
! $
! $
! $ " %
!
2000 !
$ "%
!
"
$ " % %
Storage Modulus (MPa)

! 400

Loss Modulus (MPa)

"
$ %
1500
" %
!

"
" %$ !
%
1000
Circles: G' "
Squares: G" $
"
% !
200
%
Dashed/Open: 2dpm $ "
"
Solid/Solid: 5dpm %
!
500 %
$ "
"
%
!
"% %
"% $ "
% %
" "% "%
"
% %
" "
Determined at 1.0 Hz $! " $
0 0
200 225 250 275 300 325 350
Temperature (°F) Universal V2.5H TA Instrum ents

Figure 4. Tg1 and Tg2 of a commercial epoxy prepreg.

20000

Second Heat
18000 G' Onset
Tg2 = 298 F

16000
Storage Modulus (MPa)

14000 First Heat

G' Onset
Tg1 = 207 F
12000

10000
Artifact from
additional cure
8000

6000

Determined at 1.0 Hz, 5 C/min heating rate

4000
0 50 100 150 200 250 300 350 400 450
Temperature (°F) Universal V2.5H TA Instruments
 10

Figure 5. E ffect of isotherm al tem perature on adhesive resin cure.

6000 800

61 m in
113 m in $ $ $
$ $
" $ !
$ ! !
" % $ !
% $ !
$ !
" ! 600
" % !
S torage M odulus (M P a)

$ % Solid/S olid: 75F cure

!

Loss M odulus (M Pa)

4000
" D ashed/Open: 90F cure
"%
$ ! %
G': C ircles
" " G": Squares
%
% 400
$ ! "
" %
" "
% " "% "% "
$ ! % " " "
%
% %
2000 "
%
$ !
200
"
%
" " $ 49 m in !

$
%
%
% !
! 90 m in
! D eterm ined at 1.0 H z
0 0
0 60 120 180 240 300 360 420 480
Tim e (m in) U niversal V2.5H TA Instrum ents

Figure 6. E ffect of isotherm al cure tem perature on adhesive resin Tg

8000

Tg1 = 125 F

6000
S torage M odulus (M P a)

Tg1 = 106 F
Solid Line: 75 F C ure
4000 D ashed Line: 90 F C ure

2000

Additional cure taking place

D eterm ined at 1.0 H z, 5 C /m in heating rate.

0
-50 0 50 100 150 200 250 300 350 400
Tem perature (°F) U niversal V2.5H TA Instrum ents
 11

F ig u re 7 . E f fe c t o f in itia l c u re c o n d itio n s o n T g 1 o f e p o x y p re p re g .

# #
# S a m p le # 3
19000 #
# 2 5 5 F /5 0 m in
#
" " # Tg1 = 224 F
"
"
"
! ! " #
! !
17000
! "
S to ra g e M o d u lu s (M P a )

!
# S a m p le # 2
2 0 0 F /2 4 0 m in
" Tg1 = 208 F
15000 #
!
S a m p le # 1 "
2 0 0 F /1 0 5 m in #
!
Tg1 = 187 F
13000 " !
!
" #
! !
A d d itio n a l c u re !
11000 ta kin g p la c e "#
(a ll 3 s a m p le s )

"#

9000
" #

D e te rm in e d a t 1 .0 H z , 5 C /m in h e a tin g ra te
7000
0 100 200 300 400
T e m p e ra tu re (° F ) U n iv ers a l V 2 . 5 H T A I n s t ru m en t s

F ig u re 8 . E f f e c t o f in it ia l c u re c o n d it io n s o n T g 2

20000
S a m p le # 1
! ! ! 2 0 0 F /1 0 5 m in
! ! ! ! Tg2 = 313 F
!
" !
" " " "
S to r a g e M o d u lu s ( M P a )

15000 " !
"
"
# # !
# # # # "
#
S a m p le # 2
# "
10000 S a m p le # 3 2 0 0 F /2 4 0 m in
2 5 5 F /5 0 m in Tg2 = 297 F
Tg2 = 276 F # "

# "

5000
# "

"
#

D e te r m in e d a t 1 .0 H z , 5 C /m in h e a tin g r a te . # #
0
0 50 100 150 200 250 300 350 400 450
T e m p e ra tu re (° F ) U n iv e r s a l V 2 . 5 H T A I n s t ru m e n t s

Table I. Effect of Cure and Post Cure Conditions on Tg of an Epoxy Resin

Sample Cure Temp. Time Tg 1 Tg 2 ∆Tg

#1 200°F 105 min 182°F 317°F 135°F
#2 200°F 240 min 204°F 295°F 91°F
#3 255°F 50 min 229°F 277°F 48°F
 12

(a ) (b ) (c )
A t s ta r t o f te s t.
C o h e s iv e fa ilu r e A d h e s iv e fa ilu r e
F ig u r e 9 . T e s t s e tu p a n d fa ilu r e m o d e s .

Figure 10. Effect of functional additives on adhesive resin behavior.

%
%
80 %
C urve 1,
%
% C ontrol

% C om pression
60
D im ension C hange (µm )

%
"
C urve 2

40 %
"
#
C urve 3
% "
#
!
"
%
# # #
20 "
"
!
#
% % #
#
"
! ! !
! !
!
C urve 4
!
0
!
!
!
-20 18N constant force, 2 C/m in heating rate
!

50 100 150 200 250 300 350 400 450 500

Tem perature (°F) U niversal V2.5H TA Instrum ents

Table II. Results of Compressive Lap Joint Testing

Sample Tg1 JFT Compressibility

Curve 1 164°F ~320°F 71µm
Curve 2 161°F ~270°F 24µm
Curve 3 187°F ~280°F 13µm
Curve 4 213°F >480°F 2µm
 13

1
Prepared for the Fall 2001 CFA Meeting in Tampa, Florida.. SMITH Fibercast is a Varco International
company. We are located at 25 South Main Street, Sand Springs, OK 74063.
2
J. Foreman, TA Instruments Thermal Application Publication TA-082
3
S. E. Bin Wadud, R. B. Ulbrich, TA Instruments Hotline, Summer 2000
4
M. L. Williams, R. F. Landel, and J. D. Ferry, J. Am. Chem. Soc., 77, 3701 (1955); TA Instruments
Thermal Application Publication TA-144; Ya. Gol’dman, Prediction of the Deformation Properties of
Polymeric and Composite Materials, translated by M. Shelef and R. A. Dickie, Am. Chem. Soc. Professional
Reference Book (1994), and many others.
5
Placement of the thermocouple in relation to the sample and the clamps is critical in obtaining useful Tg
values. For best results, it should be both as close to the sample and as far from the fixture clamps as pos-
sible. A correction factor can be estimated by plotting heating rate vs apparent Tg and extrapolating the
data back to zero heating rate.
6
The definition for “degree of cure,” and its measurement, can vary according to resin cure mechanisms,
but the concept is fairly constant: how much further could it have cured? The definition may be based on
the percent of reactive groups consumed during, or remaining after, cure: epoxy or isocyanate groups in
epoxy or urethane resins. On the other hand, it may be based on residual volatile monomer remaining,
such as styrene in unsaturated polyester (UPE) and related vinyl ester (VE) resins. Other definitions may
also be cure mechanism based, viz. the use of catalytic or stoichiometric curing agents, and the presence of
residual intact catalyst, like peroxides in UPEs and VEs, after cure. The pragmatic view ignores resin cure
mechanisms, and is based simply on how closely we approached the highest practical Tg achievable in the
system. Several independent methods can be used to relate the magnitude of ∆Tg to resin cure state. Calo-
rimetric determination of residual heats of reaction (DSC) is one way, infrared spectroscopy (residual
functional group count) is another.
7
If crosslinks form faster than the incipient network shrinks due to free volume losses accompanying bond
formation, high levels of crosslinking are possible, a case where kinetics can overpower thermodynamics.
The longer the network is allowed to relax before post cure, the more free volume is lost, and the harder it
is to build a tight network. This phenomenon is called physical aging. Nonuniform free volume change
during cure is one origin of cured-in stresses that are responsible for distortion of plastic parts after cool-
ing. Annealing helps to relieve these stresses by increasing the rate of segmental motions, leading to faster
attainment of equilibrium and molecular relaxation.
8
The coefficient of thermal expansion (CTE) of a polymer is larger for T > Tg, hence the steeper negative
slope at T > Tg. See for example Chapter 10 (Figures 5 and 6, pages 367 and 369) by B. L. Burton and J. L
Bertram in “Polymer Toughening”, Marcel Dekker, Inc., 1996, C. B. Arends, ed.
Steven Nahm, Ph.D.:
Chief Chemist, SMITH Fibercast, a Varco Company
20 years of industrial experience in monomer and polymer development, modification, and syn-
thesis, catalyst development, and analytical methods development related to work in fiber rein-
forced composites, coatings, and fundamental studies of reaction mechanisms; 13 published pa-
pers, 3 US Patents.