process engineering

STA 449 F5 Jupiter® – Simultaneous Thermal Analysis (STA)

Considerably Simplified
E. Post

Simultaneous Thermal Analysis (STA) is a thermoanalytical technique

which simultaneously measures two or more thermal properties on a
single sample [1]. Generally, this refers to the simultaneous recording
of mass changes and caloric data in the sample; i.e., the combination
of Thermogravimetry (TGA) and Differential Thermal Analysis (DTA) or
Differential Scanning Calorimetry (DSC).

Introduction by means of TGA and DSC measurements

During the measurement, the sample is
subjected to a freely selectable tempera-
ture program under a defined atmosphere.
By simultaneously recording mass changes
and caloric data on exactly the same sample
and under identical conditions, the measur-
ing time is decreased (by half). Another
significant advantage is that uncertainties
resulting from possible differences in sam-
ple preparation and the use of different
instruments (TGA, DSC) can be ruled out.
By employing an STA, the comparability of
the characteristic temperatures obtained
is guaranteed. For inhomogeneous sample
materials, problems due to differing sample
compositions for TGA and DSC measure-
ments can thus be eliminated.
Universal configuration for a
broad application range
The new STA 449 F5 Jupiter ® (Figs. 1–2)
combines the advantages of a highly sen-
sitive thermobalance featuring high digital
resolution with those of a true differential
scanning calorimeter. Easily exchangeable
sample carriers (Quick-Connect, Fig. 3) al- Fig. 1 STA 449 F5 Jupiter ®

low for optimum adaptation of the system

to a variety of application areas (TGA, TGA-
DTA and TGA-DSC measurements).
An SiC furnace with an exchangeable pro-
tective tube covers the temperature range
from room temperature to 1600 °C (sample
temperature). Sample masses of up to 35 g
with a resolution of 0,1 µg are possible.
Of note here is that the entire measuring

Ekkehard Post
NETZSCH-Gerätebau GmbH
95100 Selb
Germany

E-mail: ekkehard.post@netzsch.com
www.netzsch-thermal-analysis.com

Keywords: Simultaneous Thermal Analysis,

TGA, DSC, binder burnout behavior,
bentonite clay
Fig. 2 Schematic setup of the STA 449 F5 Jupiter®

cfi/Ber. DKG 92 (2015) No. 5-6 E 33

 process engineering

range of 35 g is available at a resolution of

0,1 µg for weight loss and weight gain. The
­vacuum-tight design allows for measure-
ments in defined (e.g., pure inert) atmos-
pheres. Fig. 2 shows the schematic setup of
the instrument.
1 2 3 4 5 6 Control of the system and analysis of the
measuring data are realized via a stand-
ard PC and the tried-and-tested MS®-
Windows®-software. An automatic sample
changer for 20 sample and reference cru­
cibles is optionally available for the STA 449
F5, allowing for automatic TGA or TGA-DSC
measurements overnight, on the weekend,
etc.

BeFlat® – automatic buoyancy

Fig. 3 Sample carrier systems for TGA, TGA-DTA, TGA-DSC (octagonal) and TGA with slip- correction without loss of
on plate for automatic operation raw data – not for routine
measurements only
During TGA measurements, buoyancy ef-
fects always occur since the density of the
gases surrounding the sample or crucible
and sample carrier changes with tempera-
ture. This must generally be corrected by
means of what is known as a buoyancy
correction measurement. The TGA BeFlat®
software module, however, allows for auto­
matic correction of the buoyancy effects
(Fig. 4). TGA BeFlat® takes into consider­
ation not only different sample carriers, but
also gas flow rates and types of gas.
This often makes a buoyancy correction
unnecessary, thus simplifying instrument
hand­ling and significantly increasing sam-
ple throughput. BeFlat® thus proves espe-
Fig. 4 Automatic buoyancy correction by means of TGA BeFlat ® – demonstrated with the cially useful for routine measurements.
example of calcium oxalate (sample mass: 15,6 mg)
For extremely small weight changes and for
measurements requiring very high preci-
sion, subtraction of the buoyancy correction
measurement is, of course, still available.
Buoyancy corrections – even those deter-
mined by means of TGA BeFlat® – can be
removed from and reloaded to the measur-
ing curve at any point in time by mouse-
click for a visible presentation of the raw
data; i.e., the raw data is always available
and remains unchanged.

Perfectly prepared for

gas analysis
TGA curve interpretation is simplified con-
siderably by coupling evolved gas analysis
(EGA) directly to an STA.
The mass-loss steps can be clearly charac-
Fig. 5 FT-IR and MS, simultaneously coupled with the STA 449 F5 Jupiter ® terized by identifying the gases released.

E 34 cfi/Ber. DKG 92 (2015) No. 5-6

 process engineering

With the right coupling, it is even possible

to quantify overlapping gases in a TGA step.
The STA F5 Jupiter ® offers the possibility
to couple up to two different gas analysis
instruments, such as FT-IR, MS and/or GC-
MS, simultaneously with a corresponding
control and evaluation software (Fig. 5).
In order to avoid condensation of the gases
released from the sample, the furnace out-
let (adapter head), the transfer line and the
inlet of, for example, the MS can be heated
up to 300 °C. The simultaneous “start/stop”
of the gas analysis instruments, impelled by Fig. 6 TGA and DSC curves of calcium oxalate monohydrate
the software, and the transfer of tempera-
ture values allows for the time and tem-
perature correlation of TGA-DSC data with
the EGA data.
Sophisticated import functions allow the
EGA, TGA and DSC data to be presented
and evaluated together.

Experimental and measurement

results from a broad variety
of applications
Some measurement results of typical appli-
cations will be described in the following.

Calcium oxalate monohydrate Fig. 7 TGA and DSC curves of a ZrO2 green body
CaC2O4 · H2O
Calcium oxalate monohydrate is a sub-
stance with well-defined decomposition
behaviour. The TGA steps – stoichiometric­
ally calculated from the decomposition re-
actions – are:

1st TGA step

CaC2O4 · H2O – H2O CaC2O4
12,33 mass-%
2nd TGA step
CaC2O4 – CO CaCO3
19,17 mass-%
3rd TGA step
CaCO3 – CO2 CaO
30,12 mass-% Fig. 8 TGA, DTG and DSC results on bentonite clay

Due to the good repeatability of its decom-
position steps, calcium oxalate monohy-
drate is ideally suited for testing both the
precision of the thermobalance and the
DSC/DTA performance.
Furthermore, the vacuum tightness of the
STA apparatus (e.g., the existence of a
pure inert gas atmosphere) can be easi-
ly checked. Even the smallest amounts of
oxygen in the instrument turn the second
endothermal decomposition peak (513 °C,
Fig. 6) into an exothermal effect because of
the oxidation of CO to CO2.
Binder burnout of a
zirconia green body
Due to their chemical and physical proper-
ties, zirconia ceramics (ZrO2) are applied in a
broad variety of fields. This spans from trad­
itional high-temperature ceramics to high-
temperature fuel cells or oxygen sensors.
The phase transition at approx. 1170 °C [2]
for pure ZrO2 can be suppressed by adding
small amounts of MgO or Y2O3 to the crystal
lattice. In this measurement example, the
TGA and DSC curves of a stabilized ZrO2
green body are evaluated (Fig. 7).
At approx. 67 °C, the binder in the ma-
ter­ial melts, indicated by a small endother-
mal DSC peak. The organic binder portion
burns out in two steps – with weight loss
steps of 1,2 and 2,2 mass-%. The two cor-
relating exothermal DSC peaks were evalu-

cfi/Ber. DKG 92 (2015) No. 5-6 E 35

 process engineering
ated at 197 °C and 399 °C in the heat-flow
curve. The exothermal heats of reaction dur-
ing the two-step burnout were determined
at –66 J/g and –306 J/g, respectively.
Bentonite clay
Bentonite is a mixture of different clay miner-
als with approx. 50–80 % montmorrillonite
[3] as its main component. Due to the large
internal surface of bentonite and its plastic
properties, this material is used in a great va-
riety of applications, e.g., as a sealing mate-
rial in oil drilling, a support material in struc-
tural and civil engineering, a drying agent,
an additive in paper and polymers, etc.
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Several weight-loss steps of bentonite re-
sulting from dehydration and dehydroxi-
lation of the clay minerals can be seen in
Fig. 8. In the DSC curve, these reactions ex-
hibit endothermal energetics since energy is
required for this.
The exothermal DSC effects (969  °C,
1181 °C), on the other hand, can be attri-
buted to solid-state reactions in which new
mineral phases are formed.
Summary
The STA 449 F5 Jupiter® is a favourably
priced, precise and universal instrument
for simultaneous thermal analysis cover-
ing a broad application range. The ability
to employ different sample carrier systems
and an automatic sample changer as well
as to connect a mass spectrometer, FT-IR
and/or GC-MS allows for efficient and prob-
lem-oriented adjustment and optimization
in sample analysis – as shown with these
examples.
References
[1] http://www.ictac.org/
ICTAC-IUPAC-TA_Nomenclature_2014.pdf
[2] http://en.wikipedia.org/wiki/
Zirconium_dioxide
[3] http://de.wikipedia.org/wiki/Bentonit
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