52

Thermal Analysis User

Information for Users
Com
Dear Customer, Contents 2/2020
The coronavirus (Covid-19) pandemic has made our daily lives unusually difficult in the past months.
We will no doubt have to be patient for some time to come, probably until well into the coming year, before TA Tip
life and work processes become normal again. During this phase, in which many of you have to work from 1 Moisture content, water content,
home, training possibilities are in greater demand than ever before. We offer classical professional training loss on drying, Part 2: Special
using specialist reference handbooks as well as online training with the aid of webinars and videos. In the possibilities using the TGA
past months, you have made extensive use of these different possibilities. Our wide range of training programs
and services can be quickly found at www.mt.com/ta-services. Applications
6 Polymorphism in metallic alloys,
Our new TA eNewsletter fits in perfectly with all this. The newsletter is complementary to the bi-annually Part 2: Measurement of the heat
printed UserCom magazine and will be distributed electronically four times a year, provided you subscribe at capacity of metastable phases
www.mt.com/ta-knowledge. The lead article of the TA eNewsletter deals with GLP and compliance topics. by TOPEM and Flash DSC
The newsletter also keeps you up to date on new handbooks, guides and videos as well as on upcoming 10 Innovation and standardization:
events such as webinars, training courses and conferences. The editorial team hopes you will find the The development of a standard
TA eNewsletter equally interesting and informative as our popular UserCom publication. for the Flash DSC
14 Determination of the filler content
The METTLER TOLEDO thermal analysis team. in a composite
18 TGA-IST-GC/MS-FTIR analysis

Moisture content, water content, loss of polypropylene

23 Determination of the constituents

on drying, Part 2: Special possibilities of cement clinker by TGA

using the TGA Dates

26 Exhibitions, Conferences
and Seminars
Dr. Markus Schubnell, Dr. Angela Hammer

The presence of water in polymers, pharmaceutical substances or foodstuffs is often un-

wanted. The determination of the water content in different materials is therefore of great
importance. Besides “water content”, the terms “moisture content” or “loss on drying”
(LOD) are also often used. In Part 1 of this series, we defined what the terms mean and
 described some of the methods
used to determine these quanti-
ties. In this second part, we want
to discuss special possibilities
using the TGA. In addition, we will
TA Tip
discuss the relationship between
LOD, sample weight and the accu-
racy of LOD in thermogravimetric
measurements.
Introduction
In Part 1 of this series [1], we described
two gravimetric techniques (TGA and
the halogen moisture analyzer) and the
Karl-Fischer titration for determining the
water content in materials. In contrast
to the Karl-Fischer titration, we saw that
gravimetric methods are not selective be-
cause the mass losses measured during
drying can be also be caused by the loss
of other volatile substances or decompo-
sition products and not only by the loss
of water. Gravimetric methods are only
selective with regard to water if the gas-
eous products released during the drying
process are continuously identified. This
is possible if the TGA is combined with a
suitable evolved gas analysis system.
Figure 1.
Operation of a TGA
at low pressure.
Cold trap
Vacuum pump
2 METTLER TOLEDO UserCom 52
If decomposition processes begin during
drying, decomposition and drying can
be differentiated by carrying out the dry-
ing process under reduced pressure. This
can be done by operating the TGA at low
pressure.
TGA at low pressure
Figure 1 shows schematically how a TGA
can be operated at low pressure. The low
pressure is created by connecting the fur-
nace outlet to a suitable vacuum pump
via a cold trap. The cold trap is only
necessary if the decomposition gases are
likely to damage the pump. The pressure
in the TGA is monitored by a pressure
gage connected to the purge gas inlet. A
balance protection gas (usually nitrogen)
should be used even if the TGA is oper-
ated at low pressure. As usual, the protec-
tive gas inlet is used for this. The gas flow
should be set using a suitable rotameter –
the METTLER TOLEDO gas boxes cannot
be used. If a reactive gas is also needed,
the reactive gas inlet can be used – here
again using a rotameter to set the gas
flow. The pressure in the TGA should not
be less than 10 mbar.
The experiments described in this ar-
ticle were performed using imipenem.
The structural formula of this pharma-
ceutical substance is shown in Figure 2.
Imipenem (C12 H17 N3 O 4 S, molar mass:
299.35 g/mol) is an antibiotic agent used
to treat bacterial infections. It belongs to
the group of β-lactam antibiotics and
acts by inhibiting the cell wall synthesis
of various bacteria. Imipenem is avail-
able as the monohydrate (CAS 74431-23-5;
the stoichiometric water content of the
monohydrate is 5.7%).
Figure 2. Structural formula of imipenem
(C12H17N3O4S). Possible decomposition
products are COx, NHx and H2O. Molar mass:
299.35 g/mol. Source: https://en.wikipedia.
org/wiki/Imipenem
Figure 3 shows TGA and DTG curves
obtained by measuring imipenem in
Pressure gauge
Purge gas inlet
Reactive gas inlet
Gas supply
nitrogen at a heating rate of 20 K/min Figure 3.
Imipenem at ambi-
at ambient pressure and at 26 mbar. ent and 26 mbar
pressure. TGA
The red curve in the upper diagram in curves and their
first derivatives.
Figure 3 is the TGA curve measured at The red curves
ambient pressure. It shows the typical were measured in
nitrogen at ambient
initial curve shape of substances con-
pressure and
taining moisture (the loss of mass ac- the blue curves
celerates with increasing temperature). at a pressure of
26 mbar.
At about 178 °C, the imipenem rapidly
decomposes. The corresponding DTG
curve in the lower diagram shows that
the release of moisture (including water
of crystallization) and decomposition
overlap. This means that the moisture
content cannot be determined from the
TGA curve. However, if the imipenem
sample is measured at low pressure, in
this case at 26 mbar (blue curves), the
Figure 4.
mass loss due to moisture is separated Repeatability of the
from the mass loss due to decomposition. LOD of four samples
The moisture content can therefore easily of imipenem mea-
sured at a pressure
be calculated from the TGA curve (6.5%, of 26 mbar.
of which 5.7% is water of crystallization).

The repeatability of the measurement of

moisture content at low pressure was also
excellent (see Figure 4). Measurements of
four samples of imipenem gave a mean
moisture content of 6.39% and a stan-
dard deviation of 0.09%.

TGA combined with gas analysis

Purely gravimetric methods only deter-
mine the moisture content. If we want to
determine the water content of a material
gravimetrically, we have to identify the
gases released during the drying process.
The measured moisture content only cor-
responds to the water content if the re-
sults show that we are dealing exclusively
with water. Gases released during drying
can easily be identified by connecting the
TGA to a gas analysis system. Currently
METTLER TOLEDO offers the combina-
tion of TGA with a mass spectrometer
(MS), an FTIR spectrometer, a gas chro-
matography (GC)/mass spectrometer
(MS) system, and a Micro GC/MS.
In the following example, we describe
the use of a TGA-MS combination to de-
termine the water content of imipenem.
The mass spectrometer used was a Pfeiffer
GSD320 Thermostar. The imipenem sam-
ple was heated at 20 K/min in nitrogen at
ambient pressure. The results of the mea-
surement are shown in Figure 5. The up-
per part of the figure shows the TGA curve
(black), its first derivative curve (red) and
the simultaneously measured DSC curve
(blue). The DSC curve indicates the re-
lease of moisture (broad endothermic
peak) and an exothermic decomposition
process. Based on the chemical structure
of imipenem (see Figure 2), decomposi-
tion products such as NHx, COx and water
can be expected. We therefore decided to
operate the MS in the so-called MID scan
mode. The MS then only measures ions
with mass-to-charge ratios defined by the
user. In this case, we chose m/z 16, 17, 18,
and 44. The corresponding measurement
curves are displayed in the lower part of
Figure 5. The MS ion curves (m/z 17 and
18) show that water is released right from
the beginning. If we examine the m/z 17
and 18 curves more closely we notice that
the course of the curves is practically the
same up to about 178 °C. Above this tem-
perature, the two curves show a marked
difference. This can be also seen in the
black curve in the middle of the figure
(without units). The curve corresponds to
the ratio of the m/z 17 and m/z 18 curves.
If the measured increase of m/z 17 and
m/z 18 is only due to water, the ratio
should be constant and independent of
the temperature. This is clearly no longer

METTLER TOLEDO UserCom 52 3
 the case from 178 °C onward. This means
that above this temperature products are
released that contribute to the m/z 17 ion
current but not to the m/z 18 ion current.
Since we expect NHx decomposition prod-
TA Tip
this, a calibration measurement was per-
formed using calcium oxalate monohy-
drate (the procedure is described in refer-
ence [2]). This gave an MS sensitivity for
water (m/z 18) of 510 nsA per milligram
for the water content of the sample.
The TGA/MS experiment confirms that
it really is exclusively water.
How accurately can the LOD

ucts, we assume that NH3 (m/z 17) ex-
plains why the m/z 17 and m/z 18 curves
differ. The fact that above 178 °C the
shape of the m/z 16 (NH2) curve approxi-
mately matches the shape of the m/z 17
curve confirms this hypothesis. We also
note that CO2 (m/z 44) is released from
about 150 °C onward. Apparently, the
decomposition of imipenem begins at a
temperature appreciably below the abrupt
mass loss at 178 °C.
What can we say about the water content
of the imipenem sample? Up to 178 °C
the shape of the m/z 17 and m/z 18
curves is the same. The area under the
m/z 18 curve is therefore proportional to
the amount of water released. To estimate
Figure 5.
TGA-MS measure-
ments of imipenem
using open 40-µL
aluminum crucibles.
The heating rate
was 20 K/min.
water. This allows us to quantify the re-
lease of water up to 178 °C. The result was
4.75%, which is markedly lower than the
step height between 50 and 178 °C on the
TGA curve (5.85%). The difference is due
to the fact that, at the heating rate used
(20 K/min), imipenem already begins to
decompose at 150 °C. In fact, there are
two reasons why the value of 4.75% does
not correspond to the actual water content
of the sample. First, water is a possible
decomposition product of imipenem, and
second, the release of water initially pres-
ent (water of crystallization) is not com-
pleted at 178 °C.
In this example, the vacuum method
probably gives the most credible value
be determined by TGA?
Pharmaceutical products in particular
have LOD values that are usually very low
(<1%). The question arises as to how ac-
curately such low contents can be deter-
mined by TGA and how large the sample
weight must be in order to measure an
expected LOD with a particular accuracy.
From the technical point of view, LODs
are evaluated as horizontal steps on TGA
curves. If a simple horizontal step evalu-
ation is obviously not possible, different
processes overlap and the evaluation
of the LOD is at least questionable (ex-
ample: imipenem at ambient pressure,
see Figure 3). Let us assume that the LOD
can be clearly separated on the TGA curve
from decomposition processes (example:
imipenem at 26 mbar, see Figure 3).
In this case, the accuracy with which a
step height can be evaluated is mainly
given by the resolution and the noise
level of the balance. If we furthermore
assume a combined standard deviation
of 2 ug, and also assume that the true
LOD should lie within the required ac-
curacy with a probability of 0.95, we get
the minimum sample weights listed in
Table 1. Example: if an LOD of 1% is to
be determined so that the true LOD lies
between 0.99% and 1.01% (required ac-
curacy is 1%) with a probability of 0.95,
a sample weight of at least 40 mg must
be used. Further details can be found in
reference [3].

Table 1.
The table shows Required Accuracy Expected effect in %
the sample weight in % 0.1 0.2 0.5 1 2 5 10
in milligrams nec-
essary to determine 0.1 4000 2000 800 400 200 80 40
a step-shaped LOD
mass loss with a 0.2 2000 1000 400 200 100 40 20
certain step height
and a given 0.5 800 400 160 80 40 16 8
accuracy.
1 400 200 80 40 20 8 4
2 200 100 40 20 10 4 2
5 80 40 16 8 4 1.6 0.8
10 40 20 8 4 2 0.8 0.4

4 METTLER TOLEDO UserCom 52
The sample weights given in the table
only take into account the uncertainties
that have to do with the weighing pro-
cess. If the moisture content of a sample
is low, sorption or desorption processes
that occur during sample preparation
and insertion of the sample into the TGA
also contribute to the uncertainty of the
measured moisture content. The con-
tribution depends on the sample under
investigation and is difficult to estimate.
Possibilities as to how these contribu-
tions can be quantitatively estimated
and reduced are summarized in the
green text area.
Conclusions
LOD determinations can be carried out
by TGA at ambient pressure and at low
pressure (minimum 10 mbar). Any prod-
ucts released during drying can be iden-
tified by coupling the TGA to a suitable
gas analysis system. Sufficiently large
sample masses must be used for mate-
rials with low moisture contents. If the
materials exhibit sorption or desorption
processes at room temperature, the mass
of the empty crucible must be entered in
Tips and tricks for the determination of LOD by TGA
• Samples can absorb or release moisture during the wait time on the sam-
ple turntable. In an experiment, it is therefore important to enter the mass
of the crucible as well as the sample mass. Changes in mass that occur
during the wait time on the sample turntable or during the insertion of the
sample into the TGA furnace can then be quantified.
• If the TGA is equipped with a sample robot, aluminum crucibles can be
hermetically sealed with a special lid. In this case, the crucible is opened
by a needle in the sample robot (the lid piercing kit) immediately before
the measurement. Sorption or desorption processes during the wait time
can thereby be prevented.
• If ceramic crucibles are used, they can be covered with an aluminum lid.
The sample robot removes the lid after inserting the crucible into the fur-
nace. Sorption or desorption processes during the wait time on the sample
turntable can then be practically excluded.
the experiment. This is the only way to [2] Ni Jing, Determination of the water
content of an ionic liquid, UserCom 40,
quantify mass changes that occur during
24–26.
the wait time on the sample turntable or [3] K. Fritsche, M. Schubnell, Reliable
during the insertion of the sample into determination of sample mass – the
concept of minimum sample weight,
the TGA furnace. UserCom 41, 14–17.
References
[1] M. Schubnell, C. De Caro, Moisture
content, water content, loss on drying,
Part 1: What exactly is meant and
how are these quantities determined? For more information:
UserCom 51, 1–8. www.mt.com/ta-moisture
METTLER TOLEDO UserCom 52 5
 Polymorphism in metallic alloys, Part 2:
Measurement of the heat capacity of metastable
phases by TOPEM™ and Flash DSC
Applications
Dr. Jürgen Schawe
The article describes how the specific heat capacity of metastable phases can be determined by temperature-
modulated DSC using a metal alloy as an example. It also shows how the temperature range in which the
specific heat capacity of theses phase can be measured is significantly extended by Flash DSC.
Introduction
In Part 1 of this series of articles on the
monotropic polymorphism of metallic al-
loys, we showed how the transformation
kinetics and melting points of different
metastable modifications can be investi-
gated by Flash DSC [1]. By polymorphism
of a metal alloy, we mean the occurrence
of different crystalline forms of the solid
alloy with the same macroscopic chemi-
cal composition. These forms are modi-
fications that differ in their atomic ar-
rangement. We also refer to structures as
modifications if they are composed of dif-
ferent types of crystals in sub-microscopic
dimensions (e.g. eutectic systems). The
decisive factor is that the entire modifica-
tion participates in the transformation.
To describe the stability of the modifica-
tion and understand the phase behavior,
Figure 1.
A conventional DSC
curve (a) and typical
TOPEM curves (b–e)
of the gold-based
alloy to illustrate
different measure-
ment conditions
and evaluation
ranges.
6 METTLER TOLEDO UserCom 52
we have to determine the Gibbs free ener-
gy as a function of temperature [2]. This
means we have to determine the specific
heat capacity, cp, of all the modifications
involved. The problem that arises in the
determination of the specific heat capac-
ity by conventional DSC is that the heat-
ing rate used is relatively low and that
modifications can relatively easily trans-
form. In this article, we show how the
specific heat capacity of unstable modi-
fications can be determined by Flash DSC
and stochastic temperature-modulated
DSC (TOPEM).
Experimental details
Sample
The experiments were performed with a
gold-based metal alloy (Au70Cu5.5Ag7.5Si17).
This forms a metallic glass on rapid cool-
ing at several hundred degrees per second.
Flash DSC measurements with this alloy
enabled us to demonstrate the existence
of monotropic polymorphism in metal
alloys for the very first time [3, 4, 5].
DSC
The transformation enthalpies and
temperatures were measured at a heat-
ing rate of 10 K/min using a METTLER
TOLEDO DSC 3+. The sample weight was
32.93 mg. All the DSC and TOPEM mea-
surements were performed in 40-μL alu-
minum standard crucibles.
TOPEM
The specific heat capacity was measured
with high accuracy using stochastically
temperature-modulated DSC ( TOPEM)
[6, 7]. The temperature program can be
described by
Eq (1) T (t ) = T0 + βu t + δT0 ƒmod(t )
where T0 is the start temperature, βu is
the underlying heating rate and δT0 is
the intensity of the stochastic modula-
tion function ƒmod(t) [8]. δT0 is the half-
height of the impulse in the Method Win-
dow. The modulation function is defined
by the minimum and maximum impulse
width Δt min and Δt max. The minimum
impulse width is Δt min ≈ 4τlag, whereby
τlag is the thermal lag (tau lag) deter-
mined in calibration and adjustment. For
the DSC 3+ equipped with an FRS sen-
sor and standard crucibles, τlag ≈ 3.5 s.
This means that Δt min = 15 s. For the
maximum impulse width, Δtmax = 2Δtmin
is frequently used. The temperature pro-
gram used in the experiments described Figure 2.
Specific heat ca-
here had the following additional param- pacity curves of the
eters: δT0 = 1 K and βu = ±2 K/min. A gold-based alloy,
calculation window width of 300 s was determined using
TOPEM.
used for the evaluation. All other method
and evaluation parameters were the de-
fault settings.

A calibration measurement with sap-

phire is needed for the heat capacity
measurement. The measurement and its
evaluation were performed in the tem-
perature range −30 °C to 550 °C using
the same parameters as for the sample
measurements.

Flash DSC
The Flash DSC measurements were per-
formed with a Flash DSC 1 equipped with Figure 3.
a UFS 1 sensor. To achieve heating and Flash DSC heating
curves measured
cooling rates of several thousand kelvins at 1000 K/s.
per second, the heat capacity of the DSC The “blank” curve
furnace and the sample must be very low. was measured
at 0.5 K/s.
In addition, the thermal contact between
the sample and the sensor must be very
good. The Flash DSC technique is de-
scribed in references [9, 10, 11]. The mass
of the samples used was about 1.5 μg.

Measurement of the specific

heat capacity by TOPEM
The specific heat capacity of the different
modifications was measured in different
temperature ranges using TOPEM. Some
of the measurement curves are displayed
in Figure 1. A conventional DSC curve (a)
measured at 10 K/min is shown for com-
parison. In the first heating curve (b)
before the crystallization process, the
specific heat capacity of the glass and
the supercooled liquid were determined
immediately after the glass transition
(between 276 and 352 K). The tempera-
ture region of the metastable solid x1
modification formed during crystalliza-
tion was not evaluated because crystal-
perfectioning processes occur on further
heating and the cp changes. The specific
heat capacity of the x1 modification was
determined in the second measurement
(c) in the range 276 to 440 K (i.e. be-
fore the transformation to the stable x2
modification). The c p of the x2 modi-
fication (between 276 and 620 K) and
of the melt (from 680 K) were deter-
mined in the third measurement (d).
The results were verified by performing
cooling measurements (e) in which
data of the melt and the stable crystal-
line x2 modification were measured. In
the regions of the measurement curves
that were not evaluated, structure-per-
fectioning processes or phase changes
occur.
The specific heat capacity, c p, curves
shown in Figure 2 were determined from
the TOPEM curves. This was done by
measuring two samples with masses of
68.55 mg and 54.57 mg. A third sample
(56.34 mg) was also first heated to 345 K
at 10 K/min and then quickly taken from
the furnace and placed on a metal plate
cooled with ice water. This was done to
reduce the influence of enthalpy relax-
ation on the heat capacity determination
in the glass and in the supercooled liquid
near the glass transition.
The difference of the c p values between
the samples is better than 2%. In the
temperature range investigated, the c p
of the solid phases is often described by
polynomials [5]:
Eq (2) cp,x(t ) = a x + b x T + c x T 2
For the melt, a term with a negative ex-
ponent is used [5]:
Eq (3) cp,1(t ) = a 1 + b 1 T + c 1 T –2

METTLER TOLEDO UserCom 52 7
 During the relatively low heating and
cooling rates, metastable modifications
tend to transform to more stable modi-
fications. These transformations cause
changes in the heat capacity during
Applications
Measurement of the specific heat
capacity by Flash DSC
Creation and measurement
of different modifications
1000 K/s (red curve in Figure 3) to mea-
sure the glass and the supercooled melt
above the glass transition.
The x1 modification was created by heat-

the measurement and are therefore a
basic problem in the determination of
the c p of metastable modifications by
conventional DSC. For this reason, it
is not possible to determine reliable c p
data over a wide temperature range (see
Figure 2). Equations (2) and (3) can be
used for extrapolation and interpola-
tion over a wide temperature range but
the data is associated with a relatively
large uncertainty.
Flash DSC is an experimental technique
that could be used to extend the tempera-
ture range of metastable systems because
the transformation temperatures of meta-
stable modifications are shifted due to
the high heating rates used [5]. In order
to measure the supercooled melt over
the greatest possible temperature range,
the sample was first cooled from the
equilibrated melt at 2000 K/s to 300 K.
A heating segment was then performed at
ing the glass that had previously been
cooled at 2000 K/s to 440 K and then im-
mediately cooling it at 1000 K/s. Three
temperature cycles were then performed
at ±1000 K/s between 300 K and 500 K
for stabilization. The measurement
curves of the last two cycles were identical
(blue curve in Figure 3). The x2 modifi-
cation was created by cooling from 750 K
at 0.5 K/s. The heating measurement was
then performed at 1000 K/s (black curve
in Figure 3).

Determination of the heat capacity

Figure 4.
Flash DSC heating Thermal losses in heat capacity mea-
curves from Figure 3 surements using the Flash DSC must be
after blank curve compensated by means of a blank curve.
subtraction and
normalization with With the Flash DSC, most losses are in-
respect to the heat- dependent of the heating rate. The mea-
ing rate. The usable
sured heat flow curve Φ can be described
ranges of the melting
curve are shown by eq (4):
by the rectangles.
Eq (4) Φ = m cp β + Φloss

where m is the sample mass, cp the spe-

cific heat capacity of the sample, β the
scanning rate and Φloss the thermal loss-
es. The first summand describes the sam-
ple effects and is proportional to the heat-
ing rate. If the heating rate is sufficiently
low (e.g. 0.5 K/s or 1 K/s), practically
only the loss component is measured.
Figure 5. This curve can be then be used to correct
Specific heat ca- curves measured at higher heating rates
pacity of the metal (e.g. 1000 K/s) [12]. The measured curve
alloy measured
by Flash DSC and should be adequately smoothed before
TOPEM. using it for blank curve subtraction in or-
der to avoid increasing the noise level of
the corrected curve. Heat capacity curves
(in J/K) such as those shown in Figure 4
are then obtained by normalization with
respect to the heating rate.

The specific heat capacity is calculated

by dividing the curves in Figure 4 by the
sample mass. The mass of the small Flash
DSC samples cannot be directly mea-
sured. One possibility is to adapt the Flash
DSC data to the data of the conventional
(or temperature-modulated) DSC [9].

8 METTLER TOLEDO UserCom 52
In Figure 5, the c p values of the melt
measured with TOPEM were compared
with those of the heat capacity (Cp) from
the Flash DSC measurements (Figure 4)
in a temperature interval around 700 K
and a shift factor k calculated as shown
in eq (5):
C [7] J. Schawe, DSC measurements
Eq (5) k = p∕cp
All the Flash DSC curves were multiplied
by this factor. The curves are in excellent
agreement with the data determined from
the TOPEM measurements (Figure 5).
The temperature range with measured cp
data is thereby extended, especially for
the x1 modification and the supercooled
melt. The measurement data can now be
described more accurately using the ap-
proximation functions (eqs (2) and (3)).
This means that further studies on the
thermodynamics of phase behavior can
carried out with greater certainty.
Summary and conclusions
The specific heat capacity of metals
can be measured by TOPEM or ADSC
with an accuracy of about 2% [7]. With
metastable modifications, this is how-
ever only possible in a relatively small
temperature range because the modi-
fications can undergo transformation
during the measurement. For ther-
modynamic reasons, the specific heat
capacity data should be known over the
widest possible temperature range. This
range can be extended using Flash DSC
measurements because the high scan-
ning rates shift the transformation tem-
peratures. The problem that arises with
the Flash DSC is that blank curves can-
not be directly measured and that the
sample mass is not accurately known.
The article describes how the thermal
losses of the Flash DSC measurements
can be corrected and how specific heat
capacities can be obtained. This is done
by comparing the Flash DSC data with
c p values measured using temperature
modulation in a conventional DSC.
A detailed discussion of the method pre-
sented here is given in reference [5].
References
[1] J. Schawe, Monotropic polymorphism
in metallic alloys, Part 1: Flash DSC
investigation of the melting of meta-
stable phases, UserCom 51, 19–21.
[2] D. Giron, Thermal analysis and calo-
rimetric methods in the characterisa-
tion of polymorphs and solvates,
Thermochim. Acta 248 (1995) 1–59.
[3] S. Pogatscher, D. Leutenegger,
J. E. K. Schawe, P. J. Uggowitzer,
J. F. Löffler, Solid-solid phase
transitions via melting in metals,
Nat. Commun. 7 (2016) 11113.
[4] S. Pogatscher, D. Leutenegger,
J.E.K Schawe, M. Pavithran, R.
Schaeublin, P. Uggowitzer, J. Löffler,
Monotropic polymorphism in a glass-
forming metallic alloy, J. Phys.:
Condens. Mat. 30 (2018) 234002.
[5] J.E.K. Schawe, S. Pogatscher,
J.F. Löffler, Thermodynamics of poly-
morphism in a bulk metallic glass:
Heat capacity measurements by fast
differential scanning calorimetry,
Thermochimica Acta 685 (2020)
178518.
[6] TOPEM™-The new multi-frequency
temperature-modulated technique,
UserCom 22, 6–8.
of metals by DSC and TGA/DSC,
UserCom 46, 8–11.
[8] J.E.K. Schawe, T. Hütter, C. Heitz,
I. Alig, D. Lellinger, Stochastic tempera-
ture modulation: A new technique in
temperature-modulated DSC, Thermo-
chim. Acta 446 (2006) 147–155.
[9] J. Schawe, The revolutionary Flash
DSC 1: maximum performance for
metastable materials, UserCom 32,
12–16.
[10] J. Schawe, Fast Scanning DSC:
Selected application examples,
UserCom 49, 16–20.
[11] J. Schawe, Fast Scanning DSC:
Practical tips and information,
UserCom 50, 14–19.
[12] C. Quick, J.E.K. Schawe,
P.J. Uggowitzer, S. Pogatscher,
Measurement of specific heat capacity
via fast scanning calorimetry-accura-
cy and loss corrections, Thermochim.
Acta 677 (2019) 12–20.
For more information:
www.mt.com/ta-fdsc
METTLER TOLEDO UserCom 52 9
 Innovation and standardization:
The development of a standard for the Flash DSC
Applications
Dr. Klaus Könnecke
The application of a new measurement procedure in routine analysis is frequently tied to the existence of a
corresponding standard. The article describes the development of international standards, which can save
time-consuming, costly analytical method validation.
Importance and advantages
of standardization
A standard describes a uniform, widely
recognized and applied procedure to
produce or perform something that has
proven itself in comparison with other
procedures [1]. Standardization is the
process of developing and implementing
standards. The availability of a standard
can replace method validation in analy-
sis, which is required for quality assur-
ance, accreditation or approval. This is
particularly important for new measure-
ment techniques such as the Flash DSC.
In this sense, the manufacture of met-
als in the shape of uniform bars in early
Christian times can be looked on as an
early example of standardization. On the
one hand, it facilitated the use of metals
Figure 1.
Celtic iron bars.
Source: © LAD,
Y. Mühleis,
https://books.
ub.uni-heidelberg.
de/heibooks
10 METTLER TOLEDO UserCom 52
as articles of trade and on the other hand,
metal bars served as an early currency or
means of payment (see Figure 1) [2].
Even today, metal bars are still manu-
factured in different shapes and sizes
for the exchange of goods. Besides this,
bars of precious metals, especially gold,
serve as a safe investment. Quite early
on, however, coins made of metals of
uniform size became commonly used
as currency. Their individual value was
stamped on them and they were easier
to handle due to their small size and low
weight. These early forerunners of stan-
dardization however had less to do with
the introduction of new techniques but
were rather a contract to facilitate the
exchange of goods and services.
Standardization as
pacemaker for innovation
Standardization has to the present day
still lost none of its importance for the
easier exchange of products and services.
In the course of technical progress in
the age of the industrialization, it has,
however, become increasingly important
to describe new inventions and technical
developments by uniform standards in
order to make them applicable for a wid-
er user group. The development of video
technology is a good example of this.
Worldwide, three systems known as PAL,
SECAM and NTSC were used to display an-
alog color television images; their global
distribution is shown in Figure 2 [3].
These systems enabled color television
technology to spread throughout the
world. In the meantime, of course, these
analog standards have been replaced by
digital techniques (DVB).
In the field of instrumental analysis,
standardization also plays an important
role by making innovative investigation
techniques available for less experienced
users. These new methods can only assert
themselves in industrial routine analy-
sis when standardized procedures for the
application, execution and evaluation of
new measurement techniques are avail-
able. Both instrument manufacturers
and potential users then profit from such
new developments.
In the following sections, we will first
describe the requirements placed to-
day on technical standards and explain
how these standards and regulations
originate. Following this, the practical
implementation of a standard for newly
developed measurement techniques
will be discussed using the Flash DSC as
an example.
Standardization
and interest groups
Standardization in the technical sense
describes the agreement, publication and
application of requirements, specifica-
tions, and guidelines by recognized orga-
nizations. Standards should be based on
secure knowledge derived from science,
technology and experience and ensure
that products, processes and services
are suitable and accepted world-wide for
the given purpose. Standardization can
help maximize the compatibility, safety,
repeatability and quality of products and
services.
Participation in standardization com-
mittees is voluntary and open to all
groups interested in the development,
implementation and application of the
standards such as scientific, industrial
and testing institutes, consumers, health
and environmental safety associations
and governmental and non-governmental
organizations, etc.
Organization of the ISO Inter-
national Standards Organization
The International Organization for
Standardization (ISO) has established
itself as a leading organization for the
development of worldwide recognized
standards. As a result of increasing glo-
balization, standardization activity is
increasingly shifting to the internation-
al stage. National standards organiza-
tions such as DIN in Germany or the SNV
in Switzerland are increasing engaged
in the development of ISO standards.
The importance of independent national
standards is decreasing due to their re-
gionally limited validity.
ISO is a global network of national
standards bodies. Its members are the
foremost standards organizations in
their countries. ISO has one member
per country and each member is the ISO
representative in that country. Individu-
als or companies cannot become ISO
members.
NTSC
PAL or transition from SECAM to PAL
only SECAM
not specified
Full members
Correspondent members
Subscriber members
Non-members
The work of preparing international
standards is normally carried out by ISO
technical committees. ISO has more than
250 technical committees (TC) that cover
all the main fields of work. The technical
committees are formed by the member
countries, which bundle together their
national contribution. [4].
ISO has three different membership cate-
gories namely Full members, Correspon-
dent members, and Subscriber members.
Each enjoys a different level of access and
influence over the ISO system:
• Full members (or member bodies)
influence ISO standards development
and strategy by participating and
voting in ISO technical and policy
meetings in all stages of the stan-
dardization process.
Figure 2.
Distribution of
analog video sys-
tems by country.
Figure 3.
Overview of the ISO
member countries.
• Correspondent members observe the
development of ISO standards and
strategy by attending ISO technical
and policy meetings as observers.
• Subscriber members keep up to date
on ISO’s work but cannot participate
in it.
Figure 3 shows that a large majority of
countries worldwide participate as full
members or correspondent members of
ISO. Within the different fields of work,
the interests of all participants are rep-
resented by experts from the individual
member countries. The participation in
the development of standards is voluntary
and open to all interested circles. The en-
tire standardization process is organized
by ISO and supported by the individual
member countries.
METTLER TOLEDO UserCom 52 11
 Structure of the ISO bodies
The Flash DSC is handled in TC 61 “Plas-
tics” under the more than 250 technical
committees. TC 61 is made up of a total
of 31 full members and 38 observers and
Applications
The development of a standard is possible
despite existing patent protection if the
owner of the patent guarantees to grant
licenses at standard market conditions.
1. Proposal stage. Submission of
a proposal for a new standard-
ization project
In this first step, the proposal for a new
standardization project is presented

is divided into 11 sub-committees (SC).
The Flash DSC appears again in SC 5
“Physical-Chemical Properties”. SC 5 is
divided into 4 working groups (WG), of
which WG 8 “Thermal Analysis” deals
with the Flash DSC.
The national standards institutes, such
as DIN in Germany are similarly orga-
nized and often differ only in the names
of the bodies and a slightly modified
classification.
Criteria for the acceptance of new
standardization projects [3]
Important criteria for justifying the in-
clusion of new standardization projects
in the ISO work program are sufficient
need, market relevance, and a binding
project plan. It should also be noted that
all copyrights must be transferred to ISO
and the use of trade names should as far
as possible be avoided.
Before a standardization project is accept-
ed, adequate resources must be available.
First, appropriate standards bodies have
to be defined for the intended project and
at least 2⁄3 of the full members must be in
favor. Furthermore, a project leader and
at least 5 national experts must be named
for the development of the standard and
a project plan must be prepared that in-
cludes the individual project milestones.
In addition, acceptance of the project re-
quires the creation of a draft work pro-
gram that includes all the important ele-
ments of the standard. Normally written
and spoken communication is in English.
Stages in the development
of a standardization project [3]
The development of an ISO standard
can be divided into 6 stages whereby, in
some circumstances, the optional stages
(marked with a red star *) can be skipped
(see Figure 4):
and discussed in the national and ISO
working groups, and a decision taken
as to whether an official standardiza-
tion project should be requested.
2. Preparatory stage. Inclusion of
a new standardization project in
the ISO work program
The proposal for a new standardiza-
tion project is made to ISO by a full
member. Before the ballot about
acceptance, a project leader must be
named and the field of application
must be defined. Ideally however, a
complete first working draft should
be presented. The ballot lasts three
months and the standardization proj-
ect must be supported by at least 2⁄3 of
the full members. In addition, at least
5 national experts must be named for
participation. Furthermore, the time-
frame including milestones for the
development of the standard must be

Figure 4.
Overview of the
individual stages
Comparing development processes for an IS
in the development
of an ISO standard. 6 stages Action Balloting time Default path Shortest path
Stages marked
with a red star (*)
• 3-month ballot by default

1
are optional.
Proposal Proposal to start • 2-month ballot possible
NP NP
a new project • TC/SC resolution for Straight to DIS
NP revision & amendments

2 Preparatory
WD *
Expert consensus
within working group WD

• 2-month ballot by default

3 Committee
CD *
Committee consensus
• 3 or 4 month vote
possible
• Can be skipped
CD

4 Enquiry
DIS
National consensus
• 2-month translation
• 3-month ballot
24 months to reach

DIS
12 months to reach

DIS

5
• Skipped by default
Approval YES or NO vote • Can be introduced FDIS
• 2-month ballot
FDIS *

6 ISO Up to 36 months Down to 9 months

Publication International Standard IS IS

12 METTLER TOLEDO UserCom 52
 defined. If the project is rejected, no
further work occurs. It can however be
revised and resubmitted at any time.
3. Committee stage
Taking into account the comments
received in the ballot about the new
standardization project, a new work-
ing draft is prepared on which the
full members vote within 2 months.
In the ballot, a consensus is sought,
but a majority of at least 2⁄3 is needed
for acceptance. All full members are
obliged to participate in the ballot
and any rejections must be justified.
If the project is rejected, the respon-
sible body decides whether a second
ballot can be considered after a suit-
able revision or whether the project
should be withdrawn.
4. Enquiry stage
After assessing the comments received
in the draft stage, the project leader
prepares a revised draft which must be
voted on within 3 months. Here again a
consensus is sought, but at least 2⁄3 ap-
proval and not more than ¼ rejection is
necessary. Rejection without explana-
tion and abstentions are not taken into
account. If no technical comments are
raised in the ballot, then the standard
is published after editorial review,
otherwise another formal final ballot
is necessary after taking the techni-
cal objections into account.
5. Approval stage
In this ballot, only technical com-
ments are allowed and the accep-
tance criteria (at least 2⁄3 approval
and maximum ¼ rejection) are the
same as in the previous stage. If the
ballots in the committee, enquiry,
or final draft stages are not in favor,
the responsible body decides whether
to repeat the process after suitable
revision or to withdraw the project.
6. Publication stage
Once the standard has successfully
passed the enquiry or approval stage,
the final text is released by the
project leader and published by ISO
within 6 weeks.
Maintenance
of the standard
Confirmation
of the revision
Vote on the
revision
The stages in the development process
of an ISO standard are summarized in
Figure 4.
In many cases, the development of inter-
nationally valid standards by ISO runs
parallel with the European Standards
Organization CEN as EN ISO standards.
A special feature of these standards is
that their inclusion in the national stan-
dardization bodies of the CEN member
countries is mandatory.
Review cycle of standards [3]
The current status of ISO standards is pe-
riodically reviewed every 5 years. In ad-
dition, every full member can request an
unscheduled revision. A revision requires
a simple majority of the member coun-
tries. As a result of the review, the standard
is either confirmed unchanged, revised or
withdrawn. If a revision is requested, the
responsible ISO body decides in which of
the above-mentioned stages the revision
should begin. The typical review cycle of
a standard is shown in Figure 5.
Development of a standard
To facilitate the readability and applica-
tion of standards, formatting guidelines
have been agreed that standardize the
structural organization of standards as
well as the formatting of figures and
tables.
If desired, an introduction that describes
the scientific background of the stan-
Figure 5.
Review cycle of
Periodic a standard.
review
Vote on the
review
Revision of the
standard
dard, information on its use, or special
advantages can be put in front of the
standard. Mandatory for each standard is
a section at the beginning that describes
the application field and that presents a
list of normative references as well as a
collection of terms and definitions that
are used in the particular standard.
What follows can be different depend-
ing on the purpose of the standard. For
the standardization of test methods,
however, sections usually follow that de-
scribe the measurement principle, define
equipment requirements, sampling and
sample preparation, and how to perform
and evaluate measurements. Finally, the
test report contains information on the
expected accuracy of the results and a
list of necessary details.
Optionally, normative or informative ap-
pendices to describe special aspects of a
standard and literature references can be
appended.
Example of the newly developed
standard for the Flash DSC [5]
The standard is entitled “Plastics – Fast
Differential Scanning Calorimetry – Chip
Calorimetry”. In the application field,
it is stated that the standard is valid for
non-adiabatic fast DSC instruments that
operate according to the principle of
power compensation. In addition, the
application is limited to an open sample
geometry in which samples are positioned
METTLER TOLEDO UserCom 52 13
 directly on the measuring sensors with-
out being sealed in a crucible so that ex-
tremely high heating and cooling rates of
up to several thousand kelvins per second
can be achieved. Furthermore, a series
Applications
of applications is given that can now be
performed with the revolutionary Flash
DSC technology. To date, commercial in-
struments for this new technique are only
available from METTLER TOLEDO.
Special requirements for the use of the
Flash DSC are covered, such as:
• Preparation and measurement of
samples in the nanogram to micro-
gram scale
• Special points for the calibration of
temperature, enthalpy and specific
heat capacity
• Determination of the mass of the sam-
ples that cannot be directly weighed
• Correct positioning of samples on the
sensor.
Determination of the filler content
in a composite
Dr. Markus Schubnell
The determination of the filler content in polymers is frequently performed by thermogravimetric analysis
(TGA). In this article, we discuss different methods for doing this using carbon-fiber reinforced PEEK as
an example.
Introduction
The mechanical properties of filled poly-
mers depend strongly on the filler con-
tent. For the quality assurance of such
materials, it is therefore important to
determine the filler content as accurately
as possible. In this article, we discuss
different methods for doing this. As an
example, we investigated a composite
made of carbon-fiber reinforced PEEK
(polyether ether ketone). Samples of the
polymer (PEEK) and carbon fibers used
were also available.
14 METTLER TOLEDO UserCom 52
Future prospects
The publication of a standard for the ap-
plication of the Flash DSC for polymers
makes the necessary know-how available
for using the method in routine analysis.
This enables users who are less familiar
with the method to operate the Flash DSC
properly and thereby promotes the wider
use of this new measurement technique
in industrial laboratories and commer-
cial testing institutes.
References
[1] https://de.wikipedia.org/wiki/Standard
[2] https://mittelalter.fandom.com/de/
wiki/Barren
[3] https://de.wikipedia.org/
wiki/S%C3%A9quentiel_
couleur_%C3%A0_m%C3%A9moire
[4] https://de.wikipedia.org/wiki/Interna-
tionale_Organisation_f%C3%BCr_
Normung
[5] https://www.iso.org/directives-and-
policies.html, ISO/IEC Directives, Part
1 (2019), Consolidated ISO Supple-
ment – Procedures specific to ISO
Experimental details
Measurements were performed with a
TGA/DSC 3+ equipped with a DTA sensor
as well as with a DSC 3+. The TGA/DSC
measurements were performed in nitro-
gen and in oxygen using 70-µL alumi-
num oxide crucibles. The DSC measure-
ments were carried out in nitrogen using
40-µL aluminum crucibles.
Results
Figure 1 presents the TGA, DSC and DTG
curves of the composite, the pure poly-
[6] https://www.iso.org/directives-and-
policies.html, ISO/IEC Directives, Part
2 (2018), Principles and rules for the
structure and drafting of ISO and IEC
documents
[7] https://www.iso.org/standard/77496.
html, ISO/DIS 23976, Plastics – Fast
differential scanning calorimetry –
Chip calorimetry
For more information:
www.mt.com/ta-standards
www.iso.org
mer and the carbon fibers measured in
nitrogen. The TGA curve shows that the
carbon fibers are stable in nitrogen. The
pure PEEK sample degrades to such an
extent that at about 900 °C only a large
amount of residual carbon remains,
namely 51.567%. The measured mass
losses are therefore exclusively due to the
pyrolysis of PEEK. The carbon fiber con-
tent in the composite, ξ CF, can be cal-
culated from the percentage mass loss
steps of PEEK and the composite samples
according to the equation
 Δm PEEK – Δmcomposite
ξCF [%] = 100 · Δm PEEK (1) Figure 1.
TGA, DSC and DTG
 curves of PEEK
where ΔmPEEK and Δmcomposite are the per- (blue), carbon
centage mass loss steps. The step heights fibers (green, only
TGA) and the
given in Figure 1 yield carbon fiber and composite (red),
PEEK contents of 15.6% and 84.4%. The measured in
residual carbon from the pyrolysis of nitrogen.

PEEK in the composite (100 x 0.51567 x

0.844 = 43.5%) is therefore much larger
than the fiber content.

The DSC curves (middle diagram in Fig-

ure 1) show that the PEEK sample melts
at about 350 °C. This is followed by the
mainly endothermic pyrolysis of PEEK
in two steps. This can also be seen in the
DTG curves (first derivatives of the TGA
curves; step-shaped mass changes are
shown here as peaks). The decomposition
Figure 2.
of the composite begins about 5 K lower TGA, DSC and DTG
than the decomposition of the pure PEEK. curves of PEEK
This could be the result of better thermal (blue), carbon
fibers (green) and
conductivity of the composite due to the the composite (red),
carbon fibers. measured in oxy-
gen, shown as a
function of the refer-
If the same materials are measured in ence temperature.
oxygen (Figure 2), a completely differ-
ent picture is obtained. The TGA curves
(top diagram in Figure 2) show that the
combustion of carbon fibers takes place
in a step over a broad temperature range
from about 600 to 800 °C (green curve).
The composite and PEEK samples decom-
pose in at least two steps (see also the DTG
curves in the bottom diagram of Figure 2).
The first step is between about 500 and
600 °C and the second step between 600
and about 750 °C. Figure 3.
TGA and DSC curves
The DSC curves (middle diagram in Fig- of PEEK (blue), car-
bon fibers (green)
ure 2) show that pure PEEK and the com- and the composite
posite decompose weakly exothermally (red), measured in
oxygen, shown as
up to about 600 °C. From 600 °C on-
a function of the ref-
ward, strongly exothermic heat flows are erence temperature
observed due to the combustion of the (dotted-line curves)
and the sample
polymer carbon and probably also (in the temperature (solid-
case of the composite) due to the carbon line curves).
fibers. In contrast, the pure carbon fibers
apparently do not burn until a much
higher temperature. The question is how
can we explain the apparently higher
combustion temperature of the pure car-
bon fibers. Note that the temperature axis
in Figure 2 corresponds as usual to the
program temperature (i.e. the DSC refer-

METTLER TOLEDO UserCom 52 15
 ence temperature). The strong exotherm
produced in the combustion of the PEEK
carbon heats the sample to temperatures
well above the reference temperature.
This is illustrated in Figure 3. It shows
Applications
fore be automatically used to determine
the carbon fiber content from a measure-
ment in oxygen.
Between 500 and about 600 °C, the TGA
upper temperature limits correspond to
about the temperatures at which carbon
(both residual carbon and the carbon
fibers in the composite) starts to burn.
The carbon fiber content determined in

the TGA and TGA/DSC curves from Fig-
ure 2 plotted as dotted-line curves (here
the temperature corresponds to the refer-
ence temperature). The solid-line curves
are the curves obtained when the corre-
sponding curves are plotted as a function
of the sample temperature. Comparison
of the curves shows that during the com-
bustion of the PEEK carbon the sample
temperature increases to temperatures at
which combustion of the carbon fibers
can take place. Equation 1 cannot there-
Figure 4.
DSC curves of the
composite (red)
and of PEEK (blue),
measured at
10 K/min in
nitrogen.
and DTG curve shapes for PEEK and
composite are practically the same and
are only due to the decomposition of
PEEK (Figure 2). If the first maxima on
the DTG curve (indicated by the verti-
cal dotted lines in Figure 2) are chosen
as upper temperature limits for the step
evaluation of the first decomposition
step, a carbon fiber content of 15.9% is
obtained from the two step heights using
eq 1. Comparison with the correspond-
ing TGA/DSC curves shows that these
this way thus agrees with the value cal-
culated from the measurements in ni-
trogen within the limits of uncertainty
given by the choice of the temperature
limits for the step evaluation
In principle, the PEEK content (and
hence the carbon fiber content) in the
composite can also be determined by
DSC. Both the step heights of the glass
transition as well as the enthalpies of
fusion of PEEK in the composite and in
the sample of pure PEEK can be used for
this. Measurement curves of PEEK and
the composite are shown in Figure 4.
If the enthalpies of fusion are evaluated,
the PEEK content of the composite cor-
responds to the ratio of the peak areas
(normalized to sample mass) of the PEEK
melting peak of the composite and the
pure PEEK sample. This yields a PEEK
content of 85.5%. The evaluation of the
areas of the melting peaks depends on
the choice of the baseline (Line, Spline,
etc.) as well as on the integration limits.
We estimate the associated uncertainty of
the PEEK content to be about ±4%.

If the step heights of the glass transitions

are used, the PEEK content is the ratio of
the Tg step height of PEEK in the compos-
ite and that of pure PEEK. This method
Figure 5. results in a PEEK content of 86.1%. The
TGA and TGA/DSC Tg step heights depend strongly on the
heating-cooling- choice of the tangents used for the evalu-
heating curves
of the composite ation. The degree of uncertainty of the
(three segments): PEEK content determined in this way
first segment
is therefore large (estimate: ±10 %).
(300 to 800 °C)
in nitrogen, The uncertainty of the carbon fiber con-
second segment tent is then equally large as the uncer-
(800 to 300 °C)
in nitrogen,
tainty of the PEEK content.
third segment
(300 to 800 °C) The methods described above assume
in oxygen.
that the constituents of the composites
are available in addition to the composite
itself. In this case, both the TGA method
(relatively accurate) and the DSC method
(relatively inaccurate) can be used to de-
termine the composition. But what do we
do if only the composite is available?

16 METTLER TOLEDO UserCom 52

Filler content
In nitrogen
In oxygen
N2 to 800 °C
O2 from 300 °C
The measurement of the composite
sample in oxygen showed that the com-
bustion of the residual carbon from the
PEEK and the carbon fibers cannot be
separated. If only the composite is avail-
able, an experiment will have to be de-
signed in which the combustion of the
two types of carbon (residual carbon
from PEEK and carbon fibers) can be
separated. This is possible if the two types
of carbon burn in different temperature
ranges. The results for the measurements
in oxygen prove that this is the case for
this particular composite. A method
frequently used in such cases involves
heating the sample in nitrogen to a tem-
perature at which pyrolysis is complete
(in our example about 900 °C), cooling
the residual sample in nitrogen to 300 °C
(in this cooling segment the sample mass
remains unchanged), and then heating it
in oxygen to 800 °C (combustion of car-
bon). Several TGA and TGA/DSC curves
obtained for the PEEK composite in such
an experiment are shown in Figure 5. The
first TGA heating run is the same as the
TGA curve shown in Figure 1. On cool-
ing, the sample mass remains constant
as expected. The second heating run
Table 1.
TGA DSC Filler content of
Step evaluation Enthalpy of fusion Step height Tg PEEK and carbon
fibers in a compos-
ite. Blue-shaded
15.6% ± 0.2% boxes: Results
14.5% ± 4% 13.9% ± 10% based on mea-
surements of the
15.9% ± 1.0% individual compo-
(independent of (independent of
nents (PEEK and
the atmosphere) the atmosphere)
carbon fibers) and
15.8% ± 0.3% the composite.
Green-shaded box:
Determination from
a TGA measurement
in oxygen exhibits two distinct but not tainties involved are significantly larger of the composite.
The uncertainties
completely separated exothermic mass than the uncertainties arising from the are based on
loss steps. They correspond to the com- TGA measurements. estimates.
bustion of the residual carbon of PEEK
(on the DSC curve at about 510 °C) and If only the composite is available, its
the carbon fibers (on the DSC curve at composition can only be determined
about 710 °C). This yields a value of from a TGA measurement. The method
15.9% (step height of the second mass for doing this consists of three segments:
loss step) for the carbon fiber content. In the first segment, the sample is pyro-
Due to the overlap of the two combustion lized in nitrogen. In the second segment,
processes we estimate the uncertainty of the residual sample is cooled under py-
the step evaluation to be about ±0.3%. rolysis conditions to about 300 °C. In
It should be possible to improve the sepa- the third segment, the sample is heated
ration of the two combustion processes in oxygen. This enables the combustion
by varying the heating rate during the processes of the residual polymer carbon
second heating segment. and the carbon fibers to be separated.
Summary and conclusions The results are summarized in Table 1.
We have shown how the composition The values in the blue-shaded boxes are
of a composite consisting of PEEK and based on a comparison of measurements
carbon fibers can be determined by TGA. of the composite and its individual com-
If the individual constituents of the com- ponents (PEEK, carbon fibers). The value
posite are also available in addition to in the green-shaded box results from the
the composite, the carbon fiber content measurement of the composite using the
is most easily and accurately determined (three segment) method described above.
by performing TGA measurements in
an inert atmosphere. Alternatively, the
carbon fiber or the PEEK content can be For more information:
estimated by DSC. However, the uncer- www.mt.com/ta-techniques
METTLER TOLEDO UserCom 52 17
 TGA-IST-GC/MS-FTIR analysis
of polypropylene
Applications

Nicolas Fedelich

Instrument combinations consisting of a thermogravimetric analyzer (TGA) coupled to a mass spectrometer,

an FTIR spectrometer, or a GC/MS are nowadays standard techniques that can be used to identify gases
released during a TGA measurement. In this article, we show the benefits of simultaneously coupling a GC/MS
and an FTIR spectrometer to the TGA, using polypropylene as an example.

Introduction released during a TGA measurement. hand, functional groups of molecules of

Instrument combinations involving The disadvantage of the TGA-FTIR cou- decomposition products are easy to iden-
a thermogravimetric analyzer (TGA) pling (analogous to the TGA-MS coupling) tify by FTIR, which allows conclusions
coupled to a mass spectrometer (MS), a is that IR spectra of decomposition gases to be drawn about the decomposition
Fourier-transform infrared spectrometer simultaneously evolved overlap and products that occur. The availability of
(FTIR), or a GC/MS are nowadays stan- make the interpretation of the measured GC/MS data and FTIR spectra is there-
dard techniques for identifying gases IR spectra more difficult. On the other fore very valuable to help understand the
decomposition reaction. In this article,
Figure 1.
Schematic diagram we demonstrate this using two different
showing the setup samples of polypropylene.
of the TGA-IST16-
GC/MS-FTIR experi-
ment. Experimental details
FTIR
The measurements were carried out us-
Heated transfer line
ing a TGA/DSC 3+ equipped with an
SDTA sensor coupled to an Agilent GC/MS
Inject
(7890 GC with 5975C MSD) and a Bruker
valve Alpha FTIR spectrometer. The experi-
Isolation
valve mental setup is shown schematically in
Storage Figure 1.
valve
and loops
The TGA was coupled to the GC/MS by
MS GC IST TGA
means of the SRA IST16 storage interface
as described in reference [1]. The storage
Figure 2. interface enables gas samples to be col-
TGA/DSC measure- lected at up to 16 different TGA temper-
ment curves of the atures. The samples are then individu-
two polypropylene
samples, one with- ally analyzed by the GC/MS after the TGA
out flame retardant measurement. The transfer line from the
(black curve PP-ref)
TGA to the IST16 and the storage loops
and the other with
flame retardant were thermostated at 250 °C. The tem-
(red curve PP-FR). perature of the GC injector was 280 °C.
The GC temperature program con-
sisted of an isothermal period at 50 °C
(5 min), a heating ramp (50 to 300 °C
at 10 K/min) and a further isothermal
period at 300 °C (5 min). The separating
column was an HP-5ms (60 m x 0.25 mm
x 0.25 um) and the carrier gas helium
(0.8 mL/min). The MS was set to measure
masses in the range m/z 33 to m/z 350.
The substances measured with the GC/MS

18 METTLER TOLEDO UserCom 52
were identified using the NIST/EPA/NIH Figure 3.
Total ion chromato-
mass spectral database [2]. gram (TIC) of the
gas sample taken
The Bruker FTIR spectrometer was at 450 °C for PP-FR
with the names of
equipped with a gas cell, and was con- some of the identi-
nected to the outlet of the IST16 interface fied decomposition
products.
by an additional transfer line. This en-
abled FTIR spectra of the decomposition
gases to be continuously recorded during
the TGA experiment (online). The trans-
fer line and the gas cell were heated at
250 °C. The IR spectra were scanned from
4000 to 400 cm-1 at a resolution of 4 cm-1;
averaging 16 spectra each time.

Two polypropylene samples, one contain-

ing flame retardant (PP-FR) and the
other without flame retardant (PP-ref)
were used for the experiments. The flame
Figure 4.
retardant was Exolit® AP 760 (20 wt %). Decomposition
The PP-FR also contained 10 wt % cal- product of PP-FR at
cium carbonate (CaCO3). Exolit® AP 760 a retention time of
10.73 min.
is an ammonium polyphosphate-based, Above: the measured
intumescent flame retardant. Flame re- mass spectrum.
Below: the mass
tardants like this foam at a certain tem-
spectrum from the
perature and then char. This leads to database (best fit
the formation of protective layers which with the measured
mass spectrum)
retard the decomposition of the mate- and the result of the
rial concerned. The measurements were database search –
performed in the temperature range 30 the decomposition
product is most
to 600 °C in nitrogen (30 mL/min) at a probably 2,4-
heating rate of 10 K/min using sample dimethyl-1-heptene.
masses of about 20 mg in 70-µL alumi-
num oxide crucibles.

Results

TGA measurements Figure 5.

Both samples were first measured with- Total ion chromato-
out gas analysis in order to determine grams (TICs) of the
gas samples taken
relevant temperatures for the GC/MS at 380 °C for PP-ref
analysis. The results for both materials (black curve) and
PP-FR (red curve)
are shown in Figure 2. The upper part
with the names
of the figure shows the TGA curves and of some identified
the lower part the simultaneously mea- decomposition
products (only for
sured DSC curves. The curves show that PP-FR).
the decomposition behavior of the two
polypropylene samples is slightly dif-
ferent. For example, decomposition of
the PP-FR sample begins at lower tem-
peratures than the material without the
flame retardant (PP-ref). This has to do
with the decomposition of the flame re-
tardant. The different residues (PP-FR:
10% and PP-ref: 0%) are due to the 10%

METTLER TOLEDO UserCom 52 19
 calcium carbonate in the PP-FR sample
(calcination of CaCO 3 does not begin
until about 600 °C and is not of inter-
est here).
Applications
a second experiment, marked with blue
crosses on the black curve in Figure 2).
GC/MS measurements
In a second experiment, gas samples
PP-FR are practically identical (in par-
ticular alkenes, e.g. 2,4-dimethyl-1-hep-
tane, see also Figure 4).
The total ion chromatogram (TIC) of the

The simultaneously measured DSC were collected for both materials at the gas sample taken at 380 °C for PP-FR
curves show the melting of the polypro- temperatures determined before and shows a prominent peak at 18.747 min
pylene at about 160 °C. The different spe- then analyzed by GC/MS. The results are (besides numerous smaller peaks).
cific enthalpies of fusion are the result of shown in Figures 3 to 6. They show the The MS analysis identified the peak as
the different compositions of the two ma- total ion chromatograms (TICs) of gas 1,3-benzenedicarbonitrile (see Figure 6).
terials (PP-ref: 100% polypropylene and samples taken at 450 °C (Figure 3) and This substance was only detected in the
PP-FR: 70% polypropylene, 20% flame 380 °C (Figure 5). Each peak in the two temperature range 300 to 380 °C and
retardant, 10% CaCO3). chromatograms corresponds to a dif- only for PP-FR. It is therefore a typical
ferent decomposition product; the most decomposition product of the flame re-
The two TGA curves were used to de- important decomposition products are tardant used.
fine the TGA temperatures at which gas labeled next to the peaks. At 450 °C, the
samples were collected in the IST16 (in decomposition products of PP-ref and FTIR measurements
Figure 7 shows the TGA curves of the two
samples together with their correspond-
Figure 6.
Decomposition ing Gram–Schmidt (GS) curves. A GS
product of PP-FR at curve displays the area under the FTIR
a retention time of spectra as a function of temperature and
18.747 min. Above:
the measured mass corresponds qualitatively to the DTG
spectrum. Below: curve. The GS curve is used to set the
the mass spectrum
temperatures at which the FTIR spectra
from the database
(best fit with the of the decomposition gases are exam-
measured mass ined in more detail (normally these are
spectrum) and the
result of the data-
the peak temperatures of the GS curve).
base search – The dashed vertical lines in Figure 7
the decomposition mark the temperatures at which we ana-
product is most
probably 1,3-ben-
lyzed the FTIR spectra more closely (see
zenedicarbonitrile. also Figures 9 and 10).

Figure 8 gives an overview of the mea-

sured FTIR spectra of the two materials.
It can be seen that the two “landscapes”
differ mainly due to a “hill” (red circle)
Figure 7. at about 2500 cm-1 that appears after
TGA and Gram– about 35 min (this corresponds to about
Schmidt curves for 380 °C).
PP-ref and PP-FR.
For a more detailed
analysis of the FTIR In agreement with the results from the
spectra measured
GC/MS analysis, the FTIR results also
at 460 °C and
380 °C, see Figures identified 2,4-dimethyl-1-heptene (a
9 and 10. typical decomposition product of poly-
propylene). The bands at 2950 cm-1 and
1400 cm-1 correspond to methyl groups
and the bands at 890 cm-1 to C–H defor-
mation vibrations in alkene groups. FTIR
analysis cannot therefore, for example,
easily distinguish between 5-methyl-
1-heptene (another typical decomposi-
tion product of polypropylene that was
identified by GC/MS measurements, see
Figure 3) and 2,4-dimethyl-1-heptene.

20 METTLER TOLEDO UserCom 52
 Figure 8.
Overview of the
FTIR spectra mea-
sured during the
TGA measurement.
The time axis cor-
responds to the
temperature.

Figure 9.
The spectra at 460 °C for PP-ref and PP-FR The diagram shows
differ only insignificantly from one an- the FTIR spectra for
PP-ref and PP-FR
other and show that mainly decomposi-
measured at 460 °C
tion of polypropylene occurs around this and the reference
temperature. spectrum of 2,4-
dimethyl-1-heptene
(best fit) from the
The situation is quite different at 380 °C: NIST/EPA database.
the FTIR spectra for PP-ref and PP-FR
differ considerably at this temperature
(see Figure 10). It can be seen that the
decomposition of PP-FR produces ammo-
nia and CO2 in addition to 2,4-dimethyl-
1-heptene. Ammonia is also a typical
decomposition product of the flame re-
tardant. The FTIR measurements also
confirm the result of the GC/MS analysis
namely that the initial decomposition of
PP-FR at lower temperatures is due to the
decomposition of the flame retardant. Figure 10.
The diagram shows
GC/MS and FTIR the FTIR spectra
for PP-ref and
The peak areas of the TIC peaks for the PP-FR at 380 °C
different decomposition products in the and reference
spectra from the
15 storage loops allow emission profiles
NIST/EPA database
to be created for each substance detected. for 2,4-dimethyl-
The FTIR spectra can be used to calculate 1-heptene, ammonia
and CO2.
temperature-dependent IR intensities in
selected frequency ranges and produce
so-called chemigrams. Figure 11 dis-
plays emission profiles for 2 substances
(1,3-benzenedicarbonitrile and 2,4-di-
methyl-1-heptene) and chemigrams cal-
culated for 3 different infrared frequency
ranges, 979–910 cm-1 (ammonia), 2440–
2120 cm-1 (CO2) and 3260–2640 cm -1
(C–H stretching vibrations). Also included

METTLER TOLEDO UserCom 52 21

Applications
Figure 11.
TGA curves together
with emission pro-
files (GC/MS) and
chemigrams (FTIR)
for several impor-
tant decomposition
products for PP-ref
(dotted curves) and
PP-FR (solid-line
curves).
22 METTLER TOLEDO UserCom 52
are the TGA curves for PP-ref (dotted
curve) and PP-FR (solid line curve).
The figure shows that the decomposi-
tion products characteristic for the de-
composition of polypropylene such as
2,4-dimethyl-1-heptene and alkenes
(characterized by the C–H stretching vi-
brations) occur at a higher temperature
for the flame-retarded material than for
the non-flame-retarded material. Be-
sides this, PP-FR displays decomposition
products between 280 and 400 °C (am-
monia, 1,3-benzenedicarbonitrile, CO2)
that are not related to the decomposition
of polypropylene but are produced by the
decomposition of the flame retardant.
Summary and conclusions
Two polypropylene samples with (PP-FR)
and without flame retardant (PP-ref)
were investigated by TGA/DSC-IST16/GC/
MS-FTIR [3]. More than 150 decomposi-
tion products were identified by GC/MS.
The results showed that the flame re-
tardant changed the decomposition be-
havior of the polymer. PP-FR begins to
decompose at a lower temperature than
PP-ref. The decomposition is however due
to the decomposition of the flame retar-
dant and not to the decomposition of the
polymer. This is shown by the fact that
decomposition products occur in this
temperature range (from about 280 to
about 400 °C) that cannot be related to
the decomposition of polypropylene (e.g.
ammonia, 1,3-benzenedicarbonitrile),
but are produced by the decomposition of
the flame retardant.
The intumescence behavior of the flame
retardant delays the actual decomposi-
tion of the polymer. This can be seen
by the curves for typical decomposition
products of polypropylene that were deter-
mined from GC/MS measurements (e.g.
2,4-dimethyl-1-heptene) or FTIR spec-
tra (e.g. chemigram between 3260 cm-1
and 2640 cm-1 (C–H stretching vibra-
tions, alkenes).
The advantage of the simultaneous cou-
pling of a TGA/DSC to an FTIR and an
IST/GC/MS system is that the FTIR can
detect substances that the GC/MS either
cannot detect, or only detect with more
difficulty (e.g. CO2, ammonia, water).
References
[1] N. Fedelich, Thermogravimetry and
gas analysis, Part 4: TGA-GC/MS,
UserCom 48, 1–7.
[2] NIST Standard Reference Database 1A,
NIST/EPA/NIH Mass Spectral Data-
base (NIST 11) and NIST Mass Spec-
tral Search Program (Version 2.0g).
[3] Evolved Gas Analysis, METTLER
TOLEDO Collected Applications Hand-
book, 2019, 144–150.
For more information:
www.mt.com/ta-ega
Determination of the constituents
of cement clinker by TGA
Dr. Angela Hammer

TGA is a simple technique that can be used to determine the content of individual constituents in a mixture
of different materials that do not influence one another. This is illustrated in the following example using a
sample from the cement industry.

Introduction Figure 1.
TGA and DTG
The content of minerals [1], for example curves of the
calcium carbonate in inorganic mix- decomposition
tures, can easily be determined by TGA of CaCO3.
[2] if their decomposition profiles dif-
fer. The following example shows how
the content of calcium carbonate, cal-
cium hydroxide, magnesium carbonate
and magnesium hydroxide in a sample
from the cement industry (cement clin-
ker: kiln-fired constituent of cement)
can be determined. Each pure substance
decomposes in a different temperature
range so their individual contents in a
mixture can be determined if the ma-
terials do not influence one another
during decomposition. The method was
checked by investigating a mixture with
known contents similar to those of the Table 1.
cement clinker. CaCO3 Ca(OH)2 MgCO3 ·xH20 Mg(OH)2 Overview of the
Moisture 30–200 °C 30–200 °C 30–150 °C 30–200 °C different decompo-
sition processes
Experimental details Dehydration 250–500 °C 150–300 °C and temperature
Samples of pure minerals (CaCO 3 ranges.
>99%, Ca(OH)2 >96%, MgCO 3 hydrate Dehydroxylation 500–750 °C 280–800 °C
(pharmaceutical secondary standard), Decarboxylation 600–800 °C 350–500 °C
Mg(OH)2 >99%) and an unknown mix-
ture were investigated by TGA/DSC be- Table 2.
Molar mass (g/mol) Factor Molar masses of
tween 30 and 1000 °C at a heating rate of the substances
CaCO3 100.0869 2.273
10 K/min in a nitrogen atmosphere. The investigated and
measurements were performed using Mg(OH)2 53.3197 2.96 the factors used
to determine the
sample weights of 10 to 50 mg in 70-µL Ca(OH)2 74.093 4.11 substances investi-
aluminum oxide crucibles. To check the gated in mixtures.
MgCO3 84.3139 1.916 The percentage
method, a mixture containing low con-
weight loss of the
tents of CaCO3 , Ca(OH)2 , Mg(OH)2 and CaO 56.0774
relevant decompo-
Al 2 O 3 as an inert matrix was blended MgO 40.3044 sition step is
multiplied by the
and measured using the same tempera- CO2 44.01 relevant factor.
ture program.
Ca 40.078
Measurements and results O 16
The pure substances were first measured H 1
to determine the temperature range in
Mg 24.305
which they decompose (Figures 1–4).

METTLER TOLEDO UserCom 52 23
 • CaCO3 shows a decomposition step
(decarboxylation) from CaCO3 to CaO
between 600 and 800 °C in addition
to the initial loss of moisture between
30 and 200 °C.
Applications

• Ca(OH)2 shows the dehydroxylation

of Ca(OH)2 to CaO and H2O between
500 and 750 °C after the loss
of moisture and dehydration up
to 500 °C.
• MgCO3 shows the loss of moisture
and dehydration up to about 300 °C
followed by the decarboxylation of
the MgCO3 to MgO and CO2 between
Figure 2.
TGA and DTG
350 and 500 °C.
curves of the • Mg(OH)2 shows the dehydroxylation
decomposition of Mg(OH)2 to MgO and H2O above
of Ca(OH)2.
about 280 °C after the initial
evaporation of moisture between
Figure 3.
TGA and DTG 30 and 200 °C.
curves of the
decomposition of The TGA decomposition curves of the
MgCO3 hydrate.
pure minerals are shown in Figures 1 to 4.
Table 1 presents an overview of the dif-
ferent processes (loss of moisture, dehy-
dration, dehydroxylation and decarbox-
ylation) and the temperature ranges in
which they occur.

Since each pure substance decomposes

in a different temperature range, the
individual contents in a mixture can
be determined if the materials do not
influence each other during decom-
position. We can therefore expect that
magnesium hydroxide first decomposes
followed by calcium hydroxide, magne-
Figure 4. sium carbonate and calcium carbonate.
TGA and DTG To determine the contents of substances
curves of the in an unknown mixture, we first deter-
decomposition
of Mg(OH)2. mine factors based on stoichiometry.
The content is then obtained by multi-
plying the factor by the percentage
step height.

This is explained using CaCO3 as an ex-

ample: The starting material CaCO3 has a
molar mass 100 g/mol; the decomposition
product CO2 a molar mass of 44 g/mol;
the residue CaO a molar mass of 56 g/mol.
Dividing 100 g/mol by 44 g/mol gives a
factor of 2.273 which is used to determine
the content of CaCO3 from the percentage
weight loss step. The molar masses and
factors are given in Table 2.

24 METTLER TOLEDO UserCom 52
Figures 5 and 6 show the TGA curves of Figure 5.
TGA and DTG curves
the cement clinker (Figure 5) and a mix- of the decomposi-
ture of known composition (Figure 6). tion of an unknown
The calculated content of cement clinker mixture (cement
clinker).
together with the contents of the known
mixture (by weight, and measured by
TGA) is summarized in Table 3. The re-
sults showed that the contents determined
for the known mixture agree well with the
amounts weighed in.

Conclusions
TGA is a simple technique that can be
used to determine the quantitative con-
tent of individual constituents in a mix-
ture of different materials that do not
influence one another. In the example de-
scribed, moisture, Mg(OH)2, Ca(OH)2 and
CaCO3 were identified and quantified in a
Figure 6.
sample of unknown composition. The ce- TGA and DTG curves
ment clinker was found to contain 0.3% of the decomposi-
moisture, 0.3% Mg(OH)2, 0.8% Ca(OH)2 tion of a mixture of
known composition.
and 0.2% CaCO 3 in addition to other
inorganic constituents (about 98.4%).
The method was checked by preparing
and analyzing a mixture containing
(known) small amounts of Mg(OH)2 ,
Ca(OH)2 and CaCO3.

The results showed that the contents de-

termined for the known mixture agree
well with the weighed-in sample amounts.
We conclude that the method is suitable
for determining constituents in mixtures
of unknown composition.

References
[1] Lehrbuch der anorganischen Chemie, Table 3.
Unknown mixture
Hollemann Wiberg, 80. Auflage, Substance Mixture with known contents Content of inorganic
Walther de Gruyter & CO., 1971,
(cement clinker) minerals in an
page 469. Weighed in Measured unknown mixture
[2] Barbara Lothenbach, Paxel Durdzinski, (cement clinker)
Klaartje De Weerdt, A Practical Moisture 0.3% 0.2% and in a mixture
Guide to Microstructural Analysis of containing known
Cementitious Materials, Chapter 5, Mg(OH)2 0.3% 1.2% 1.3% contents of
CRC Press. substances.
Ca(OH)2 0.8% 0.6% 0.4%
MgCO3 –
CaCO3 0.2% 1.3% 1.4%
For more information: Other inorganic
98.4% 96.9% 96.7%
www.mt.com/ta-tga constituents

METTLER TOLEDO UserCom 52 25
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Seminarios de TA: Aplicaciones de las técnicas TMA y DMA 23 de noviembre de 2021 On-line
Congresos: GEP-SLAP 2020-21 (www.gep-slap2020.eu) 9–13 de mayo de 2021 San Sebastián

Brasil Para maiores informações sobre os seminários, por gentileza entre em contato com: Mr. Pierre Delmorio, Tel: +55 11 98709-4688, e-mail: pierre.delmorio@mt.com
Seminários e
workshops de TA Análise Térmica Aplicada a Indústria Química Março, 2021 São Paulo
Introdução da Análise Térmica e suas principais aplicações Maio, 2021 São Paulo
Análise Térmica aplicada à Indústria Alimentícia Agosto, 2021 São Paulo

India For details of training courses and seminars, please contact: Pradeep Palshikar, Mettler-Toledo India Private Limited, Amar Hill, Saki Vihar Road, Powai, Mumbai 400 072
TA Customer Courses Tel: +91-22-28031 111 / 42910380 / 28031 380, Fax: +91-22-2857 5071, e-mail: pradeep.palshikar@mt.com
and Seminars Introduction to MT Thermal Analyzers / Focused Segments: All Each Month in 2021 Not specified
Thermal Analysis Tips and Hints / Focused Segments: All February 2021 Not specified
Innovative Applications of Thermal Analyzers to Pharmaceutical Industry / Focused Segments: Pharma May 2021 Not specified
Choosing the right crucibles for DSC and TGA analysis / Focused Segments: All August 2021 Not specified
Applications of Thermal Analyzers to Polymers / Focused Segments: MPE, Chemical (Polymer and Plastics) November 2021 Not specified

Malaysia For details of training courses and seminars, please contact: Ms. Lee Ching Huey, Mettler-Toledo (M) Sdn. Bhd, Unit 1-01, Lot 8, Jalan Astaka U8/84, Seksyen U8,
TA Customer Courses Bukit Jelutong, Shah Alam 40150 Selangor, Malaysia, Tel: (+603)-78445888, Fax: (+603)-78458773, e-mail: mtmymarketing@mt.com
and Seminars Good Thermal Analysis Practice – DSC (Central) March 16, 2021 MTMY Shah Alam
Good Thermal Analysis Practice – TGA (Central) June 15, 2021 MTMY Shah Alam
Good Thermal Analysis Practice – DSC and TGA (Northern) April 6, 2021 MTMY Penang
Good Thermal Analysis Practice – DSC and TGA (Southern) August 23, 2021 MTMY Johor

Singapore For details of training courses and seminars, please contact: Lim An Loon, Mettler-Toledo (S) Pte Ltd., 28 Ayer Rajah Crescent, #05 – 01, Singapore 139959
TA Customer Courses Tel: +65 68900011, Fax: +65-68900012, e-mail: gina.chan@mt.com
and Seminars TA School July 2021 MTSG

Thailand For details of training courses and seminars, please contact: Saowanij Kulthiwalert, Mettler-Toledo (Thailand) Limited, Tel: +66-2-7230338, Fax: +66-2-7196479
TA Customer Courses e-mail: saowanij.kulthiwalert@mt.com
and Seminars Advanced polymer applications October 4–8, 2021 Rayong and Center
Performance QC/Library software/LabX October 4–8, 2021 Rayong and Center
TGA – Evolved gas analysis October 4–8, 2021 Rayong and Center
Increased productivity by automation (Robot) October 4–8, 2021 Rayong and Center
Promote data integrity via TA products October 4–8, 2021 Rayong and Center
Flash DSC for Electronics segment October 4–8, 2021 Rayong and Center

Korea For details of training courses, workshop and seminars, please contact: Inyoung Kim at Mettler-Toledo Korea, Tel: ++82 2 3498 3535, e-mail: inyoung.kim@mt.com, www.mt.com
TA Customer Courses
and Seminars 열분석 Application Webinar 2021년 3월 온라인
열분석 School 2021년 5월 온라인 또는 오프라인
열분석 Application Webinar 2021년 6월 온라인
열분석 Application Webinar 2021년 9월 온라인
열분석 School 2021년 11월 온라인 또는 오프라인
열분석 Application Webinar 2021년 12월 온라인

METTLER TOLEDO UserCom 52 27
 China For details of training courses and seminars, please contact: Nicole Dong at Mettler-Toledo Instruments (Shanghai) Co. Ltd.
TA Customer Tel: ++86 21 6485 0435, Fax: ++86 21 6485 3351, e-mail: huicong.dong@mt.com
Courses and TA Course (热分析用户培训) 2021/01/15–2021/01/16 Live broadcast
Seminars
TA Course (热分析用户培训) 2021/03/17–2021/03/20 Beijing + Live broadcast
TA Course (热分析用户培训) 2021/04/14–2021/04/17 Guangzhou+ Live broadcast
TA Course (热分析用户培训) 2021/05/14–2021/05/15 Chengdu + Live broadcast
TA Course (热分析用户培训) 2021/06/16–2021/06/19 Shanghai + Live broadcast
TA Course (热分析用户培训) 2021/09/15–2021/09/18 Beijing+ Live broadcast
TA Course (热分析用户培训) 2021/10/13–2021/10/16 Guangzhou+ Live broadcast
TA Course (热分析用户培训) 2021/11/17–2021/11/20 Shanghai+ Live broadcast
TA Course (热分析高级用户培训) 2021/12/17–2021/12/18 Shanghai
TA Webinar (在线研讨会) 2021/01/20 Live broadcast
TA Webinar (在线研讨会) 2021/03/10 Live broadcast
TA Webinar (在线研讨会) 2021/04/07 Live broadcast
TA Webinar (在线研讨会) 2021/05/21 Live broadcast
TA Webinar (在线研讨会) 2021/06/22 Live broadcast
TA Webinar (在线研讨会) 2021/07/16 Live broadcast
TA Webinar (在线研讨会) 2021/07/23 Live broadcast
TA Webinar (在线研讨会) 2021/09/22 Live broadcast
TA Webinar (在线研讨会) 2021/10/20 Live broadcast
TA Webinar (在线研讨会) 2021/11/24 Live broadcast

Local TA Customer Courses:

UK: Call: 0116 235 7070, e-mail: enquire.mtuk@mt.com
Schweiz und Österreich: Frau Janine Schindler, Tel: +49 641 507 405, e-mail: labtalk@mt.com
Netherlands: Bart Baggen, Tel: ++31 344 63 83 63, e-mail: bart.baggen@mt.com
Belgium: Philippe Larbanois, Tel: ++32 2 334 02 11, e-mail: philippe.larbanois@mt.com
Slovenia: Keith Racman, Tel: +386 1 547 4900, e-mail: keith.racman@mt.com
Türkiye: İstanbul, Tel: +90 216 400 20 20, e-mail: onur.cebeci@mt.com, nurdan.tarakci@mt.com
České republice a Slovensku: Michaela Veberová, Tel: +420 226 808 153, e-mail: michaela.veberova@mt.com
Polska: Piotr Witukiewicz lub Grazyna Czaplicka, Tel: +48 22 440 67 00
Россия: Егор Филатов, тел.: +7 495 777 07 77вн. 81-83, e-mail: egor.filatov@mt.com
Sweden, Norway and Denmark: Sebastian Östlund, Tel: +46 7245 392 32, e-mail: sebastian.ostlund@mt.com
Finland: Oy G. W. Berg & Co Ab, Tel: +358 201 255 255, e-mail: gwb@gwb.fi
Latin America: Francesc Català, Tel: ++34-932 237 615 (Spain), e-mail: francesc.catala@mt.com
Japan: ラボインスツルメンツ事業部, Tel: 03-5815-5515, e-mail: marcom.jp@mt.com
Taiwan: Karen Chen at Mettler-Toledo Taiwan, Tel: +886-2-26578898 p102, Fax: +886-2-26570776, e-mail: karen.chen@mt.com
USA and Canada: Danielle Kimmel, Tel: +1 614-438-4851, e-mail: danielle.kimmel@mt.com
México: Erik Alba, Tel: +52 1946 2827, ext: 522827, e-mail: erik.alba@mt.com
Australia and New Zealand: Kai Robinson, Tel: +61 455 068 037, e-mail: kai.robinson@mt.com

For further information regarding meetings, products or applications, please contact your local
METTLER TOLEDO representative and visit our Website www.mt.com

Editorial Team

Dr. A. Hammer Dr. D. P. May Dr. R. Riesen Dr. J. Schawe Dr. V. Chaudhary Dr. S. Domann S. Dandekar Dr. T. Oberholzer Dr. G. Raihani U. Jörimann
Chemist Chemist Chem. Engineer Physicist Polymer Engineer Journ. and Chem. Physical Chemist Biochemist Biologist Electr. Engineer

N. Fedelich Dr. E. Hempel Dr. M. Wagner Dr. M. Schubnell Dr. A. Bach Dr. S. Kakade N. Jing Dr. T. Dennenwaldt Dr. M. Reber Dr. J. Chee
Chem. Engineer Physicist Chemist Physicist Chemist Chemist Chemist Chemist Chemist Chemist

METTLER TOLEDO Group

Analytical Division
Local contact: www.mt.com/contacts www.mt.com/ta
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