39

Thermal Analysis User

Information for Users
Com

Dear Customer, Contents 1/ 2014

This year, we celebrate two milestone anniversaries, namely 50 years of METTLER TOLEDO thermal analysis TA Tip
and 20 years of UserCom. With this in mind, we are delighted to announce a new STARe software version and - Curve interpretation, Part 2:
three new instruments. Details can be found in the News section. We are convinced that thermal analysis Variation of heating and cooling rates 1
will continue to play an important role in the testing, characterization and development of materials, and in News
research. As in the past, new technologies will lead to new innovations and open up new application areas, in
- STARe System enhancements 8
the same way as we have recently seen with the Flash DSC 1.
- The TGA-IST-GC/MS system –
In the twentieth year of UserCom, we hope that we can once again surprise you with interesting application unprecedented detailed insight 10
examples and look forward to your comments and feedback.
- 50 years of innovation in
thermal analysis 11
- Cooling with the latest instruments
from Huber 13
- Quantos HPD – A clever handheld
Curve interpretation, Part 2: solution for powder dosing 15
Applications
Variation of heating and cooling rates - Measurement of vapor pressure
curves and the enthalpy of
vaporization of liquids by HPDSC 16
Dr. Jürgen Schawe
- Composition of water-in-oil
ammonium nitrate emulsions
using TGA and DSC 18
In practice, heating measurements are frequently performed at just one heating rate. The - Thermomechanical analysis of
properties of many substances and materials however depend on their production and natural and cosmetically treated hair 22
storage conditions. In such cases, important additional information can be obtained by - Determination of heat capacity by
simply varying the heating and cooling rates. These possibilities are illustrated with the temperature-modulated DSC at
aid of typical examples. temperatures above 700 °C 24
Dates
- Exhibitions 26
- Courses and Seminars 27
 Introduction
Thermal analysis methods are now well
established as standard analytical meth-
ods in industry and research because
they provide comprehensive and reli-
TA Tip
able information about a material or a
substance in a relatively short time. The
full potential of these methods is often
not fully realized because the analysis
is based on measurements at one single
heating rate. For example, in differen-
tial scanning calorimetry (DSC) this is
10 K/min.
This series of articles describes analyti-
cal approaches that greatly expand the
information obtainable from thermal
analysis measurement curves and that
improve the quality of the evaluation and
interpretation.
In Part 1 [1] we showed how further in-
formation about the sample can be ob-
tained by varying experimental condi-
tions such as the temperature range or
the atmosphere. In this article, Part 2, we
discuss the additional information that
can be gained by varying heating and
cooling rates.
Here, we will concentrate mainly on
conventional DSC, temperature-modu-
lated DSC (TMDSC) and fast DSC (Flash
DSC). The analysis of reaction kinetics is
demonstrated using thermogravimetric
(TGA) measurements.
Variation of the cooling
rate between two heating
measurements
If a substance forms metastable struc-
tures, for example polymorphic phases,
information about the structures in-
volved can be obtained by varying the
cooling rate between heating measure-
ments. On cooling from the melt, crystal-
lization or partial crystallization often
occurs.
At high cooling rates, the crystallization
process shifts to lower temperatures. Dif-
ferent structures can then be formed that
differ in their stability. At a sufficiently
high cooling rate, vitrification (glass for-
mation) may also occur.
2 METTLER TOLEDO UserCom 39
The sample can be cooled externally or
in the instrument. The cooling rate can
be controlled or the sample can be al-
lowed to cool freely in contact with a cold
medium.
Rapid ballistic cooling
By ballistic cooling, we mean the free
cooling of a sample when it is quickly
transferred from a hotter (at temperature
T1) to a cooler environment (at tempera-
ture T2).
The cooling rate is not constant but is
proportional to the difference between
the temperature of the sample and that
of the environment and to the heat ca-
pacity of the sample being cooled. In
conventional DSC measurements, three
main types of ballistic cooling are used:
1. Cooling from a higher temperature to
room temperature: The sample is rap-
idly removed from the hot DSC furnace
and placed on a metal plate at room
temperature. This occurs automati-
cally if the sample is removed from the
DSC furnace by the sample robot at the
end of the measurement.
2. Cooling from room temperature to a
lower temperature: The sample is in-
serted into the DSC furnace that has
been cooled to T2. This can also be
done by the sample robot.
3. Cooling from above room temperature
to below room temperature: The sam-
ple is heated to T1 on a heating plate
near the DSC and then quickly insert-
ed into the precooled DSC furnace.
In the following sections, an example
of each of the first two types will be dis-
cussed.
Influence of the cooling rate on the
formation of a polymorphic sub-
stance (sulfapyridine)
The red curve in Figure 1 displays the
first heating run of a sample of sulfa-
pyridine. The blue curve was measured
at 10 K/min after cooling from the melt
at 220 °C.
In this second heating run, the melting
peak appears at a slightly lower tempera-
ture and is somewhat broader.
The original sample measured in the
first heating run was crystallized from
solution, which led to the formation of
crystals of the most stable form. Before
the second heating run, the sample crys-
tallized from the melt on cooling. In this
case, a crystal modification formed that
melted at a lower melting temperature.
Before the third measurement (green
curve), the sample was cooled ballisti-
cally from 210  °C to room tempera-
ture. It was removed from the hot DSC
furnace by the automatic sample robot
and placed on the sample turntable. The
measurement curve shows that the cool-
ing rate was so high that the sample had
no time to crystallize during the cooling
process but solidified to a glass (vitri-
fied). The glass transition can be seen at
about 60 °C.
On further heating, an exothermic crys-
tallization peak occurs between 90 and
110 °C. The sample crystallizes with a
degree of supercooling of about 100 K.
The crystalline phase that forms is not
very stable and therefore melts at a rela-
tively low temperature. On further heat-
ing, reorganization takes place. Above
160 °C, three melting peaks are observed;
three mesophases of different stability
have been produced.
The formation and reorganization of
mesophases in polymorphic substances
can therefore be studied by varying the
cooling rate.
Influence of the cooling rate on the
structure formation of a metastable
mixture (sucrose and water)
Many mixtures form different solid
phases depending on the cooling rate.
Examples of major practical importance
are mixtures of carbohydrates and water.
In this example, we examine the sucrose-
water system. In thermodynamic equilib-
rium, it is a eutectic system.
This means that both constituents are
ideally miscible in the liquid phase and
immiscible in the solid phase. Hydrogen
bonding, however, takes place between
the sugar and the water molecules and Figure 1.
DSC heating curves
leads to metastable associations of sugar of sulfapyridine.
and water. Since these associations do Red: first heating
not crystallize but vitrify, the mixture run.
Blue: measured
forms metastable structures that depend after cooling at
on the cooling rate. 10 K/min.
Green: measured
after rapid cooling.
A detailed study of this particular sys-
tem is given in reference [2]. Here, we
restrict ourselves to the measurement of
a mixture with a sucrose mass fraction
of 0.664. The sample was cooled rapidly
(ballistically) and at 2 K/min.

In the ballistic cooling experiment, the

sample was inserted at room tempera-
ture into the DSC furnace that had been
cooled to –100 °C using the sample ro-
bot. The heating measurements were
Figure 2.
then performed up to 30 °C at 5 K/min DSC heating curves
(Figure 2). of a sucrose-water
mixture measured
after cooling at dif-
The curve measured after rapid cooling ferent rates.
(blue) exhibits a glass transition at about
–75 °C. Free water of the sample, which
is then liquid, crystallizes between –40
and –25 °C. The ice melts immediately
afterward. The curve measured after slow
cooling (red) shows a glass transition
at –45 °C followed by a melting process
from about –30 °C onward.

The reason for the different behavior of

the sample after slow and rapid cooling is
the interaction between the water and the
carbohydrate molecules. On rapid cool-
ing, there is not enough time for separa-
tion into different phases. The original
homogeneous solution supercools with-
out crystallization and forms a homoge-
neous glass.
The glass transition temperature of this
glass depends on its composition. With
higher water concentrations, it decreases.
In this example, this glass transition
temperature is at –75 °C (blue curve in
Figure 2). On further heating, ice crystals
are formed that melt immediately after-
ward.
At a cooling rate of 2 K/min, ice already
forms on cooling. This lowers the con-
centration of water in the liquid water-
sucrose mixture. However, the entire
amount of water cannot crystallize to
ice because of the hydrogen bonding
between the carbohydrate and water
molecules (association). A mixture of a
glassy water-sucrose association and ice
is formed. The glass transition tempera-
ture of the association depends on its wa-
ter content.
The red curve in Figure 2 shows that this
is at about –45 °C. On further heating,
the ice crystals formed on slow cooling
then melt.
Cooling with defined variation
of the cooling rate
The cooling rate can also be varied in
a defined way, depending on the cool-
ing possibilities of the instrument used.
This enables you to obtain further in-
formation on the kinetics of phase for-
mation. Conventional DSC instruments
allow cooling rates in the range 0.01 to
100 K/min. This is adequate for relatively
slow structure formation.
However, much higher rates occur in
many technical processes. Further-
more, in many materials the processes
of structure formation are also much
faster so that cooling rates of several
hundred K/min are not fast enough for
systematic investigations.
In particular, you also have to take into
account the fact that the kinetics of pro-

METTLER TOLEDO UserCom 39 3
 cesses frequently follow exponential laws
so that the corresponding cooling rates
must be varied by orders of magnitude
(several decades).
TA Tip
The Flash DSC 1 was developed [3–5]
to investigate the kinetics of structure
formation in cases like this. The instru-
ment offers cooling rates from several
Kelvin per minute to several thousand
per second. By combining results from
the DSC 1 and the Flash DSC 1, the cool-
ing rate can effectively be varied by more
than seven orders of magnitude.
Isotactic polypropylene (iPP) is a poly-
mer that crystallizes relatively rapidly
but remains amorphous at cooling rates
from about 1000 K/s onward [5, 6].
Figure  3 shows two heating curves of
iPP samples that were measured with
the Flash DSC 1. The heating rate was
1000 K/s. Before the two heating runs,
the sample was cooled from the melt at
200 °C down to –80 °C at 1000 K/s (blue
curve) and at 10 K/s (red curve).
The blue curve shows that after cooling
at 1000 K/s, the sample is amorphous.
The glass transition is observed as a step
at about 0 °C. At 40 °C, the sample crys-
tallizes. Because of the large degree of
supercooling, the so-called mesophase is
formed [7]. The small endothermic peak
at 90 °C is due to the melting of the me-
sophase.
Figure 3.
Flash DSC heating
curves of isotactic
polypropylene (iPP)
measured after
cooling at 1000 K/s
and 10 K/s. Heating
rate: 1000 K/s.
4 METTLER TOLEDO UserCom 39
After this, recrystallization to the mono-
tropic α-form (110 °C) occurs; this then
melts at 130 °C. Comparison of the melt-
ing and crystallization enthalpies shows
that the sample was amorphous before
the heating measurement (the sum of the
melting and crystallization enthalpies is
practically zero).
After cooling at 10 K/s (red curve), the
sample is semicrystalline. Compared
with the blue curve, the glass transition
is shifted to a slightly higher temperature
and has a smaller step height.
Crystallization and reorganization do
not occur on heating. The melting peak
is shifted to higher temperature (145 °C).
Compared with the previous case, the
crystallites that melt are more perfect.
Variation of the heating rate
after defined cooling
Reorganization on heating
The reorganization of a sample on heat-
ing depends on the heating rate and on
the structure of the original sample.
A defined structure can be obtained by
choosing a particular cooling rate. The
kinetics of reorganization can then be
investigated by varying the heating rate.
This is illustrated in Figure 4, which
displays DSC measurements of sulfapyri-
dine. The curves were measured at two
different heating rates and have been
normalized with respect to mass and
heating rate for better comparison.
The samples were cooled ballistically be-
fore the measurement by melting them
in the DSC and removing them from the
DSC furnace using the sample robot. The
sample was then amorphous. The heat-
ing runs were performed at 5 K/min (red
curve) and 10 K/min (blue curve).
The curves were normalized with respect
to sample mass and heating rate for bet-
ter comparison. The crystallization peaks
show that the crystallization temperature
increases with higher heating rates.
In the melting range 165 to 200  °C,
several different polymorphic forms are
observed. The less stable forms melt at
lower temperatures. The variation in
relative peak size is due to the different
proportions of monotropic phases in the
sample and the different reorganization
processes that occur during heating.
In the heating curve at 5 K/min at about
183 °C, you can see the exothermic re-
crystallization to the next stable phase.
The melting peak of the most stable mea-
sured form at 193 °C is larger in the sam-
ple heated at 5 K/min than in the mea-
surement performed at 10 K/min. At the
higher heating rate, the sample had less
time to form this modification through
reorganization.
Reorganization during a DSC measure-
ment is also known in polymers. This
is illustrated in Figure 5, which displays
Flash DSC measurements of PET 5 [3, 8].
Before each measurement, the amor-
phous sample was crystallized at 140 °C
for 10 min and then measured at various
heating rates.
Two peaks are clearly visible in the curve
at the relatively low heating rate of
50 K/s. At higher heating rates, the low
temperature peak shifts to higher tem-
perature and the high temperature peak
to lower temperatures.
At 1000 K/s, the two peaks coincide with
one another. The low temperature peak
is caused by the melting of the crystals Figure 4.
DSC heating curves
formed during the isothermal crystalli- of amorphous
zation process. Its slight shift to higher sulfapyridine mea-
temperature is a result of the time lag sured at 5 K/min
and 10 K/min.
due to thermal conductivity.

The crystallites that cause the second

peak were formed through reorganization
on heating. The lower the heating rate,
the more time there is for their formation.

The result is that the crystals formed

at the lowest heating rate are the most
perfect and therefore melt at the high-
est temperature. The measurements show
that the sample must be heated at least at
1000 K/s to suppress reorganization dur-
ing the measurement. Only then does the
melting behavior represent the structure
Figure 5.
of the original sample. The Flash DSC is Flash DSC curves
essential for measurements like this. of a sample of
PET measured at
different heating
Reaction kinetics rates. The sample
The kinetics of chemical reactions can was crystallized at
140 °C for 10 min-
also be investigated by evaluating mea- utes beforehand.
surements performed at different heating
rates.

A fresh sample is needed for each heat-

ing run. Figure 6 summarizes the evalu-
ation of the kinetics of decomposition of
polystyrene by TGA. The TGA curves were
measured at heating rates of 2, 5 and
10 K/min.

The reaction is shifted to higher temper-

ature at higher heating rates. This shift
provides the data we need to determine
the reaction kinetics. The evaluation was
performed using the Model Free Kinetics
software (MFK) [9]. One important re-
sult is the apparent activation energy as a
function of conversion.
This curve allows you to obtain informa-
tion about the kinetics of the reaction and
to make predictions about the course of
the reaction under different conditions.
The curves in the bottom right diagram
in Figure 6 show predictions for the
course of the isothermal reaction at 325,
350 and 375 °C. Results like this can be
used to compare the thermal stability of
different materials.
Temperature-modulated DSC
Temperature-modulated DSC (TMDSC)
is the name for a group of techniques in
which a conventional temperature pro-
gram (consisting of heating, cooling or
isothermal segments) is overlaid with a
small modulation function.
The modulation function can be a tem-
perature step (IsoStep [10]), sinusoidal
temperature changes (ADSC [11]), or
stochastic temperature fluctuations
(TOPEM® [12, 13]).
In a TMDSC heating experiment, the
actual heating rate changes while the
mean heating rate remains constant.
These techniques allow the heat flow to
be separated into several different com-
ponents:
• The total heat flow corresponds to the
heat flow caused by the mean heating
rate. This heat flow component corre-
sponds to the conventional DSC curve.
• The reversing heat flow is caused by
the temperature modulation. This
component corresponds to the heat
flow caused by external temperature
changes due to the modulation func-
tion. It has to do with heat capacity
contributions.
• The non-reversing heat flow does not
follow the temperature modulation.
This component is due to internal
processes in the sample, for example

METTLER TOLEDO UserCom 39 5
 chemical reactions and crystallization
processes.
TOPEM® differs from other two modula-
tion techniques in several respects:
TA Tip
• It is more robust because the modula-
tion function does not require a par-
ticular form.
• The heat flow components are better
and more exactly separated due to the
patented evaluation procedure.
• It is a multi-frequency analysis in
which the heat flows can be assigned
to quasi-static conditions. The fre-
quency dependence of the thermal
events can then be determined in the
same measurement.
Modulated DSC measurements are fre-
quently used to investigate postcuring re-
actions. In these reactions, a material is
partially cured in a production process or
through its thermal history. Generally, the
glass transition temperature of the mate-
rial has increased to such an extent that it
lies above the ambient temperature.
The reaction rate then decreases drasti-
cally due to restricted molecular mobility
[14]. When the material is heated again
and the glass transition temperature is
reached and exceeded, molecular mobil-
ity increases and the postcuring reaction
begins. Very often, the step of the glass
transition and the reaction peak overlap
and the two events cannot be properly
evaluated.
Figure 6.
Evaluation of the ki-
netics of decompo-
sition of polystyrene
from TGA heating
curves.
6 METTLER TOLEDO UserCom 39
This is illustrated in Figure  7, which
displays curves obtained from a typical
TOPEM® measurement. The total heat
flow curve (red) corresponds to a conven-
tional DSC curve. Evaluation of the reac-
tion peak yields an apparent enthalpy of
reaction of 10 J/g. There is no indication
of a glass transition.
The glass transition can however be seen
as a step in the reversing heat flow curve
(green) with a midpoint at 100.4 °C. The
non-reversing heat flow curve (blue)
shows the (separated) reaction peak with
the true enthalpy of reaction of 16 J/g.
Comparison of the measurement curves
shows that the conventional DSC mea-
surement (total heat flow curve) does not
exhibit a glass transition and that the en-
thalpy of reaction determined is wrong by
more than 50%.
Furthermore, comparison of the revers-
ing and non-reversing heat flow curves
indicates that the postcuring reaction
starts at the beginning of the glass tran-
sition. In this case, a minimum of mobil-
ity is sufficient to initiate the postcuring
reaction.
A further consequence of this is that
measurements cannot be performed at
low underlying heating rates because
the glass transition temperature shifts
to higher temperatures during the mea-
surement. Preliminary experiments
at underlying heating rates of 1, 2 and
5 K/min showed that the glass transition
temperature was always at about 140 °C,
which is the glass transition temperature
of the fully cured material.
For this reason, the measurement had to
be performed at a heating rate of 10 K/
min. This heating rate is relatively high
for a TMDSC measurement if the purpose
is to correctly measure quantitative val-
ues such as the enthalpy of reaction. It
is also difficult to achieve with the other
modulation methods The robustness of
the TOPEM® technique allows heating
rates of up to about 25 K/min to be used
to measure such reactions.
TMDSC techniques can be used to ob-
tain additional information about ki-
netic processes in samples by varying the
modulation function (e.g. amplitude or
frequency).
Other methods
Many thermal effects of samples can be
identified and evaluated by varying the
measurement conditions as described so
far in this article and in Part 1 of this se-
ries. In practice, many more variations
are used.
These include:
1. Varying the gas exchange between
sample and the environment:
This is always successful in applica-
tions in which gaseous components have
a significant effect on the behavior of
the sample. The simplest method is to
change the gas exchange by means of the
crucible lid.
In the DSC, the standard 40-µL crucible
can be hermetically sealed or a defined
gas exchange can be established by
means of a hole in the lid. There are sev-
eral possibilities to accomplish this, such
as:
• by using a hermetically sealed lid,
• using a lid with a defined 50-μm hole,
• piercing the lid with a thin needle
(0.35 mm),
• piercing the lid with a thick needle
(about 1 mm),
• no lid.
These possibilities allow the partial pres-
sure over the sample to be varied. This
shifts the temperature of vaporization
of volatile components such as water or
plasticizers. Besides this, the kinetics of
chemical reactions can also be signifi-
cantly influenced.
2. The crucible and sample can react
with each other or the crucible material
can act as a catalyst in the reaction of
a sample. The use of a different crucible
can lead to additional information.
3. The pressure exerted on the sample
can be increased through the use of her-
metically sealed crucibles, and medium
pressure or high pressure crucibles. The
pressure can be varied and set to defined
values in the high-pressure DSC (HP
DSC1).
This allows reactions in which gaseous
constituents play an important role to be
investigated under different conditions.
Samples can be exposed to different con-
centrations of reactive gases (e.g. oxy-
gen) or gases that act as plasticizers (e.g.
carbon dioxide) by varying the gas pres-
sure. This allows their effect on thermal
events to be investigated.
Conclusions
In practice, the thermal analysis meth-
ods are frequently used for just one single
heating measurement.
The information content of such mea-
surements, the reliability of the inter-
pretation and not least the accuracy of
the measurement result can, however, be
greatly increased by using a series of dif-
ferent heating and cooling cycles and an
intelligent variation of the experimental
conditions. This prevents errors and saves
time for the analysis.
References
[1] J. Schawe, Curve interpretation,
Part 1 : Variation of experimental
conditions, UserCom 28, 1 – 7.
[2] J.E.K. Schawe, A quantitative DSC
analysis of the metastable phase be-
havior of the sucrose-water system,
Thermochemica Acta, 451 ( 2006 )
115 – 125.
[3] J. Schawe, The revolutionary new
Flash DSC 1 : Optimum performance
for metastable materials, UserCom
32, 12 – 16.
[4] J. Schawe, Practical aspects of the
Flash DSC1 : Sample preparation
for measurements of polymers,
UserCom 36, 17 – 24.
[5] J.E.K. Schawe, Influence of proces-
sing conditions on polymer crystal-
lization measured by fast scanning
DSC, J. Therm. Anal. Calorim.
DOI 10.  1007 / s10973 - 013 - 3563 - 8.
[6] F. De Santis, S. Adamovsky, G.
Titomanlio, C. Schick, Scanning
Nanocalorimetry at High Cooling
Rate of Isotactic Polypropylene, Mac-
romolecules 39 ( 2006 ) 2562 - 2567.
[7] D. Mileva, R. Androsch, E. Zhuravlev,
C. Schick, The temperature of melting
of the mesophase of isotactic poly-
propylene, Macromolecules
42 ( 2009 ) 7275 - 7278.
[8] J. Schawe, D. Neff, Kunststoffanalytik
für Materialien der Zukunft, Plastver-
arbeiter 09 ( 2011 ) 70 – 72.
Figure 7.
A postcuring reac-
tion measured
by TOPEM® at an
underlying heating
rate of 10 K/min.
[9] Tips on model free kinetics,
UserCom 8, 1 – 3.
[10] IsoStep, UserCom 15, 8.
[11] S. Montserrat, F. Roman, P. Colomer,
Investigation of the cold crystallizati-
on and melting of amorphous linear
polymers by ADSC, UserCom 16
( 2002 ) 13 – 15.
[12] J. E. K. Schawe, T. Hütter, C. Heitz, I.
Alig, D. Lellinger, Stochastic tempe-
rature modulation : A new technique
in temperature-modulated DSC,
Thermochimica Acta, 446 ( 2006 )
147 – 155.
[13] TOPEM ® – The new multi-frequency
temperature-modulated technique,
UserCom 22, 6 – 8.
[14] J. Schawe, Kinetic studies of complex
reactions. Part 1 : model free kinetics,
UserCom 18, 13 – 16.
METTLER TOLEDO UserCom 39 7
 STARe System enhancements

STARe Software Version 13.0 • The graphical user interface with TGA/DSC 2
News

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ports all previous and new METTLER • Almost any programmable complex The TGA/DSC 2 incorporates the latest
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Some licensed functions such as the cre- • Stress-Strain experiments and creep proved even more.
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using Relative Loop and the subtraction • Standard-compliant sapphire method The TGA/DSC 2 is a top-of-the-line in-
of straight lines are now available free of for the accurate determination of ex- strument. Besides the TGA signal, a qual-
charge for all users. pansion coefficients at high tempera- itatively first-class DSC signal is available
tures (ASTM E2113) that simultaneously measures effects
New features Besides these new functions, a number that do not exhibit a weight loss.
at a glance: of other improvements have also been
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TMA/SDTA 1 strate the new software. at a glance:
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temperature to 1600 °C
STARe V13.00 Installation Method Experiment Evaluation • Modular design allows later conver-
Main Menu bar Window Window Window Window sion to a fully automated system
• Very wide measurement range of 5 g
with a resolution of 0.1 µg over the
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Figure 1. • Application-specific sensors for the
STARe software with DSC sensor with the proven Multi-
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Figure 2. DSC 2
View of the new fur- We are delighted to announce the DSC 2, TMA/SDTA 1
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The most important features and the number of instrument versions
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• Robust ceramic sensor with the • Room temperature to 1600 °C
unique MultiSTAR® multiple thermo- • The frictionless parallel guidance sys-
couple arrangement tem of the probe allows measurements
to be performed in the nanometer

8 METTLER TOLEDO UserCom 39
 range with almost zero force and with New DSC and TGA crucibles Figure 4.
New high-temper-
amazing resolution. This allows the We have added four new types of crucible ature TMA/SDTA 1
smallest expansion coefficients to be to our already very comprehensive range with the ceramic
measured with great accuracy. of crucibles. You can always use the op- and sapphire sup-
port and probe.
timum crucible with regard to material,
The most important features volume, signal resolution, and sealing for
at a glance: your particular measurement.
• Wide temperature range from –150 to
1600 °C The current range of crucibles can be
• Wide measurement range of ±5 mm found at:
with constant resolution in the nano- www.mt.com/ta-crucibles
meter region
• Simultaneous SDTA measurement, Figure 5.
which also measures thermal effects The new 600-µL
aluminum oxide
that do not exhibit a change in length crucible.

The new crucibles at a glance:

Order number Description Instrument Advantages
300 858 50 25 µL, aluminum, DSC (TGA) Improves enthalpy
100 pieces reproducibility
300 771 39 High-pressure cruci- DSC High-pressure cru-
ble 25 µL, steel/gold, cible with smaller
25 pieces signal time constant
(better temperature
resolution)
300 772 60 600 µL, aluminum TGA Large and particularly
oxide, 4 pieces tight crucible, suitable
for metal melts
300 772 66 Special lid for the TGA Lid that the sample
600-µL crucible, robot can remove be-
40 pieces fore the measurement
51 140 845 70 µL, PCA/sapphire, TGA (DSC) Absolutely tight cru-
4 pieces cible made of poly-
crystalline aluminum
oxide with properties
similar to those of
sapphire

TA News at a glance:
For further details see:
www.mt.com/ta-news

METTLER TOLEDO UserCom 39 9
 The TGA-IST-GC/MS system –
unprecedented detailed insight
News
Thermogravimetric analysis combined
with gas chromatography and mass
spectrometry (TGA-GC/MS) is nowadays
the preferred method for qualitative and
quantitative evolved gas analysis, EGA.
This combination of methods allows
thermal effects to be correlated with in-
formation about the molecular nature,
structure and composition of materials.
METTLER TOLEDO now goes a step fur-
ther by announcing the availability of
the new IST16, a 16-channel storage in-
terface that allows 16 gas samples from
a single TGA measurement to be stored.
Figure 1. The complete TGA-IST-GC/MS system.
10 METTLER TOLEDO UserCom 39
Later on, the gas samples can be indi-
vidually analyzed and evaluated, which
enables the decomposition gases to be
uniquely assigned to individual TGA
steps.
Features and benefits of the
METTLER TOLEDO TGA-GC/MS
• Gas analysis by GC/MS – Determina-
tion of the molecular composition
and information about the molecular
structure of the sample
• IST16 interface with 16 storage loops
– allows a single TGA measurement
to be divided into a maximum of
16 separate GC/MS experiments
• Independent TGA- and GC/MS ex-
periments – GC/MS analysis does
not require the TGA experiment to be
interrupted and thus saves time
The IST16 Storage Interface
The unique IST16 Storage Interface can
be operated in several different modes:
• Storage mode
The IST16 allows the user to collect 16
gas samples from the TGA at freely se-
lectable times for subsequent GC/MS
analysis. The stored gas samples are then
automatically sequentially analyzed by
GC/MS. Each stored gas sample can be
analyzed differently.
• Continuous mode (with or without
IST16)
In the continuous mode, only one storage
loop is used. Gas samples are collected
from the TGA at defined time intervals
and transferred to the GC injector. This
can lead to mixing of the currently in-
jected gas sample with the previous gas
sample.
Besides the GC/MS solution, we also offer
our existing TGA combinations with MS
and FTIR.
50 years of innovation in thermal analysis

This year, we are proud to celebrate 50 years of thermal analysis from METTLER TOLEDO. What started in
1964 with the introduction of the TA 1 instrument has developed into a comprehensive and very attractive
portfolio of products. Important concepts such as modularity, high performance, and Swiss quality have
been retained.

The beginning Figure 1.

The TA 1 thermal
of thermal analysis analysis system.
Let’s start at the beginning: In the early
1960s, 15 years after Dr. Erhard Mettler
founded the Mettler company, Mettler
had already earned an excellent reputa-
tion for analytical balances in laborato-
ries. The introduction of the substitution
balance helped the young company enjoy
a period of rapid growth.

Dr. Mettler, decided the time was ripe to

expand his business and initiated the de-
velopment of thermal analysis products
in the company. He engaged Dr. H-G. Wi-
edemann, an East German scientist, to
develop the thermal analysis instrument
line.
In 1964, this led to the introduction of
the first commercially available high-
performance TGA/DTA research instru-
ment, the TA 1.
The introduction of thermal analysis re-
sulted in the very successful, present-day
analytical instrument part of the com-
pany.
A key component of the TA 1 was an
electrically compensated substitution
balance: This allowed the measurement
errors common in other balance technol-
ogies used at the time to be eliminated.
Besides this, the TA 1 had other unique
features:
• Seven different furnaces, from a low
temperature furnace, a furnace for
vapor atmospheres, through to a
high-temperature furnace capable of
2400 °C,
• Six different sensors for the simulta-
neous measurement of a DTA signal,
• Integrated high-vacuum system and
• Comprehensive accessories with dif-
ferent crucibles made of different
materials.
Technical bulletins describing interest- Figure 2.
TA 1 and TA 2
ing applications were already available. sensors.
The 1960s saw the introduction of the
TA 2, an instrument that offered similar
features but which was more compact
and which could be installed on a labo-
ratory bench.
The first simple automated melting point
instrument was also developed in the
same period. Later came the well-known
hot stage microscope with simultaneous
measurement of the DSC signal.
In the early 1970s, followed the introduc- ity control. The TA3000 System included
tion of the TA2000 family of instruments, a TMA measuring cell besides the TGA
which was lower priced and had a DSC and DSC cells. Measurement results were
measuring cell. evaluated in the instrument and the doc-
umented by a printer.
Thermal analysis specially
for quality control The present-day STARe System
In the 1980s, thermal analysis became The cornerstone of the present-day fam-
available to the chemical industry in ily of instruments was then laid in the
the form of attractively priced compact 1990s. Computer technology had already
stand-alone instruments with integrated developed at a tremendous rate. Measure-
intelligence. This was largely due to the ment curves could be much more eas-
use of microprocessors. The instruments ily and rapidly evaluated with new soft-
were very successful in the field of qual- ware. This system was further developed

METTLER TOLEDO UserCom 39 11
 through to the present-day STARe System
and has been continuously expanded and
enhanced so that today we offer a com-
prehensive portfolio of products that sat-
isfies almost all customer wishes.
News
The core component is the STARe soft-
ware. This software is used to create
methods and start experiments. The
measurements are then manually or au-
tomatically evaluated and analyzed.
The system is also available as a server
version, can be integrated in a LIMS sys-
Figure 3. The TA3000/4000 system.
Figure 4. The Flash DSC 1.
12 METTLER TOLEDO UserCom 39
tem, and satisfies the technical require-
ments of CFR 21 Part 11.
In addition, many special software evalu-
ation programs are available for kinet-
ics, modulated techniques, mathematical
evaluations of all types as well as stan-
dard-compliant evaluations, for example
for the determination of the glass transi-
tion temperature.
Calibration and adjustment has also
been optimized; thanks to FlexCal® the
results today are considerably more ac-
curate than before.
Summary
The present-day STARe System is based
on modern technologies that guarantee
the highest possible measurement per-
formance. It combines the features of
earlier Mettler thermal analysis instru-
ments and is ideal for scientific research
but can equally well be used in quality
control. Thanks to its modular design,
it can easily be adapted to new require-
ments even years after purchase.
The TGA houses the very best METTLER
TOLEDO ultramicro balance; the DSC
measures with a patented sensor with
120 thermocouples, making it the most
sensitive DSC sensor on the market; the
TMA offers nanometer resolution; and
the DMA measures at frequencies of up
to 1000 Hz.
Thanks to the introduction of reliable
and robust automation, the efficiency of
measurements has been greatly increased
without loss of measurement accuracy.
Recently, METTLER TOLEDO once again
made a major breakthrough in thermal
analysis with the introduction of the
Flash DSC 1. No commercial instrument
was previously able to heat and cool so
rapidly; scientists were therefore not able
to investigate many effects.
The Flash DSC 1 offers unique features
that are absolutely essential for the inves-
tigation of crystallization processes.
(www.mt.com/ta-fdsc).
Besides our analytical products, we
have also greatly expanded our services
(www.mt.com/ta-services).
From simple beginnings with the techni-
cal bulletins, a comprehensive documen-
tation program has been developed:
• A scientific customer magazine pub-
lished twice a year with many practi-
cal tips on thermal analysis
(www.mt.com/ta-usercom).
This year our renowned UserCom
magazine celebrates its 20th anni-
versary
• A series of handbooks on special
application areas (www.mt.com/
ta-handbooks)
• Training possibilities in courses
(www.mt.com/ta-training) or online
(www.mt.com/ta-webinars)
• A comprehensive application database
with more than 500 application exam-
ples (www.mt.com/ta-applications)
and also
• The online availability of important
thermal analysis information via apps
(www.mt.com/ta-app).
From the very start, service was an
important component of METTLER
TOLEDO’s business model ( w w w.
mt.com/ta-service). A dense global
network of METTLER TOLEDO trained
service engineers guarantees rapid and
competent service.
This includes:
• Installation,
• Instrument qualification (IQ/OQ),
• Calibration and adjustment,
• Maintenance and
• Repair
Services are nowadays offered under the
name “Good Thermal Analysis Practice”
GTAP (www.mt.com/gtap).
We would be delighted to inform you
about innovative developments and so-
Cooling with the latest instruments from HUBER
The modular concept of an analytical in-
strument from the METTLER TOLEDO
Thermal Analysis Excellence series com-
bined with an external cooling system of-
fers users maximum flexibility for many
different applications. Depending on the
particular analytical instrument, differ-
ent cooling options with corresponding
cooling rates are available that extend
the temperature range and allow precise
temperature control.
Besides the usual liquid nitrogen cool-
ing system, the TC series IntraCoolers
and cryostats from the HUBER company
have proven to be excellent solutions for
external connection to an analytical in-
strument.
Users can upgrade their systems econom-
ically and adapt them to their current
needs. The temperature control systems
Figure 5.
Tutorial handbook
with sample set for
self-study.
lutions for our instruments and services If you have any questions about our
and thank you for the trust that you have products and services, please contact one
placed in us. of our sales engineers.
You can find comprehensive information
on METTLER TOLEDO Thermal analy-
sis Excellence products on the Internet at
www.mt.com/ta.
offer advantages when liquid nitrogen is Figure 1.
Modern technology:
not available or its use is not desired.
the Pilot ONE® Plug
and Play controller.
Furthermore, the handling of a liquid
nitrogen cooling system is often difficult
because of the size of liquid nitrogen ves-
sels. In such cases, the small dimensions
of the temperature control instruments
offer additional advantages.
The IntraCoolers for example are ideal
for cooling the METTLER TOLEDO DSC
instruments and are easily connected to
the DSC via their cooling probe.
The temperature control systems avail- At the same time, the IntraCoolers and
able offer a wide choice of temperature cryostats are also very advantageous be-
ranges and allow flexible temperature cause of their rapid cooling times and
control of different thermal processes for easy operation.
the determination of material properties.
Low temperature measurements can be Furthermore, the temperature of the
rapidly and economically performed. sample material is controlled both pre-
METTLER TOLEDO UserCom 39 13
 cisely and in an environmentally friendly
way. The compact Minichiller®, the TC
series IntraCooler and the Ministat® have
used the R290 propane refrigerant for
many years. R290 contains no ozone-
News
of safety even in continuous operation or
in long-term measurements.
Advantages:
Whether you are using differential scan-
ning calorimetry (DSC), thermogravi-
metric analysis (TGA) or thermomechan-
ical analysis (TMA), Huber temperature
control instruments make an important

depleting substances and has a very low
global warming potential.
The cooling agent offers both maximum
environmental safety and excellent en-
ergy efficiency. The energy saving (up to
20%) leads to a significant reduction in
operating costs. R290 is flammable but
the integrated safety systems and the
high-quality construction of the instru-
ments offer the user a maximum degree
• Environmentally friendly R290 contribution to excellent results and con-
refrigerant tribute to a positive environmental bal-
• Models with 5.7” Pilot ONE® ance.
touch screen controller
• High quality and robust stainless For more information, please see:
steel construction www.huber-online.com
• Space saving due to small
dimensions
• High temperature stability
according to DIN 12876

METTLER TOLEDO Huber cooling device Temperature range

TC45-MT-RC –35 to 700 ° C
DSC 1 TC100-MT-RC –85 to 700 ° C
TC125-MT –100 to 550 ° C
TC45MT-FDSC –35 to 450 ° C
Flash DSC 1
TC100MT-FDSC –95 to 420 ° C
HP DSC 1 Ministat 230-MT
TGA 1 or TGA/DSC 2 SF MiniChiller
TGA 1 or TGA/DSC 2 LF Unichiller (006)
TGA/DSC 2 HT Unichiller (007)
RT to maximum
TGA / DSC 1 SF / LF Ministat 230-MT
temperature
TGA / DSC 1 HT CC-415-MT
TMA / SDTA840
Ministat 230-MT
TMA / SDTA 1
TMA / SDTA841e
Ministat 230-MT 1100 ° C
CC-415-MT 1600 ° C
TMA / SDTA 1
CC-K6-MT and TC45MT-TMA –30 to 600 ° C
Figure 2. Ministat ®, compact and high-performance
cooling circulator. CC-K6-MT and TC100MT-TMA –80 to 600 ° C

14 METTLER TOLEDO UserCom 39
Quantos HPD –
A clever handheld solution for powder dosing
Dispensing small amounts of powder when preparing samples for analytical methods, for example in ther-
mal analysis, can be a tedious laboratory task. The new Quantos HPD accomplishes this work precisely and
reliably and replaces the spatula.
Simple and convenient like a
pipette
The first step in sample preparation in
analytical methods such as TGA is to
weigh small quantities of substances into
a crucible. A major challenge here is to
dose these very small amounts using a
spatula. Substances can easily be spilled.
In any case, the process takes time, is
subject to disturbances, and sample loss
can be high. With its innovative technolo-
gy, Quantos HPD offers a unique solution.
Dosing at the press of a button
Up until now, sample preparation could
only be performed manually. For labo-
ratory personnel this means high con-
centration and care in routine work.
Quantos HPD with its highly precise
mechanical design allows the smallest
amounts of free flowing substances to be
precisely dosed without spillage. With the
new semiautomatic system, dosing can
be performed at the press of a button.
Quantos powder dosing
systems
The Quantos powder dosing system is
suitable for a wide range of applica-
tions. For material research, Quantos of- Figure 1.
Quantos HPD for
fers a series of disposable dosing heads. powder.
One click and the dosing head with the
substance is attached to the HPD and is
ready for use.
After the dosing process, the highly pre-
cise mechanism closes reliably and tight-
ly. This eliminates the risk of contami-
nation on changing the head.
Ergonomic design
Due to the use of FDA-compliant mate-
rials in the dosing head, the HPD can
also be used for sample preparation in
regulated environments. The handle of
the HPD is contoured for convenient han- Figure 2.
Dosing into a
dling and allows smooth and fatigue-free
sample vial.
operation the whole day:
Swiss technology and quality down to the
final detail.
RFID technology
The RFID chip in the dosing head stores
all relevant information such as the sub-
stance ID, quantity, date, and so on for
traceability documentation.
For more information:
www.mt.com/quantos-hpd-starter-kit
METTLER TOLEDO UserCom 39 15
 Measurement of vapor pressure curves and the
enthalpy of vaporization of liquids by HPDSC
Applications

Dr. Samuele Giani

Measurement of the boiling point of a liquid at different pressures allows you to determine its vapor pressure
curve. Besides this, the enthalpy of vaporization of the liquid can be determined from such measurements
using the Clausius–Clapeyron equation. In this article, we show how such measurements are performed in a
high-pressure DSC using water as an example.

Introduction The enthalpy of vaporization can also be Experimental details

The boiling point of a liquid depends
on the pressure of the surroundings:
the lower the pressure the lower the
temperature at which the liquid boils.
For example, on Mount Everest, the air
pressure is only about 325 mbar and
water boils at about 70 °C and not at
100 °C like at sea level. The pressure
dependence of the boiling point can
be easily measured by high-pressure
DSC (HPDSC).
Figure 1.
DSC curves of water
at different pres-
sures. The onset
temperature of the
vaporization peak
corresponds to the
boiling point.
determined from such measurements us-
ing the Clausius–Clapeyron equation [1].
The Clausius–Clapeyron equation de-
scribes the relationship between the va-
por pressure of a substance, p, and the
temperature at which it boils, T:
(1)
The measurements were performed us-
ing an HP DSC 1 equipped with an FRS 5
sensor and a PC10 pressure controller.
The evaporation of a liquid leads to DSC
curves with broad endothermic peaks.
The evaporation must be suppressed as
far as possible to obtain a sharp vapor-
ization peak and thus allow an accurate
determination of the boiling point.
To do this, the crucibles are sealed with
a lid in which a small hole has been
pierced. Investigations of an ASTM task
group showed that the optimum size of
the hole depends on the pressure. At pres-
sures above 1 bar, diameters of 50 µm are
recommended [2, 3].
For our measurements, we used alumi-
num crucibles that were sealed with a lid
with a 50-µm hole (ME 51119873). The
sample weight was typically 2 mg and the
heating rate 5 K/min. Nitrogen was used
as the pressurizing gas.

Results
Figure 1 shows the measurement curves
recorded at different pressures. The boil-
ing point corresponds to the onset tem-
perature of the vaporization peak. At the
boiling point, the vapor pressure of the
liquid equals the external pressure.
Figure 2. Here ΔH stands for the enthalpy (heat)
Black: vapor pres-
sure curve for water of vaporization, L is a substance-specific The applied pressure therefore corre-
between 100 and constant, and R is the universal gas con- sponds to the vapor pressure of the liquid
220 °C.
stant, 8.314 J/(mol K). In this article, we at the temperature at which it boils.
Blue: experimental
results from HPDSC use water as an example and show how
measurements. boiling points can be measured by HP- In Figure 2, the temperature dependence
DSC at different pressures and how the of the vapor pressure of water is displayed
enthalpy of vaporization can be calcu- together with the results from our mea-
lated from this data. surements.

16 METTLER TOLEDO UserCom 39
The figure shows that there is good Figure 3.
Vaporization peak
agreement between the measured values of water at 20 bar
and the literature values. in aluminum and
gold-plated alumi-
num crucibles.
Closer inspection of the DSC curves in
Figure 1 at higher pressures shows a
small exothermic peak immediately af-
ter the vaporization peak. This peak is
due to the reaction of water vapor with
aluminum [4]. To suppress this reaction,
inert crucibles must be used, for example
gold crucibles or gold-plated aluminum
crucibles.

The black curve in Figure 3 shows the

vaporization peak measured in an alu-
minum crucible at a pressure of 20 bar.
The small exothermic peak after the va-
porization peak can be clearly seen. If
the same measurement is performed (red
curve) in a gold-plated aluminum cru-
cible (ME 51142973), the baseline is as
expected flat after vaporization.
The broader vaporization peak obtained
with the gold-plated aluminum crucible
is due to the fact that a lid with a 50-μm
hole is not available for this crucible.
Instead of this, a lid was used that was
pierced manually with a needle with a
nominal diameter of 100 μm. The four-
times-larger pin hole allowed much more
water to evaporate before the water ac-
tually boiled and thus led to a broader
vaporization peak.
Figure 4 displays a plot of the natu-
ral logarithm of the vapor pressure as
a function of the reciprocal boiling
point. According to the Clausius–Clap-
eyron relationship (see equation 1), the
enthalpy of vaporization can be deter-
mined from the slope of the curve. This
yields a value of 40.0 kJ/mol for water
and agrees well with the literature value
of 40.1 kJ/mol.
Conclusions
The vapor pressure curves of liquids
can be easily determined by HPDSC. To
do this, the boiling point of the liquid
is measured in crucibles sealed with a
pierced lid at different pressures.
The vaporization enthalpy can also be
determined from such measurements
using the Clausius–Clapeyron equa-
tion. Using water as an example, we have
shown that the resulting vapor pressure
curve and the vaporization enthalpy
agree well with the literature values.
Figure 4.
The Clausius–
Clapeyron diagram
for water.
References
[1] ASTM E2071, Standard Practice for
Calculating Heat of Vaporization or
Sublimation from Vapor Pressure
Data ( 2010 )
[2] ASTM E1782, Standard Test Method
for Determining Vapor Pressure by
Thermal Analysis ( 2008 )
[3] B. Perrenot, P. de Valliere, G. Wid-
mann, Journal of Thermal Analysis
( 1992 ), 381 – 390 )
[4] R.J. Seyler, R. Moody, ASTM Spe-
cial Technical Paper 1326 ( 1997 ),
212 – 231

METTLER TOLEDO UserCom 39 17
 Composition of water-in-oil ammonium
nitrate emulsions using TGA and DSC
Applications

Romana Cerc Korošec and Peter Bukovec, Faculty of Chemistry and Chemical Technology,
University of Ljubljana, Slovenia

The determination of the composition of ammonium nitrate emulsions is essential for monitoring the qual-
ity criteria of the emulsions as well as their stability during storage in order to predict their shelf life. The
investigation of these types of emulsions can be time-consuming because a combination of various methods
is usually necessary. With the aid of complementary thermal analysis techniques (TGA and DSC), nearly all
the constituents of the emulsion can be quantitatively determined with just a minimum of analytical work.
The different methods are presented in this article.

Introduction Ammonium nitrate makes up about 60 Experimental details

“Water-in-oil” ammonium nitrate emul-
sions are the main components of emul-
sion explosives. In comparison with tra-
ditional nitroglycerine-based dynamites,
these explosives have several advantages.
Following their development in 1962
[1, 2], they have become widely used due
to their good safety properties (handling,
insensitivity to temperature change),
their high detonation rate, and their low
basic cost.
The emulsion itself is not an explosive.
An effective commercial explosive is ob-
tained when glass or plastic microbub-
bles, which lower the density of the sys-
tem, and metal particles (optionally) like
aluminum powder as high-energy fuel
are mixed into the emulsion. The explo-
sive can be prepared in a mobile unit on
site before the final explosive is pumped
into the borehole [1].
In the emulsion, the aqueous phase con-
sists of a supersaturated solution of am-
monium nitrate (AN), which is metasta-
ble due to supersaturation. Sometimes,
other salts such as sodium nitrate (SN)
or calcium nitrate are added.
The aqueous phase with a droplet size
of around 1 µm is emulsified in a small
volume of hydrocarbon oil, which forms
a thin film around the droplets. The
dispersed aqueous phase contains ap-
proximately 90 mass percent of the liq-
uid fraction and the remaining 10 mass
percent corresponds to the oil phase.
to 80 percent of the overall composition
and is the major ingredient of the emul-
sion. An emulsifier enables the formation
and stabilization of the emulsion, which
consists of two phases with very different
polarity [1].
During storage, evaporation of water can
cause the ammonium nitrate to crystal-
lize. Crystallization leads to breakdown
of the emulsion and loss of the explosive
properties. On the other hand, a water
content that is too high inhibits detona-
tion.
For this reason, stability tests require ac-
curate and precise results for the water
content and the state of the ammonium
nitrate with respect to its amorphous or
crystalline phases [1]. The contents of
ammonium nitrate and hydrocarbon oil
are important for monitoring the quality
control of the emulsion.
Quantitative analysis of the emulsion can
be time-consuming because a combina-
tion of different methods is usually nec-
essary to detect and determine a range of
chemical compounds [3]. With the aid of
complementary thermal analysis tech-
niques (TGA and DSC), only a minimum
of analytical work is needed to quanti-
tatively determine nearly all the compo-
nents in ammonium nitrate emulsions.
Besides this, the time-consuming sepa-
ration of the aqueous and oil phases is
not necessary so that no errors can arise
from this.
Ammonium nitrate 99.999% (AN stan-
dard) and sodium nitrate 99.999% (SN
standard) from Sigma–Aldrich were used
as standard substances. Two commer-
cial explosive samples used in Slovenia
were analyzed. Both were “water-in-oil”
emulsions. In Sample 1, ammonium ni-
trate was the sole oxidizing agent, where-
as in Sample 2, some sodium nitrate was
added.
Thermogravimetric measurements were
performed using a METTLER TOLEDO
TGA/SDTA 851e instrument in a dynam-
ic air atmosphere using a flow rate of
100 mL/min. In dynamic measurements,
about 20 to 30 mg of Sample 1 or 2 was
weighed into a 150-µL aluminum oxide
crucible and covered with a pierced lid.
The measurements were performed in
the temperature range 25 to 850 °C at a
heating rate of 5 K/min using baseline
subtraction.
The DSC analyses were carried out using
a METTLER TOLEDO DSC 822e with the
same atmosphere as in the TGA measure-
ments. The samples (mass about 4 mg)
were weighed into 40-μL Al crucibles.
Several heating and cooling cycles in
the temperature range 25 to 135 °C were
performed at heating and cooling rates
of 5 K/min with the ammonium nitrate
standard and with Samples 1 and 2 us-
ing crucibles covered with pierced lids
(50-µm hole). The reference was an emp-
ty crucible with a pierced lid.

18 METTLER TOLEDO UserCom 39
The DSC instrument was calibrated with Figure 1.
Comparison of
high purity gallium, indium and zinc. the TGA curves of
Gallium was supplied by the Physika- the ammonium
lisch-Technische Bundesanstalt Braun- nitrate emulsion
(Sample 1) and the
schweig, Germany; zinc and indium by ammonium nitrate/
METTLER TOLEDO. The DSC standards sodium nitrate
and the samples for DSC analysis were emulsion (Sam-
ple 2).
carefully weighed using a METTLER
TOLEDO MX5 balance.

DSC measurements were used to con-

struct part of the ammonium nitrate/
sodium nitrate phase diagram. The
temperature range was 25 to 150 °C or
170 °C and the heating rate 2 K/min. The
samples were measured in 40-μL alumi-
num crucibles covered with a pierced lid
(50-µm hole).
Figure 2.
Results and discussion DSC heating-cool-
ing cycles of Sam-
ple 1, ammonium
Determination of the water content nitrate emulsion.
Figure 1 displays the dynamic TGA mea-
surements of Samples 1 and 2. Dehydra-
tion occurs from room temperature to
about 150 °C [5]. The dehydration step,
however, is overlapped by a reaction that
begins at about 200 °C and is completed
by about 320 °C. In this reaction, am-
monium nitrate (AN) reacts with the hy-
drocarbon oil according to the equation:
3nNH4NO3 +( CH2 )n  nCO2 + 7nH2O +
3nN2.

The TGA curve of Sample 2, which also

contained sodium nitrate, shows a fur-
ther step in the temperature range 610
to 720 °C. This is due to the thermal de-
composition of sodium nitrate (SN) [4].
Further TGA measurements showed that
ammonium nitrate already exhibited a
considerable vapor pressure at 100 °C [5],
although a published value at this tem-
perature is only 2.05 Pa [6]. The water
content was therefore determined in an
isothermal TGA measurement at 100 °C
lasting 6 hours using an aluminum
crucible covered by a lid pierced with a
50-μm hole. This type of lid prevented
evaporation of the ammonium nitrate
[5].
The ammonium nitrate content in the
sample was determined differently de-
pending on whether the oxidizing agent
present in the emulsion was pure am-
monium nitrate or whether it contained
some sodium nitrate. Both procedures
are separately described below.
Ammonium nitrate emulsion
(Sample 1)
The content of ammonium nitrate was
determined from the enthalpy of the sol-
id-solid phase transition at 126 °C. To do
this, the water must first be evaporated
and the ammonium nitrate crystallized.
This was done by subjecting Sample 1
(contained no sodium nitrate) to ten
heating and cooling cycles in the DSC
between 25 and 135 °C in order to obtain
stable crystalline ammonium nitrate (see
Figure 2).
No peaks are observed in the DSC curve
during the first heating and cooling
curves. In the second heating curve,
two small peaks appear in the range
125 to 131 °C and three peaks in the
third heating curve. The fourth heating
curve shows two pronounced peaks. The
formation of these effects has to do with
the fact that water evaporates during the
heating and cooling cycles and ammo-
nium nitrate begins to crystallize.
Ammonium nitrate undergoes at least
two phase transitions from room temper-
ature until it melts at 169 °C (Figure 3,

METTLER TOLEDO UserCom 39 19
 Event 3). Some transition temperatures
(for example Event 1, solid-solid transi-
tion) depend on the thermal history of
the sample as well as on the water and
impurity contents [7].
Applications
The peak at 126 °C (Event 2, transition
from crystal Form II to Form I) is not
affected by the conditions; and its tran-
sition enthalpy, ΔHsample, shows good re-
producibility. The amount of pure am-
monium nitrate can be easily calculated
by dividing ΔH sample by the enthalpy of
the phase transition of pure ammoni-
um nitrate at 126 °C (ΔHstandard 55.20 ±
0.20 J/g), that is ΔHsample /ΔHstandard.
In the 8 th cycle, ΔHsample reaches its
maximum value and remains constant
for several dozen cycles. The estimated er-
ror for the AN determination is ±0.7% [5].
The value of ΔH standard for the phase
transition from tetragonal to the cubic
modification at 126 °C was determined
by performing several heating and cool-
ing cycles of pure ammonium nitrate be-
tween 25 and 135 °C. We found that it was
best to weigh the ammonium nitrate into
the crucible and then seal it with a 50-μm
pierced lid in order to prevent evaporation
of the ammonium nitrate [5].
TGA experiments performed similarly
to the DSC cycles showed that water first
evaporated and then ammonium nitrate.
In open crucibles and in crucibles with a
Figure 3.
DSC curve of dried
ammonium nitrate.
20 METTLER TOLEDO UserCom 39
large 1-mm hole, a weight loss was ob-
served from cycle to cycle. When crucibles
with a 50-μm hole were used, the weight
of the sample remained stable after 5 cy-
cles when the water had evaporated.
On the basis of the DSC and TGA results,
we concluded that crystallization of the
ammonium nitrate was not complete af-
ter dehydration (after 5 cycles) and that
three additional heating and cooling cy-
cles were needed to obtain the maximal
value of ΔH for the phase transformation
at 126 °C.
After the determination of the water
content by isothermal measurement at
100 °C and the ammonium nitrate con-
tent during the DSC cycling experiment,
the content of organic phase (oil and
emulsifier) is calculated from the differ-
ence to 100%.
Ammonium nitrate/sodium
nitrate-emulsion (Sample 2)
The sodium nitrate content in the AN/SN
mixture in Sample 2 was determined
using a dynamic TGA measurement. It
corresponds to the mass that remains
after thermal decomposition at 470 °C
(see Figure 1). The water content is deter-
mined in the same way as for Sample 1.
The ammonium nitrate content in Sam-
ple 2 could not be determined using the
procedure described above. The top curve
in Figure 4 shows the DSC curve of the
10th heating run of the emulsion, which
was previously cycled 9 times between 25
and 135 °C (as for Sample 1).
During this experiment, water evaporat-
ed and ammonium nitrate crystallized.
As the DSC curve in Figure 4 shows, a
mixture of ammonium nitrate and so-
dium nitrate melts as a eutectic mixture
at 121.3 °C (Event C), shortly before the
phase transition from the tetragonal to
the cubic crystalline modification takes
place at 126 °C (Event D).
This peak at 126 °C shows the amount of
unmelted ammonium nitrate. On further
heating, the rest of the solid ammonium
nitrate melts (Event E). The temperature
at which the DSC curve again reaches
the baseline, corresponds to the liquidus
curve of the AN/SN composition present
in the aqueous phase. For the dried Sam-
ple 2, the final temperature of melting,
the liquidus point was 137.6 °C.
The unknown ratio of AN/SN in the
emulsion was determined from the liq-
uidus curve of the binary phase diagram,
part of which was constructed for this
purpose. Based on TGA results (Figure 1),
AN/SN mixtures with percentage weights
of ammonium nitrate (AN) from approx-
imately 76 to 92% were prepared by care-
fully by weighing both the salts.
The DSC curves of these samples were
measured at a heating rate of 2 K/min
(Figure 4, curves a to d). The ammo-
nium nitrate content increases from a
to d. The peak intensity corresponding
to the melting of the eutectic composition
(121.3 °C), therefore decreases, whereas
the peak intensity of the phase transition
II solid→I solid of the ammonium nitrate
(126 °C) increases. As with Sample 2, the
liquidus points were determined for each
mixture (see Figure 5).
From this data, a liquidus curve of the
AN-rich part of a phase diagram was
constructed [5] and from this the per-
centage of AN in the mixture with SN was
determined. Sample 2 shows an AN/SN
ratio that lies between the concentrations
of b and c.
The content of AN in the original sample Figure 4.
Top: DSC curve of
is calculated on the assumption that the 10th heating run
mass ratio of AN and SN is the same in of Sample 2: tem-
the original sample as in the aqueous perature program
is 25 to 100 °C
phase. The ratio of the two salts in the at 5 K/min, then
aqueous phase is determined with the aid 100 to 170 °C at
of the phase diagram. Taking into ac- 2 K/min.
Effect A is the solid-
count that the accuracy of the final melt- solid transition of
ing point determination is ±1 degree and Form IV to II.
the SN content in the original sample At B, the heating
rate changes. C to
±0.5%, the uncertainty of the AN content E, see text.
is ±2%. a to d: DSC curves
of AN/SN mixtures
with increasing AN
Conclusions content.
Thermal methods of analysis (TGA and
DSC) proved to be suitable for determin-
ing the water content and the amounts of
ammonium nitrate (AN) sodium nitrate
(SN) and organic phase in “water-in-oil”
Figure 5.
emulsions. The water content was deter- DSC heating curves
mined by isothermal TGA measurement of specially mixed
AN/SN composi-
at 100 °C. tions showing the
curves displayed in
In Sample 1, the ammonium nitrate con- Figure 4 (a to d) on
an expanded scale.
tent was determined by performing ten
DSC heating and cooling cycles between
25 and 135 °C. During this experiment,
water evaporated and ammonium nitrate
crystallized. The ammonium nitrate
content was calculated from the enthalpy
of the phase transition at 126 °C. The
content of the organic phase (oil plus
emulsifier) was calculated from the dif-
ference to 100%.

In Sample 2, with ammonium nitrate

and sodium nitrate in the solution, the
content of sodium nitrate corresponded
to the weight remaining at 470 °C in the
dynamic TGA measurement. The un-
known ratio of AN/SN in an emulsion
was determined from the liquidus curve
of the binary phase diagram, part of
which was constructed for this purpose.
The content of ammonium nitrate in
this sample was calculated by assuming
that the ratio of AN and SN in Sample 2
is equal to that in the aqueous phase.
The water content was again determined
by an isothermal TGA measurement at
100 °C. The difference to 100% was as-
signed to the sum of hydrocarbon oil and
emulsifier.
References
[1] H. A. Bampfield and J. Cooper, In :
Encyclopedia of Emulsion Techno-
logy ; P. Becher ( Ed. ) ; Applications ;
Marcel Dekker Inc., New York, Vol. 3
( 1988 ), 282– 306.
[2] C. Oommen et al, J. Hazard. Mater.,
Vol. A67 ( 1999 ), 253 – 281.
[3] D. T. Burns et al, J. Anal. Chim. Acta,
Vol. 375 ( 1998 ), 255 – 260.
[4] M. Sweeney, Thermochim. Acta,
Vol.11 ( 1975 ), 409 – 424.
[5] R. Cerc Korošec and P. Bukovec,
In : Explosive Materials – Classifica-
tion, Composition and Properties,
T. J. Jansen ( Ed. ) ; Nova Science
publishers, Inc., New York ( 2011 ),
125 – 144.
[6] J.D. Brandner et al, J. Chem. Eng.
Data, Vol. 7 ( 1962 ), 227 – 228.
[7] I. Dellien, Thermochim. Acta, Vol. 55
( 1982 ), 181 – 191.

METTLER TOLEDO UserCom 39 21
 Thermomechanical analysis of natural
and cosmetically treated hair
Applications

Rasika Haldankar

Nowadays, natural protein or keratin treatment is used to straighten hair, to stop it from frizzing, and at the
same time to make it look shinier. There are, however, risks associated with many types of treatments and
it is important to be fully aware of possible adverse effects in order to choose a safe treatment. Thermome-
chanical analysis (TMA) is a good technique to characterize the mechanical and physical properties of hair.

Introduction Different measurement modes with suit-
Thermomechanical Analysis (TMA) able clamping accessories are available.
measures the expansion and shrinkage These allow bars, films or thin fibers like
behavior of materials as a function of hair to be analyzed.
time or temperature while they are sub-
jected to a defined force [1, 2]. Even very fine hairs can be mounted in
the tension accessory with the aid of cop-
Figure 1.
TMA sample holder per clips.
for fiber measure-
ments with a hair
In this application example, two different
sample installed.
hairs, an untreated natural hair and a
natural hair that had been subjected to
a shine and bond hair treatment, were
measured in the tension mode up to a
temperature of 230 °C. The hair sam-
ples were compared with regard to their
shrinkage and expansion behavior and
thermal stability.
Hair from the head of a human being is a
natural fiber produced by keratin, a pro-
tein containing a high concentration of
sulfur originating from the amino acid
cysteine. The cortex occupies most of the
Figure 2.
Shrinkage behav-
ior of natural and
cosmetically treated
human hair.
hair area. The keratin fibers of the cor-
tex make the hair strong; its long chains
are compressed and form a regular
structure. The most important physical
property of hair is resistance to tear, but
elasticity and hydrophilic properties are
also important.
In general, hair treatments are common-
ly used to obtain a desired appearance,
shape or texture. However, treatments
can cause damage to the hair on a mo-
lecular level resulting in hair that looks
dry, thin and weak. The desire for prod-
ucts that improve the appearance and
feel of hair has created a huge industry
for hair care.
Characterization of the structure and
physical and mechanical properties of
hair are essential for the development
of innovative cosmetic products. Tech-
niques like TMA can be very useful for
this type of work.
Experimental details
An untreated natural hair and a natural
hair after a shine and bond hair therapy
were investigated by TMA and the re-
sults compared. The procedure for hair
therapy involves several steps that are de-
scribed below. First, the hair was exam-
ined with regard to texture, porosity and
history of former chemical treatments.
The hair was then washed with a clean-
ing shampoo.

Afterward, it was washed with water and

dried with a hair dryer. A perm solution
was then applied followed by a cream
to increase the elasticity and stretching
properties of the hair.

22 METTLER TOLEDO UserCom 39
The cream was allowed to take effect for
about five minutes, after which the hair
was thoroughly rinsed with water fol-
lowed by the application of an enriched
moisturizing mask. The latter was com-
pletely rinsed off with water after two
to three minutes. Finally, the hair was
dried and ironed to achieve voluminous
straight hair with a smooth look.
The TMA measurements of the natural
hair before treatment and the hair after
treatment were performed using a TMA/
SDTA 840 equipped with the accessory
for fiber measurements. The results were
evaluated using the STARe software.
The hair fibers were inserted in copper
clips and fixed in place by mechanically
squeezing the clips together. Samples
prepared in this way were mounted be-
tween the hooks of the sample holder
(see Figure 1).
(see Figure 4). The thermal stability of
the treated natural hair is greater than
for natural hair and confirms the posi-
tive effect of this particular hair treat-
ment.
Conclusions
Thermomechanical Analysis is an excel-
lent technique for characterizing the ex-
pansion and shrinkage behavior and the
thermal stability of thin fibers like hair.
The TMA fiber clamping accessory with
copper clips allows very fine fibers to be
easily and reproducibly mounted.
In these studies, the effect of a special
hair therapy was investigated. The hairs
were measured and compared before and
after hair therapy. The results obtained
were very reproducible and showed that
the treated hair showed greater thermal
stability than the untreated natural hair
and confirmed the positive effect of the
hair care treatment.
The TMA technique and the resulting in-
formation can therefore be of great use
for developing products in the cosmetic
industry and for obtaining information
about their effects on hair.
References
[1] PET, Physical curing by DLTMA,
UserCom 5, 15
[2] Interpreting TMA curves,
UserCom 14, 1
Figure 3.
Thermal expansion
coefficient of natu-
ral and cosmetically
treated human hair.

The TMA measurements were performed

from 25 to 250 °C at a heating rate of
5 K /min using a tensile force of 0.02 N.

Results and discussion

Figure 2 shows the TMA curves of natu-
ral and cosmetically treated human hair.
The curves are displayed up to 140 °C
and illustrate the shrinkage behavior of
natural (blue curve) and treated hair
(red curve). Both hair samples shrink up
to about 110 °C due to drying. For natu-
ral hair, this amounts to about 0.7% of
the original sample length, and for treat- Figure 4.
ed natural hair to about 1.0%. Repeat determina-
tions of the TMA
measurements.
As a result, we can conclude that after
applying the shine bond therapy to the
hair, the results show a small difference
in the shrinkage value.

In Figure 3, the curves are displayed from

130 to 240 °C. They show that decompo-
sition begins above 220 °C and that the
hairs then rapidly tear. In this case, the
mean value of the onset of melting calcu-
lated for natural hair was about 223 °C
and for treated natural hair 226 °C.

The values obtained show excellent re-

producibility in a repeat determination

METTLER TOLEDO UserCom 39 23
 Determination of heat capacity by temperature-
modulated DSC at temperatures above 700 °C
Applications

Dr. Elke Hempel

The heat capacity of a material can be determined with high accuracy using temperature-modulated DSC.
Measurements up to 700 °C can be performed by conventional DSC. In this article, we show how good re-
sults can also be obtained above 1000 °C using the TGA/DSC 1. To do this, we present ADSC measurements
of nickel, sapphire and molybdenum in the temperature range 900 to 1400 °C. The work originated as part
of an interlaboratory test organized in 2012/2013 by the Thermophysics Group of the German Society for
Thermal Analysis (Gefta).

Introduction
Several different procedures for determin-
ing the specific heat capacity by DSC are
available, such as for example the sap-
phire method [1, 2]. The maximum tem-
perature of the DSC is however 700 °C.
The article in reference [3] describes
how specific heat capacities can be deter-
mined using the sapphire method up to
a temperature of 1400 °C with an accu-
racy of about 10%. Application examples
are presented in reference [4].
When the TGA/DSC is used to determine
specific heat capacity, the heat flow signal
measured simultaneously with the TGA
signal is evaluated just as in DSC mea-
surements. Other DSC methods that are
available include the temperature-mod-
ulated techniques IsoStep® [5], Steady-
State [3], ADSC [6] and TOPEM® [7, 8].
TOPEM® is currently not implemented
for TGA/DSC.
Compared with the sapphire method,
temperature-modulated methods have
the advantage that they are less affected
by drift and can therefore achieve accura-
cies of up to 2%. Heat capacities can also
be determined for isothermal conditions
using Steady-State, ADSC and TOPEM®.
In addition, information is obtained
about the contributions of sensible and
latent heat capacity. However, these
methods require considerably longer
measurement times compared with the
sapphire method. In this article, we pres-
ent specific heat capacity measurements
determined by ADSC in the temperature
range 900 to 1400 °C. The measurements
were performed using the TGA/DSC 1.
ADSC method
The temperature-time program T(t)
of an ADSC measurement is a function
consisting of a constant heating rate β0
overlaid with a sinusoidal component:
T(t) = β0 *t + TA*sin(ωt) with a tem-
perature amplitude TA and a frequency
ω = 2π/p (with a period p).
The time-dependent heating rate β(t) is
given by β(t) = β0 + βA*cos(ωt) with the
heating rate amplitude βA = TA*ω.
The period p must be considerably larger
than the thermal lag of the furnace. Our
measurements were performed using a
TGA/DSC 1 equipped with a high-tem-
perature furnace and the so-called DTA
sensor. The time constant of this is about
100 s. The period should be in the range
5 to 10 min.
The heat capacity corresponds to the
contribution of the complex heat capac-
ity, which is calculated from the ratio of
the amplitude of the heat flow and the
heating rate. The calibration factor is
determined from measurements using
a reference material of known specific
heat capacity.
Normally sapphire is used as the refer-
ence material. In addition, we have also
used molybdenum from NIST (National
Institute of Standards and Technology)
in order to have another material of a
known specific heat capacity.
Measurements and results
General comments
To determine the specific heat capacity
by ADSC, three measurements have to
be performed under identical conditions,
namely measurement of the sample,
measurement of the reference substance,
and measurement of the empty crucible
for the determination of the blank curve.
A practical working procedure is:
• Measurement with empty crucibles,
• Sample measurement,
• Measurement of the reference
material,
• Measurement with empty crucibles.
The first measurement with the empty
crucibles is not used for the evaluation.
The curves of the sample and reference
material are corrected using the second
blank measurement. The ADSC evalua-
tion then yields the uncorrected complex
specific heat capacity cp,sampleuncorr.
This must be corrected with the mea-
sured complex specific heat capacity of
the reference material c p,ref uncorr and its
literature values cp,reflit. To do this, the lit-
erature values cp,reflit are stored as a curve
by the STARe software. The STARe soft-
ware then calculates the specific heat ca-
pacity curve of the sample from the three
other curves according to the equation
cp,sample = cp,sampleuncorr / cp,refuncorr × cp,reflit.
The ADSC measurements presented here
were performed for nickel, molybdenum
and sapphire using 30-µL platinum
crucibles. The sample and reference
crucibles were identical for all measure-

24 METTLER TOLEDO UserCom 39
ments. The underlying heating rate was Figure 1.
Blank curve sub-
1.5 K/min, the temperature amplitude tracted heat flow
5 K and the period 6 min. The measure- curves for the ADSC
ments were performed in the temperature measurement of
nickel, sapphire and
range 900 to 1400 °C. The blank curve molybdenum.
subtracted heat flow curves are displayed
in Figure 1.

Measurement of nickel and

molybdenum using sapphire as
reference material
First, let us look at the results of the mea-
surements of the specific heat capacities
of nickel and molybdenum (Figure 2).
The sapphire measurement is used as the
reference measurement. The literature
values for nickel [9] and molybdenum
[10] are given in addition. The curves of
the specific heat capacities for molybde-
Figure 2.
num are within 2% of the literature val- Comparison of the
ues. The deviation for nickel is about 5%. measured spe-
cific heat capacities
(thick lines) with
Measurement of nickel and literature values
sapphire using molybdenum as (symbols and line)
reference material for nickel (above)
and molybdenum
Instead of sapphire, we now want to use (below); the refer-
molybdenum as the reference material. ence substance
was sapphire.
Figure 3 displays the results for nickel
and sapphire together with the literature
data as well as the curves for deviations
of 2% and 5%. The results for nickel are
independent of the reference substance
used.

Summary
Using ADSC, the specific heat capacity
of sapphire and molybdenum could be
determined with an accuracy of 2%. For Figure 3.
nickel, the deviation from the literature Comparison of
values was 5%. The literature values were the measured
specific heat
determined using a pulse calorimeter capacities (thick
with an accuracy of 2%. The additional line) with literature
values (symbols
deviation can possibly be explained by
and line) for sap-
the nickel alloy having a slightly different phire (above) and
composition. Since the Curie tempera- nickel (below); the
reference substance
ture is sensitive to the composition of the was molybdenum
alloy, the Curie temperature determined (red). In addition,
using TOPEM ® measurements should the result for nickel
using sapphire
be given for comparison: Tc = 358.2 °C. (blue) from Figure 2
This value is 1.6 K less than the value of is shown.
Tc = 359.85 °C given by Meschter [9] and
could therefore explain the somewhat
higher deviation of 5% compared with
deviations of only 2% for the sapphire
and molybdenum measurements.

METTLER TOLEDO UserCom 39 25
 Tips and tricks
Similar recommendations for the mea-
surement of specific heat capacity by
TGA/DSC apply as for measurements us-
ing the DSC:
Dates
the platinum crucible sticks to the
sensor at high temperatures. This
can be prevented by placing a sap-
phire disk between the sensor and the
crucible.
the possibility of determining isothermal
heat capacities.
It was shown that the heat capacity can
be determined with an accuracy of better

• Make sure the instrument has been
switched on long enough before begin-
ning the measurement and that the
purge gas flow is stable.
• Make sure that the substance under
investigation does not react with the
crucible material or the purge gas.
• Pay attention to the stability of the
substance in the temperature range of
the measurements.
• If possible, the same crucible should
be used for the blank, sample, and
reference measurements. Possible dif-
ferences in mass when using different
crucibles should be taken into account
in the calculation of the heat capacity.
• Aluminum crucibles cannot be used
because of the high temperatures.
Crucibles made of platinum can be
used instead. They exhibit good ther-
mal conductivity. Crucibles with vol-
umes of 30, 70, and 150 μL are avail-
able. The size of the crucible should
be as small as possible. To minimize
heat losses, the crucibles are used with
a lid.
• If the TGA/DSC is equipped with the
platinum sensor, there is the risk that
• Likewise, at high temperatures, the
platinum crucible can stick to the
platinum lid. This can be prevented by
using a ceramic paste (e.g. Cerama-
bond), which is applied to the rim of
the lid.
• The mass of the sample, ms, and the
mass of the reference substance, mref,
should be chosen so that the heat ca-
pacities are about the same:
Cp,sample = msample × Cp,sample ≈ mref ×
cp,ref = Cp,ref.
• The crucibles should be precisely posi-
tioned on the sensor.
Conclusions
Temperature-modulated measurements
using the heat flow signal measured si-
multaneously with the TGA signal by the
TGA/DSC 1 can be used to determine
heat capacities in the same way as in DSC
measurements. This allows you to benefit
from the advantages that temperature-
modulated procedures offer compared
with the sapphire method when using
the TGA/DSC. The advantages include
the elimination of drift, the separation
of sensible and latent heat capacity, and
than 5% for temperatures above 1000 °C.
References
[1] Measuring specific heat capacity,
UserCom 7, 1 – 5.
[2] G. W. H. Höhne, W. Hemminger and
H.-J. Flammersheim : Differential
Scanning Calorimetry,
Springer Verlag, 1996, 118.
[3] Heat capacity determination at high
temperatures by TGA / DSC, Part 1 :
DSC standard procedures,
UserCom 27, 1 – 4.
[4] Heat capacity determination at high
temperatures by TGA / DSC, Part 2 :
Applications, UserCom 28, 1 – 4.
[5] Iso-StepTM : UserCom 15, 8, The
investigation of curing reactions with
IsoStep™ : UserCom 15, 18 – 19.
[6] Alternating differential scanning
calorimetry, ADSC, opens new
possibilities, UserCom 2, 5 – 6.
[7] J. Schawe, The separation of sensible
and latent heat flow using TOPEM ®,
UserCom 22, 16 – 19.
[8] J. Schawe et. al., Stochastic tempe-
rature modulation : A new technique
in temperature modulated DSC, Ther-
mochimica Acta 446 ( 2006 ) 147.
[9] P.J. Meschter, J. W. Wright, C. R.
Brooks, T. G. Kollie ( 1981 ), Physical
Contributions to the heat Capacity of
Nickel, J. Phys. Chem. Sol, Vol.42,
No. 9, 861.
[10] Certificate Molybdenum from NIST :
https : / / w ww-s.nist.gov / srmors / view_
cert.cfm ?srm=781d2

Exhibitions, Conferences, Seminars and Training Courses

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Handbooks : Our specialist application handbooks provide valuable www.mt.com / ta-handbooks
background information
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thermal analysis services at

26 METTLER TOLEDO UserCom 39
 International and Swiss TA Customer Courses:

TA Customer Courses and Seminars in Switzerland – Information and Course Registration:

TA-Kundenkurse und Seminare in der Schweiz – Auskunft und Anmeldung bei:
Veronica Feroce-Ring, Perla Irmler, Mettler-Toledo AG, Analytical, Schwerzenbach
Tel: ++41 44 806 73 57, Fax: ++41 44 806 72 60, e-mail: veronica.feroce-ring@mt.com or perla.irmler@mt.com

Autumn: Kurse / Courses

Course TAK47 SW Basic (Deutsch) 17. November 2014 Course TAK48 SW Basic (English) November 24, 2014
Course TAK47 TMA (Deutsch) 17. November 2014 Course TAK48 TMA (English) November 24, 2014
Course TAK47 DMA Basic (Deutsch) 17. November 2014 Course TAK48 DMA Basic (English) November 24, 2014
Course TAK47 DMA Advanced (Deutsch) 18. November 2014 Course TAK48 DMA Advanced (English) November 25, 2014
Course TAK47 TGA Basic (Deutsch) 18. November 2014 Course TAK48 TGA Basic (English) November 25, 2014
Course TAK47 TGA Advanced (Deutsch) 19. November 2014 Course TAK48 TGA Advanced (English) November 26, 2014
Course TAK47 DSC Basic (Deutsch) 19. November 2014 Course TAK48 DSC Basic (English) November 26, 2014
Course TAK47 DSC Advanced (Deutsch) 20. November 2014 Course TAK48 DSC Advanced (English) November 27, 2014
Course TAK47 TGA-FTIR (Deutsch) 20. November 2014 Course TAK48 TGA-FTIR (English) November 27, 2014
Course TAK47 SW Advanced (Deutsch) 21. November 2014 Course TAK48 SW Advanced (English) November 28, 2014
Course TAK47 TGA-MS (Deutsch) 21. November 2014 Course TAK48 TGA-MS (English) November 28, 2014
Course TAK47 Kinetics / TMDSC(Deutsch) 21. November 2014 Course TAK48 Kinetics / TMDSC (English) November 28, 2014

Local TA Customer Courses:

TA-Kundenkurse Nähere Informationen unter www.mt.com/labtalk oder durch:
und Seminare Frau Frau Janine Schindler, Mettler-Toledo GmbH, Giessen, Tel: ++49 641 507 401, e-mail: labtalk@mt.com
in Deutschland DSC-Workshop 23. und 24.09.2014 Giessen
und der Schweiz Online-Seminare zu div. Themen 23. und 24.09.2014 www.mt.com/ta-webinars

TA Basic Courses For details of training courses and seminars, please contact: Netherlands: Bart Baggen, Tel: ++31 344 63 83 63, e-mail: bart.baggen@mt.com
and Seminars in Belgium: Philippe Larbanois Tel ++32 2 477 40 40 36, e-mail: philippe.larbanois@mt.com
Benelux DSC Customer Course October 7, 2014 Brussels, Belgium
DSC Customer Course October 9, 2014 Tiel, Netherlands

Cursos y Para detalles de los cursos y seminarios, por favor contacte con:
Semianros de TA Francesc Català Mettler-Toledo S.A.E., Tel: ++34 93 223 76 00, e-mail: francesc.catala@mt.com
en España Curso de Formación Usuarios TA 8 de octubre 2014 Barcelona
Reunión del Grupo Especializado de Polímeros 7–10 de septiembre 2014 Girona

Cours et Renseignements et inscriptions par Claire Catry, Mettler-Toledo S.A., Tél: ++33 1 3097 1717, e-mail: serviceclients@mt.com
séminaires Principe de la TMA/DMA 01 décembre 2014 Viroflay (France)
d’Analyse DSC: notions de base 02 décembre 2014 Viroflay (France)
Thermique en
DSC: perfectionnement 03 décembre 2014 Viroflay (France)
France
Principe de la TGA 04 décembre 2014 Viroflay (France)
Logiciel STARe: perfectionnement 05 décembre 2014 Viroflay (France)
Congress MATERIAUX 2014 November 24–28, 2014 Montpellier, France
Congress Thermal Analysis Seminar October 30, 2014 Montpellier, France

Corsi e Seminari Per ulteriori informazioni Vi preghiamo di contattare:

di Analisi Simona Ferrari, Mettler-Toledo S.p.A., Novate Milanese, Tel: ++39 02 333 321, e-mail: simona.ferrari@mt.com
Termica in Italia DSC base A richiesta, date da definire Novate Milanese DSC avanzato A richiesta, date da definire Novate Milanese
TGA A richiesta, date da definire Novate Milanese TMA A richiesta, date da definire Novate Milanese

Контактная Подробную информацию о приборах вы можете найти на сайте www.mt.com/ta или узнать по телефону +7 495 651 98 86. Контактное лицо: Алексей
информация Важинский или написать письмо на электронный адрес Alexey.Vazhinskiy@mt.com. Наш почтовый адрес: 101000 РФ, Москва, Сретенский бульвар, дом
МЕТТЛЕР ТОЛЕДО в 6/1, офис 6. E-mail: Alexey.Vazhinskiy@mt.com
России Современное оборудование для термического анализа Октябрь, 2014 Москва
Современное оборудование для термического анализа Октябрь, 2014 Уфа

TA Customer Courses For details of training courses and seminars, please contact: Oy G. W. Berg & Co Ab, Tel: +258 201 255 255, e-mail: gwb@gwb.fi
and Seminars in ESTAC11” August 17–21, 2014 Espoo, Finland
Finland TA Workshops & Infodays September 9–11, 2014 Several locations

Seminários e Para maiores informações sobre os seminários, por gentileza entre em contato com: Mr. Pierre Delmorio, Tel: +55 11 4166 7936, e-mail: pierre.delmorio@
workshops de TA no mt.com, Ms. Kíria Serranegra de Arruda Tel +55 11 4166 7435, e-mail: kiria.arruda@mt.com
Brasil Boas práticas em Análise térmica e avaliação de resultados Agosto 2014 Alphaville, Barueri
Análise Térmica em Polímeros Outubro 2014 Alphaville, Barueri
CBRATEC Novembro 2014 Serra Negra, São Paulo

TA Customer Courses For details of training courses, workshop and seminars, please contact:
and Seminars in SangKoo Lee or Kyungho Chung at Mettler-Toledo Korea, Tel: ++82 2 3498 3500, e-mail: sangkoo.lee@mt.com, Kyungho.chung@mt.com
Korea TA Academy July 2014 / October 2014 Seoul
TMA School July 2014 Seoul DMA School October 2014 Seoul
TA Academy for the Province September 2014 DaeJeon, Ulsan, KwangJu (3 times)
Public Seminar November 2014 DaeJeon

METTLER TOLEDO UserCom 39 27
 TA Customer For information, please contact: BU Laboratory Instruments, Mettler-Toledo KK,
Courses and 1F Ikenohata Nisshoku Budg. 2-9-7 Ikenohata, Taito-ku, Tokyo 110-0008, Japan,
Seminars in Tel: +81-3-5815-5511, Fax: +81-3-5815-5521, e-mail: sales.admin.jp@mt.com
Japan 熱分析基礎セミナー 2014年6月20日 東京：本社1Fセミナールーム
熱分析基礎セミナー 2014年10月7日 東京：本社1Fセミナールーム
熱分析アドバンスセミナー 2014年10月8日∼10日 東京：本社1Fセミナールーム

TA Customer For details of training courses and seminars, please contact:

Courses and Mr. Kuan Eng Seang, Mettler-Toledo (M) Sdn. Bhd, Unit 1-01, Lot 8, Jalan Astaka U8/84, Seksyen U8,
Seminars in Bukit Jelutong, Shah Alam 40150 Selangor, Malaysia
Malaysia Tel: (+603)-78445888, Fax: (+603)-78458773, e-mail: mtmymarketing@mt.com
TA Seminar June 2014 Southern Malaysia
TA School and Product Launch Sept 2014 Central Malaysia

TA Customer For details of training courses and seminars, please contact: Gina Chan, Mettler-Toledo (S) Pte Ltd.,
Courses and 28 Ayer Rajah Crescent, #05 – 01, Singapore 139959, Tel: +65 68900012/13, Fax: +65-68900012,
Seminars in e-mail: Gina.Chan@mt.com
Singapore TA School in Q4 2014 November 2014 Singapore
TA Seminar (Thermal mechanical TMA/DMA) August 2014 Singapore

TA Customer For details of training courses and seminars, please contact: Lu LiMing at Mettler-Toledo Instruments
Courses and (Shanghai) Co. Ltd., Tel: ++86 21 6485 0435, Fax: ++86 21 6485 3351, e-mail: liming.lu@mt.com
Seminars in TA User Meeting 2014 July 23–25, 2014 Chengdu
China TA Training Courses End of September, 2014 Shanghai, Guangzhou
End of December, 2014 Beijing
TA Infoday September 2014 Dalian
TA Infoday October 2014 Shanghai, Beijing
TA Infoday November 2014 Xian, Zhengzhou
TA Infoday December 2014 Hangzhou

TA Customer For details of training courses and seminars, please contact: George McLean, Marketing Manager,
Courses and Materials Characterization, METTLER TOLEDO, 1900 Polaris Parkway, Columbus, Ohio 43240, USA
Seminars in Tel: 614-438-4853, Fax: 614-985-8061, e-mail: george.mclean@mt.com
North America TGA Basics November 11, 2014 Columbus, Ohio
STARe Software Basics November 12, 2014 Columbus, Ohio
DSC Basics November 13, 2014 Columbus, Ohio
DMA Basics November 14, 2014 Columbus, Ohio
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. S. Giani Dr. D. P. May Dr. R. Riesen Dr. J. Schawe Dr. V Chaudhary Dr. S. Domann S. Dandekar
Chemist Chemist Chemist Chem. Engineer Physicist Polymer Journalist Physical Chemist
Engineer and Chemist

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

Mettler-Toledo AG, Analytical

Postfach, CH-8603 Schwerzenbach
Phone +41 44 806 73 87 www.mt.com/ta
Fax +41 44 806 72 60 For more information
Contact : urs.joerimann@mt.com

 
© 06 / 2014 Mettler-Toledo AG, 30208673
Marketing MatChar  /  MarCom Analytical