1 Introduction

The objective of calorimetry is the measurement of heat. To measure heat means

to exchange heat. The exchanged heat tends to effect a temperature change in a
body that can be used as a measure of the heat exchanged, or the process of heat
exchange creates a heat flow which leads to local temperature differences along
its path which again serve as a measure of the .flowing heat.
As chemical reactions and many physical transitions are connected with the
generation or consumption of heat, calorimetry is a universal method for inves-
tigating such processes. Measuring devices in which an exactly known amount
of heat is input into a sample, or abstracted from it, and the temperature change
in the sample is measured (determination of the heat capacity, for example), are
also referred to as calorimeters.
Caloric measurements have been carried out since the middle of the 18th cen-
tury. Although modern Differential Scanning Calorimeters (DSC) are widely
used today, the "classic" calorimeters cannot be dispensed with in precision
measurements and for special applications. The most important classic calorime-
ters will be described only briefly in Appendix 2 to give the reader a more com-
prehensive survey of the field of calorimetry (for a more general presentation of
calorimetry, cf. Hemminger, Hohne, 1984; Oscarson, Izatt, 1992).
The topic of this book is Differential Scanning Calorimetry (DSC) using as a
measuring instrument the Differential Scanning Calorimeter (DSC) available
in various designs (see Chapter 2). In addition to the measurement of heat,
DSCs are used to measure heat flow rates (power) and characteristic tempera-
tures of a reaction or a transition as well. The precise measurement of heat
capacities, which is of an increasing importance, has distinctly been improved
with modern DSCs. The measurement of heat not only includes integral (total)
heats of reaction or transition but also the determination of "partial heats"
developed within a selected temperature interval. Such values are of impor-
tance for kinetic evaluations, determination of crystallinity and purity (see
Chapter 6).
An accurate definition of Differential Scanning Calorimetry (DSC) is as
follows:

Differential Scanning Calorimetry (DSC) means the measurement of

the change of the difference in the heat flow rate to the sample and to a
reference sample while they are subjected to a controlled temperature pro-
gram.

G. W. H. Höhne et al., Differential Scanning Calorimetry

© Springer-Verlag Berlin Heidelberg 2003
2 1 Introduction

It is important to understand that DSC measures the change of a property -

namely of a heat flow rate difference - which normally is released due to an al-
teration of the sample temperature. When there is no alteration of the sample
temperature, no change of a heat flow rate difference can be measured (except
for possible chemical reaction heat flow rates). That means, a distinct tempera-
ture program, or in general a "mode of operation", is always part of a DSC mea-
surement (cf. Chapter 2). In the case of thermally activated reactions/transitions,
e. g. by a controlled stepwise change from one constant temperature to another,
the sample's temperature undergoes an alteration by internal processes and
causes the DSC signal.
It should even be mentioned, that heat only flows if there is a temperature
difference present. In other words, a non-zero heat flow rate difference implies
always a temperature difference between the sample and the reference and their
surroundings and a change of the heat flow rate difference implies a change of
the temperature as well.

Differential Thermal Analysis (DTA)

To distinguish a heat flux DSC from an apparatus for Differential Thermal

Analysis (DTA), the latter will be characterized in the following.
Differential Thermal Analysis is applied to measure the temperature differ-
ence between the sample to be investigated and a reference sample as a function
of temperature (or time). This temperature difference indicates a heat exchange
qualitatively. DTA is of more recent date than classic calorimetry. Its advantages
as compared with conventional calorimetry are the dynamic mode of operation
("scanning") which allows reactions or processes to be investigated which can
be thermally activated, and the high sensitivity to anomalies of the temperature-
time function. DTA allows characteristic temperatures to be determined and
qualitative statements made on heat due to reaction. The further development of
DTA has led to the construction of Differential Scanning Calorimeters (DSCs)
with disk-type measuring systems.
The widely used term Differential Thermal Analysis (DTA) means a thermo-
analytical method, which is more than a thermoanalytical (measurement) tech-
nique (see the following definition), because the method (analysis) includes in
principle the thermoanalytical investigation procedure, i. e. the evaluation and
interpretation of the measured values. An accurate definition for the thermo-
analytical technique is:

Differential Thermometry (DT) means the measurement of the change

of the difference in temperature between the sample and the refer-
ence sample while they are subjected to a controlled temperature pro-
gram.

The accurate term for the affiliated thermo analytical method is then Differen-
tial Thermal Analysis (DTA). For a short description of the principle of DTA
measuring systems in comparison with DSC, see Appendix 1.
1 Introduction 3

Calorimetry and OTA Today

Owing to the new materials and sensors used and the application of modern
mechanical manufacturing (micro and nano technologies), advanced data pro-
cessing by modern electronic systems, all calorimeters available today - includ-
ing the so-called "classic" calorimeters - are instruments which allow precise
measurements to be carried out with high sensitivity and repeatability (see Sect.
7.2), their operation being relatively simple or perhaps even automated. Caloric
methods are used in many fields for quality assurance purposes (cf. series of
standards ISO 9000). The standards to be applied in the field of quality assur-
ance (e.g., the standard ISO/IEC 17025, 1999: General requirements for the
competence of testing and calibration laboratories) demand a large variety of
measures to ensure reliable measurement results, for example, the application of
well-proven methods for the preparation of samples, reliable measurement
methods, calibration methods and calibration materials traceable to standards
(see also Chapter 4).
In the following, reference is made to some of the fields in which calorimeters
are widely used today (see Hemminger, Hohne, 1984; Wunderlich, 1990; Oscar-
son, Izatt, 1992). A suggestion how to classify calorimeters is given in Appendix 2.

- With bomb calorimeters, combustion heats (gross calorific values) are mea-
sured on a large scale in industry (costs of fossil fuels) (Sunner, Mansson,
1979).
- Gas calorimeters (flow calorimeters) are used for the continuous or discon-
tinuous measurement of the calorific value of fuel gases (e.g., natural gas),
both in frontier-crossing commercial transactions (between supplier and
buyer) and for the calculation of the costs for the individual consumer (Hyde,
Jones, 1960; Hemminger, 1988; Sarge, 1997; Ulbig, Hoburg, 2002; Jaeschke,
2002; Dale et al., 2002; Alexandrov, 2002).
- Drop calorimeters (usually self-made) allow mean heat capacities or enthalpy
differences to be quickly measured. Drop sample temperatures of up to
2000°C are realized (Chekhovskoi, 1984).
- Different types of isoperibol mixing calorimeters are used to investigate reac-
tions between two fluids or between a fluid and a solid (reaction heats, heats
of solution, heats of mixing, adsorption heats) (see, e.g., Parrish, 1986).
- Reaction calorimeters and safety calorimeters allow model tests of procedures
applied in industrial chemistry to be carried out. These instruments provide
valuable support in development and optimization tasks, as all test parame-
ters (temperature, time, addition of substances etc.) are completely docu-
mented and can be varied automatically (Landau, 1996).
Questions of process technology which are also important for the dimen-
sioning of production facilities, may be well in the fore here (Regenass,
1985). Reaction heat released is connected with the degree of conversion
and exploitation, for example, in biotechnology, where calorimetric studies
are carried out on industrial production plants (large-scale calorimetry,
mega-calorimetry, see, e.g., von Stockar, Marison, 1991 in Lamprecht et aI.,
1991).
4 1 Introduction

Special calorimeters (commercially available) are also used to investigate

aspects of safety technique, for example, to determine characteristic temper-
atures of decomposition or the kinetics of reactions (decompositions, run-
away reactions) under certain boundary conditions (see, for example, Grewer,
1987; Schwanebeck, 1991; Singh, 1993; for a survey,cf. Grewer,Steinbach, 1993).
- In highly sensitive flow calorimeters (usually of the isoperibol type, i. e., with
surroundings at constant temperature), the heat generation of biological sys-
tems and their change at varying conditions of life are investigated (for ex-
ample, addition of pharmaceuticals to bacterial cultures). In different types of
biocalorimeters, the metabolism of organisms and their change due to exter-
nal influences (optical, acoustical, mechanical, thermal, chemical) are studied
(see, e.g., Spink, Wadso, 1976; Lamprecht, Schaarschmidt, 1977; Beezer, 1980;
Lamprecht et aI., 1991).
- Heat capacities and heats of transition are directly measured with high accu-
racy using adiabatic calorimeters. The characteristic data of materials deter-
mined with their aid are an indispensable basis for the calibration of the DSCs
(see, e.g., Gr0nvold, 1967; Kagan, 1984; Jakobi et aI., 1993; Gr0nvold, 1993).
Properly calibrated DSCs allow specific heat capacities to be measured with
an accuracy of 1 to 2 % (see Sect. 6.1; cf. Richardson, 1992a).
New fields of application are constantly being opened up for the modern, highly
automated DSCs. DSC is increasingly used in the field of quality assurance for
many purposes: for the inspection of raw materials, as an accompanying mea-
sure in the manufacture and for the control of the finished products. The basic
limitations to, and the problems of these instruments should not, however, be
forgotten in view of the ease of operation and evaluation.
DSCs allow reaction heats and heats of transition, or heat flow rates and their
changes at characteristic temperatures, to be quickly measured on small sample
masses (milligram range; in the case of classic calorimeters: gram range), in wide
temperature ranges and with an accuracy which is usually sufficiently high for
the respective purpose. DSCs are applied in the following fields (among others):
- characterization of materials (in particular polymers),
- comparison (relative) measurements (quality control, identification of sub-
stances or mixtures),
- stability investigations,
- evaluation of phase diagrams,
- purity determinations,
- kinetic investigations,
- safety investigations,
- determination of heat capacity and complex heat capacity (with TMDSC).
Now as before, instruments used for Differential Thermal Analysis (DTA) offer
particular advantages when special problems are to be investigated:
- they can be used at very high temperatures (up to about 2400°C),
- they are highly sensitive,
- they are most flexible as regards the volume and form of the crucibles,
- their reasonably-priced measuring system can be easily exchanged.
1 Introduction 5

Characteristic temperatures of transitions or reactions can be very well deter-

mined by DTA. Heats can still be estimated with an uncertainty between 20 and
50 %. DTA is applied in the following fields:
- comparison (relative) measurements (identification, control, comparison),
- safety research (stability investigations, also long-time investigations), see,
e. g., Hentze, 1984; Hentze, Krien, 1986,
- investigation of transitions, decompositions, reactions with gases,
- evaluation of phase diagrams.
DSC and DTA are also used together with other methods of thermal analysis or
other analytical techniques (simultaneous thermal analysis), most frequently
in connection with thermogravimetry (TG), more rarely with Evolved Gas Ther-
moanalysis (EGA), Thermomicroscopy (TOA) or Thermosonimetry (TS).
The coupling of DSC or DTA with Thermogravimetry (TG) is of particular
importance. In addition to information on changes in the heat flow rate (due, for
example, to changes of Cp) and heats of transition, the TG signal provides infor-
mation on whether volatile components are involved and which changes in mass
are to be attributed to a transition.
The different methods of gas analysis used together with DSC or DTA (usual-
ly together with TG/DSC or TG/DTA systems) are of increasing importance.
Via a carrier gas stream, gaseous reaction products from the calorimeter or DTA
device are transported to an apparatus (e. g., IR or mass spectrometer) in which
these products are analyzed. This allows a correlation between the characteris-
tic temperature of a reaction, gravimetric and/or enthalpic information and
the composition of the volatile reaction product to be made (see examples in
Mathot,1994a).
It is difficult to transfer the volatile products without adulteration from the
hot sample to the analysis system (condensation must be avoided). Various sys-
tems for coupling quadrupole mass spectrometers are commercially available
(up to temperatures of 2400 0c). Examples of the investigation of volatile com-
ponents applying methods of gas analysis can be found in Ohrbach et al., 1987;
Matuschek et al., 1991; Matuschek et al., 1993; Kaisersberger, 1997.
The advantage of simultaneous measurements is that the same sample is
investigated under identical conditions and that diverse information is ob-
tained by one measurement run which is important for interpretation pur-
poses. The following potential disadvantages of simultaneous instruments
should be mentioned: lower sensitivity, higher susceptibility to failure, in-
creased time and effort required for preparation and operation, higher instru-
ment costs.
In Differential Scanning Calorimetry which is widely applied, there are still
some actual problems of which one should be aware:
- The theoretically well-founded complete understanding of DSC is not yet
totally accepted. The average user does not yet know the limits to this method
and the sources of the systematic errors by which it is affected. This is in par-
ticular true for the temperature-modulated DSC, its theoretical background
is still a matter of controversial discussion.
6 1 Introduction

- There are not yet any practicable and experimentally tested recommenda-
tions for temperature and heat calibration and for measurement procedures
which are internationally accepted (see Chapter 4; and some examples in
Della Gatta et al., 2000).
- There is no international agreement on a single set of substances for the tem-
perature and heat calibration of DSC which have been measured with suffi-
cient accuracy, including a metrologically sound traceability to national/in-
ternational standards; instead there is a confusing variety of "certified refer-
ence materials" whose characteristic data are in part contradictory. Sub-
stances which are certified on a metrologically basis (i. e., traceable to the SI
units) are offered by the German Metrology Institute (PTB) (cf. Sect. 4.6).
Due to the rapidly increasing use of DSCs in various fields of application, some
negligence has gained ground - favored by the ease of operation and evaluation
- which would be inconceivable in "classic" calorimetry. Remedial measures
should be taken; for example, the national societies of the International Con-
federation for Thermal Analysis and Calorimetry (ICTAC) should offer special
training courses, and precise specifications for instruments and programs
should be drawn up.
The following can frequently be observed:
- A realistic estimate of the uncertainty of measurement is rarely made (cf.
Sect. 7.3). The calibration capability (cf. Chapter 4), different influencing
quantities (cf. Sect. 5.2) and known theoretical considerations (cf. Chapter 3)
should be taken into account. In many cases, the repeatability of a DSC is, for
example, simply, but wrongly, indicated as accuracy of the measured data (cf.
Sect. 7.3).
- Interpretation of the DSC measurement results is often insufficient or faulty,
when
- uncertainties of measurement are not taken into consideration;
- systematic error sources are disregarded;
- the measured curve is not "desmeared" (cf. Sect. 5.4);
- the laws of thermodynamics, kinetics, are not taken into account;
- uncritical confidence is placed in the evaluation programs provided by the
manufacturer;
- the results are not confirmed by other measuring methods.
A great number of calorimetric methods has not been mentioned here as, in
comparison with DSC, they are used only in specific fields. To name a few ex-
amples:
- low-temperature calorimetry for measuring heat capacities (see, e. g., Gmelin,
1987),
- more recent techniques of cp measurement (see, e.g., Lakshmikumar, Gopal,
1981; Maglic et aI., 1984),
- measurement of the energy of particle radiation (see, e. g., Domen, 1987),
- measurements on biological systems (see, e. g., Lamprecht et al., 1991; Wadso,
1993 and Kemp, 1993; Kemp et aI., 1998; Hansen, 2000),
1 Introduction 7

- deformation calorimetry on polymers (see, e. g., Kilian, Hahne, 1983; Godovsky,

Hahne, 1994),
- high-temperature calorimetry in material science (see, e.g., Bruzzone, 1985;
Bros, 1989).
- (high)-pressure calorimetry (see, e. g., in Mathot, 1994 b; Hahne, 1999 b),
- AC calorimetry (Sullivan, Seidel, 1968) and 3w calorimetry (Rosenthal, 1961).

Summary

During the last decades the development of Differential Scanning Calorimetry

from a half-quantitative DTA method (producing "thermograms") toward a true
calorimetric method (yielding quantitative caloric quantities) forged ahead.
This becomes manifest from the following items which hopefully will be proved
within this book.
- The theory of (heat-flux) DSCs is well-known and the function principle un-
derstood.
- Systematic (unavoidable) error sources and methods of correction are
known.
- Modern data treatment and powerful computers make it possible for every-
one to make the necessary evaluations without problems.
- Metrological founded calibration and measurement procedures improved the
certainty of the results which nowadays are comparable with those obtained
with classical calorimeters.
- The difference in quality of the results from heat-flux and power-compensat-
ed DSCs has diminished.
- Precise heat capacity measurements are possible and open the door for other
well-defined thermodynamic quantities.
- Coming to terms with the problem of the thermal inertia (thermal lag) en-
ables kinetic investigations which otherwise need much more experimental
efforts.
- DSC is a fast and reliable method in a wide field of different applications.