Handbook of Thermal Analysis and Calorimetry. Vol. 1: Principles and Practice.

M.E. Brown, editor.

9 1998 Elsevier Science B.V. All rights reserved. 497

Chapter 11

SIMULTANEOUS T H E R M A L ANALYSIS

J. Van H u m b e e c k

Dep. MTM-K.U.Leuven, W. de Croylaan 2, 3001 Leuven (Heverlee), Belgium

1. I N T R O D U C T I O N

Simultaneous thermal analysis, STA, is a standard term to indicate the

simultaneous application of different types of (thermal analysis) techniques.
Generally the word simultaneous has to be interpreted very strictly: on one and
the same sample at the same time. This means that different types of sensors are
(in-)directly connected to the same sample. This sample is further heated or
cooled in a single furnace. It should thus be clear that we do not discuss results
obtained from two different samples, even if they are heated or cooled in a
single furnace at the same time. Simultaneous measurements must thus be
distinguished from parallel measurements, where different samples are
examined using different instruments.
There are many reasons for performing simultaneous thermal analysis:

1. Simultaneous measurements need much less time to perform all required

measurements than when each of the recorded properties is measured
separately.
2. Accurate correlation of the observed different events is assured.
3. Because of a synergetic effect in that the total amount of information about
the sample that is obtained is greater than the sum of the information
obtained from the individual techniques [ 1].
4. The same sample (size, mass, surface, morphology, composition) is
monitored by different techniques but under identical external factors
(heating or cooling rate, gas-flow, gas-composition, type of furnace, ...).
This can lead to a much more correct interpretation and correlation than for
the results obtained by different techniques.
 498

. The price of a STA-instrument is lower than the purchase of each thermal

analysis instrument separately if all those instruments are necessary for use at
similar intensity.

As a drawback, simultaneous thermal analysis instruments are generally more

complicated, because different sensors have to be combined. This might lead to a
reduction of sensitivity for one or more signals because of compromises in
instrumental design. Compromises in measurement parameters can also lead to less
clear signals. Regarding the combination of sensors, there is basically no limit. It
is only restricted by the ingenuity of the investigator and, to some extent, by the
technological state of the art of the different sensors and signal detectors.
Complementary techniques might include all forms of physical, chemical and
mechanical property measurements and all forms of spectroscopy, such as X-ray
diffraction, mechanical spectroscopy, electron- and optical spectroscopy. It is not
the purpose to discuss all of these potential combinations in this chapter. A very
well-known coupled simultaneous measurement, TG-EGA (evolved gas analysis)
is treated in Chapter 12. In this chapter we will deal mainly with combinations of
classical thermal analysis techniques with less common, but for some research areas,
successful techniques.

0 SIMULTANEOUS T H E R M O G R A V I M E T R Y - D I F F E R E N T I A L
SCANNING C A L O R I M E T R Y TG-DSC (DTA)

2.1. Calibration
The most common single sample simultaneous thermal analysis technique is the
combination of DSC (or DTA) and TG. A first important advantage of this
combination is the possibility of temperature calibration by using the DSC (DTA)
sensor (see also Chapter 13). Endo- or exothermic effects at invariant point
transitions (i.e. melting, eutectic points, ...) can be much more accurately detected
than weight changes, occurring at particular temperatures. According to
ANSI/ASTM 1582-93 a TG can be calibrated by two methods: one method uses an
indirect melting point measurement by dropping a part of the sample, causing a
disruption of the weight. It is evident that the TG-fumace may need cleaning
afterwards. The second method uses Curie point standards. A magnet placed at/or
around the fiamace will not affect the magnetic sample above the Curie point of the
sample, but causes a "balance disruption" when the sample passes through crossing
the Curie point. Drawbacks of this method are: availability of (sometimes) complex
materials, instability of the sample _due to oxidation (thermal history),....
 499

Heating m a DSC is done primarily by conduction, while, due to the large size
and construction of the TG-fumace, heating of the sample occurs by convection and
radiation [2]. The sensitivity of the calibration constant to the heating rate will thus
be more important for TG-DSC than for DSC alone.
Another important advantage is the fact that any endo- or exothermic flux can
be directly related to the actual mass of the sample or the reacted fraction of the
sample. Since both measurements are made on a single sample, a high accuracy of
the heat exchange per unit mass (reacted, evaporated, sublimated, ...) can be
obtained. Since the heat released is thus proportional to the transformed (reacted)
volume fraction, the derivative of the sample mass dm/dt (derivative
thermogravimetry) will have a similar appearance to the heat flux (DSC) or DTA
signal. Of course, this is only valid for chemical reactions, where the mass change
is responsible for the energetic effect. The conclusion is not valid for solid state
transformations (without mass change) and meltmgs. The software available allows
easy plotting of m, dm/dt as function of temperature. This makes detailed
interpretation easier and more correct.

2.2. Technical aspects of TG-DTA (DSC) equipment

Almost every supplier of TG and DSC equipment has STA available. Except
in case of power-compensated DSC, TG and DSC can be combined with relative
ease. As mentioned earlier, the TG-DTA and TG-DSC cells are generally so
conceived that they contain the sensor elements (thermocouples, heat-flux plate
sensor) in the lever arm of the TG-balance at the position of the sample and
reference, as illustrated in Figure 1.

SampleCup/SampleThermocoupleConfiguration

Figure 1. Schematic view of sample cup/sample.

Thermocouple configuration for TG-DSC (TA Instruments).
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The Setaram TG-DSC 111 is an exception (Figure 2). There is no

mechanical contact of the sample pans with the detectors of the DSC tubes
(Calvet principle). The whole concept is claimed to result in very accurate
weighing. This instrument is promoted for measurement of vaporisation and
sublimation enthalpies: the TG signal measures the mass that is evaporated and
the DSC signal gives the corresponding heat of evaporation. For such an
experiment, a Knudsen-type cell is used [3].

/ \

gas-tight
enclosure

symmetrical
microbalance

gas supply

suspensions

access pits

-sample" crucible

"reference" crucible

surrounding
heatflux transducers

calorimeter

gas flow
control output

Figure 2. Schematic view of the SETARAM TG-DSC 111 with two hanging
arms, each arm surrounded by a heat flux sensor.
 501

The exact value of the sample mass is not needed for the heat calculation. A
good stable baseline for TG and DSC is most important.

-1) _ DSC deviation ( W )

~vap (J g (1)
D T G d e v i a t i o n (g s -1)

A similar derivation can be obtained for any instrument and the final
resolution is dependent on the accuracy of measurement of the separate signals.
Depending on the supplier, different types of systems are constructed. The
accuracy of weighing ranges from 0.1 ~tg to 1 ~tg, depending on the allowed
mass of the sample, which ranges from 200 mg up to 500 g. There is also a
wide choice in temperature ranges starting at low temperatures, -125 ~ up to
1100 ~ or even 1500~ Some instruments offer measuring temperatures up to
2000~ and higher. Most of the equipment can be easily changed from TG to
TG-DTA or TG-DSC depending on the sensor. Generally a wide choice of
sensors and sample containers is available.
Figure 3 shows a schematic vertical-standing single arm STA that can be
equipped with different types of sensors, while Figure 4 shows a schematic
balance of a horizontal double-arm balance.

- - protective tube
for gas flow

he~ing element conhd ~enT~cou~e

TG-DSC-sompte
corrler

rodlalton shields
vacuum seal

lt~mostattc controt
K r n p ~ gas inlet
balance gas Inlet

vocuLrn S ~ T I
tTansducer

electTomagnetlc
con3pE~sofloR

Figure 3. Schematic view of a vertical single-arm STA (Netzsch).

502

Figure 4. Schematic view of a horizontal double arm TG-DSC

(TA instruments).

The mode of construction is quite different, dependent on the company

providing the equipment. As usual the best choice is a personal decision depending
on the specific requirements for the samples, the economic situation of the purchaser
and, in some cases, the wide variety of samples and users, i.e. universities require
student-proof msmmaents. For discussion of the weighing principle (null-deflection
balance or not, compensation for buoyancy effects, the influence of a "chimney-
effect" depending on the gas-inlet), refer to Chapter 4 on TG.
Table I summarises the concept of some instruments as could be deduced from
information brochures. This list is certainly not exhaustive.
 503

Table 1
Company System TGA-DSC (DTA)

TA Instruments Horizontal - two separate lever arms

Seiko Horizontal - two separate lever arms
Mettler Horizontal - a single arm - no reference sample
(based on the SDTA principle)
B~hr Horizontal - a single arm with serial mounting
of sample and reference
Rheometrics Scientific Vertical - a pending arm with parallel mounting
(former Stanton Redcroft) of sample and reference
Netzsch Vertical - a standing arm with parallel mounting
of sample and reference
Setaram I Vertical - a standing arm with parallel mounting
of sample and reference
Setaram II Vertical - two hanging separate arms with heat-
sensors surrounding the reference and the
sample separately

3. S I M U L T A N E O U S T H E R M O M E C H A N I C A L ANALYSIS-
DIFFERENTIAL THERMAL ANALYSIS (TMA-DTA)

Although not difficult to construct, because there are no free moving or driven
parts included, the combination of TMA-DTA is uncommon. Nevertheless, the
same arguments as given in the introduction can be applied to this technique. The
different methods of TMA (linear expansion, penetration, volume change
measurements), allow collection of quite different types of information, such as
weakening, melting, demixing, etc., but not all of those effects are accompanied by
heat exchange. A combination with DTA or DSC could give simultaneous
information for the same sample, measured in identical circumstances.
The combination of Dynamic TMA and DTA can also give interesting
information on the dimensional changes and rigidity accompanying melting.
504

Mettler has released in 1998 a special module TMA/SDTA840 with high

dimensional resolution and temperature accuracy. A schematic view is given in
Figure 5 [4]. TMA is discussed in detail in Chapter 6.

1 Gas outlet stopcock 11 Thermostated cell housing

2 Clamp with screw 12 Force generator
3 Furnace windingsg 13 Length sensor (LVDT)
4 Water-cooled furnace jacket 14 Bending Bearings
5 Sample support 15 Adjustment weights
6 Furnace temperature sensor 16 Protective gas inlet
7 Sample temperature sensor 17 Reactive gas inlet
8 Reactive gas capillary 18 Vacuum and purge gas inlet
9 Measuring probe 19 Watercooling
10 Gaskets

Figure 5. Schematic view of the TMA-SDTA (Mettler).

 505

4. SIMULTANEOUS DIFFERENTIAL SCANNING C A L O R I M E T R Y -

T H E R M O P T O M E T R Y MEASUREMENT (DSC-TOA)

Heating stages for microscopes are available in a very wide temperature range
(liquid nitrogen to 2000~ Visual inspection of the sample is thus possible as
function of temperature. Information like colour change, decomposition, melting,
polymorphism can be easily observed. In combination with a photomonitor, the
light intensity of a reflected beam can yield information on the sample that is
difficult to detect by other methods. This allows a certain quantification of the
envisaged effects. This visual inspection can be combined with another quantitative
measurement such as DSC or DTA (see also Chapter 10).
Mettler developed a special module that can operate in the temperature range
- 60~ to 375~ based on a s-element thermopile DTA sensor deposited on a
special glass disc. The sample is placed in a sapphire crucible in transmitted light
(Figure 6).

CONVENTIONAL MICROSCOPY WITH DSC

DSC

A !

i K \ "k \ \ \ ' i
:1 I
SYMMETRIC CELL ASYMMETRIC CELL

Figure 6. Conventional DSC and Thermomicroscopy- DSC [5] (Mettler).

In reference [5] a method is described for the purity determination of an

eutectic mixture by DSC-TOA. The observation of the molten fraction as
function of temperature is used as parameter for purity determination on a single
sample, without the need for a pure reference sample. The method can be used
in the area of dyes, liquid crystals, pharmaceuticals, fats and various organic
compounds (more details are given in Chapter 10).
506

5. SIMULTANEOUS DYNAMIC M E C H A N I C A L ANALYSIS-

DIELECTRIC THERMAL ANALYSIS (DMA-DETA)

Although recommended by ICTAC, the nomenclature DETA is clearly poorly

accepted by the users, who are more familiar with DEA. So it should be clear that
the difference between DEA and DETA is purely semantic. Although both
techniques DETA (Chapter 7) and DMA (Chapter 6) are quite different, basically
they rely on the same principle: measuring a phase shift between an applied
sinusoidal signal and the response signal from the sample. DETA gives information
on the mobility of charged sites in a material (ions, dipoles) and DMA provides
information on the mechanical behaviour of the material. Perkin-Elmer has
developed an apparatus in which both techniques are applied to the same sample
[6]. The DETA measuring system is mounted on the Perkin-Elmer DMA equipped
with the DETA interface, so that the sample can be loaded m the fimaace and DETA
can be started simultaneously. Figure 7 illustrates DMA-DETA parallel plate
geometry. The combined technique can be used to correlate the DETA viscosity
and the DMA storage modulus of prepregs, by establishing a relationship between
the curing properties and the viscoelastic properties and determining the gel and
vitrification points, as well as the viscosity change and rate of reaction.

Simultaneous DMA-DETA
DMA7e

Mid Conductivity
Interface

g..~

Perkin- ElmerDMA7e MicrometInstruments

DynamicMechanical EumetricSystemIII
Analyzer Dielectrometer

Figure 7. Schematic view of the simultaneous DMA-DETA (Perkin-Elmer).

 507

6. OTHER TECHNIQUES

In spite of important advantages, simultaneous thermal analysis remains less

popular than single or parallel measurements. Nevertheless, the above examples of
S TA have illustrated the potential of this methodology and the list of possible
combinations is certainly not Complete. Indeed for specific materials, such as
metals or ceramics, "home-built" equipment for simultaneous temperature-
dependent measurements could reveal specific information. As such, the
simultaneous measurement of thermal energy and acoustic emission produced by
a solid-solid martensitic transformation in intermetallic Cu-based alloys has been
applied to study the growth kinetics of martensite variants during cooling and
heating [7]. The influence of fatigue on the constitution of thermoplastic
vulcanisates for biomedical applications has been studied by combined DSC-SAXS-
WAXS (Differential Scanning Calorimetry-Small and Wide Angle X-ray
Scattering)[8].
The main questions or problems related to STA remain whether the results
obtained are as accurate as in single experiments, and whether the resolution and
sensitivity of each signal obtained in STA are the same as those in single TA mode.
If resolution and sensitivity are not critical, the advantages of STA, as enumerated
in the introduction, should be taken into account when selecting appropriate
experiments.

ACKNOWLEDGEMENTS

The author thanks the representatives of all mentioned companies for providing
documentation, literature and permission for publication related to their specific
products for STA.

REFERENCES

1. M.E. Brown, Introduction to Thermal Analysis, Chapman and Hall, London,

1988, Chap.4.
2. J.P. Redfem, Polymer Intemational, 26 (1991) 51.
3. G. Della Gatta, L. Benoist, P. Le Parlouer, 22th NATAS Conference
Proceedings, Denver, September 1993.
4. Mettler, private communication.
5. Mettler Application Note No. 806, H.G. Wiedemann and R. Riesen, Purity
Determination by Simultaneous DSC-Thermomicroscopy.
6. Perkin-Elmer, Thermal Analysis Newsletter, PETAN-55.
508

7. C. Picomell, C. Segui, V. Torra, J. Hemaer, C. Lopez del Castellio,

Thermochim. Acta, 91 (1985) 311.
8. J.A. Helsen, S.V.N. Jacques, Recent Research Developments in Polymer
Science, 1 (1996) 19.