37

Thermal Analysis User

Information for Users
Com

Dear Customer, Contents 1/2013

The market for mobile communication is growing rapidly. More and more people want to be reached any-
where, at any time, and can in fact be reached with all the well-known advantages and disadvantages. The TA Tip
STARe System keeps pace with developments and now offers you a number of interesting new communica- - Sorption experiments
tion possibilities. These new options are presented in detail in the News section. with the TGA/DSC 1 1
We now offer e-Training courses on DSC curve interpretation (www.mt.com/ta-etraining ). These Internet-
New in our Sales Program
based, online courses begin with an e-Learning course that you can work through whenever you want. After
you have completed the course, you will receive an invitation to a live Webinar on curve interpretation dur- - Mobile communication
ing which you can discuss outstanding questions with experts. possibilities with the STARe System 6
- The new METTLER TOLEDO
micro and ultramicro balances 7
- Complete deformulation
of your sample 8

Sorption experiments with the TGA/DSC 1 Applications

- The strange behavior of
a bouncing modeling putty 9
Dr. Markus Schubnell, Dr. Angela Hammer
- Study of the curing behavior
of a trifunctional epoxy resin 12
- New methodology developed
The moisture content of a material has a large influence on its melting behavior, glass
for DSC for the analysis of phase
transition temperature, stability, and other properties. Sorption behavior also allows con- change materials 16
clusions to be drawn about amorphous regions in a product. Knowledge of the moisture
- Thermoanalytical characterization
uptake and drying behavior of materials is particularly important in the food and pharma-
of oxo-biodegradable polymers 19
ceutical industries, for example to optimize production processes with regard to product
quality or to define suitable storage conditions. In this article, we will show how such Dates
investigations can be performed using a TGA/DSC 1. - Exhibitions 22
- Courses and Seminars 23
 Introduction
The influence of relative humidity on the
behavior of materials can be investigated
by exposing a sample isothermally to a
defined level of relative humidity (RH)
TA Tip
croorganisms such as molds or bacteria,
and so on.
For example, foodstuffs are not affected
by microbial attack until the water activ-
higher than the condensation tempera-
ture of the humidified gas generated by
the humidity generator.
For this reason, we recommend the use of

for a certain time and continuously mea-
suring its mass using a balance.
The measurement time should be long
enough for the mass of the sample to
reach a constant value. The RH is then
increased in steps keeping the tempera-
ture constant and allowing sufficient
time for the sample mass to stabilize
each time at the new RH level. The equi-
librium moisture content of the sample is
determined for the different values of RH
and plotted as a function of the RH.
This yields a so-called sorption isotherm.
Under these conditions (equilibrium), the
RH corresponds to the water activity (aw)
of the water in the sample. Water activity
is related to the partial pressure of water
above the sample and is not the same as
the water content. It is a measure of the
relatively free or unbound water present
in a raw material, food or product that
is available to support processes such as
non-enzymatic browning (Maillard re-
action), fat oxidation, the growth of mi-
Figure 1.
Schematic diagram Temperature and Humidity Sensors
of a system for
measuring sorption
isotherms by TGA.
Protective Gas
ity is greater than about 0.7. The mois-
ture content that corresponds to a water
activity of 0.7 can vary between a few
percent and several tens of percent de-
pending on the product. A sorption curve
allows the corresponding water content
in a product to be determined for a par-
ticular water activity.
Experimental details
Sorption isotherms can be measured by
attaching a specially designed humidity
generator to a TGA/DSC 1 (Figure 1).
The humidity generator produces a well-
defined gas flow with a precise RH. The
gas flow from the humidity generator
passes into the furnace chamber of the
TGA/DSC 1 through a humidity interface
attached to the outlet of the TGA furnace.
T he f low rat e is t y pica lly about
100 mL/min. About 5 mL/min dry gas
is also required as protective gas for the
balance. To prevent condensation, the
temperature of the interface must be
Control Unit
Dry Flow
two thermostats. One is used to thermo-
stat the balance and to cool the furnace
flange and furnace jacket, the other to
thermostat the humidity interface.
METTLER TOLEDO offers two humid-
ity generators that can be coupled to the
TGA/DSC 1. The two humidity generators
differ mainly in the way the RH is con-
trolled. Both types of humidity genera-
tor were used for the measurements de-
scribed in this article.
Temperature dependence
of relative humidity
The relative humidity depends strongly
on temperature because the vapor pres-
sure of water is very temperature depen-
dent. This is illustrated in Figure 2, which
shows the corresponding RH levels at dif-
ferent temperatures for initial RH levels
of 30%, 40%, 60% and 80% at 40 °C.
If, for example, the RH of air at 40 °C is
40% (red curve), the RH of the same air
at 30 °C is 68% (see the horizontal red
arrow). At about 23 °C, the RH of this air
is 100%. This means that at lower tem-
peratures part of the water vapor would
condense (dotted red line) – which ex-
plains why drops of water form in the
refrigerator (after opening it) or on cold

Mass
Mixing Unit

Water water pipes in the cellar when the weath-

Dry Gas

Humid Gas Reservoir Flow

Con- er is humid.
TGA Sensor trollers
Wet Flow
Interface

Saturator
The pronounced temperature depen-
TGA Furnace Humidity Generator dence of RH means that a small un-
certainty in temperature leads to a
Gas Outlet
large uncertainty in the RH. This is
demonstrated in Figure 3. It shows the
Table 1. temperature dependence of the relative
Temperature LiCl MgCl26 H2O Mg(NO3)26 H2O NaCl
Deliquescence uncertainty of the RH for a temperature
relative humidity for in °C in % in % in % in %
uncertainty of 1 K.
different salts at dif-
ferent temperatures.
20 11.3 33.1 54.4 75.5
30 11.3 32.4 51.4 75.1 Example: Let us assume that the RH
40 11.2 31.6 48.4 74.7 at 60 °C is 50%. An uncertainty of the
50 11.1 30.5 45.4 temperature of 1 K (i.e. the tempera-
ture is 60 ± 1 °C) results in a relative
60 11.0 29.3
uncertainty of RH of 4.6% (see arrows in
70 10.8 27.8 Figure 3).

2 METTLER TOLEDO UserCom 37
This gives a value of 50 ± 2.3% for the Figure 2.
Dependence of the
RH. Small uncertainties in the tem- relative humidity on
perature (in this example 1 K) therefore temperature.
cause large uncertainties in the RH. This
effect is more pronounced at low temper-
atures than at high temperatures.

Calibration of relative humidity

The calibration of the RH in the fur-
nace chamber of the TGA/DSC 1 makes
use of the deliquescence of certain inor-
ganic salts. Deliquescence is the process
in which the salt absorbs water vapor
from the air from a critical RH onward
at a particular temperature to form a
solution. This property can be used to
calibrate the RH generated by a humidity
generator.

Figure 3.
Table 1 lists some of the salts used as cal- Relative change of
ibration substances together with the cor- RH at a particular
responding values of the deliquescence temperature when
the temperature is
relative humidity at different tempera- changed by 1 K.
tures. There are two possible experimen-
tal approaches.

Method 1:
The sample is exposed to a relative hu-
midity in the TGA/DSC 1 that is higher
than the deliquescence relative humidity
of the substance used. Under these cir-
cumstances, the sample absorbs water
and the sample mass increases. The RH
in the furnace chamber is then reduced
in steps. When it reaches the deliques-
cence relative humidity, the sample be-
gins to lose water and the sample mass
decreases. Figure 4.
Determination of
The maximum in the TGA curve is the deliquescence
relative humidity
therefore reached when the RH in the of MgCl26 H2O
furnace chamber corresponds to the at 27.5 °C using
Method 1 (see text
deliquescence relative humidity of the
for details).
sample. This is illustrated in Figure
4, which shows results obtained using
MgCl26 H2O.

Method 2:
The sample is exposed to a relative hu-
midity in the TGA/DSC 1 that is lower
than the deliquescence relative humidity
of the material used. Under these condi-
tions, the sample does not absorb water
and the sample mass remains constant.
The RH in the furnace chamber is then

METTLER TOLEDO UserCom 37 3
 increased in steps. When it reaches the
deliquescence relative humidity, the
sample begins to absorb water and the
sample mass increases.
TA Tipp

The onset of the increase therefore cor-

responds to the deliquescence relative
humidity. This is illustrated in Figure 5,
which again shows results obtained us-
ing MgCl 26 H 2 O. Comparison of Fig-
ures 4 and 5 shows that both methods
yield equivalent results.
Figure 5.
Measurement of Application 1: Sorption
the deliquescence
of MgCl26 H2O
behavior of wheat starch
at 27.5 °C using A plant stores water-soluble glucose
Method 2 (see text produced during photosynthesis by
for details).
transforming it into starch. Starch is a
polysaccharide, 25% of which consists
Figure 6.
Sorption and de- of linear polymer chains with a helical
sorption measure- structure (amylose) and 75% of strongly
ments of wheat branched structures (amylopectin).
starch.

Starch is used in the food industry,

mainly in the production of confection-
ery, milk products and bread, cakes and
pastries. There are also an increasing
number of applications in the chemical-
technical industry, in particular the pa-
per industry. Because of the wide number
of possible uses, the sorption behavior of
starch is of great practical importance.

Figure 6 shows the results of a sorption

experiment performed at 30 °C using
wheat starch. The blue curve corresponds
to the relative humidity, and the red
Figure 7. curve to the TGA signal. At the beginning
Sorption and de- of the measurement, the starch loses
sorption isotherms its residual water and is practically dry.
for wheat starch at
30 °C. The starch then absorbs more and more
moisture.

A plot of the relative increase in weight

with respect to the dry weight of the sam-
ple (this corresponds to its moisture con-
tent, W) as a function of the RH (= water
activity, aw) yields the sorption isotherm
shown in Figure 7.

This presentation shows that a water ac-

tivity of 0.7 (the value, according to the
literature, at which microbial attack of
the starch is expected) is reached at a
moisture content of about 15% (see blue

4 METTLER TOLEDO UserCom 37
arrow). Figure 7 also shows that a hys-
teresis effect occurs between the sorption
and desorption processes. Sorption hys-
teresis is in fact a phenomenon that oc-
curs quite generally; the reason for this is
not yet fully understood.
Different models are used to describe
sorption isotherms (for details see the
books listed under Literature). In prac-
tice, the Guggenheim–Anderson–de
Boer (GAB) model is often used. In its
polynomial form, it describes the rela-
tionship between the water activity (aw)
normalized with respect to the moisture
content (W) and water activity accord-
ing to Formula 1, where k, c and m0 are
parameters determined from the experi-
mental data.
This is done as follows: the water activity
determined from the sorption isotherm
normalized with respect to the moisture
content (aw/W) is plotted as a function
of aw (see Figure 8) and fitted to Formula
1 using a second order polynomial (this
yields values for the coefficients ,  and
, red curve in Figure 8).
The GAB parameters can then be deter-
mined from the coefficients ,  and 
according to the formulas given in For-
mula 2.
The most important result of the GAB
analysis is the value for the monolayer
moisture content (m0). This is of great
practical importance. If the moisture
content, for example of a foodstuff, is be-
low m0, then usually no changes in the
product are to be expected. The mono-
layer moisture content therefore repre-
sents a type of maximum (and in certain
cases an optimum) moisture content that
a product may exhibit if it is to be stored
for a longer period of time without loss
of quality.
aw k 1  2 1  2 1
=  –1 + 1– a + = α · a2w + β · aw + γ
w m0  c  aw m0  c w m0· k · c
k=√
2
β – 4αγ – β β 1
, c= + 2, m0 =
2γ γ⋅k
Typically, a water activity between 0.2
and 0.4 corresponds to the monolayer
moisture content. For the wheat starch
investigated, a monolayer moisture con-
tent of 7.45% was obtained.
Conclusions
The TGA/DSC 1 combined with a hu-
midity generator is an inexpensive way
to study the sorption and desorption be-
havior of different materials and prod-
ucts. To do this, the relative humidity in
the furnace chamber of the TGA/DSC 1
is varied in steps or continuously under
isothermal conditions by means of a hu-
midity generator.
In the equilibrium state (the sample
mass reaches a constant value at a cer-
tain relative humidity level), the rela-
Formula 1
Formula 2
γ⋅k⋅c
Figure 8.
GAB fit for the mea-
sured sorption data
of wheat starch.
tive humidity corresponds to the water
activity of the water present in the prod-
uct. The sorption isotherm can be used
to estimate the optimum water content
for storing a product. Knowledge of the
relationship between water content and
water activity is particularly important in
the food and pharmaceutical industries
in order to optimize production processes
for product quality or to define suitable
storage conditions.
Literature
[1] L. N. Bell, Th. P. Labuza, Moisture
Sorption, American Association of
Cereal Chemists, 2000,
ISBN 1-891127-18-7.
[2] G. V. Barbosa-Canovas, A. J. Fon-
tana, S. J. Schmidt, Th. P. Labuza,
Water Activity in Foods, Blackwell
Publishing, 2007,
ISBN-13: 978-0-08138-2408-6.
METTLER TOLEDO UserCom 37 5
 Mobile communication
possibilities with the STARe System
New in our Sales Program

E-mail notification
In the last issue of UserCom, we introduced the new e-mail and
SMS functionality that informs you about the status of your in-
strument. You know whether your measurement series has been
completed without having to look in the laboratory. You define
in advance the events you want to be informed about. The fol-
lowing information can be transmitted:
• Measurement completed
• Error on TA module during the experiment,
measurement stopped
• Warning on TA module during the experiment,
possible malfunction
• Waiting for sample insertion
• Waiting for sample removal

Figure 1. Possible settings in the Experiment memory. Each experi-

ment can contain other settings.

Figure 2. TA Analysis App and online access

TA Analysis App
with News, User-
There are now two new mobile applications:
Com, On-Demand • “TA Analysis” App (for iOS and Android):
Webinars and Video This new App is free and allows you to access UserCom,
sections.
On-Demand webinars, and other interesting services when-
ever you like using your mobile device. You can search
through previously published issues of UserCom or study
an On-Demand webinar on your way home by bus or train
(Figure 2).
u  www.mt.com/ta-app
• Online access to the measuring module from a mobile device:
You can now access the instrument or just check the status
of the instrument on an intranet using a VNC viewer
(Figure 3).

Figure 3. DMA 1 remotely controlled via a mobile telephone.

6 METTLER TOLEDO UserCom 37
The new METTLER TOLEDO
micro and ultramicro balances

The METTLER TOLEDO XP2U and XP6U
ultramicro balances set new standards in
terms of weighing accuracy and speed.
The balances are designed to boost effi-
ciency and reliability as well as support
network compatibility.
Excellent repeatability
Thanks to an improved weighing cell,
new electronics and optimized signal
processing, the ultramicro balances
combine excellent reproducibility, higher
capacity and a short stabilization time.
The XP2U and XP6U offer unsurpassed
repeatability of up to 0.15 µg; reduction
of sample weight requirements allows
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ly structured customizable user interface
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Numerous quality management func-
tions support regulatory requirements.
Even sample sizes of less than 1  mg
conform to the strict process tolerances
and satisfy the current international USP
standards.
Built-in safety functions
Together with extensive antistatic mea-
sures and the optional LabX balance
software for reliable and safe data man-
agement, the XP2U and XP6U ultramicro
balances provide a complete weighing
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requirements.

Short stabilization time

In addition, the XP6U has an unparal-
leled capacity of 6  g and unmatched
61 million digits resolution. This leads to
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cations and usable sample weights. The
average settling time has been reduced
to about ten seconds to accelerate the
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Configurable,
color touch screen
All the high performance XP balances
are equipped with a color TFT touch
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eration. Users profit from intuitive and
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Functions and
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• Short stabilization time maxi-
mizes sample throughput and
improves efficiency. For further information visit:
• Customizable color touch screen www.mt.com/micro
and infrared sensors for hands-
For further information about
free operation ensure simple, fast,
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mum weight control make the Im Langacher, 8606 Greifensee, Schweiz
XP2U and XP6U ideal instruments T +41 44 944 2211, F +41 44 944 3320
for regulated environments. www.mt.com

Maximum Settling Draft

Model Readability Repeatability Terminal User settings
capacity time shield operation
XP2U 2.1 g 0.1 μg 0.25 μg ∼10 s color automatic yes
XP6U 6.1 g 0.1 μg 0.4 μg ∼15 s color automatic yes
XP6 6.1 g 1 μg 0.8 μg ∼8s color automatic yes
XS3DU 0.8 g / 1 μg / 5 μg / ∼10 s monochrome manual no
3g 10 μg 6 μg

METTLER TOLEDO UserCom 37 7
 Complete deformulation of your sample

Procedures like failure analysis, process • Right-click functionality for simple The OMNIC Mercury software extracts
Applications

validation and competitive investigations
often require that a sample be deformu-
lated to identify components and to un-
derstand processing differences.
searches
• Transfer to an OMNIC™ Specta™ for
multi-component mixture searching
• One-Click analysis of the entire data
set through Mercury TGA software
• Extensive gas phase spectral libraries
for searching
Ideally, deformulation via TGA-IR entails
getting three pieces of information:
• Weight loss for quantitation
• Identification of off-gassing material
for compositional analysis
• Time profiles for component evolution
to probe processing conditions
everything – what and when – giving
you a full profile of your sample:
• Total gas evolution profile showing the
overall IR signal
• Component search results plus re-
sidual
• Time profiles for each component re-
vealing underlying chemistry
• Visual comparison window permitting
the analyst to determine completeness
of the result
• Total analysis time reduced from 30 to
60 minutes to less than 2 minutes
• Consistent results from user to user
• Makes TGA-IR a practical tool

The first item is extracted from the TGA Mercury TGA: One Click and Done Defor-
data through weight loss curves. The se- mulation Analysis.
cond is extracted by searching the spect-
ra, while the third comes from profiling
a particular component in time.
The Thermo Scientific™ Nicolet™ iS™50
FT-IR provides excellent tools for this Critically, the TGA-IR gas evolutions Nicolet iS™50 Modules
application: do not occur one at a time. Individual The Nicolet iS™50 modules expand
the materials analysis capability
• Excellent quality spectra across the components can be evolved severely over-
further:
mid-IR lapped with other gases, and the compo-
• Simple linkage to Thermal Gravimetric nents do not evolve with the same time • Built-in, diamond mid/far-IR ATR
Analysis (TGA) systems profile. - Bulk material analysis before
the TGA experiment
• Optimized gas cell providing rapid re-
- Residue analysis after TGA-IR
sponse to off-gassing materials This can provide crucial information
for inorganics, ash
• 3-Dimensional graphic viewing of about processing, like heat treating of a
time-based data sets for manual review rubber. • iS™50 Raman module
- Mount the TGA-IR module in
Figure 1. an external sample com-
Mercury TGA reveals partment iS™50 AEM
what (lower right) - Gain morphology insights and
and when (lower
complementary search results
left) and offers a
visual comparison to FTIR
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ter Exchanger
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For further information

about iS™50 FTIR visit:
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8 METTLER TOLEDO UserCom 37
The strange behavior of a bouncing modeling putty
Nicolas Fedelich
“Horst die Hüpfknete” is the German name for a make of bouncing modeling putty used as a toy for children.
The material exhibits two quite different types of behavior at room temperature: On the one hand, it can be
easily shaped and stretched and flows like a viscous liquid. In contrast, if it is rolled into a ball and allowed
to fall to the ground, it behaves elastically and bounces back up like a tennis ball.
Introduction
How can this most unusual behavior be
explained? – In this article, we will try to
answer this question.
DSC measurements
The putty was first measured by DSC us-
ing a METTLER TOLEDO DSC 1 equipped
with an FRS5 sensor and a liquid nitro-
gen cooling system. The measurement
results are shown in Figure 3.
The DSC heating curve shows a step-
like change at about –120 °C, which we
interpret as a glass transition. At about
–79 °C, there is a small exothermic peak
followed by an equally large endothermic
peak at –54 °C.
These two effects correspond to the
crystallization and melting of part of
the sample. This behavior is typical for
silicone rubber. Comparison of the step
height of the glass transition of the putty
with the step height of pure silicone rub-
ber (see small inset diagram) shows a
difference of about 10%.
This indicates that the putty consists not
only of silicone rubber but also contains
another compound that does not produce
any detectable effects on the DSC curve.
The DSC experiment does not of course
provide any information about the me-
chanical behavior of the putty. For this
reason, we decided to perform several
different DMA experiments.
DMA measurements
The viscoelastic behavior of the putty
was investigated using a METTLER TO-
LEDO DMA/SDTA861e dynamic mechani-
cal analyzer. The measurements were
performed in the shear mode using the Figure 1.
“Horst die Hüpf­
shear sample holder for liquids. The sam- knete”– the German
ple thickness was 1 mm. name for a make of
bouncing modeling
putty.
Temperature scan at 1 Hz
Figure 4 shows a temperature scan mea-
sured at a heating rate of 3 K/min and
a frequency of 1  Hz. Below –120  °C,
the putty is in the glassy state at this
frequency. The decrease in the storage
modulus (G') and the peak in the loss
modulus (G'') at –110 °C as well as the
peak in tan delta at –105 °C are due to
the glass transition of the silicone con- The putty is soft and at this frequency
tent of the putty. flows better with increasing temperature.
The rather weak effects due to cold The results obtained from the DSC and
crystallization (increase of the storage DMA measurements are summarized in
modulus, G', at –75 °C) and melting (de- Table 1.
crease of G' at –45 °C) are also clearly
visible in the curve. Frequency measurements
To confirm the interpretation of the
Following this, the G'' and tan delta curves shown in Figure 4, a DMA mea-
curves exhibit broad peaks with maxima surement was performed at several differ-
at about –10 °C and 40 °C respectively. ent frequencies (0.2, 1.5, 5, 10, 100 Hz).
We interpret this as being due to the glass
transition of the second component in The measurement curves are displayed in
the putty, which we suspected from the Figure 5. They demonstrate the expected
DSC measurements. frequency dependence of the two glass
transitions. In contrast, the effects due to
After the glass transition, G'' becomes cold crystallization and the melting pro-
increasingly larger than G' from about cess are independent of the measurement
–10 °C onward. frequency.
Figure 2.
The unusual be-
havior of the putty:
If it is rolled into a
ball and left on a
flat surface (right)
it gradually flows.
If it is allowed to
fall to the ground,
it bounces back up
like a tennis ball
(left).
METTLER TOLEDO UserCom 37 9
 The second glass transition exhibits very
strong frequency dependence: the peak
temperature of G'' in the measured fre-
quency range shifts by more than 8 K.
Applications

Figure 5 can be used to explain the un-

usual behavior of the putty at room tem-
perature (see the crosses marked at about
25 °C). In an experiment in which the
characteristic time is of the order of sev-
eral minutes (the putty rolled to a ball
flows within minutes), the typical fre-
quencies are less than 0.1 Hz and G'' is
significantly greater than G', so the putty
"flows".
Figure 3.
DSC heating run of In contrast, if the characteristic time
the bouncing putty.
is much shorter (when the ball of putty
bounces on the floor, the contact time is
Figure 4.
DMA temperature merely several milliseconds), the typical
scan showing the frequencies are higher than 100 Hz and
shear storage mod- G' is significantly greater than G'' and
ulus (G'), loss mod-
ulus (G'') and tan the ball bounces back up. The reason
delta of the putty for the unusual behavior of the putty is
measured at 1 Hz therefore the marked frequency depen-
between –150 °C
and +100 °C. dence of its complex modulus at room
temperature.

The frequency dependence of the storage

and loss moduli can also be directly mea-
sured in an isothermal experiment using
a frequency sweep. Figure 6 displays the
resulting G' and G'' curves at 25 °C.

The curves show that at frequencies

above about 8 Hz the viscoelastic be-
havior of the putty is determined by the
Figure 5. storage modulus (the putty behaves more
DMA measure- and more elastically with increasing fre-
ments performed quency). At frequencies below 8 Hz, G''
at a series of fre-
quencies showing is increasingly larger than G', which ex-
the shear storage plains the flow properties of the putty at
modulus (G’) and
room temperature.
loss modulus (G’’)
of the putty at dif-
ferent frequencies The values for the storage modulus ob-
between –150 °C
and +90 °C.
tained from the multifrequency mea-
surement (see Figure 5) are also plotted
in the diagram as circles.

Summary and conclusions

In this article, we studied the strange
behavior of a bouncing modeling putty.
At room temperature, the putty exhibits
both flow properties and excellent elastic
properties.

10 METTLER TOLEDO UserCom 37
A DSC measurement indicated that the Table 1.
Effect DSC DMA at 1 Hz
Summary of the
putty consisted of silicone rubber (about
Onset G’ Peak G’’ DSC and DMA mea-
90%) and another component (about 10%). surements of the
Glass transition 1 in °C –121.2 –116.2 –114.6 putty.
This second material was directly de- Crystallization in °C –78.6 –84.6 –84.2
tected by DMA measurements and had Melting in °C –53.8 –50.9 –50.2
an unusually broad glass transition of Glass transition 2 in °C Not observed –15.6 –13.6
about 40 K. DMA measurements at differ-
ent frequencies clearly demonstrated why Figure 6.
the putty exhibits both elastic and flow Isothermal frequen-
cy sweep show-
properties at room temperature. ing the frequency
dependence of the
The measurements showed that, at low shear storage mod-
ulus (G') and loss
frequencies, the loss modulus was signif- modulus (G'') of the
icantly greater than the storage modulus. putty at 25 °C.
This explains the flow properties of the
putty. At higher frequencies, the storage
modulus was considerably greater than
the loss modulus and the putty behaves
elastically.

The pronounced frequency dependence

of the complex modulus can be easily be
measured using a DMA/SDTA861e and is
crucial for understanding of the behavior
of the material.

METTLER TOLEDO UserCom 37 11
 Study of the curing behavior
of a trifunctional epoxy resin
Applications

J. M. Hutchinson, F. Shiravand, Y. Calventus, I. Fraga Departament de Màquines i Motors Tèrmics, ETSEIAT,

Universitat Politècnica de Catalunya, Colom 11, 08222 Terrassa, Spain

This article describes how the curing behavior of a highly crosslinked epoxy resin system was investigated
using conventional DSC and TOPEM® measurements. The results showed that the curing behavior is much
easier to study by TOPEM® than by conventional DSC. Furthermore, the glass transition temperature of the
completely cured material can only be determined by TOPEM®.

Introduction The resulting rigid, three-dimensional curing process as efficiently as pos-

Epoxy resins are thermosetting polymers
that are used for many different applica-
tions, for example, as adhesives, surface
coatings, matrix materials for fiber-rein-
forced composites or for polymer-layered
silicate nanocomposites (PLS).
One of the most frequently used ep-
oxy resins for these applications is the
bifunctional epoxy diglycidyl ether of
bisphenol-A (DGEBA). However, many
high-performance applications, for ex-
ample in the aerospace industry, put
greater demands on the properties of the
resin and require very highly crosslinked
composites that are stable up to tempera-
tures of 250 °C.
One resin that is suitable for producing
such materials is the trifunctional epoxy
triglycidyl p-aminophenol (TGAP). The
resin is cured with a diamine.
Figure 1.
Above: isothermal
curing of a TGAP/
DDS sample at
150 °C (curing time
3 hours). Below:
the following first
and second heating
runs. The heating
rate was 10 K/min.
crosslinked polymer has a higher net-
work density, a correspondingly high
glass transition temperature, and better
thermal stability compared with DGE-
BA. Conventional differential scanning
calorimetry (DSC) is a technique widely
used to investigate the curing behavior
of crosslinking systems. Both isothermal
and dynamic methods are employed.
Nevertheless, the technique has certain
disadvantages when used to character-
ize the curing reaction of TGAP with a
diamine:
• Due to the large reaction enthalpy
involved in the curing reaction, the
curing of TGAP is usually performed
in several isothermal steps at tempera-
tures below the final glass transition
temperature. In this process, the mate-
rial vitrifies during each individual
curing step. To perform the multistep
sible, the vitrification time (the time
taken by the material to vitrify at a
certain temperature) has to be known.
However, the determination of the
vitrification time by conventional DSC
requires considerable experimental
time and work.
• The glass transition of the fully cured
TGAP/DDS thermoset cannot be mea-
sured by conventional DSC. The net-
work density is so high that the change
in heat capacity at the final glass tran-
sition is too small to detect. The glass
transition temperatures given in the
literature for this system are therefore
usually determined by DMA [1, 2].
In this article, we will show how these
difficulties can be elegantly solved using
TOPEM® .
Experimental details
Sample
TGAP epoxy resin (Araldit MY0510) and
4,4-diamino diphenyl sulphone, DDS
(Aradur 976-1) as the curing agent from
Huntsman Advanced Materials were used
without further purification.
The TGAP and DDS were mixed to-
gether with a slight excess of the epoxy
(TGAP to DDS ratio (1:0.9 molar ratio
or 1:0.52 mass ratio). Samples weighing
about 15 mg were measured in 40 µL alu-
minum crucibles.

Methods
The conventional DSC experiments were
performed using a METTLER TOLEDO

12 METTLER TOLEDO UserCom 37
DSC821e and theTOPEM ® measure-
ments with a DSC823e. TOPEM® is an
advanced temperature-modulated DSC
technique in which stochastic tempera-
ture pulses are superimposed on the un-
derlying DSC temperature program. The
amplitude of these temperature pulses is
constant (typically 0.1 K).
The duration of the pulses is varied ran-
domly within a certain range (typically
10 to 40 seconds) [3]. This technique has
been used with great success in applica-
tions involving glass transitions [3], solid-
solid transitions [3], the aging behavior of
polymers [4], the thermal degradation of
polystyrene [5] and the vitrification and
devitrification of thermosets (see User-
Coms 29 and 30 [6, 7], and [8–12]).
Procedure
The investigation of the curing behavior of
TGAP was carried out in several steps:
• Isothermal curing for 3 hours at 150 °C
• Rapid cooling
• First heating run (DSC: 50 to 300 °C
at 10 K/min; TOPEM® : 100 to 290 °C
at 2 K/min)
• Second heating run after cooling the
sample rapidly (only by conventional
DSC, same conditions as for the first
heating run)
Results of the conventional
DSC measurements
Figure 1 displays the DSC curves ob-
tained from the isothermal curing of a
TGAP sample at 150 °C (above) and the
first and second heating runs that fol-
lowed (below). The isothermal curing
curve (red) shows that at this tempera-
ture the curing reaction is completed
after about 160 minutes but there are no
Curing time 0.5 1 1.5
in h
Tg in °C 23.3 94.5
Vitrification no no
The postcuring reaction was completed
by about 280 °C. The exothermic in-
crease of the heat flow above 280 °C
indicates that the sample begins to de-
grade. In principle, it should now be pos-
sible to determine the glass transition of
the completely cured sample from the
second heating run (blue). The curve
however shows no indication of a glass
transition.
The reason for this is that the network
density of the completely cured sample
is so high that it is not possible to detect
the glass transition by DSC. The curve
shows that degradation begins at about
260 °C.
The vitrification time of the material at
150 °C was determined by conventional
DSC by performing a series of isothermal
curing experiments. Identical samples
were first cured isothermally for differ-
ent times and then cooled. The glass
transition temperature of each precured
sample was then measured in a series of
separate heating runs.
Vitrification occurs when the glass
transition temperature of the material
reaches and exceeds the curing tempera-
ture (in this case 150 °C).
Table 1.
2 3 5 6
Glass transition
temperatures after
139.2 158 175.8 194.2 198.1 curing for different
times at 150 °C.
no yes yes yes yes
The heating runs are shown in Figure 2.
Table 1 presents an overview of the iso-
thermal curing times used and the mea-
sured glass transition temperatures. The
results in the table indicate that the vit-
rification time at 150 °C is between 1.5
and 2 hours.
This data is also presented graphically
in Figure 3. It shows the relationship be-
tween the glass transition temperature
and the curing time. The vitrification
time of about 102 minutes at the curing
temperature (here 150 °C) can be read
off from the graph (see the black ar-
rows). Several measurements are there-
fore needed to determine the vitrification
time by conventional DSC.
Results from the TOPEM®
measurements
TOPEM ® is a temperature-modulated
DSC technique in which the heat flow
and the specific heat capacity of a sample
can be simultaneously measured. The
method is therefore ideal for monitoring
the vitrification and curing process of a
material [3].
Figure 4 displays the results for the iso-
thermal curing of a sample of TGAP/DDS
at 150 °C. The upper diagram shows the
Figure 2.
Heat flow curves for
samples of TGAP/
DDS cured for differ-
ent times at 150 °C
and then heated at
10 K/min.

signs that vitrification of the material

occurred.

The first heating run (green curve), how-

ever, shows that vitrification did in fact
occur because the curve exhibits a glass
transition at about 175 °C as well as a
strongly exothermic postcuring peak im-
mediately afterward. The material must
have vitrified during isothermal curing
because otherwise there would be no post-
curing peak.

METTLER TOLEDO UserCom 37 13
 modulated heat flow curve (blue) from
which the total heat flow curve (red) is
obtained. This curve corresponds to the
heat flow curve of a conventional DSC
measurement.
Applications
The total heat flow curve once again
gives no indication that vitrification of
the sample has occurred. The strongly
exothermic curing reaction is however
observed just like in a conventional DSC
experiment.
The lower curve shows the specific heat
capacity curve cp0 (green). This is calcu-
lated from the amplitude of the modulat-
ed heat flow. As a result of the crosslink-
ing process, cp0 first gradually increases.
Then, during vitrification, the sample
changes from an initially viscous liq-
uid to an amorphous solid and the spe-
cific heat capacity decreases (vitrifica-
tion). The vitrification time corresponds
roughly to the midpoint of the change of
the heat capacity.
In the example, this is about 100.4 min-
utes, which agrees well with the value
of 102 minutes estimated from the con-
ventional DSC measurements. TOPEM®
however has the advantage that the vit-
rification time can be determined from
just one measurement.
If the partially cured sample is then
cooled rapidly and measured by TOPEM®
in a second heating run at a sufficiently
Figure 3.
Graph showing
the relationship
between the glass
transition tempera-
ture and the curing
time at 150 °C. The
vitrification time
corresponds to the
curing time at which
the glass transi-
tion temperature
reaches the curing
temperature (see
the black arrows).
14 METTLER TOLEDO UserCom 37
low heating rate, curves such as those
displayed in Figure 5 are obtained. The
upper diagram shows the total heat flow
curve and the lower diagram the specific
heat capacity curve, cp0.
The first event observed on the cp0 curve
at about 181 °C corresponds to the glass
transition of the sample after curing
isothermally at 150 °C for 3 hours. Nor-
mally the glass transition temperature
of an isothermally cured material is
only a slightly above the curing tem-
perature.
During the curing process, the momen-
tary glass transition temperature of
the material steadily increases. When
it reaches the curing temperature, the
material vitrifies and the reaction rate
of curing drastically decreases; curing
more or less stops. As a result, the glass
transition temperature remains only
slightly above the curing temperature
(typically 10 K).
In the case of TGAP/DDS, our measure-
ment yields a difference of 31 K between
the curing temperature and the glass
transition temperature after curing.
Other authors have even observed dif-
ferences of up to 50 K for the TGAP/DDS
system [1, 2].
Due to the increased molecular mobility
of the reactants after the glass transi-
tion at 181 °C, the curing reaction con-
tinues while the sample is slowly heated.
This leads to the exothermic heat flow
(red curve in the upper diagram of
Figure 5).
The momentary glass transition tem-
perature of the material continues to
increase due to the on-going curing re-
action. If the heating rate is sufficiently
low (here 2 K/min), the sample again
vitrifies. As a result, the reaction rate
slows down and the total heat flow de-
creases.
However, because the sample is still be-
ing heated, the curing reaction continues
slowly and leads to a broad exothermic
effect in the total heat flow curve. The
curing temperature and the glass tran-
sition temperature are almost the same
– curing practically takes place in the
glassy state. When the degree of cure of
the sample is almost complete, the total
heat flow decreases.
At the same time, the curing tempera-
ture then exceeds the glass transition
temperature. This leads to an increase
in the specific heat capacity as in a glass
transition (devitrification). The increase
can be clearly seen on the cp0 curve with
a midpoint at about 257 °C.
To a good approximation, this tempera-
ture therefore corresponds to the glass
transition temperature of the completely
cured material [9, 10].
If the heating experiment is performed
at a lower heating rate, the agreement
is better, although for this particular
system an experiment performed at a
heating rate von 0.5 K/min gave no sig-
nificant increase of the glass transition
temperature. DMA measurements of the
same TGAP/DDS system yielded a glass
transition temperature of 264 °C.
This temperature agrees well with the
glass transition temperature of 257 °C
that we found. However, glass transi-
tions measured by DMA and DSC cannot
always be directly compared because of
the frequency dependence of the glass
transition.
Conclusions Figure 4.
Isothermal mea-
If the isothermal curing behavior is in- surement of TGAP/
vestigated using conventional DSC, the DDS for three hours
measured isothermal DSC curves show at 150 °C using
TOPEM®. Above:
no indication of possible vitrification. the modulated heat
flow curve (blue)
Vitrification during isothermal curing scaled with a factor
of 0.15 and total
can only be identified by measuring the heat flow curve
glass transition of the cured material in (red). Below: the
a second dynamic measurement – in this specific heat capac-
ity curve (green).
case, a postcuring peak occurs immedi-
ately after the glass transition.

Estimation of the vitrification time by

conventional DSC is only possible with
considerable experimental time and ef-
fort: several isothermal and dynamic
measurements have to be performed each
time with new samples. In this case, the
Figure 5.
glass transition of the completely cured Dynamic TOPEM®
TGAP/DDS system could not be deter- measurement of a
sample of TGAP/
mined by conventional DSC.
DDS at 2 K/min that
had previously been
In contrast, in a TOPEM® measurement, cured for 3 hours
at 150 °C. Above:
vitrification can be easily identified in the total heat flow
an isothermal curing experiment due to curve. Below: the
the change in the specific heat capacity specific heat capac-
ity cp0 curve.
signal.

The vitrification time can therefore be

directly determined. TOPEM® also al-
lows the glass transition temperature of
the completely cured resin to be mea-
sured.

In this method, one takes advantage of

the fact that if the heating rate is suffi-
ciently low, complete curing of the resin
takes place in the glassy state; when the
curing reaction is finished, the mea-
sured glass transition corresponds to a
good approximation to the glass transi-
tion temperature of the completely cured
system.
If TOPEM ® is not available, the glass
transition of a completely cured TGAP/DDS
system can only be determined by DMA.
TOPEM ® measurements therefore al-
low one to understand both the isother-
mal and the dynamic curing behavior
of a material and to determine the glass
transition temperature of the completely
cured material.
References
[1] Becker, O.; Cheng, Y-B.; Varley,
R.J.; Simon, G.P.: Layered silicate
nanocomposites based on various
high-functionality epoxy resins: The
influence of cure temperature on
morphology, mechanical properties,
and free volume. Macromolecules 36
(2003) 1616–1625.
[2] Frigione, M.; Calò, E.: Influence of an
hyperbranched aliphatic polyester
on the cure kinetic of a trifunctional
epoxy resin. J. Appl. Polym. Sci. 107
(2008) 1744–1758
[3] Schawe, J.E.K.; Hütter, T.; Heitz,
C.; Alig, I.; Lellinger, D.: Stochastic
temperature modulation: A new
technique in temperature-modulated
DSC. Thermochim. Acta 446 (2006)
147–155.
[4] Vyazovkin, S.; Chen, K.: Increase
in effective activation energy during
physical aging of a glass. Chem.
Phys. Letters 448 (2007) 203–207.
[5] Chen, K.; Harris, K.; Vyazovkin, S.:
Tacticity as a factor contributing to
the thermal stability of polystyrene.
Macromol. Chem. Phys. 208 (2007)
2525–2532.
[6] Fraga, I.; Montserrat, S.; Hutchinson,
J.M.: Vitrification during the isother-
mal cure of a thermoset studied by
TOPEM®. METTLER TOLEDO Thermal
Analysis UserCom 29, 2009, 17–20.
[7] Fraga, I.; Montserrat, S.; Hutchinson,
J.M.: Vitrification and devitrification
during the non-isothermal cure of
a thermoset studied by TOPEM®.
METTLER TOLEDO Thermal Analysis
UserCom 30, 2009, 9–12.
[8] Mu, Y.C.; Qiu, T.; Li, X.C.; Guan, Y.D.;
Zhang, S.W.; Li, X.Y.: Layer-by-layer
synthesis of multilayer core-shell la-
tex and the film formation properties.
Langmuir 27 (2011) 4968–4978.
[9] Fraga, I.; Montserrat, S.; Hutchinson,
J.M.: Vitrification during the isother-
mal cure of thermosets. Part 1.

METTLER TOLEDO UserCom 37 15
 An investigation using TOPEM®, a
new temperature modulated tech-
nique. J. Thermal Anal. Calorim. 91
(2008) 687–695.
[10] Fraga, I.; Montserrat, S.; Hutchinson,
J.M.: Vitrification during the isother-
mal cure of thermosets: Compari-
Applications
temperature-modulated DSC and
dielectric analysis. Macromol. Chem.
Phys. 209 (2008) 2003–2011.
[11] Fraga, I.; Montserrat, S.; Hutchinson,
J.M.: Vitrification and devitrification
during the non-isothermal cure of a
thermoset. Theoretical model and
ments. Macromol. Chem. Phys. 211
(2010) 57–65.
[12] Fraga, I.; Montserrat, S.; Hutchinson,
J.M.: Vitrification and devitrification
during the non-isothermal cure of
a thermoset: A TOPEM study. J.
Thermal Anal. Calorim. 99 (2010)

son of theoretical simulations with comparison with calorimetric experi- 925–929.

New methodology developed for DSC

for the analysis of phase change materials
Camilla Barreneche 1,2, Aran Solé 1, Laia Miró 1, Ingrid Martorell 1, A. Inés Fernández 2, Luisa F. Cabeza 1
1) Universitat de Lleida y 2) Universitat de Barcelona, Spain

The level of thermal comfort nowadays needed in buildings has led to an increase in energy consumption in
the residential and service sectors. Thermal energy storage (TES) is an important alternative for reducing
high energy consumption. Phase change materials (PCMs) have been studied as suitable materials for stor-
ing thermal energy due to their high heat storage capacity.

Introduction
The authors of this article have devel-
oped and tested a phase change mate-
rial (PCM) incorporated in a polymer
matrix. Unexpected difficulties however
arose in the measurement of the thermal
properties of this material using differ-
ential scanning calorimetry (DSC). The
thermal effects of the polymer matrix
and the PCM overlapped.
A new method was therefore developed
to overcome this problem. This consist-
ed of using a reference crucible contain-
ing the polymer matrix as a blank in-
stead of the usual empty crucible. This
enabled a clear signal of the PCM to be
obtained.
PCM
Phase change materials (PCMs) are
ideal for storing thermal energy due to
their large heat storage capacity at the
phase change: The thermal energy is
released again below the temperature of
the phase change.
Paraffin materials can be used as PCMs
to climatize rooms due to their heat stor-
age capacity of about 130 kJ/kg and their
melting temperature of 15 to 30 °C [1]. In
most countries, this temperature range
is accepted as being optimal for thermal
comfort in buildings.
Consequently, PCMs based on paraffin
materials are integrated as composite
materials in thermal insulation systems.
These materials increase the thermal in-
ertia of the building envelope and com-
bined with insulation material reduce
energy consumption and temperature
fluctuations [2].
The thermal behavior of composite ma-
terials normally used in building enve-
lopes is difficult to characterize due to
the large dimensions and heterogeneity
of the materials. For this reason, thermal
analysis of PCMs is necessary at an early
stage of the design of building because it
is a key point for the thermal character-
ization of the building envelope.
DSC
Differential thermal analysis (DSC) is
one of the most powerful techniques [3]
for measuring thermal properties such
as the specific heat capacity (cp), and the
enthalpy and temperature of phase tran-
sitions. This has been discussed by Cas-
tellón et al. [4]. The main limitations of
the technique when used for this particu-
lar application are the sample require-
ments, namely small size, purity, and
homogeneity [5]. These are important
limitations because many PCM samples
are mixtures of different components.
Paraffinic PCMs
The authors have developed a new mate-
rial for the building envelope [6]. The

16 METTLER TOLEDO UserCom 37
composite material is a shape-stabilized Table 1.
Components Characteristics Percentage weight Material compo-
paraffinic PCM containing 10 to 12 nents and composi-
Polymer matrix (PM) Ethylene/octene 20
weight percent PCM in a polymer ma- copolymer + EVA tion of the compos-
trix. To determine the concentration ite material studied.
Filler (EAFD) Inorganic residue from 70
of the PCM in the polymer matrix, the
electric arc furnace dust
material was analyzed by DSC using
the conventional measurement method Paraffin (PCM) RT-21: Tm = 20.14 °C; 10
∆Hm = 96.22 kJ/kg
with an empty crucible as the reference
sample.
Table 2.
Experiment Reference sample Experiments and
The main goal of this study was to design Run 1 Empty crucible runs performed in
and evaluate a new experimental DSC this study and the
Run 2 Empty crucible different reference
method to separate the PCM signal from samples.
that of the polymer matrix. More infor- Run 3 Polymer matrix
mation on this work has been published Run 4 Polymer matrix with EAFD
by Barreneche et al. [7].
the sample material. This improved the Furthermore, the values for the enthalpy
Experimental details PCM signal; the peaks were sharper and of fusion from Runs 1 and 2 listed in
better defined at the phase transition and Table 3 do not correspond to the esti-
Materials the matrix overlap in the DSC curve was mated values. A value between 9.6 and
The samples investigated were composite reduced. 11.5 kJ/kg is expected for the composite
materials consisting of a polymer matrix, material investigated if an enthalpy of
an inorganic filler and a PCM in different Measurements and resultats fusion of 96.22 kJ/kg and a melting tem-
formulations. Details of the samples are Table 2 summarizes the experiments perature of 20.14 °C is assumed for the
presented in Table 1. performed and the corresponding blank PCM investigated.
samples. Two measurements were first
The composite material was manu- performed with empty crucibles as refer- As can be seen in the DSC curves in
factured on a large scale. An internal ence samples as is usual in conventional Figure 1, the inaccurate values obtained
Banbury mixer was used to obtain ho- DSC analysis (Runs 1 and 2, repeat mea- for the enthalpy of fusion could have to
mogeneous material. The material was surements). do with the unclear peak shape leading
laminated at room temperature using a to incorrect integration values. Since the
two-roll mill. The heat flow curves are shown in results obtained were unsatisfactory, two
Figure  1. The curves were not clearly further experiments were performed in
Due to its complex composition, it was defined and indicated that the melting which non-conventional reference sam-
difficult to analyze and understand the process took place between 11 and 30 °C. ples were used. Figure 2 shows the DSC
thermal properties of the material using This is not in agreement with the expect- curves of the two samples measured us-
DSC. The expected enthalpy of fusion due ed behavior (between 18 and 24 °C). ing different reference samples, namely
to the PCM content was about 10 kJ/kg Figure 1.
but the PCM peak was overlapped by ther- DSC curves of two
mal effects of the matrix and filler. heating runs of the
composite material.
Empty crucibles
Methodology were used as ref-
Samples weighing about 15  mg were erence samples
(Run 1 and 2).
measured in 100  μL aluminum cru-
cibles in nitrogen using a flow rate of
80  mL/min. The DSC measurements
were performed in the temperature range
10 to 35 °C at heating and cooling rates
of 0.5 K/min [3].

Conventional DSC measurements use

empty reference crucibles [8]. The new
method developed for this work is based
on the subtraction of different blank
samples from the measurement curve of

METTLER TOLEDO UserCom 37 17
 the polymer matrix in Run 3 and the
polymer matrix with EAFD in Run 4. The
DSC signal was clearly improved by the
use of these unconventional reference
samples.
Applications
The peaks of the phase change transition
are sharper and better defined and the
PCM measurement signal is improved.
An optimization of the DSC curves was
observed when the new reference samples
curve response signal. To eliminate the
overlap due to the matrix signal, two
different blank reference samples were
used; one was the pure polymer matrix,
the second the polymer matrix and the

were used (Figure 2). EAFD filler.

The effect of overlap was significantly re-
duced. Furthermore, it is clear that this
is due to subtraction of the effect of the
polymer matrix because the result was
the same when the reference sample con-
taining EAFD (an additive of the formu-
lation) is used. However, conventional
DSC methodology should be used to mea-
sure the enthalpy of fusion of the PCM
polymer composite as a whole.
The results obtained using the different
reference samples (Runs 3 and 4) are
presented in Table 3. The values of the
enthalpy of fusion are in the expected
range, proportional to the percentage
weight of the PCM.
The new blank reference methodology
led to an important improvement of the
DSC results. The new methodology de-
scribed in the article has been successful.
Figure 2.
DSC curves of the
composite material
using two different
types of reference
samples: Run 3:
polymer matrix,
Run 4: polymer ma-
trix with EAFD.
Thanks to this new methodology, well-
defined peaks were obtained and the
PCM signal was separated from the ma-
trix contribution. This new methodology
can be used to analyze complex samples
in which the signal from the matrix over-
laps the signal of interest. This allows
composite materials containing PCM to
be analyzed by DSC.
Results and conclusions
Composite materials were first analyzed
by DSC in the conventional way using an
empty crucible as the reference sample.
The initial results showed rather poorly
defined DSC curves (Figure 1).
In addition, the measured thermal
properties of the PCMs did not corre-
spond to the expected values. This was
attributed to the overlap of contribu-
tions of the matrix and PCM in the DSC
The first important result of this study is
that DSC curves were improved through
the use of the new blank samples. Thanks
to the new methodology, the peaks were
better defined and the PCM peak was
separated from the matrix signal.
Another important conclusion is that the
overlap of the signals is due to the poly-
mer matrix because there was no sig-
nificant difference in the result when the
polymer matrix or the polymer matrix
with EAFD was used as the reference.
To sum up, a new experimental method-
ology for analyzing composite materials
containing PCM by DSC has been devel-
oped and tested. Improvements in the
signal and hence accurate curve evalua-
tion have been achieved.
This is a very important point because
the method allows signals to be differ-
entiated when composite materials are
used. This methodology is strongly rec-
ommended for applications in which the
matrix signal has to be separated from
signals of other components.

Acknowledgements
This work was partially funded by
the Spanish government (ENE2011-
28269-C03-02), the European Union
(COST Action TU0802) and the Program
“PPV University de Barcelona-Santand-
er”. The authors would like to thank the
Catalan Government for the quality ac-
creditation given to their research group
GREA (2009 SGR 534) and research
group DIOPMA (2009 SGR 645).
Table 3.
Evaluation of the
Enthalpy of fusion Melting Type of References
enthalpy of fu- in kJ/kg temperature in °C reference used [1] Cabeza L.F, Castell A, Barreneche C,
sion and melting de Gracia A, Fernández A. I. Materials
temperature of the
Run 1 6.16 21.44 Conventional used as PCM in thermal energy sto-
composite using Run 2 5.85 21.49 Conventional rage in buildings: A review. Renewable
different types of & Sustainable Energy Reviews 2011;
reference samples. Run 3 10.03 20.92 Polymer matrix 15: 1675–1695.
[2] Cabeza L.F, Castell A, Medrano M,
Run 4 9.89 21.04 Polymer matrix/EAFD Martorell I, Pérez G, Fernández A.I. Ex-

18 METTLER TOLEDO UserCom 37
 perimental study on the performance
of insulation materials in Mediterrane-
an construction. Energy & Buildings
2010; 42(5): 630–636.
[3] Mehling H, Cabeza L. F. Heat and cold
storage with PCM. An up to date intro-
duction into basics and applications.
Springer-Verlag Berlin Heidelberg;
Berlin (Germany), 2008.
ISBN: 978-3-540-68556-2.
[4] Castellón C, Günther E, Mehling H,
Hiebler S, Cabeza L.F. Determination
of the enthalpy of PCM as a function
of temperature using a heat-flux DSC
– A study of different measurement
procedures and their accuracy. Inter-
Thermoanalytical characterization
of oxo-biodegradable polymers
Dr. Melanie Nijman
One of the major problems of the plastics we use today is their great stability – they impact the environment
for years without undergoing decomposition. Recently, a number of research projects have been started to
develop plastics that degrade within a short time in the environment.
Introduction
Up until now, two different approaches
have been followed for making biologi-
cally degradable polymers.
The first approach is to produce plastics
from biomaterials such as maize (corn)
or wheat, which rapidly decompose to
smaller, biologically degradable com-
pounds after use.
The other approach is to modify com-
monly used polymers such as polyeth-
ylene so that they degrade more quickly
and can then be digested by microorgan-
isms. This article deals with this second
category of polymers, also referred to as
oxo-biodegradable polymers.
The degradation of such polymers is
accelerated by the addition of small
amounts of metal salts that act as cata-
national Journal of Energy Research
2008; 32(13): 1258–1265.
[5] Lázaro A, Günther E, Mehling H, Hieb-
ler M, Marín M.M, Zalba B. Verification
of a T-history installation to measure
enthalpy versus temperature curves
of phase change materials. Measure-
ment Science & Technology 2006; 17:
2168–2174.
[6] Fernández A.I, Cabeza L.F, Barreneche
C, Chimenos J.M,Espiell F, Segarra
M, Solé C. Waste removal of EAFD by
means of its stabilization integrating it
into a building material [Inertización
de polvo de acería mediante su integ-
lysts and promote oxidization of the
polymer chains. Since oxidation can only
take place when oxygen is present, this
type of decomposition only works when
the plastic is exposed to an open-air en-
vironment. If the plastic is disposed of in
a landfill under anaerobic conditions,
decomposition is no faster that with or-
dinary plastics.
The metal salts added are only present
in catalytic amounts and do not have a
negative effect on the environment. They
are salts of iron, magnesium, manga-
nese, zinc or nickel, which are in any
case present in nature, for example in
metalloproteins.
Experimental details
The polymers were investigated by per-
forming DSC and TGA/DSC measure-
ments. The polymeric composition of an
ración estabilizante en un material de
construcción]. P201131272. 2011.
[7] Barreneche C., Solé A., Miró M.,
Martorell I, Fernández A.I., Cabeza
L.F. New methodology developed for
the differential scanning calorimetry
analysis of polymeric matrixes in-
corporating phase change materials.
Measurement Science and Technolo-
gy. 2012; 23: 085606, 5 pp.
[8] Höhne G. W. H, Hemminger W.F,
Flammersheim H.J. Differential scan-
ning calorimetry, Springer–Verlag
Berlin Heidelberg. Berlin (Germany),
2003. ISBN: 3-540-00467-x.
oxo-biodegradable packaging film was
determined from its melting curve. Pure
PE-LD in the form of pellets was mea-
sured for comparison.
Small pieces were cut out from the film
and placed in the DSC or TGA crucibles. A
PE-LD pellet was cut into thin slices. The
sample mass used for the DSC measure-
ments was approximately 3 mg. Appre-
ciably more (approx. 30 mg) was used for
the TGA measurements because only very
small residues were expected.
DSC experiments were performed on both
materials to measure the OOT (Oxidation
Onset Temperature). The onset of oxida-
tion is determined by the stability of the
polymers. If the stability of a polymer is
artificially decreased, as in an oxo-bio-
degradable polymer, one expects a lower
oxidation temperature.
METTLER TOLEDO UserCom 37 19
 Results and discussion
DSC measurements
Figure 1 shows the DSC melting curves of
the two materials. Both samples have very
Applications
OOT (Oxidation Onset Temperature)
measurements were then performed to
compare the stability of the two materi-
als. The curves obtained are displayed
in Figure 2. Care was taken to make sure
yielded an oxidation onset temperature
of 201.3 °C for the oxo-biodegradable
film and 214.7 °C for the PE-LD pellet.
The temperature difference is significant
and very reproducible. The onset of oxi-

similar melting temperatures. The oxo-
biodegradable film is however a blend of
PE-LD and PE-LLD. It exhibits two clear
melting peaks at 112 °C and 121 °C. The
mean degree of crystallinity is compa-
rable with the values usual for PE-(L)LD.
The curves shown in Figure 1 are second
heating runs of the individual samples
in order to eliminate the effects of pro-
duction and storage history on the DSC
curves. The heating rate was 10 K/min
with a gas flow of 50 mL/min nitrogen.
Figure 1.
DSC measurements
(second heating
runs) of an oxo-bio-
degradable (OBD)
film and a pure PE-
LD pellet.
that the samples had about the same
mass and that they rested flat on the
bottom of the crucible.
The measurements were performed in
oxygen (50 mL/min) and with no lid on
the crucible. The same heating rate of
10 K/min was used as before. The mea-
surements were automatically stopped
when an exothermic heat flow of 5 W/g
was reached in order to protect the DSC
furnace from decomposition products.
Evaluation of the OOT measurements
dation of the oxo-biodegradable PE film
is in fact about 13 K lower than that of
the pure PE-LD pellet and indicates that
it is much less stable.
TGA measurements
TGA measurements were also performed
in addition to the DSC measurements.
The resulting curves for the two mate-
rials are displayed in Figure 3. A large
difference can be seen between the de-
composition of the two materials. The
first part of the curves was measured in
nitrogen up to 600 °C.
The pure PE-LD sample is completely py-
rolyzed in nitrogen, with a characteristic
onset at 457 °C (extrapolated onset). At
600 °C, the purge gas was switched from
nitrogen to air: oxidation of polymer
residues began immediately. All the TGA
measurements were performed at a heat-
ing rate of 20 K/min.

Pyrolysis of the oxo-biodegradable film

begins a bit later at 472 °C. On switching
to air, there was a slight loss of weight.
It seems that the sample still contained
something that was not completely pyro-
lyzed or that in air showed a weight loss.
In the DSC curve, this process is surpris-
ingly endothermic. With the PE-LD sam-
Figure 2.
ple, no further weight loss is observed.
Repeat measure-
ments showing the Table 1 summarizes the results of the
OOT (Oxidation
Onset Tempera- evaluations. The melting enthalpies of
ture) curves of an the DSC curves shown in Figure 3 in-
oxo-biodegradable dicate a degree of crystallinity of about
(OBD) film and a
PE-LD pellet. Gas 40%. Both materials were also measured
flow: oxygen at by TGA/DSC in air at 50 mL/min. The
50 mL/min. measurements are shown in Figure 4.
Smaller samples (about 5 mg) were used
compared with those in the measure-
ments shown in Figure 3 (about 30 mg)
because oxidation generates much more
heat than pyrolysis.

In this measurement in air, as in Fig-

ure 3 in nitrogen, it seems that decom-
position of the PE-LD pellets begins at

20 METTLER TOLEDO UserCom 37
a lower temperature than for the film. Table 1.
Onset Pyrolysis Oxidation Residue
Overview of the TGA
However, close examination of the simul- in °C in % in % in % weight losses of the
taneously measured DSC curves shows Oxo-biodegradable film, 471.4 91.73 0.60 7.67 oxo-biodegradable
that oxidation of the oxo-biodegradable sample 1 film and the PE-LD
pellet.
film begins earlier. Oxo-biodegradable film, 472.2 91.73 0.61 7.67
sample 2
The DSC measurements are much more PE-LD pellet, sample 1 457.6 99.99 – 0.01
sensitive to the onset of oxidation than the PE-LD pellet, sample 2 457.7 100.0 – –
TGA measurements. The rate of decompo-
sition in air is greater for PE-LD compared Figure 3.
with for the oxo-biodegradable film; in ni- TGA/DSC curves
of an oxo-biode-
trogen, the rates are about the same.
gradable film and a
PE-LD pellet mea-
The measurements in air also show that sured in nitrogen
to 600 °C and then
the oxo-biodegradable film leaves a resi- in air to 900 °C, at
due whereas the PE-LD pellets burn com- 50 mL/min.
pletely. In addition, the oxo-biodegradable
film still exhibits the endothermic effect
at about 600 °C in air. This effect is also
visible in the measurements in Figure 3.

The enthalpy of the decomposition reac-

tion of the pure PE-LD sample is about
25% larger than that of the oxo-biode-
gradable film; the smaller enthalpy can
be partly explained by the inorganic filler
content of the oxo-biodegradable film
and partly by the overlap with the endo-
thermic reaction at 600 °C. Figure 4.
TGA/DSC curves of
an oxo-biodegrad-
Conclusions able film and a PE-
LD pellet measured
The oxidation behavior of the oxo-bio-
in air at 50 mL/min.
degradable film is significantly different
compared with that of a normal PE film.
The behavior confirms that the films de-
grade more rapidly in an air atmosphere.
Anaerobic decomposition under nitrogen
is not accelerated by the added salts;
their presence might even be a disadvan-
tage for decomposition.

The TGA curves show that the oxo-biode-

gradable films more contain inorganic
additives and that the amounts can be
easily determined.

References
[1] http://en.wikipedia.org/wiki/Oxo_Bio-
degradable
[2] Assessing the Environmental Impacts
of Oxo-degradable Plastics Across
Their Life Cycle, Loughborough
University (document EV0422) /
Department for Environment, Food
and Rural Affairs (DEFRA), UK.

METTLER TOLEDO UserCom 37 21
 Exhibitions, Conferences,
Seminars and Training Courses
Dates

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22 METTLER TOLEDO UserCom 37
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Editorial Team

Dr. A. Hammer Dr. S. Giani Dr. D. P. May Dr. R. Riesen Dr. J. Schawe Dr. S. Domann
Chemist Chemist Chemist Chem. Engineer Physicist Journalist & Chemist

N. Fedelich Dr. M. Nijman Dr. E. Hempel Dr. M. Wagner Dr. M. Schubnell U. Jörimann
Chem. Engineer Chemist Physicist Chemist Physicist Electr. Engineer

Mettler-Toledo AG, Analytical

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