Thermal Methods of Analysis: Principles, Applications and Problems

Thermal Methods of Analysis

Principles, Applications and Problems

Thermal Methods
of Analysis
Principles, Applications
and Problems
P.]. Haines
With contributions by

M. Reading T.J. Lever

F.W. Wilburn J.W. Brown
D. Dollimore M.R. Worland
E.L. Charsley w. Block
S.B. Warrington
SPRINGER-SCIENCE+BUSINESS MEDIA, B.V. I~n

First edition 1995
© 1995 Springer Science+Business Media Dordrecht
Origina11y published by Chapman & Hali in 1995
Typeset in 10/12 pt Times by Photoprint, Torquay, Devon
ISBN 978-0-7514-0050-2 ISBN 978-94-011-1324-3 (eBook)
DOI 10.1007/978-94-011-1324-3
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Preface
The wide range of applications of thermal methods of analysis in measuring

physical properties, studying chemical reactions and determining the
thermal behaviour of samples is of interest to academics and to industry.
These applications prompted the writing of this book, in the hope that the
descriptions, explanations and examples given would be of help to the
analyst and would stimulate the investigation of other thermal techniques.
Thermal studies are a fascinating means of examining the samples and
the problems brought to us by colleagues, students and clients. If time
allows, watching crystals change on a hot-stage microscope, or measuring
the properties and changes on a DSC or TG or any thermal instrument can
be a rewarding activity, besides providing valuable analytical information.
This book started from a series of lectures delivered at Kingston
University and at meetings of the Thermal Methods Group of the United
Kingdom. The collaboration and information supplied to all the contribu-
tors by colleagues and instrument manufacturers is most gratefully ack-
nowledged, as are the valuable contributions made at meetings of the
International Confederation for Thermal Analysis and Calorimetry
(ICTAC) and at the European Symposia on Thermal Analysis and
Calorimetry (ESTAC).
I am particularly grateful to Dr Michael Reading and Dr Fred Wilburn
and to all the other contributors for lending their expertise to the
production of this book. Thanks are also due to Dr Trevor Lever of TA
Instruments and Dr John Barton of DRA, Farnborough for most helpful
discussions. I thank the publishers for their support and advice throughout.
To Dr Fred Wilburn I should like to express the greatest personal thanks
for his many helpful suggestions and contributions and for his invaluable
assistance in reading the whole manuscript.
The completion of this book would not have been possible without the
help, sustenance and support provided by my wife, Elizabeth. I thank her
for her patience and calm during many hours of work.
Peter J. Haines
Contributors
Professor E.L. Charsley TACS, Leeds Metropolitan University, Calverley

Street, Leeds LSI 3HE
Professor D. Dollimore Department of Chemistry, University of Toledo,

2801 W Bancroft Street, Toledo, OH 43606-3390, USA
Mr P.J. Haines 38 Oakland Avenue, Weybourne, Farnham, Surrey GU9

9DX
Dr T.J. Lever TA Instruments Ltd, Europe House, Bilton Centre, Cleeve

Road, Leatherhead, Surrey KT22 7UQ
Dr M. Reading Physics Section, Research Department, ICI Paints,

Wexham Road, Slough, Berkshire SL2 5DS
Dr. F.W. Wilburn 26 Roe Lane, Southport, Merseyside PR9 9DX

Acknowledgements
The authors wish gratefully to acknowledge permissions to reproduce

figures in this book granted by the instrument manufacturers, authors and
publishers listed below and identified by the references throughout the
book.
American Laboratory for Figures 4.22, 4.33 and 5.12
British Antarctic Survey for Figure 6.4.6
C I Electronics Ltd for Figure 2.3
Chapman & Hall Ltd for Figure 4.20
Elsevier Science Limited for Figures 2.13,3.44, 5.13, 5.22, 5.28 and 5.31
from Thermochimica Acta, and for Figure 2.18 from Talanta
EMAP-Maclaren for Figure 1.3
International Labmate for Figure 5.6
Laboratory Practice for Figure 1.3
Linkam Scientific Ltd for Figure 5.24a, and for help with the hot-stage
microscope photographs of Figures 5.26 and 6.3.3
Mettler-Toledo for Figures 3.17, 3.28, 4.9 and 5.24b
Netzsch-Mastermix Ltd for Figures 2.5, 2.6 and 5.1
Perkin-Elmer Ltd for Figures 2.23,3.5,3.26,4.14, 5.18 and 5.20
Rheometric Scientific Ltd (formerly Stanton Redcroft Ltd and Polymer
Laboratories) for Figures 2.17,2.22,2.25,3.40,3.41,4.20--4.22,4.24,4.30,
5.10b, 5.11 and 5.17.
The Royal Society of Chemistry for Figures 3.33 and 4.26-4.28
Dr A.l. Ryan for Figure 5.35
Setaram for Figures 3.48, 4.17 and 5.7
Shimadzu for Figures 6.21a and b
Solomat Instruments Ltd for Figures 4.31 and 4.32
TA Instruments Ltd (formerly DuPont Instruments) for Figures 2.20, 2.26,
3.4,3.51,3.53-3.56,4.5,4.12,4.15,4.18,5.3, 5.lOa, 6.2.7, 6.3.5 and 6.4.6
Thermal Analysis Consultancy Services, Leeds for Figures 5.2, 6.1.2 and
6.2.4
The Thermal Methods Group (UK) for Figures 3.38 and 3.39
John Wiley & Co Ltd for Figures 2.27,2.28,3.15,3.24,3.45,5.13,5.16,
5.29, 5.32-5.34 and 6.4.1a-e from the Journal of Thermal Analysis, for
Figure 5.9 from Proceedings of 2nd European Symposium on Thermal
Analysis 1981, and for Figures 2.8 and 5.30 from Proceedings of the 7th
ICTA Conference, 1982.
Contents
1 Introduction to thermal methods 1

P.J. HAINES
1.1 Introduction 1
1.2 Historical development 3
1.3 Definitions 3
1.3.1 Thermal analysis 4
1.3.2 Equilibrium 7
1.3.3 General apparatus 9
1.4 Computers and thermal methods 11
1.4.1 The computer as an instructional tool 12
1.4.2 The computer as a data gatherer 12
1.4.3 The computer as a data processor 13
1.4.4 The computer as a research tool 13
1.5 Factors affecting thermal analysis results 13
1.5.1 The sample 14
1.5.2 The crucible 15
1.5.3 The rate of heating 15
1.5.4 The atmosphere 16
1.5.5 The mass of the sample 18
1.6 Simultaneous and complementary techniques 18
1.7 Problems 19
References 20
General Bibliography 20
2 Thermogravimetry 22
P.J. HAINES
2.1 Introduction 22
2.2 Historical 22
2.3 Definition of thermogravimetry 23
2.4 Apparatus 23
2.4.1 The balance 24
2.4.2 Furnace 28
2.4.3 Programmer 28
2.4.4 Samples 28
2.4.5 Temperature calibration 29
2.4.6 Atmosphere 31
2.5 Kinetics of reactions 31
2.5.1 Measurement of (l and dwdt 34
2.6 Applications of thermogravimetry 42
2.6.1 Thermogravimetric curves 42
2.6.2 Analysis of mixtures 48
2.6.3 Oxidation studies 54
2.6.4 Reduction studies 54
x THERMAL METHODS OF ANALYSIS
2.7 Controlled rate thermogravimetry and Hi-Res™ TGA 56
2.7.1 Polymer blends 56
2.7.2 Fuel additives 57
2.7.3 Drugs 58
2.8 Problems 59
References 60
Bibliography 62
3 Differential thermal analysis and differential scanning

calorimetry 63
P.J. HAINES and F.W. WILBURN
3.1 Introduction 63
3.2 Historical 63
3.3 Definitions 64
3.3.1 Differential thermal analysis (DTA) 64
3.3.2 Differential scanning calorimetry (DSC) 65
3.4 Apparatus 66
3.4.1 The sensors 66
3.4.2 The furnace and controller 68
3.4.3 The computer and display 69
3.4.4 The reference material 69
3.5 Theory of DTA and DSC 69
3.6 Heat flux DSC 74
3.7 Power-compensated DSC 76
3.7.1 The effect of higher temperatures 76
3.7.2 Sample size 76
3.8 Calibration 77
3.9 Applications 78
3.9.1 Physical changes and measurements 78
3.9.2 Chemical reactions 97
3.9.3 Inorganic compounds and complexes 99
3.9.4 Synthesis of compounds at high temperatures 104
3.9.5 Pyrotechnics 106
3.9.6 Superconductors 108
3.9.7 Organic compounds 108
3.10 Specialist DSC systems 114
3.10.1 Pressure DSC (PDSC) 114
3.10.2 Photocalorimetric DSC 114
3.10.3 Modulated DSC (MDCS1M) 115
3.11 Problems 118
References 119
Bibliography 122
4 Thermomechanical, dynamic mechanical and associated

methods 123
M. READING and P.J. HAINES
4.1 Introduction 123
4.2 Definitions 123
4.2.1 Thermomechanical analysis (TMA) 123
4.2.2 Dynamic mechanical analysis (DMA) 123
4.2.3 Mechanical moduli 124
4.3 Thermomechanical analysis 128
4.3.1 Apparatus 128
4.3.2 Applications 131
CONTENTS xi
4.4 Dynamic mechanical analysis 139
4.4.1 Apparatus 142
4.5 Dielectric thermal analysis 151
4.5.1 Definition of dielectric thermal analysis 152
4.5.2 Apparatus 152
4.5.3 Frequency range 152
4.6 Thermally stimulated current analysis and relaxation map analysis 154
4.6.1 Definition of thermally stimulated current analysis 155
4.6.2 Apparatus 155
4.7 Problems 156
References 159
Bibliography 160
5 Simultaneous techniques and product analysis 161

P.l. HAINES
5.1 Introduction 161
5.2 Simultaneous thermal analysis 162
5.2.1 Simultaneous TG-DTA and TG-DSC 162
5.3 Evolved gas analysis 167
5.3.1 Instrumentation 169
5.3.2 Apparatus 169
5.4 Detection and identification of evolved gases 169
5.4.1 Physical methods 170
5.4.2 Chemical methods 171
5.4.3 Spectroscopic methods 171
5.4.4 Simultaneous thermal analysis-gas chromatography-mass
spectrometry 175
5.5 Infrared and simultaneous T A-infrared 176
5.5.1 Apparatus 177
5.5.3 Gas chromatography and pyrolysis GC-FTIR 182
5.6 Infrared product analysis 184
5.6.1 Application to polymer samples 184
5.6.2 Polymorphism 185
5.6.3 Metal complexes 186
5.7 Thermomicroscopy 186
5.7.2 Phase equilibria 189
5.7.4 Hydrated salts 191
5.8 X-ray methods 192
5.9 Electron microscopy and associated techniques 198
5.10 Conclusion 200
5.11 Less common thermal analysis techniques 200
5.12 Problems 201
References 202
Bibliography 205
6 Problem solving and applications of thermal methods 206

Introduction 206
List of examples 207
xii THERMAL METHODS OF ANALYSIS
PROBLEMS/SOLUTIONS
6.1 Inorganic materials 209/245
6.1.1 Tin(II) formate decomposition 2091245
6.1.2 Mixtures of carbonates 210/246
6.1.3 Strontium nitrate decomposition 212/246
6.1.4 Calorimetry and phase transitions of potassium nitrate 2131247
6.1.5 Decomposition of barium perchlorate 215/249
6.1.6 Solid-state reactions 2161250
6.2 Polymeric materials 2171251
6.2.1 Characterisation of a polymer 2171251
6.2.2 Polymer blend analysis 219/251
6.2.3 Kinetic studies of polymer cure 2211252
6.2.4 Polymer decomposition studies 2241253
6.2.5 Oxidative stability of polymers 2261254
6.2.6 Studies of epoxy-glass composite 227/256
6.2.7 Characterisation of a thin adhesive film 2281256
6.3 Fine chemicals and pharmaceuticals 228/257
6.3.1 Purity determination 228/257
6.3.2 Phase diagrams of organic chemicals 230/260
6.3.3 Liquid crystal studies 232/260
6.3.4 Stability and polymorphism of pharmaceuticals 233/261
6.3.5 Dynamic mechanical analysis of food products 2351263
6.4 Other materials 2361263
6.4.1 Carbon oxidation 236/263
6.4.2 Proximate analysis of coals 2381266
6.4.3 Oil testing 239/268
6.4.4 Soil analysis 240/268
6.4.5 Catalyst studies 2411269
6.4.6 Survival of Antarctic micro-arthropods 2421269
References 270
Appendix: Solutions to problems in Chapters 1-5 273
Index 283
Introduction to thermal 1
methods
P.J. Haines
1.1
The effects of heat on materials have fascinated and benefited humanity Introduction
since the very earliest times. Even the observation of fires and the burning
process was both a pleasurable, and if uncontrolled, painful experience.
The use of fire to cook foods, and of ice to preserve foods, probably
contributed greatly to the settlement and welfare of early peoples and
cooking was perhaps the very first 'chemical experiment'. The production
of both organic and inorganic pigments by heating natural materials
allowed the decorative arts to develop [1].
The skills which people first acquired in the controlled use of heat
allowed the manufacture of ceramics, mortars, glass and metals. Primitive
apparatus dating from around 2500 Be [2] is known and the problems that
arose with burning materials and the damage caused by fire are frequently
seen in early settlements.
These skills, and the products they gave, were largely empirical 'arts'
and their spread was jealously guarded by those who first discovered the
most satisfactory technique. However, with the spread of information
through travel, the methods were transmitted to people in other countries,
who added their expert knowledge to improve the methods still further.
The alchemists were responsible for many discoveries and their experi-
ments in the synthesis and decomposition of natural and artificial sub-
stances laid the basis for modern chemistry [3,4]. Jabir ibn Hayyan wrote a
Book of Furnaces and a Book of Balances around AD 800, but we have no
evidence that he combined both [5]! In studying the history of materials,
we also come to realise the effects that ageing has on their properties.
As the study of chemistry became more disciplined, the range of
substances studied increased and it became necessary for scientists to be
able to distinguish between different substances and materials. By studying
their properties and reactions, it became possible to identify not only the
constituents of a substance, but often the particular source from which it
came. This is the beginning of the discipline known as analytical chemistry.
2 THERMAL METHODS OF ANALYSIS
The modem student of chemistry or materials science may well start his or
her experimental study of the subject by observing the nature of a range of
materials, their appearance, mechanical properties and density and may
then choose to heat the materials as a first attempt at classification [6].
A small sample, heated in a test tube, may undergo both physical and
chemical changes and may alter in a large number of ways, or it may be
completely stable. Table 1.1 gives some examples of behaviour that may be
observed when solid substances are heated in air [6,7].
It must be noted that a single observation is often not complete in itself,
but requires additional chemical or physical measurements. For example,
we cannot know what gas is evolved without a simple chemical test or
physical measurement, such as a spectrum. The need to use complementary
analytical techniques must be recognised throughout any investigation.
The addition of some simple apparatus to determine accurately the
temperature of the event, and to control the heating, or to measure colour,
Table 1.1 The effects of heat on solid materials
Effect Possible conclusion Example
Colour change
Charring, burning with
little residue Organics, polymer Paper, burning
Blackening with large residue Metal oxide formed CuC0 3 =CUO+C02
Metal changes to powder Oxidation 2Mg+0 2=MgO
Colour change Transition metal salt or HgI2, red -> yellow
phase transition
Substance melts
Melts at low temperature Covalent? Organics
Melts at high temperature Ionic salts NaCI
Substance sublimes
White sublimate Volatile solid
Ammonium salts
Violet sublimate Iodine
Vapours evolved (and characterised by additional tests)
Water vapour (droplets) Hydrates CuS04·SH20
Oxygen Nitrates, chlorates 2KN0 3 =2KN0 2+02
Oxides of nitrogen (brown
fumes) Nitrates 2AgN03 =2Ag+2N0 2+02
Carbon dioxide Carbonates ZnC03 =ZnO+C02
Physical changes
Becomes more pliable Plastics above Tg
Expansion: (a) gradual General expansion
(b) abrupt Phase change
Swelling Some intumescent materials Polyphosphates
Shrinkage Some strained polymers Fibres
No effect Stable oxides or temperature MgO, Al 20 3
too low
INTRODUCTION TO THERMAL METHODS 3
plus any change in weight, or perhaps the extent of expansion or the nature
of the volatiles evolved, gives a great deal more information to the analyst.
1.2
The history of the development of thermal methods from earliest times is Historical development
considered in papers by Mackenzie [2] which include an account of
thermometry from the sixteenth century.
The definition of thermometric scales and the start of practical calorimetry
in the eighteenth century, particularly by Lavoisier and Laplace [8] really
brought about a revolution in our thinking and in the practical approach to
studying the effects of heat. It led directly to the work of Fourier on heat
conduction [9] and to the elegant experiments of Joule on electrical heating
and calorimetry [10]. The chief drawbacks of their equipment were that it
often required large samples and a long time to complete the experiment.
Chemical reactions and physical measurements on gases were forerunners
of today's analytical techniques
The development of scientific instruments during the earlier part of the
twentieth century allowed the principles of thermal measurements to be
established - for example, the measurement of the coefficients of expansion
of silica by Henning [11] using an optical method led to the development of
modem interferometric dilatometers [12] and the design of the thermo-
balance, especially by Honda [13], has led to the modem TG systems.
In the second half of the twentieth century, vast improvements in
instrumentation, sensors, data acquisition, storage and processing have
been made, especially with the advent of microprocessors. The precision,
sensitivity and reproducibility of modem instruments are high, and their
range of temperature of operation has extended, together with the quality
of temperature control.
Thermal methods of analysis are now used in a very large range of
scientific investigations. Besides the more 'chemical' areas, such as polymers,
fine organic chemicals and pharmaceuticals, they have applications to
electronics, in construction, geology and engineering, in materials science
and in quality control. They often give information impossible to obtain by
other analytical methods. Very often, a complex material, such as a
polymer composite, will show definite and characteristic effects on heating
which relate to its nature, composition and history. These observations are
informative about its properties and working life.
1.3
Because thermal methods have been developed by many workers, it was Definitions
necessary to agree on a common terminology, and the International
Confederation for Thermal Analysis and Calorimetry (lCTAC) has pro-
duced definitive publications and articles, both on the nomenclature and
on the calibration methods to be used [14-17]. There are still some
differences in usage, but in this text we shall use the ICTAC definitions and
symbols throughout.
1.3.1 Thermal analysis
Thermal analysis (TA) is defined [17] as:

A group of techniques in which a property of the sample is monitored
against time or temperature while the temperature of the sample, in a
specified atmosphere, is programmed.
The programme may involve heating or cooling at a fixed rate of
temperature change, or holding the temperature constant, or any sequence
of these.
The word sample is interpreted to mean the substance placed into the
apparatus at the beginning of the experiment, and its reaction products.
The adjective is 'thermoanalyticaf.
The graphical results obtained are called the 'thermal analysis curve', or by
the specific name of the method.
The property used for study may be chosen from an extensive list, shown
in part in Table 1.2.
In Table 1.2 careful distinction should be made between the terms
derivative and differential. Differential techniques involve the measure-
ment of a difference in the property between the sample and a reference -
for example, in differential thermal analysis (DTA) where the difference in
temperature between the sample and a reference is measured. Derivative
techniques imply the measurement or calculation of the mathematical first
derivative, usually with respect to time. For example derivative thermo-
gravimetry (DTG) is the measurement of the rate of mass loss (dm/dt)
plotted against temperature T.
In discussing the theories and results of thermoanalytical studies, we
shall always use the 'SI' system of units and symbols [18] and, where
necessary, conversion from older units will be made with the occasional
exception of temperature which may be quoted in the (more familiar)
degree Celsius eC). The principal symbols and units to be used are given in
Table 1.3. The usual prefixes are used, e.g. 10-3 m = 1 mm, 106 Pa= 1
MPa, 103 g = 1 kg, etc.
EXAMPLES OF SYMBOLS USED IN THERMAL METHODS
(a) If the symbol refers to an object (the sample, the furnace) then it should
have a CAPITAL LETTER subscript:
Temperature of reference TR K
Sample mass ms kg
Temperature difference AT K
(b) If the symbol refers to a phenomenon (melting, bending) or to a point,
then it should have a small letter subscript:
Table 1.2 Thermal methods
Technique Abbreviation Property Uses
1. Thermogravimetry TG Mass Decompositions

(Thermogravimetric analysis) TGA Dehydrations
Oxidation
2. Differential thermal analysis DTA Temperature Phase changes
difference Reactions
3. Differential scanning DSC Power difference Heat capacity
calorimetry Phase changes
Reactions
Calorimetry
4. Thermomechanical analysis TMA Deformations Mechanical changes
Expansions
5. Dynamic mechanical analysis DMA Moduli Phase changes
Polymer cure
6. Dielectric thermal analysis DETA Permittivity Phase changes
Polymer changes
7. Evolved gas analysis EGA Gases Decompositions
Catalyst and surface
reactions
8. Thermoptometry Optical Phase changes
Surface reactions
Colour changes
Less frequently used techniques

9. Thermosonimetry TS Sound Mechanical and
chemical changes
10. Thermomagnetometry TM Magnetic Magnetic changes
Curie points
11. Thermoluminescence TL Light emitted Trap depths
12. Emanation thermal analysis ETA Gas released Structural changes
Also used
13. Simultaneous thermal STA Two or more techniques used on the
analysis same sample at the same time.
14. Controlled-rate thermal CRTA The rate of change of the property is
analysis held constant
Glass transition temperature K

Melting temperature K
Initial temperature K
Final mass kg
A THERMODYNAMIC DIVERSION
When a substance is heated, its physical properties and sometimes its

chemical nature change, and these may be represented by chemical
Table 1.3 SI units and symbols for therrmal methods [14, 18]
Quantity Symbol Unit(s) and abbreviation(s)
Basic units
length metre m
mass m kilogram kg
time t second s
electric current I ampere A
temperature T kelvin K
amount of substance n mole mol
Derived units
energy E joule J = kg m2/s2
power p watt J/s
force F newton N(= kg m1s2)
pressure p pascal Pa (= N/m2)
concentration c molarity molldm 3
frequency 11 hertz S-l
Combined units
heat q J
heat capacity C JIK
internal energy U J
enthalpy H J
free energy G J
entropy S JIK
thermal conductivity k J/(s m K)
density p kglm3
rate of reaction v moll(m 3 s)
order of reaction n
fractional extent of reaction III
rate constant of nth-order reaction k S-l (mollm3)n-l
activation energy E J/mol
molar gas constant R J/(K mol)
stress (J Pa
strain e
bulk modulus K Pa
tensile modulus E Pa
shear modulus G Pa
equations and by thermodynamic functions showing the properties of the

system. For a fuller treatment of the discipline of thermodynamics, the
reader is advised to study a good textbook on physical chemistry, such as
those listed in [19].
The First Law of Thermodynamics expresses the principle of conservation
of energy. When heat is absorbed by a system under specified conditions -
for example, at constant pressure - the heat energy of that system changes.
At constant pressure this is represented by a change in the enthalpy H.
(1.1)
Under standard conditions - which are, for gases, 1 atmosphere pressure,
and for liquids and solids, pure material at 1 atmosphere - we may write the
standard enthalpy change 6.W, generally expressed per mole of substance.

One very important value for 6.B is the standard enthalpy of formation
6.B/7 which is the standard enthalpy change when 1 mol of substance is
formed from its elements in their standard states. For example:
Cu (pure solid) + V202 (gas, 1 atm) = CuO (pure solid)
6.B/7CuO solid = -157.3 kJ/mol
The amount of heat that is absorbed by an unreacting system in raising
its temperature by lK at constant pressure is defined as the heat capacity at
constant pressure, Cp , which is itself a function of temperature:
Cp = (aB/a1)p (1.2)
and
Cp = a + bT + c]'2 (1.3)
Typical values of the specific heat capacity are:
Substance Cp J/(K.g) at 20°C
Air 1.01
Glycerine 2.43
Paraffin wax 2.09
Aluminium oxide 0.763
Aluminium 0.904
For a reacting system the difference in enthalpy between the products
and the reactants under the specified conditions is realised as the heat
produced by the system:
CaCOis) = CaO(s) + CO 2(g) 6.W = 178.3 kJ/mol
Heat is absorbed in this endothermic reaction.
6.W = -890.4 kJ/mol
Heat is evolved in this exothermic reaction.
The value of 6.B obtained will depend on the states of the reactants and
products and on the temperature of the reaction.
Correction of 6.B to the value at a different temperature requires a
knowledge of the values of Cp for all the reactants and products involved
[19].
For pure substances, changes of phase from one crystal form to another,
or from solid to liquid under 1 atmosphere pressure, take place at definite
temperatures and with definite values of 6.B referred to as the 'latent heat'.
We shall use this later in calibration of equipment.
1.3.2 Equilibrium
Most reactions tend to proceed to an equilibrium state. This may be almost

completely reactants, or almost completely products, or any stage in
between. At equilibrium, the pressures p, or concentrations c, or more
strictly the activities, a (that is, the pressures or concentrations corrected
for non-ideal behaviour) give an equilibrium constant K which is fixed for
that reaction at that temperature.
NOlg) ~ NO(g) + 1f202(g)
Kp = {(PNO) . (POJ!')!(PN0 2 ) } equilibrium
which has a value of about 0.04 atm'!' at 500 K.
Where substances are in their standard states, we may consider their
activities as 1, so that, for the calcium carbonate reaction:
CaC0 3(s) ~ CaO(s) + CO2(g)
reduces to
Kp = {Peo) equilibrium
The Second Law of Thermodynamics deals with the tendency of
reactions to proceed. The driving force of a reaction depends on both the
enthalpy change aH and the entropy change as. The entropy S of a system
is related to W, the number of different molecular energy level arrange-
ments of the system, where k is the Boltzmann constant:
S = kIn W
or, rather loosely, to the randomness of the system. Thus, gases have high
entropies; regular crystalline solids low entropies.
The Third Law of Thermodynamics states that the entropies of perfect
crystalline solids at 0 Kelvin may be assigned a value of zero.
These thermodynamic quantities are combined to give the free energy G:
G = H - TS
For a process at constant temperature:
aG = aH -T as
For a reaction to proceed spontaneously, the free energy must decrease, so
the value of aG must be negative.
For a reaction at equilibrium, aG is zero; but aGB- is related to the
equilibrium constant by the reaction isotherm equation:
ac-e- = -RT In K
and the variation of K with temperature can be shown to be
In K = -aHB-/RT + astrlR
known as the van't Hoff equation, or reaction isochore. Similar equations
may be applied to physical equilibria, such as solution, adsorption or

vaporisation.
A KINETIC DIVERSION
Chemical reactions occur at particular rates, defined by the rate of change

of amount of substance with respect to time. Often it is more convenient to
use a quantity related to the amount, such as pressure, concentration, or,
in the case of solids, the fraction reacted a.
The rate of reaction is defined as dnldt and is related to the amounts of
reactants by a rate law:
dnldt = k . f(n)
where k is the rate constant, andf(n) is a function of the amount, n. For
example, when we consider the random degradation of a polymer, we may
write the rate equation as:
da/dt = k . (I-a)
Other reactions need much more complicated functions of n or a, which
will be discussed in Chapter 2.
The rate of reaction varies with temperature, chiefly due to the
Arrhenius condition that species must possess energy in excess of the
activation energy, E, if the reaction is to be effective. This gives rise to the
Arrhenius equation:
k = A . exp (- EIRT)
where A is referred to as the 'pre-exponential factor' and depends on the
orientation and structure of the reactants.
For most reactions involved in thermal methods, the rate laws are
complex, but it is important to realise that the rate of change will depend
very greatly on two factors:
(a) the amount of substance reacting and
(b) the temperature.
Anything which affects these, such as the heat evolved by an exothermic
reaction or the loss of reactant by vaporisation, will change the rate. It is
worth noting that a derivative curve, such as a DTG curve, indicates the
rate of reaction.
1.3.3 General apparatus
Almost all thermal methods use a similar arrangement of apparatus, as

shown in Figure 1.1.
Thermocouple
Fumace- +7+<
~
',' ,',.
II
Temperature
'::,-::fI,..--+L..--p_r_o9_r_a_m_m_e_r____--'
1-
Sample -+H-,~,,HI,f----.!",=!1
;.;.;.:
rl Sensors amplifier;
data collection
l
~~
Sensor ~=~="'="'~:-""'h·l~~
assembly t Gas in Display-recorder
computer
Figure 1.1 Schematic diagram of thermal analysis system.
:\ ......, -----
Signal
\
:\)1 :
(,
, I
, I
I, '
I
I I I
I ! I
TfOC
Figure 1.2 Typical thermal analysis curves showing initial, peak and final temperatures.
The sample is often put into a container or crucible which is then placed
in contact with the sensor which is to measure the particular property. A
temperature sensor must also be present at (or very near) the sample to
follow its temperature as the experiment progresses.
The sensor assembly then fits into a special furnace and the atmosphere
around the sample is established. This is most important, because we may
wish to study (or to avoid!) reactions with air or other reactive gases.
The furnace is controlled by a temperature programmer and is set by the
operator to raise (or lower) the temperature of the furnace at whatever
rate has been chosen as most suitable. The data are collected by the sensor
system and, after processing, are displayed on a screen or recorder as a

thermal analysis curve.
1.4
If you go into any modern laboratory, there are often as many computers Computers and thermal
as there are instruments. The computer forms a vital part of the 'armoury' methods
of any analytical laboratory, and its use in combination with thermal
analysis techniques is very important.
The use of computers may be divided into approximately four parts:
1. As a means of instruction in the operation of the instrument.
2. To make the collection, interpretation, storage and retrieval of
instrumental data easier for the operator.
3. To allow the user more easily, and more accurately, to calculate the
results of an experiment.
4. To simulate the behaviour of the instrument, or of the sample, under
special conditions.
The general interconnections of a computer with a thermal analysis
system is shown in Figure 1.3.
One or more instruments are connected to the computer via the
experimental control interface and also via the data acquisition interface.
The user interacts with the computer via the keyboard and the VDU
screen. The data produced may be stored in a large variety of ways, but
most systems involve both hard disc and floppy disc storage. Display of
results, hard copy of thermal analysis curves and of calculated parameters,
such as coefficients of expansion from a TMA experiment, may be
produced on printers or plotters.
Thermal Analyser(s)
t
Experimental
Control
High res. color
b
(or gre scale)
V U Data
'"
Interface Acquisition
Keyboard Interface
l' 'f -t t
Computer
t t .; t l' t
Data storage
___RaM___
I RS232
Expansion
Capability
I choice of graphics
plotters
(printer option)
Disk system(s)
II
Figure 1.3 Schematic of a typical computer system. (From [20] with permission.)
Computers may be used in the planning of the experimental work by
writing a method into the computer system. The method can preset the
analyser to the selected starting conditions, load the sample from a robotic
autosampler into the analyser and carry out the run, controlling the heating
programme and the purge gases. The data obtained may then be analysed
according to a selected regime and a report presented to the analyst with
the thermal analysis traces, the results for, say, melting point and heat of
fusion from a DSC trace, plus an assessment of the results on each sample
for purposes of quality control [21].
1.4.1 The computer as an instructional tool
There are several 'computer-aided learning' schemes available for analytical

chemistry, notably from the ACOL organisation [22]. Similar systems may
be written for most commercial instruments, and are often available from
the manufacturers. As an example, the 'PL-Show' computer programs [23]
give both an overview, and also specific applications for a wide range of
thermal analysis equipment.
The program can instruct, as a 'bench textbook' in the definitions, mode
of operation and applications of a selected thermal method. A menu
system leads the user through the choice of method and conditions, such as
sample size and heating rate, and gives specific instructions for the
operation of the particular instrument involved. Many such systems are
'fail-safe'. For example, they will not allow you to continue if you choose
the wrong temperature limits (which might burn out the furnace), or if you
have not turned on the analyser, or even if there is an obstruction that
would impede the movement of the furnace!
1.4.2 The computer as a data gatherer
The earliest commercial thermal analysis instruments produced signals that

were transmitted to a chart recorder. This had the advantage of simplicity,
and presented an immediate, visual reminder of the 'state of the experi-
ment'. It was, however, impossible to retain the signal that was produced,
and so to process or do direct calculations on it. With the coming of
mechanical and then electronic integrators, the analyst was no longer
forced to measure peaks with a planimeter, or cut them out and weigh
them!
The modern computer-linked thermal analysis system will do much more
than replace a recorder. A large memory allows for storage of both the
data and the applications programs. Special software for particular tech-
niques is provided. While a run is in progress, data from a previous run
may be analysed.
1.4.3 The computer as a data processor
The software available with computer-linked thermal analysis instruments

allows the rapid, accurate determination of results from the experimental
runs. Most of the examples and problems presented in this book have been
analysed by computer. The integration of peaks in DTA and DSC, the
determination of the glass transition temperature from DSC or TMA and
the accurate measurement of mass loss in TG may all be most easily carried
out using the computer software. Calculations of any type are much
quicker, and probably more accurate, for the average operator when
carried out by the computer. Because of this, it is becoming more
important to consider, and report, the computer specifications that were
used. What type of AID conversion was used and how many bits were
involved? How much smoothing was used and what algorithm was
employed? How many signal points were taken and how were they treated
and stored [24]?
While modern instruments should produce excellent data with a low
signal/noise ratio, the sample does not always do what is expected! Often
complex, overlapping and sloping traces make the reasoning unclear.
Computer users often quote the acronym 'GIGO': 'Garbage In - Garbage
Out.' In some cases, it is possible that the user has not thought sufficiently
about the experimental conditions, or the sample preparation. In such a
case, however good the computer or the software, the result is likely to be
wrong!
1.4.4 The computer as a research tool
The design and operation of thermal analysis equipment, even more so

than other analytical instruments, depends very much on the conditions
used. Obviously, a change in the original amount of sample will alter the
change in mass observed in a TG experiment, but it may also alter the type
of chemical reaction that will occur. The effects of sample size, heating
rate, the thermal conductivity of the sample and its container may all be
simulated using suitable computer programs. Attempts to discover the
most appropriate kinetic equation to describe the chemical reactions
occurring may be tried using the computer. Side-by-side comparison
of runs obtained from samples of different origin may reveal subtle
differences.
1.5
Many analytical methods give a result that is specific to the compound Factors affecting
under investigation. For example, the infrared spectrum of polystyrene is thermal analysis results
characteristic of that material, and depends little on the sampling method,
or instrument, or the time taken to perform the run. Many thermal
Fumace
Figure 1.4 The dynamic nature of a thermal analysis experiment, showing the flow of
heat (dashed lines) and of gases (solid lines), plus the progress of sample reaction.
methods are much less 'compound specific' and the results obtained may
depend upon the conditions used during the experiment. The reasons for
this will become apparent in later chapters of this book, but may briefly be
summarised as due to the dynamic nature of the processes involved (Figure
1.4). The signal generated by the sensors will depend on the extent and
rate of reaction, or the extent and rate of change of the property measured.
The transfer of heat by conduction, convection and by radiation around the
apparatus, and the interaction of the surroundings with the sample all
affect these changes.
It is therefore essential, whenever a thermal analysis experiment is
reported, that the precise conditions used are included in the report.
Similarly, comparison of samples should only be made when their curves
are run under the same conditions, or when differences in conditions are
clearly stated.
The main factors which must be considered and reported for every
thermal analysis experiment are given below.
1.5.1 The sample
The chemical description of the sample should be given, together with its
source and pre-treatments. It is also important to state its purity, chemical
composition and formula, if these are known. If the sample is diluted with
another substance, such as an inert reference material, then the compo-
sition of the mixture should be given. This diluent can greatly alter the
thermal conductivity of the sample. Even the particle size may alter the
shape of the curve, especially where a surface reaction is involved.
For example: hydrated copper sulphate, CuS04'5H20, powder 50-60
j.Lm, XYZ Co. Ltd, GPR grade, diluted 50% in alumina.
All of these factors could affect the thermal analysis curve. A change in
the chemical composition would alter the decomposition of a copper
sulphate sample, as would a change in purity. The diluent will alter the
heat transfer characteristics and the shape of the curve.
The 'history' of the sample, and possibly its method of preparation, can
affect the curve. Trace amounts of impurity can catalyse decompositions,
or cause different reaction sequences.
1.5.2 The crucible
The material of the sample holder or crucible should be stated, together

with a guide to its geometry. Sample holders are chosen because they will
not interact with the sample during the course of the experiment.
However, changing from aluminium to platinum, or to silica or alumina,
may well alter the heat transfer because of the different thermal con-
ductivity, and possibly the chemistry of the process - for example, if a
reaction occurs that could be catalysed by platinum and we are using a
platinum crucible.
The geometric shape of the sample holder is also important, since a
shallow, wide holder will allow free diffusion of reactant gases to the
sample and the diffusion of product gases away, while a narrow, deep
holder may restrict gas flow.
1.5.3 The rate of heating
Experiments may be carried out at heating rates (dT/dt) from 0 Klmin -

that is, under isothermal conditions - through the 'normal' rates of 10
Klmin, to very high rates over 100 Klmin, which are sometimes used to
simulate burning of materials. Similarly, experiments may be conducted
with different cooling rates Since the rates of heat transfer, of physical
change and of most reactions are finite, the sample will react differently at
different heating rates.
The transfer of heat between the source, such as the furnace, and the
different parts of the sample or reference materials is not instantaneous,
but will depend on the conduction, convection and radiation that can occur
within the apparatus. There is bound to be a thermal lag between different
parts of the apparatus, and the higher the rate of heating, the greater this
lag is likely to be. General equations describing the corrections to be
applied when working at different heating rates, [3, are often of the form
[25]:
where Te is the observed, uncorrected temperature at heating rate [3, Te 0 is

the corrected temperature at [3 = 0, a is a constant, [3 is the heating rate (in
Klmin) and, c is a correction determined by calibration.
For example, for gallium melting:
Te = 303.56 + 0.074'[3 - 0.2 = 304.10 K

A rapid heating rate may allow some of the sample to melt before it
decomposes, while at a slow heating rate all reaction has occurred below
the melting temperature. In order to approach equilibrium conditions
more closely, we should use a very small heating rate, preferably less than
1 Klmin. The heating rate will affect the start, range and finish of a change:
Ti,fast > Ti,slow

Tf , fast > Tf,slow
(Tf - Ti)fast > (Tf - Ti)slow
The resolution of two changes which occur at temperatures close to each
other is likely to be much better at slow heating rates than at fast.
Heating rates need not be linear, and may follow a complex pattern
which must be specified in detail: isothermal at 25°C for 2 min, followed
by 50 Klmin up to 300 °C; isothermal at 300 °C for 10 min, then cool at
5 Klmin to room temperature.
1.5.4 The atmosphere
The transfer of heat and the chemistry of the sample reaction will depend
greatly upon the atmosphere surrounding the sample and its products.
Even if there is no reaction between the sample and the atmosphere, the
heat transfer by the gas will affect the results. Consider four gases
commonly used in thermal methods:
Gas at 1 atm Thermal conductivity at 373 KI(1O-2 J/(smK)

Helium 17.77
Nitrogen 3.09
Air 3.17
Carbon dioxide 2.23
1.0,--_ __
0.8
'?
~
i
'0 0.6
<II
!!! 2 3 4 5 6
c
0
ti
e! 0.4
u..
0.2
Or------4------~--~--+_~~~~~--~~
500 700 100>
Temperature °C
Figure I.S The effect of carbon dioxide pressure on the TG curves of AR calcium
carbonate. 100 mg heated at 1°C/min in (1) 1.0 atm N2 , (2) 0.1 atm CO 2 , (3) 0.3 atm
CO 2 , (4) 0.5 atm CO2 , (5) 0.7 atm CO2 , (6) 1.0 atm CO 2 , In runs (2)-(5), N2 was mixed
with CO 2 to give a total pressure of 1 atmosphere. (From [29] with permission.)
The heat transfer by conduction through helium will be nearly eight times
greater than through carbon dioxide.
When reaction occurs, the nature of the thermal event will change
completely. While a metal may be stable in helium, it could oxidise in air.
When a chemical equilibrium exists, for example, between calcium
carbonate, calcium oxide and carbon dioxide:
then Le Chatelier's Principle tells us that the presence of a large

concentration of product will force the equilibrium back towards the
reactants. Thus, although calcium carbonate may start to decompose
below 700 °C in air containing little CO2 , in CO 2 at 1 atmosphere pressure
the decomposition does not occur until over 900°C [26-28]. Figure 1.5
shows this effect.
Sometimes the sample produces its own 'self-generated atmosphere'.
This can affect the equilibrium, the kinetics and the heat transfer of the
experiment.
We should also consider the flow rate of the gas. A static atmosphere will
not sweep away reaction products from the sample, or act as a heat transfer
agent.
1.5.5 The mass of the sample
The physical properties, size and the packing or density will alter the
results obtained. If very small samples are used, perhaps less than 1 /-Lg,
then the signal produced will be small, and in certain cases each crystal may
react at a different time producing multiple peaks. Very large samples will
produce a much greater effect, but if several changes occur they may not be
fully resolved. When we wish to analyse mixtures in which small amounts
of one component need to be detected - for example, a coating on a filler
used in a plastic formulation - then large samples may be necessary.
Comparison of thermal analysis curves should be done only when comparable
sample masses are used.
These parameters are important for any thermal analysis experiment,
and for particular methods other details may also be needed. As an aid to
remembering the five most important parameters, perhaps the acronym
'SCRAM' may be helpful:
Sample
Crucible, or sample holder
Rate of heating
Atmosphere
Mass of sample.
1.6
Simultaneous and A single thermal method does not always give sufficient information to
complementary allow the analyst to be sure what is occurring. For example, a 'downward'
techniques peak produced by a DTA experiment means that an endothermic event
occurs over this temperature range. It does not tell you whether this is a
chemical reaction or a physical change such as melting, or whether any
gases are evolved. A TG experiment on the same sample may show a mass
loss over this temperature range, thereby ruling out melting, but still not
identifying any volatiles. Conversely, if the TG curve showed no mass loss,
the process of melting could be confirmed by direct observation of the
sample. It is clear that combining several analytical methods gives a better
profile of the changes taking place, although we may have to sacrifice the
optimum conditions for each separate technique.
If the two techniques are performed on different samples, or at very
different times, then the methods are referred to as complementary. If a
DTA experiment is done on one sample of a polymer, and a TG
experiment is done on a second sample of the same polymer, the
techniques are complementary.
Such a scheme might also involve a thermogravimetric experiment from

which the solid product is then removed and used to produce an X-ray
diffraction pattern.
If two techniques are performed on a single sample at the same time,
then they are simultaneous techniques. Since a hyphen is often used to
separate the abbreviations, for example TG-DTA, they are also called
'hyphenated techniques'. An apparatus which allows a combination of
differential scanning calorimetry and simultaneous sample observation
using a microscope would be DSC-thermoptometry [17].
Wherever possible, simultaneous techniques are to be preferred, since
different samples and different conditions may alter the thermal analysis
curves, as we have noted above. However, optimum conditions may be
very different for the two methods. For example, the highest sensitivity of
a DTA experiment is attained at high heating rates while, for TG, the best
resolution is attained at low heating rates!
Very nearly every analytical method has been employed as a comple-
mentary technique to a thermal method. Gases evolved during a reaction
have been separated by gas chromatography, dissolved and titrated,
measured electrochemically and spectroscopically, particularly by infrared
and by mass spectrometry. Solid products have been analysed for their
surface area and catalytic activity and by every sort of compositional
analysis method. It must be stressed as firmly as possible that these
additional analyses and experiments are vital to a full understanding of the
results obtained by thermal analysis.
1.7
1. A small sample of a white powder is provided, and you decide to Problems
examine the effects of heat on it. On gentle heating over boiling water, (solutions on p. 273)
it melts. On stronger heating in air, on a spatula, it bums, leaving little
residue. What conclusions do you make about the nature of this sub-
stance, and what simple technique or thermal methods might you use to
study it further? How could you prevent it burning in the apparatus?
2. A second sample is provided. It is a pink, crystalline solid. On gentle
heating it changes to blue and gives off a vapour which condenses to
droplets on the cooler part of the tube. On stronger heating it gives
brown fumes and leaves a black solid. What conclusions can you draw
from these observations?
3. A thermal analyst performs an experiment in which the dimensions of a
sample are measured as it is heated. Suggest a name for this technique
and decide whether it is a special case of one of the major thermal
methods.
4. Complete the following definition, by comparison with the standard
definition of thermal analysis:
Thermoelectrometry is a family of techniques in which an ..... .
property of the . . . . . . is measured against . . . . . . or temperature
while the . . . . of the . . . . . . in a specified . . . . . . is pro-
grammed.
Are any of the techniques in Table 1.2 members of this family?
5. Can you spot the error(s) or omissions in the following experimental
details? 'A sample of a complex compound was heated in a thermal
analysis apparatus, in a platinum sample holder, up to 500°C and the
thermal analysis curve recorded.'
6. What complementary or other techniques could be used to study the
changes and reactions in questions 1 and 2 above?
References 1. G.!. Rochlin (ed.), Scientific Technology and Social Change, Scientific American, New
York, 1977.
2. R.C. Mackenzie, Thermochim. Acta, 1984, 73, 249.
3. J. Read, Prelude to Chemistry, Bell, London, 1939.
4. W.H. Brock, The Fontana History of Chemistry, Fontana Press, London, 1992.
5. E.J. Holmyard, Alchemy, Pelican Books, London, 1957.
6. Vogel's Textbook of Qualitative Inorganic Analysis (5th edn; revised, G. Svehla),
Longman, London, 1979.
7. H.T. Clarke, A Handbook of Organic Analysis (5th edn; revised, B. Haynes), Arnold,
London, 1975.
8. A.L. Lavoisier, P.S. de Laplace, Mem. R. Acad. Sci., Paris, 1784, 355.
9. J.B. Fourier, Theorie Analytique de la Chaleur, Paris, 1822.
10. J.P. Joule, Collected Works, The Physical Society, London, 1884.
11. F. Henning, Ann. Physik, 1907,23,809.
12. R. Kato et aI., Thermochim. Acta, 1988, 134, 383.
13. K. Honda, Sci. Rep. Tohoku Univ., 1915, 4, 97.
14. R.C. Mackenzie et al., Talanta, 1969, 16, 1227; 1972, 19, 1079.
15. R.c. Mackenzie et al., J. Thermal Anal., 1975,8,197; Thermochim. Acta, 1981,46,333.
16. R.C. Mackenzie in Treatise on Analytical Chemistry, P.J. Elving (ed.), Pt I, Vol. 12,
Wiley, New York, 1983.
17. J.O. Hill, For Better Thermal Analysis and Calorimetry III, ICTA, 1991.
18. (a) IUPAC Manual of Symbols, Pure Appl. Chem., 1979,51, 1; 1982,56, 1239. (b) I.
Mills, Quantities, Units and Symbols in Physical Chemistry, IUPAC, Blackwell, Oxford,
1988.
19. (a) P.W. Atkins, Physical Chemistry, OUP, Oxford, 1978; (b) G.M. Barrow, Physical
Chemistry (5th edn), McGraw-Hill, Singapore, 1988.
20. J.A. Hider, Lab. Practice, 1986, Feb., 19.
21. B. Wunderlich, Int. Lab., 1982, 32.
22. Analytical Chemistry by Open Learning (ACOL), Wiley, Chichester, England.
23. Rheometric Scientific Ltd, Surrey Business Park, Epsom, Surrey.
24. J.G. Dunn, J. Thermal Anal., 1993,40, 1435.
25. E.L. Charsley et al., J. Thermal Anal., 1993, 40, 1409.
26. E.L. Simons, A.E. Newkirk, Talanta, 1964, 11, 549.
27. F.W. Wilburn, J.H. Sharp, D.M. Tinsley, R.M. Mcintosh, J. Thermal Anal., 1991,37,
2003.
28. R.M. Mcintosh, J.H. Sharp, F.W. Wilburn, Thermochim. Acta, 1991, 165,281.
29. F.W. Wilburn, J.H. Sharp, J. Thermal Anal., 1993,40, 133.
General bibliography Note Books which deal specifically with ONE thermal method will be listed at the end of the
most relevant chapter. All the books listed here discuss a range of thermal methods.
A. Blazek, Thermal Analysis, Van Nostrand, London, 1972.

M.E. Brown, Introduction to Thermal Analysis, Chapman & Hall, London, 1988.
E.L. Charsley, S.B. Warrington (eds), Thermal Analysis - Techniques and Applications,
RSC, Cambridge, 1992.
T. Daniels, Thermal Analysis, Kogan Page, London, 1973.
J.W. Dodd, K.H. Tonge, Thermal Methods, ACOUWiley, London, 1987.
J.L. Ford, P. Timmins, Pharmaceutical Thermal Analysis, Ellis Horwood, Chichester, 1989.
P.D. Gam, Thermoanalytical Methods of Investigation, Academic Press, New York, 1965.
G. van der Plaats, The Practice of Thermal Analysis, Mettler, 1991.
D.N. Todor, Thermal Analysis of Minerals, Abacus Press, Tunbridge Wells, 1976.
E.A. Turi, Thermal Characterisation of Polymeric Materials, Academic Press, New York,
1981.
W.W. Wendlandt, Thermal Analysis (3rd edn), Wiley, New York, 1986.
G. Widman, R. Reisen, Thermal Analysis: Terms, Methods, Applications, Huthig, Heidelberg,
1987.
B. Wunderlich, Thermal Analysis, Academic Press, New York, 1990.
CHAPTERS IN GENERAL ANALYTICAL TREATISES AND TEXTBOOKS
G.W. Ewing, Instrumental Methods of Chemical Analysis, Wiley, New York, 1969.
F.W. Fifield, D. Kealey, Principles and Practice of Analytical Chemistry (3rd edn), Biackie,
Glasgow, 1990.
I.M. Koithoff, P.J. Elving, c.B. Murphy (eds), Treatise on Analytical Chemistry, Part 1:
Theory and Practice (2nd edn), Vol. 12, Section J, Wiley, New York, 1983.
D.A. Skoog, D.M. West, Principles of Instrumental Analysis, Holt-Saunders, Tokyo, 1980.
C.L. Wilson, D.W. Wilson (eds), Comprehensive Analytical Chemistry, Vols XII, A-D,
Elsevier, Amsterdam, 1981-4.
JOURNALS IN ENGLISH
Thermochimica Acta, Elsevier, Amsterdam.

Journal of Thermal Analysis, Wiley, Chichester.
Journal of Chemical Thermodynamics, Academic Press, New York.
Very many papers in chemical, polymer, mineral and instrumental journals.
Abstracts were collected in Thermal Analysis Abstracts, which became Thermal Analysis
Reviews and Abstracts (TARANDA), but which has now ceased publication.
2 Thermogravimetry
P.J. Haines
2.1
Introduction The measurement of the mass of a sample is often one of the earliest
quantitative experiments we do. Every day, many portions of foods,
pharmaceuticals, containers, chemicals, polymers or engineering parts are
weighed and recorded. The extension of this simple technique into analysis
provides the discipline of gravimetric analysis. This has been defined [1] as
'quantitative analysis by weight' and is the process of isolating and
weighing an element or a definite compound of the element in as pure a
form as possible. Gravimetric experiments to determine water of crystal-
lisation, and to study oxidation and reduction, are used to teach the
principles of stoichiometry, formulae and analysis. Many gravimetric
techniques involve a reaction to produce a definite compound and then
heating it to convert to a stable material of known composition. For
example, bismuth may be precipitated as a cupferron complex, but must
then be ignited 'strongly' to give the stable oxide Bi20 3 [1].
The samples that the analyst is given need to be studied in the form 'as
received' and frequently this neither is a definite compound nor is it pure!
While we shall try to perform quantitative analysis, the answers will often
be very dependent on the treatment regime and the method of analysis. As
a practical example, the moisture content of a sample of soil may be
measured by drying below 100 °C and its content of organic materials by
igniting at around 500 °C [2].
If we can follow all the effects of heat on the changing mass of the
sample, we should be able to extract information on the stages of analysis
and on the temperatures needed to bring each stage to completion.
Measurement of mass on a balance is done by the process of weighing. That
is, a balance compares the unknown mass with a standard mass by comparing
their weights, which have the units of force (newtons) and the magnitude of
mass times gravitational acceleration. The mass of a body stays constant, but
the weight will alter if the acceleration acting on the body alters.
2.2
Historical The origins of thermogravimetry have been fully documented by Duval [3],
Keattch and Dollimore [4] and Wendlandt [5]. The most significant
THERMOGRAVIMETRY 23
TG
mass
DTG , '"~ ,,
(I I
I
,,
,
,,
. I
I
,
dmldt , ,-
."
'. '
,,,-'
,
Figure 2.1 Typical TG (solid) and DTG (dashed) curves.
contribution was made by Honda [6] in 1915 who used a lever-arm balance
fitted with an electrical furnace to investigate manganese oxysalts. Simple
experimental apparatus has been described which uses modified manual
analytical balances and controlled electric furnaces [7]. The Chevenard
thermobalance was the first to record weight changes automatically using a
photographic method. This was used extensively from 1936 by Duval and
others [8].
The development of the electronic microbalance [9] allowed smaller
samples and furnaces to be used, and work to be carried out in controlled
atmospheres and in vacuum.
2.3
Thermogravimetry (TG) [10] is a technique in which the mass of the Definition of
sample is monitored against time or temperature while the temperature of thermogravimetry
the sample, in a specified atmosphere, is programmed.
It should be recognised that several manufacturers and users prefer to
call this technique thermogravimetric analysis (TGA). This avoids con-
fusion with the glass transition temperature, Tg • The apparatus is called a
thermobalance, or less frequently, a thermogravimetric analyser.
In order to enhance the steps in the thermogravimetric curve, the
derivative thermogravimetric (DTG) trace is frequently drawn. Remember
that this is the plot of the rate of mass change, with time, dm/dt.
2.4
As with most thermal analysis systems, the thermobalance has four major Apparatus
parts:
Electrobalance Balance control unit
.
Gas in
GT 2 Programmer
Furnace -
"
Sample """
=r:
I
Thermocou pie •••
Recorder and/or computer
= =
•
Gas out
Figure 2.2 Schematic diagram of thermobalance system.
Figure 2.3 Schematic of a microbalance: A, lamp; B, shutter; C, photocells.

(Courtesy CI Electronics Ltd.)
• the electro balance and its controller

• the furnace and temperature sensors
• the programmer or computer
• the recorder, plotter or data acquisition device.
2.4.1 The balance
The balance used in many of the commercial apparati is a modified

electronic microbalance. One example is shown in Figure 2.3. The light-
weight arm is pivoted about an electrical coil suspended in a magnetic field.
The position of the arm is measured by an optical sensor and any deflection
THERMOGRAVIMETRY 25
...... .. ,.
.....
~
..... ~
::::::
......
::::::
.. ...
:::::
:::::
:::::: :::::
Balance
...... .
::::::
...... :::::
.. .
......
. ....
.::::::
...... .:::::.. .
....
Balance
(a) (b)
Balance
[ I
Balance
~B~
~fSl
(c) (d)
Figure 2.4 Arrangements of thermobalanl:es, showing the furnace (shaded), sample

position and casing: (a) and (c) suspended; (b) top-loading; (d) horizontal. The magnet
position for Curie point calibration is shown in (c). (After [11].)
causes a current to be supplied to the coil which restores it to the 'null'

position. This is important for maintaining a constant position of the
sample in the same zone of the furnace. The sample suspended into the
furnace from one arm of the balance is counterbalanced by a tare, either
electrically applied to the coil or added to the reference pan. The balances
will often give a resolution of 1 J.Lg or better, and sample sizes range from a
few milligrams up to 30 g. With this very high sensitivity, freedom from
vibration is essential.
Several different arrangements of the balance and furnace are possible,
as shown in Figure 2.4 [11], and the geometry may affect the results
obtained.
The difficulties that may affect the operation of a balance used in
conjunction with a furnace are most important. The presence of corrosive
or oxidising gases near the balance mechanism is most undesirable, and the
balance enclosure is often purged with an inert gas such as nitrogen at room
temperature. Problems with static electricity, which can cause the attrac-
tion of the sample pan onto the glass enclosure, may be overcome by
coating the surfaces with a conducting film or use of antistatic spray.
The movement of the gas surrounding the sample due to convection may
cause noise and affect the observed mass. This may be reduced by intro-
ducing baffles within the sample enclosure. Usually experiments are
conducted in a flowing atmosphere, and suitable design reduces convective
effects.
Thermomolecular flow may occur when the balance is operated at low
pressure [12]. If the sample or its suspension or the counterpoise experi-
ence temperature gradients when the pressure is low and the mean free
path is comparable to the dimensions of the apparatus, the flow of gas
molecules causes an apparent mass change.
With a temperature difference of 100 K, and a pressure of to-I torr, the
effect can be as much as 100 /-Lg.
When samples of large volume must be used, there is an effect due to
Archimedes' Principle that 'when a body is immersed in a fluid it
experiences an upthrust equal in magnitude to the weight of fluid
displaced' [13]. If the volume of sample plus sample holder is V m3 and the
pressure p Pa, then the mass of an ideal gas of molar mass M displaced at
temperature T will be:
m = MpVIRT
As the sample is heated, so the density of the gas decreases, while the
density of the solids hardly changes. Therefore the upthrust will decrease,
and the sample will apparently gain in measured mass.
As an example, consider a sample plus crucible of volume 1 cm3, that is
to- 6 m3, at atmospheric pressure, approximately HP Pa of nitrogen gas
(M = 0.028 kg). If the molar gas constant R is 8.314 J/(K mol) then the
buoyancy will change by about 0.8 mg between 300 K and 1000 K, so there
will be an apparent weight gain of 0.8 mg.
There are several ways to compensate for this effect. Firstly, we may run
a 'blank' buoyancy curve with an inert sample of similar volume and
subtract this curve from the experimental curve for our sample.
Secondly, the use of very small samples and crucibles will reduce the
effect. If the volume is reduced to 2.8xto- 3 cm3 , equivalent to to mg of
MgO, then the apparent gain in mass is only 2.2 /-Lg.
Thirdly, if we use a twin furnace system as shown in Figure 2.5 [14,15]
where a counterpoise of similar volume is heated at the same time, the
effects largely cancel.
Thermogravimetry in very corrosive atmospheres may be carried out
using a magnetically suspended balance [16,17]' as shown in Figure 2.6. An
electromagnet suspended from the microbalance holds a glass-encased
permanent magnet in the measuring cell. The sample in the furnace is
connected by a suspension wire to the permanent magnet and each mass
change is transmitted back without contact. This allows the use of very
reactive atmospheres, or of samples which produce corrosive or toxic
products, without their coming into contact with the balance mechanism.
THERMOGRAVIMETRY 27
Thermo-Microbalance TG 439
Principle of the symmetrical weighing
syslem with connections for protective
gas. purge gas and vacuum pump
1) thermostat
2) radiation shield
3) water cooting
4) crucible
5) furnace
6) manometer
7) flow mcter
8) batance
9) vacuum pump
10) piping
-";)"- magnetic valve

-t'['l- control valve
purge gas
Figure 2.5 Diagram of a symmetrical thermo-microbalance.

(Courtesy Netzsch-Mastermix Ltd [15].)
weighing system I !If= 111

JJI
magnetic
suspension coupling
~
/I
connection block r9 ~ -{;:k:)-- ~
for gas inlet
thermostated housing 11 '~eaction gas inlet
furnace
(
sample pan
l
y
gasexhaust ~
Figure 2.6 Diagram of a magnetic suspension thermo-microbalance.
(Courtesy Netzsch-Mastermix Ltd [17].)
2.4.2 Furnace
The furnaces used are generally non-inductively wound electrical resistance

heaters, although infrared and microwave heating have been suggested.
The furnace and balance arrangements are shown in Figure 2.4. The most
important features needed from the furnace are listed below:
1. The furnace should have a zone of uniform temperature which is
considerably longer than the sample plus holder. This is much easier
to achieve with small samples and holders.
2. The heat from the furnace must not affect the balance mechanism.
Often baffles are placed between the two to reduce transfer of heat.
3. The furnace should be capable of rapid response and a range of
heating and cooling rates, and should be capable of heating to
temperatures well above those of interest. Rapid cooling is also most
useful when a quick 'tum round' time is needed when many samples
must be run.
4. The furnace lining should be inert at all temperatures used. A tube of
ceramic such as alumina or mullite, or, for lower temperatures, silica
glass may surround the sample, or in some cases, furnace and sample.
2.4.3 Programmer
The furnace temperature is measured by a thermocouple, generally

platinum-platinum 13% rhodium, which is most suitable up to 1600 DC,
is chemically fairly inert but has a fairly low output of about 8--12 ,""VIK.
Another thermocouple often used is chromel-alumel which is suitable to
1100 DC, has a larger response of about 40 f.L VIK, but is more easily
oxidised.
The signal from the furnace (or control) thermocouple is transmitted to
the programmer and the temperature it represents is compared with that
required by the programme set by the operator. If the temperature is too
low, the system must respond by supplying more power to the furnace,
and, if too high, by reducing the power. The response times of the
controller and of the furnace govern the thermal lag of the instrument and
hence the range of heating rates that is achievable. A slow response
programmer controlling a very large furnace may only allow heating rates
below 10 Klmin, whereas a small mass furnace and a fast controller will
allow rates up to 100 Klmin [18].
2.4.4. Samples
Thermogravimetry is most frequently carried out on solids. The sample

should be obtained in an approved way [19,20] so that it provides a
THERMOGRAVIMETRY 29
meaningful analysis. This is easy with pure, homogeneous compounds, but

very difficult with large samples which may differ from one region to
another. Procedures such as 'coning and quartering' of a finely ground
sample may give better reproducibility, but often the very differences that
we observe between samples are significant. One region of a sample may
be more porous, or more easily oxidised, or have a higher moisture content
than the bulk of the sample. Crystalline samples may behave differently
from fine powders, especially where surface reactions are involved. It is
also very often difficult to produce a fine powder from samples such as
thermoplastics.
Samples should ideally be small, powdered and spread evenly in the
crucible. Typical thermogravimetric runs might be done under the con-
ditions given below.
Sample: Calcium oxalate monohydrate

Crucible: Platinum pan
Rate: 10 Klmin
Atmosphere: Nitrogen, 20 cm3/min
Mass: 10.5 mg
Other examples are given later in the book.
2.4.5 Temperature calibration
In order that the balance shall operate with as little interference as

possible, the sample temperature is often measured by a thermocouple
placed near to, but not in contact with the sample.
Sample temperature thermocouples are generally of the same types used
for furnaces, but frequently rather smaller and more delicate, since they
are nearer the sample and the products of reactions.
The temperature measured by a thermocouple which is not in contact
with the sample must be subject to a thermal lag which could be several
degrees. Unless the experiment is carried out isothermally on a very small
sample, this lag will vary with temperature and with the reactions
proceeding, the furnace atmosphere, the heating rate and the geometry
of the system. It is very important to calibrate the thermobalance in
conditions which reproduce those which will be used in actual experi-
ments, and to be able to reproduce the conditions on a variety of instru-
ments. A survey was carried out by ICTAC of the most appropriate
method of temperature calibration of thermo balances and concluded that
a sharp, reproducible physical change would give the best results. The
materials selected are metals and alloys which are ferromagnetic at low
temperature, but which lose their ferromagnetism at a well-defined Curie
point [21].
~
~
Apparent
mass
value
-~
\ ~
Temperature
Figure 2.7 Curie point curve using the arrangement of Figure 2.4(c). For nickel, the
reported values are: Tl = 351.4 °C; T2 = 352.8 °C; T3 = 354.4 0c. T2 is taken as the
Curie point for calibration.
Table 2.1 Curie point

calibration samples for TG
Sample TCiWC)
Permanorm 3 259
Nickel 353
Mumetal 381
Permanorm 5 454
Trafoperm 750
If the magnetic material is placed in the sample holder and a magnet

placed below the sample, as shown in Figure 2.4(c), the magnetic force on
the sample will cause an apparent increase in mass. In a thermogravimetric
run in nitrogen, the force will disappear fairly abruptly at the Curie point,
as shown in Figure 2.7. The mid-temperature, or the peak of the DTG
curve, is now used as a fixed point for calibration using the NIST materials
listed in Table 2.1 [11,22].
Another method of calibration uses wires made from the high purity
materials of very accurately known melting points such as those used in
calibrating DTA [see Chapter 3]. These wires are used to attach a mass to
the sample pan, which will detach immediately the wire melts [23].
A rough check on the calibration may be performed with known
reactions, such as those given as examples later in this chapter, and
THERMOGRAVIMETRY 31
ensuring that the DTG peak temperatures match those obtained on the
apparatus when it has been recently calibrated by a standard method.
2.4.6 Atmosphere
The need to surround the sample in an inert or a reactive atmosphere, and

to control the evolution of gases from the sample, generally means that
thermogravimetry is conducted in a flowing gas stream. Too high a flow
rate can disturb the balance mechanism, while too Iowa flow rate will not
remove product gases or supply reactant gas. Therefore, a flow rate of
about 10-30 cm 3/min is often used. The flow of gas can also contribute to
the transfer of heat and assist the transfer of products to any external gas
analysis system [see Chapter 5].
If we wish to investigate a reaction that produces gas:
A(s) = B(s) + C(g)
e.g. CaC03 = CaO + CO 2
then we can conduct the experiment in a flowing inert atmosphere such as
nitrogen, where the carbon dioxide will be swept away as soon as it is
formed, or in an atmosphere of carbon dioxide, which will shift the
position of equilibrium, according to Le Chatelier's Principle. If we
consider a simple thermodynamic approach to the reaction, we have shown
in Chapter 1 that the equilibrium constant for the reaction is given by:
Kp = {Pco,} equilibrium
Since the reaction is endothermic, Kp increases as the temperature
increases according to the van't Hoff equation:
In (Kp) = - flH-B-IRT + constant
so the equilibrium pressure of CO2 becomes greater.
At a low partial pressure of CO2 , decomposition will take place at a
lower temperature than when the partial pressure is high.
If the sample is confined, then the atmosphere around it is made by the
sample itself, that is, it is self-generated. This will cause similar effects to an
externally imposed high pressure of product gases [24,25].
If we want the best contact between sample and surrounding gas, we
must spread the sample thinly, or use a porous or gauze container, taking
care that the sample holder is inert to all samples and gases [26,27].
2.5
The study of reactions can be divided into three parts: Kinetics of reactions
1. The stages, intermediates and products of reaction.
2. The energetics of the reaction stages.
3. The reaction mechanism and reaction kinetics.
The first two parts may readily be studied by TG and DSC, and the third
may also be investigated by thermal methods.
Consider a typical endothermic solid-state reaction:
A (solid) = B (solid) + C (gas)
As this reaction proceeds, gas and mass will be lost and heat absorbed.
Several equations are used to model the process, but they may not be valid
in all situations!
1. The extent of reaction ~ is a quantity having the dimension amount of

substance and defined by:
nB = nB,o + VB • ~
where nB is the amount of substance B, nB,O is a chosen amount of B, e.g. at

t = 0, and VB is the stoichiometric number of B, positive if B is a product,
negative if B is a reactant [28].
For reactions in solution the progress of reaction is usually followed by
the changes in concentration CB of the species B with time, but for solid-
state reactions this is hardly appropriate and it is more usual to follow the
changes in the fraction reacted, a, with time.
The rate of reaction may now be written in terms of a:
Rate = daldt
The rate of a reaction, even if measured at constant temperature, usually
varies with time and with the value of a. It is therefore common to write:
Rate = daldt = kT,f(a) (2.1)

where kT is the rate constant at temperature T, and f( a) is a mathematical
expression in a.
It would be nice if the same mathematical f(a) applied throughout the
reaction, as is quite often the case for solution and radiochemical reactions,
but it sometimes alters to a different rea)
part-way through the reaction,
due to the changes in mechanism, geometry or chemistry. It is easy to see
why this should be so if we consider a thermogravimetric experiment where
the different reaction stages overlap!
If a reaction is studied simultaneously by thermogravimetry and by a
group-specific technique such as IR, the values of a may not be the same,
since the IR-active species may not contribute to the greatest mass loss!
Relations used for the kinetics of solid-state reactions

Sestak and Berggren [29] summarised the many equations relating the rate
of solid-state reactions to a. They may be written as a combined equation:
da/dt = kT . am . (l-a)n . (-In(l-a)Y'
THERMOGRAVIMETRY 33
Table 2.2 Kinetic equations
Type f(o.) = Ratelk g(o.)=kt
Order equations
Fl First order (1-0.) -In(l-o.)
F2 Second order (1-0.)2 1/(1-0.)
Geometric
R2 Contracting area 2(1-0.)112 1-(1-0.)112
R3 Contracting volume 3(1-0.)213 1-(1-0.)1/3
Acceleratory
PI Power law (m>l) m(o.)(m-l)/m o.lIm
Sigmoid curves
An Avrami-Erofe'ev (n=2, 3 or 4) n(l-o.). [ -In(l-o.)]lIn
( -In(l-o.))(n-l)Jn
Bl Prout-Tompkins 0.(1-0.) In(a/(I-o.» +c
Diffusion
D1 I-D diffusion 1/(20.) 0.2
D2 2-D diffusion [-In(l-o.)r [(I-o.)ln(l-o.)] +a
D3 3-D diffusion (3/2)(1-0.) 3 [1-(1-0.)1I3j2
[1-(I-o.)lI~r
D4 Ginstling-Brounshtein (3/2[(1-0.)1 -ltl [1-2al3]-(I-o.f3
It is sufficient to quote three examples and refer to the more comprehen-

sive list in Table 2.2.
(a) One-dimensional diffusion-controlled reaction:
da/dt = kr/2a
(b) Two-dimensional growth of nuclei (Avrami equation):

da/dt = kr(l-a)·( -In(1-a))112
(c) First-order reaction: random decay of active species:
da/dt = kr(l-a)
Upon integration, this last equation gives:

In(l/(l-a)) = kT·t
or, for a general kinetic equation:
The interpretation of the kinetic equation considers the way in which the
reaction starts, by a process of nucleation, then how those nuclei grow and
what reaction or interface geometry is involved, and finally, how the

reactants decay [30].
2. The rate constant, k, depends greatly on temperature and is thus
sometimes written k T • The equation used for many reactions is that of
Arrhenius:
kT = A exp( -EIR1) (2.2)
where A is the pre-exponential factor; E is the activation energy (J/mol)
and R is the molar gas constant (8.314 J/(K mol».
Several thermal analysis papers lament that different values of E have
been found by different workers [31]. This may be due to a change in
reaction mechanism during reaction, to a true variation in E or to
differences caused by experimental procedure. The validity of the Arrhenius
equation is very often assumed, and deviation attributed to changes in the
mechanism· [32].
3. The temperature in a non-isothermal experiment is ideally controlled,
often to fit a linear programmed rise, ~ Klmin:
(2.3)
This again is an ideal situation and for large sample masses, highly
exothermic or endothermic reactions may cause changes in the real sample
temperature. Urbanovici and Segal [33] suggest a modified equation:
Tt = To + ~ . t + set) (2.3a)
where set) is the difference between the sample temperature and the
programmed temperature.
Therefore, it is as well when starting to study the kinetics of a reaction to
beware of these pitfalls. A good guide to strategy for studying kinetics is
given by Galwey [34] who advises the use of isothermal methods as well as
rising temperature methods.
It may be as well to stress that the scheme recommends using comple-
mentary techniques, such as hot-stage and scanning electron microscopy,
to confirm the mechanism of reaction.
Problems arise when equations (2.1)-(2.3) are combined and manipu-
lated mathematically.
2.5.1 Measurement of nand da/dt
For a thermogravimetric curve showing a single step, such as Figure 2.9,

we may calculate n at a particular time, or temperature from the measured
mass m t and the initial and final masses, mi and mf'
n = (mi - m t ) I (mi - mf) = m i I (mi - mf) - m t I (mi - mf)
THERMOGRAVIMETRY 35
START I .
I Use isothermal methods?
Yes No
I
Kinetic measurements Kinetic measurements
~ at constant temperatures at rising temperatures
$
Test obedience to rate equation (f{a) = kl]
I +
a, T (I) J
nucleation (f{N) = kl and growth (f{r) = kt] kinetics
No No
Is comparison satisfactory?
I Is comparison satisfactory?
J
Yes Yes
Microscopic
measurements
Note model and Note model and
calculate k calculate A and E
Yes
More temperatures? Supplementary

evidence
No
No
Is behaviour isokinetic?
I Interpret model, A and E
+ further investigations if
Yes necessary
Calculate A and E +
Reaction mechanism:
t (i) interface geometry
(ii) interface chemistry
Interpret effect of T
on model
+
STOP I
Figure 2.8 Schematic representation of the steps involved in the kinetic analysis of solid-
state reactions. (From [34] with permission.)
TfOC
Figure 2.9 Schematic TG curve and the analysis for kinetics.
Differentiating this gives:

da/dt = -[dm/dt] I (mj - mf)
and we may therefore measure the rate of reaction from the slope of the
mass-time curve. Since the DTG curve already measures dm/dt, this may
be used to find da/dt directly.
If we combine the linear heating equation (equation (2.3)), then:
dTldt = 13 (2.4)
and da/dt = (da/d1) . (dTldt) = (da/d1) . 13.
For a DSC curve, if the total area A represents the total reaction over the
whole time or temperature interval and the fractional area a gives the
partial reaction up to time t, then
a = alA
It has also been pointed out that the ordinate deflection Yt in DSC
represents the rate of heat supply in J/s, so that we might also use it to find
the rate, since da/dt is proportional to Yt.
DIFFERENTIAL EQUATIONS
From equations (2.1) and (2.2):

da/dt = A· exp (- EIRT) . f( a)
Combining with equation (2.4)
da/dT = (AII3) . exp (-EIR1) . f(a) (2.5)
THERMOGRAVIMETRY 37
Table 2.3
T(K) 103klT IX (I-IX) In(I-IX) IOS.dIX/dT In(dllld1)
929 1.076 0.005 0.995 -0.005 6.25 -9.680

938 1.066 0.011 0.989 -0.011 8.86 -9.332
966 1.035 0.047 0.953 -0.048 19.28 -8.554
994 1.006 0.118 0.882 -0.125 37.51 -7.888
1013 0.987 0.194 0.806 -0.215 52.10 -7.560
1032 0.969 0.297 0.703 -0.277 68.77 -7.282
1050 0.944 0.432 0.568 -0.566 86.48 -7.053
1069 0.935 0.598 0.402 -0.911 102.6 -6.882
1078 0.928 0.691 0.309 -1.175 105.2 -6.857
Rearranging the variables and taking logarithms:

In(da/dT) - In(f(a)) = In(AIJ3) -EIRT (2.6)
By plotting the left side of equation (2.6) against liT, the activation energy
can be obtained from the slope, and A from the intercept. In order to do
this, we must have some idea of which/(a) we should use from Table 2.2!
Example For the decomposition of calcium carbonate, the kinetic

equation could be one of many possible, for example:
1. Diffusion (D2: 2-D diffusion):
da/dt = k· (-In(l-a))-l
2. Prout-Tomkins (Bl: interacting nuclei):
da/dt = k . a . (I-a)
3. Mampel (R3: contracting sphere):
da/dt = 3k . (l-a)213
We can test these by plotting the appropriate data according to equa-
tion (2.6). For example, the R3 plot would be of {In(daldT) -
(2/3)· In(l-a)} against liT.
For this experiment 10 mg of CaC0 3 powder was heated at 10 °C/min
in a platinum crucible in flowing nitrogen. The TG plot was measured
and selected data are given in Table 2.3 above.
It is very clear that the most appropriate kinetic equation is R3, the
contracting sphere or Mampel equation. This agrees well with published
data [35,36] although some references suggest an R2 law. The slope of
the Mampelline is -EIR, and gives a value of E of about 190 kJ/mol.
This is a little high, but comparable to some published data. Reading has
pointed out [31] that the range of values quoted for the activation energy
of this reaction is very large indeed! The pre-exponential factor A is
about 107 S-l.
mass %
TG
50
-------
-
....
"-
,,
,
I
---- -- ----
, I
\
,, ,I
I DTG
,,
I
(dm/dt)
\
,, I
\ ,, I
I
'-'
600 700 BOO 900 1000
T/K
Figure 2.10 TG and DTG curves for 10 mg of CaC0 3 powder heated at 10 Klmin in
flowing nitrogen (30 cm3/min).
REDUCED TIME PLOTS
In order to check the validity of the kinetic equation and whichf(a) should
be used, it is good practice to plot all results onto the same graph [4,37].
For isothermal cases, plotting the value of a against (tlto.s) often gives a
single trace of characteristic shape, as shown in Figure 2.12. If the value of
f(a) is evaluated from the equations of Table 2.2, the fit of the observed
data can identify the kinetic rate equation. For example, for a first-order
(F1) mechanism,
a = 1 - exp( -0.693(tlto.s))
Similar reduced plots have been suggested for non-isothermal results
[38] and for constant rate results [39].
INTEGRAL METHODS
If we attempt to use the integrated rate equations represented by the

functions g(a) in Table 2.2, the integration of equation (2.5) is required.
g(a) = fdalf(a) = (A/~) . f (exp (-EIRT») dT (2.7)
THERMOGRAVIMETRY 39
-4
Function
-8
-12
-3
1.00x10-3 1.1Ox10
1 x KIT
Figure 2.11 Plots of In(dald1) - In(f(a)) against liT for diffusion (D2), Prout-Tomkins
(Bl) and MampeJ (R3) kinetics applied to calcium carbonate decomposition.
This involves the difficult integration of the right-hand side temperature

integral. If we assume that a = 0 until the reaction starts at Ii, we may
change the limits of integration and integrate from 0 to T:
I (exp( -E/RT)) dT = (E/R) . I [(exp( -x))/x2) dx = (E/R) . p(x)
where x= E/RT and p(x) = [(exp( -x))/r).
Approximations to determine p(x) have been proposed, one of the best
of which is
p(x) = exp( -x )/[x(x+ 2))
Values of the function p(x) may be calculated by computer and have been
tabulated. Various approximations have been suggested for the temperature
integral, for example: Doyle [40);
10gIO p(x) = -2.315 - 0.4567x (for x > 20) (2.8)
Coats and Redfern [41):
g(a) = (ART2/~E) [1-(2RT/E)) . exp( -E/RT)
Brown [42) gives an excellent discussion of the mathematics used and the
treatment of kinetic results. Ozawa [43) and Flynn and Wall [44) have
1.0 .---_ _ _ _~_ _ _ ____,::::::=_----------__,
.8
(l
.6
.4
.2
2 3 4
tlIO.S
Figure 2.12 Reduced time plots for Avrami (A3), first-order (Fl) and 3-D diffusion (D3)
kinetics.
shown that if different heating rates, (3, are used, the temperature Ta for a
given conversion a may be shown, by combining equations (2.7) and (2.8),
to be
10glO (3 = -2.315 + 10glO (AEIR) - 10glO g(a) - 0.4567(EIRTa ) (2.9)
Plotting log a against lITa generally gives good straight lines of slope
-0.4567 (EIR). The pre-exponential factor, A, is also obtained by equation
(2.10)
A = (3 . (EIR'J'2) . exp(EIRT) (2.10)
A revision of the value of E determined by this method uses a correction

value of D = - d In(p(x))ldx, which is tabulated in ASTM E 698, or may
be evaluated by computer.
Example Since the kinetics of decomposition of polymeric materials is

a very important study and relates to their stability and performance, the
thermal decomposition of poly(tetrafluoroethylene), PTFE, was studied
by TG [45] using samples of about 10 mg, and flowing air at 30 cm3/min.
THERMOGRAVIMETRY 41
Rate, (3(Klmin) T(K) (2%) T(K) (10%)

2.5 775 798
5.0 781 805
10 791 818
20 802 829
The slopes of the plots are -1.80 X 104 and -1.67 X 104 K, so that
E -(1/0.4567) x R x slope ;:::;< -2.19 x R x slope
;:::;<
E ;:::;< 328 kJ/mol and 304 kJ/mol, giving an average

E = 316 kJ/mol
The values are refined by calculating x = EIRT for a temperature in the
middle of the range, say 790-810 K, and looking up D in tables. For an
average value:
x = 47.5, so that D = 1.042
E ;:::;< -2.303xRxslopelD = 319 kJ/mol
This procedure may be repeated until a constant value of E is obtained.
Using the mid-point value of 10 Klmin
A = 10 (319 000/(8.314 x 8002)) • exp(319 000/(8.314 x 800))
A = 4.05 X 1020 min- j
It may be noted that, for reactions having several stages, the value of E
may change as a function of the degree of conversion, and this has been
illustrated with the pyrolysis of poly(1,4-phenylene-di(methoxyphenyl)-
vinylene) in argon [46] where the reaction shows three stages with
activation energies of 200, 263 and 258 kJ/mol.
CONSTANT RATE METHODS
If we consider that the rate of reaction (da/dt) is controlled by the value of

the temperature, the fraction reacted and the nature of the atmosphere, then
control of these parameters could be used to control the rate directly.
Rouquerol [47] proposed that 'a quantity directly related to the
decomposition rate is kept constant'. This quantity may be the evolved gas
flow, the thermal flow or the DTG signal. This is the technique of constant
rate thermal analysis (CRTA). The quasi-isothermal, quasi-isobaric tech-
niques of the Pauliks [48] controlled their system in such a way as to keep
the rate of mass loss constant, and to confine the reaction gases so that they
were lost at constant atmospheric pressure.
Reading [39] has described the 'rate jump' technique, where the
temperature and pressure are controlled such that, at a temperature T j , the
rate of mass loss is constant at (da/dt)j, and when it is rapidly raised to a
new temperature T2, the new constant rate is (da/dt)2' For a small interval,
the value of In[f(a)] changes little during the jump, so that:
mass
I
I
-{I..-------4
I05mv~~-
Thermocouple
Signal
time
Figure 2.13 Typical results for rate jump constant rate thermal analysis [39].
E = - R lnl( daldt)/( daldt)i!

(T2 - T1)/(T(T2)
For calcium carbonate, a value of E= 193 kJ/mol was reported.
2.6
Applications of A selection of examples is given below, but the range of applications is very
thermogravimetry large indeed. Readers are advised to study the specialist texts on thermo-
gravimetry for further particulars.
Note! It must be remembered that TG will ONLY detect changes where

the mass of the sample changes, by reaction, or vaporisation, or because a
physical property changes its interaction with an imposed external force,
e.g. the magnetic permeability in an imposed magnetic field.
2.6.1 Thermogravimetric curves
DEcoMPosmoN OF MAGNESIUM HYDROXIDE (Mg(OH)2)
This is found as a natural mineral, brucite; it is used in gravimetric analysis

and as a fire-retardant additive in polyamides, polyolefins and polyesters.
THERMOGRAVIMETRY 43
---------
1oss-30.9%
I'
50 60 150 240 330 510 SlO 690 700 870' 960
Terrperalure fcl
Figure 2.14 TG and DTG curves for magnesium hydroxide, 7.04 mg, heated in a Pt
crucible at 10 Klmin, nitrogen.
The thermogravimetric trace of a commercial sample given in Figure 2.14

shows a single mass loss over a fairly broad temperature range. The sample
is stable up to about 200 °C, and then loses about 27% of its mass rapidly
by 450 °C; a much slower loss then occurs up to 800 °C with a total mass
loss of 30.9%.
The chemical equation for the reaction is:
Mg(OH)z(s) = MgO(s) + H20(g)
and the water evolved can be detected by chemical, physical or spectro-
scopic techniques (see Chapter 5). The stoichiometry of the above reaction
suggests that the calculated loss should be
% Loss = 100 x M(H20)/ M(Mg(OH)2) = 100 x 18.0/58.3
= 30.87%
Thus we see a very good agreement between theory and experiment in this
case. The reason for the two stages shown on the TG and DTG curves is
less obvious. It has been attributed to the rapid reaction to decompose all
the hydroxide and to lose the majority of the water vapour, followed by the
gradual slow diffusion of water vapour adsorbed on, or trapped within, the
oxide [49]. Another alternative is the presence of a small amount of
carbonate impurity [50].
Samples prepared by different reactions, or stored under different
100 , r~~~~,
.... r , -----_ ..
\
\ \ I \
\ \
loss = 12.4%
\
\
82.5
\
\
\
'1-. I
i 65
\I t01alloss = 31.5%
\/ I I
I I
I
I I ~ /
47.5
II ~
\/
t01alloss = 61.7%
, -T3o.-eW:-
30
3D 130.
I
230. Mo. 430. 7M. a30: -L--.
930.
Temperature ("C)
Figure 2.15 TG and DTG curves for calcium oxalate monohydrate, 12.85 mg,
Pt crucible, 20 Klmin, nitrogen.
conditions, or subjected to different packing [51] have all been shown to

give different TG curves, although the quantitative nature of the change is
unaffected.
The endothermic nature of the dehydration reaction is one reason for
the use of magnesium hydroxide as a fire retardant, and it is found that
incorporating it into a polymer changes the decomposition of both the
polymer and the hydroxide.
The oxalate hydrates of the alkaline earth metals, calcium, strontium and
barium, are all insoluble and have been used in gravimetric analysis. For
example, a calcium salt in a solution made acidic with ethanoic acid, when
treated with an excess of sodium oxalate solution, precipitates calcium
oxalate monohydrate quantitativel~ill]. The precipitate is washed with
ethanol, and may then be analysed as one of three compounds:
• as Ca~04'H20, by drying at 100--115 °C for 1-2 hours;
• as CaC03 by heating to 475-525 °C in a furnace;
• as CaO by igniting at 1200 °C.
When we heat this compound on a thermobalance, we obtain the curves
shown in Figure 2.15. A single run in air at 10 °C/min up to 1000 °C shows
three distinct changes:
THERMOGRAVIMETRY 45
1. Between room temperature and about 250 DC there is a loss of about

12% to give a stable product.
2. Between 300 and 500 DC a loss of some 19% occurs to give a second
stable product.
3. Above 600 DC there is a final loss of about 30% to give a final product
stable to the highest temperature used.
Can we suggest a set of reactions to explain these losses?
1. Since the first loss-starts around 100 DC, we might consider loss of
water vapour:
Cac;04·H20(S) = CaC20 4(s) + H 20(v)

Calculated % loss = 100 x 18.01146.1 = 12.3%
This loss corresponds with what is found, so this reaction is possible.
2. Previous analytical methods produced calcium carbonate by heating
to about 500 DC, so let's consider that:
Cac;04(s) = CaC03(s) + CO(g)
Calculated % loss = 100 x 28.0/146.1 = 19.2%
This, too seems a likely reaction!
3. The decomposition of calcium carbonate is a well-established reaction:
CaC0 3(s) = CaO(s) + CO2(g)
Calculated % loss = 100 x 44.0/146.1 = 30.10/0
Words of caution! Despite the excellent agreement of the calculated and

experimental values, it is most unwise to deduce reaction schemes from this
evidence alone! The products, both gaseous and solid, should be character-
ised by other analytical methods, such as X-ray diffraction for solids and
chemical tests for gases.
In the particular case of calcium oxalate described above, these tests
have been made, and the stages of decomposition confirmed. The presence
of calcium oxalate hydrate in kidney stones [53] extends the use of this
analysis to biological fields.
If the conditions of analysis are changed, the temperature ranges of the
events may alter, and the shape of the curve change, but the stable
products will still be obtained. We shall see later that this analysis may be
adapted to determine calcium, strontium and barium simultaneously [52].
COPPER SULPHATE PENTAHYDRATE (CuS04·5H20)
Blue hydrated copper sulphate is a very well known material and has been
used to demonstrate many thermal techniques. In this example, we shall
Mass TG --'C"""""-
loss = 14.4%
dm/dt
----, \
~-=~-,..---- - - - - - - -- --- , ,- - - - ~ DTG
\ \
\ \
\
1055=36%
\
I \ I
1'1 I
\, I I
" I I
II
I,
I,
\,
total loss = 68.2%
200 400 600 800 T/OC
Figure 2.16 TG and DTG curves for copper sulphate pentahydrate, 10.61 mg, alumina
crucible, 10 Klmin, air.
show how the DTG curve may be used to help obtain quantitative data.
Depending on the conditions, the stages of the reactions may be resolved
to different extents. If a very fast heating rate and large sample is used, the
stages tend to 'blur' together. Conversely, at slow heating rates, or where
the rate of reaction is controlled, the stages are well resolved.
The sample heated for Figure 2.16 shows a mass loss starting below
100 °C, closely followed by a further loss up to 160 °C. The DTG curve
shows a minimum from which the mass losses for the two overlapping
stages may be calculated, using the construction shown.
By checking the mass losses, you can confirm the following possible set
of decomposition reactions. (RAM are: Cu = 63.55; S = 32.06; 0= 16.00;
H = 1.00.)
1. CuS04·5HzO(s) = CuS04·3HzO(s) + 2H20(v)

2. CuS04·3HzO(s) = CUS04·HZO(S) + 2HzO(v)
3. CuS04·H20(s) = CuSOls) + HzO(v)
4. CuSOls) = CuO(s) + SOz(g) + V202(g)
What does the DTG curve suggest about the reaction above 700 °C? One
explanation given is that a basic sulphate, CuO·CUS04, is formed.
THERMOGRAVIMETRY 47
DEGRADATION OF POLYMERS
The effects of heat on polymeric materials varies greatly with the nature of
the polymer, ranging from natural polymers like cellulose, which start to
decompose below 100 °C, to polyimides which are stable up to 400 °C. The
presence of additives and the atmosphere used also affect the changes
greatly.
When heated in an inert atmosphere, polymeric materials react by two
general routes, often related to their mode of polymerisation and the heat
of polymerisation. They may either depolymerise or carbonise [4,54].
Polymers such as poly(methyl methacrylate) (PMMA) and polystyrene
(PS) may depolymerise or 'unzip' back to the monomer. Such polymers
generally have a low Ml of polymerisation. Random scission of poly-
(alkenes) like poly(ethylene) (PE) will produce unsaturated hydrocarbons
from chain fragments of varying lengths like butenes, hexenes and dienes.
The kinetics of this random process is approximately first order, and the
temperatures of degradation are much affected by the substitution. Thus,
with fluorine substitution, poly(tetrafluoroethylene) (PTFE) decomposes
at a much higher temperature than PE, and with methyl substitution,
poly(propylene) (PP) at a lower temperature than PE, as shown in Figure
2.17.
0r--_=----.......
10
20
30
40
50
60
70
80
PTFE
90
PVC
100'--_ _ _ _ _ _ _ _- - - - - - -
o 100 200 300 400 500 600 700 800 900 1000
Temperature "C
Figure 2.17 TG curves for polymer samples in air. Samples all about 1 mg, heated at
50 Klmin.
Poly(vinyl chloride) (PVC) and poly(acrylonitrile) (PAN) may eliminate
small molecules initially and form unsaturated links and cross-links before
finally degrading by complex reactions to a char, which will oxidise in air.
R-(CH2-CH·Cl-)n-R' ~ R-(CH=CH)-R' + HCl ~ etc.
This stage is shown in Figure 2.17 as a loss of about 60%.

Polymers containing polar groups, such as polyamides (e.g. nylon 66),
may absorb moisture which is usually lost below 100°C, sometimes in
stages if the moisture is in different environments.
Cellulose polymers, polyester resins and phenol-formaldehyde polymers
have extremely complex decomposition schemes, eliminating small mole-
cules, often flammable or toxic, and eventually leaving a charred mass. If a
polymer melts during degradation, a coke is formed.
In an oxidising atmosphere, these reactions are further complicated,
both by the oxidative attack on the polymer, forming peroxides, and also
by the oxidation of the products and char.
Flame-retardant additives in polymers may be studied since their mode
of action may alter the nature of the reactions and the amounts of
products.
In Figure 2.17, several polymers are compared and their relative
stabilities may be assessed. The initial temperature of degradation may not
be comparable to the maximum continuous use temperature, since thermo-
plastics may melt, and this would not show on TG, and other polymers
degrade slowly over a long period, even at low temperatures.
A cautionary note on the use of thermal methods of stability assessment
was sounded by Still [56], whose review considers instrumental and
procedural problems and the effects of polymer structures. Cullis and
Hirschler [57] consider thermal methods as applied to the combustion of
polymers, and Turi [58] provides a comprehensive review of polymer
applications of thermal methods.
2.6.2 Analysis of mixtures
When we wish to analyse an unknown mixture of chemical substances in a

real sample, several options are open to us. We may use the wide range of
separation techniques such as chromatography to isolate each component
of the mixture, which may then be identified and measured separately, or
we may use a solution technique such as inductively coupled plasma
spectrometry which can determine all the elements present simultaneously.
However, neither of the above methods is suitable to the entire range of
solids from minerals to polymers, and both require a change in the original
material before analysis.
Thermogravimetry shows the differences between the behaviours of
THERMOGRAVIMETRY 49
substances on heating, and if those behaviours are sufficiently different on

the temperature scale, the individual reactions of substances may be
identified and measured. Three examples will be given from a wide range.
MIXTURES OF ALKALINE EARTH OXALATES
We have already seen how the decomposition of calcium oxalate hydrate

may be followed by TG. The oxalates of magnesium, strontium and barium
are also precipitated under similar conditions, but decompose in rather
different ways [52].
Magnesium oxalate dihydrate breaks down in only two stages: firstly, to
the anhydrous oxalate by about 250°C, and then directly to the oxide by
500 °C.
Strontium oxalate monohydrate and barium oxalate hemihydrate lose
water by 250°C and the anhydrous oxalates decompose to the carbonates
by 500 °C. The strontium carbonate decomposes between about 850 and
1100 °C while the barium carbonate is stable until even higher temperatures.
An illustration of the decomposition of the mixture of calcium, strontium
and barium oxalate hydrates is shown in Figure 2.18 and the percentages of
each may be found from the TG trace.
A comparison of the thermodynamics of decomposition of metal oxides
or metal carbonates (Figure 2.19) may be done by the construction of
Ellingham diagrams [59]. These involve the plotting of !:iGB- against T for
the reaction of importance, for example:
MmC03(s) = MmO(s) + CO2(g)
For this reaction !:iG and !:iR are generally positive at 298 K (25°C) and !:is
is very positive since gaseous carbon dioxide is produced. For calcium
carbonate, for example, at 298 K:
!:iaB- = 130.1 kJ/mol;
!:iJIB = 177.9 kJ/mol; and !:iSS = 160.4 J/(K mol)
The slope of the Ellingham plot is:
(a!:iaB-/a1)p = -!:isB-
and is negative since !:isB- is very positive. This means that !:iaB- becomes
less positive and finally passes through zero to become negative as the
temperature increases. When !:iGB- is zero, the equilibrium pressure of
carbon dioxide is 1 atmosphere and the carbonate will decompose. We may
call this a 'decomposition temperature Ti, although the material may
decompose at other temperatures under other conditions.
It has been shown that the value of Td depends upon the cation radius, r,
and a good correlation is found plotting !:iRB- vs (r'l2/z*) where z* is the
effective nuclear charge.
Galvanometer
readings r----~
30
20
OTA
Scale
-20
-30
-40
Scale 0
I
I
I
I
30 1030:
I
I
Massloss 40 I
I
% I
r----
E I
!
I
;--10
20~ I
G---j---------- T~
~-l~~~~~-~~~~~~~~~-______ i
50 200 400 600 800 1000 1200
·C
Figure 2.18 Derivatograph trace for a mixture of calcium, strontium and barium oxalate
hydrates, about 0.3 g, heated at 10 Klmin [52]. The stages are as follows: loss of water of
crystallisation (E); loss of CO from decomposition of the oxalates (F) and loss of CO2
from calcium carbonate (G) and from strontium carbonate (L).
Mixtures of carbonates and mixtures of nitrates may be analysed

quantitatively by TG and examples are given at the end of this chapter and
in Chapter 6. Dollimore et al. [60] have shown the applicability of the
thermodynamic treatment to more complex systems.
POLYMER BLENDS
Since the decomposition profiles of polymers are characteristic, some

polymer blends [61,62,63] may be analysed by TG. Figure 2.20 shows the
TG of a ethylene-vinyl acetate (EVA) copolymer heated at 20 Klmin in
nitrogen. The first loss may be shown to be ethanoic acid (acetic acid) from
the vinyl acetate, while the second shows the decomposition of the residual
material.
THERMOGRAVIMETRY 51
200
AG%J mol- 1
100
Sa
Sr
O~------~----~~--------------~~--------~
Ca
500 1000 1500

T/K
Figure 2.19 Ellingham diagram for the decomposition of carbonates:
MmC03 = MmO + CO 2 , Full points represent phase transitions [35].
120
100
80
~
0
!IJ
!IJ 60
CU
E
40
20
° 200 300 350 400

Temperature (OC)
450 500
Figure 2.20 TG curves for ethylene-vinyl acetate blends. Samples of about 10 mg run in
nitrogen at 20 Klmin. (Courtesy TA Instruments Ltd.)
~------------------------ '00%
Mass
'-----<;.:---------- 17%
' - - - - 9.5%
200 400 600 800

Figure 2.21 TG curve for polyolefin polymer with CaC03 filler. Sample of 10.5 mg
heated at 10 Klmin in nitrogen. Residue at 500 °C gives the filler content (17%) and the
temperature and percentage mass loss for decomposition (about 700 °C and 44% loss)
suggest CaC0 3 •
Polymers containing· additives, especially fillers like calcium carbonate

and fire-retardants such as aluminium hydroxide, are often studied by TG.
The decomposition stages may be altered, but the residue at high
temperature is characteristic of the filler. For example, calcium carbonate
shows the normal decomposition to calcium oxide around 800 °C and
aluminium hydroxide leaves a stable residue of A120 3 • Figure 2.21 shows
one example of this.
The quantitative analysis of filled polymers and rubbers may also involve
oxidation. Figure 2.22 shows a rubber material filled with carbon_~ The
stages of decomposition are well defined, and start in nitrogen atmosphere
with the loss of a volatile oil component below 200 °C followed by the
degradation of the main polymer components. The residue at 600 °C is
stable in nitrogen, but on switching to air the carbon-black filler is oxidised
away, leaving the small ash content. We thus have four analyses performed
in one TG run. It should be noted that the decomposition products of the
polymer are often very flammable and care must be taken to remove them
before introducing any air!
SOILS
The composition of soils [2,64,65] is complex, and varies with the

geological and biological nature of the area, the level from which the soil
THERMOGRAVIMETRY 53
a
%
mass
loss
200 400 600 600 700 800 900

Temperature °C
Figure 2.22 TG curve for carbon-black filled rubber. (Courtesy PL-Thermal Sciences.)
was collected and the human and biological interaction that has taken
place. After soil samples have been collected, they should be stored under
reproducible conditions, e.g. constant relative humidity for about 1 week.
There are generally three stages of soil decomposition on heating:
1. Loss of hygroscopic moisture and of simple volatiles produced from
organic compounds between room temperature and 150°C.
2. Ignition of organic matter starts at about 250 °C and is complete by
550°C. The organic matter may be determined by the mass loss
between these two temperatures, provided no other reactions inter-
fere. The largest interference comes from clay minerals, but provided
the clay content is less than about 40%, the loss to 500 °C is a very
good guide to the organic matter. An alternative is to remove the
organics by wet oxidation using hydrogen peroxide, and then run the
residue.
3. Hydrated minerals such as aluminium and iron oxides, and micas and
gypsum may complicate matters, but high-temperature decompo-
sitions can show the content of minerals such as carbonates.
COALS
The analysis of coals [66,67] for moisture, total volatiles, fixed carbon and
ash content is referred to as a 'proximate analysis'. Thermogravimetry,
especially when computer controlled, has great advantages over traditional
methods for proximate analysis. Figure 2.23 shows the TG curve of a
typical coal, and the alterations in heating rate and in atmosphere required
100 I----~-.....,
Volatiles: 23.5%
80
60
'!-
W
III
13 Fixed carbon
~ 40 67.0%
Cycle time:
30min.
20
/--_-' 110·C Ash:8.5% O'---r---.......---:-:---:-:---I
o Temperature Valve time: 15mln. N2 2
Time
Figure 2.23 Proximate analysis of coal using microcomputer-controlled thermogravimetry

[67].
to obtain results in the optimum time. It is most important that each stage
is completed before starting the next, especially when switching to an
oxidising atmosphere, where any remaining flammable gases may combust
explosively at high temperature in oxygen or air.
2.6.3 Oxidation studies
Besides the oxidation of organics and of carbon, studies have been made of
the oxidation of metals and alloys [68-70] and of compounds [71] using
thermogravimetry.
In this instance it is often useful to run the sample isothermally. Figure
2.24 shows the oxidation of metallic copper in air at 800 °C. The curve is
unusual in showing a weight gain! Where this is observed in other traces it
often indicates metal oxidation. The oxidation of copper forms CU20 first.
The shape of the curve may be fitted to the parabolic law governing the
kinetics of metal oxidation and may show a broken parabola if the oxide
surface cracks [72].
2.6.4 Reduction studies
The preparation of catalysts often involves a reduction step. The use of

TG apparatus and of special temperature programmed reduction (TPR)
apparatus, which measures continuously the consumption of hydrogen
during the reduction process, has given much useful data on catalyst
preparation and allowed the detection of overlapping reactions and the
study of kinetics [73,74].
THERMOGRAVIMETRY 55
20 r-------~--------~~------------------~--_.
Relative mass increase

100. (dm/m)
/
15
/
10
/
/
5 /
50 100 150 200 250 timel s
Figure 2.24 Isothermal TG oxidation curve for copper metal. Sample of copper turnings,
20 mg, heated at 800 °C in air. Relative mass increase (full line) and (Amlm? (dashed
line) for parabolic rate law.
Dehydration
of metal salt
%
Mass Decomposition
loss of metal salt
Reduction
of metal oxide
1 - - - - Air atmosphere----I- Hydrogen atmosphere-
o 200 400 600 o 10 20 30

Temperature 0 C Time (minutes)
Figure 2.25 TG curve for the decomposition of a metal salt in air. When the
decomposition to the oxide is complete at just above 600 °C, the temperature is held
constant and the atmosphere changed to H2 , causing reduction to the metal [75].
In a similar way to that described in section 5 above, the atmosphere

may be changed during the run so that the product is reduced. This is
2.7 In the usual TG experiments, the analyst sets a constant heating rate and
Controlled rate measures the temperature and mass as dependent variables, as a function
thermogravimetry and of time. If several reactions occur, it is important that we try to resolve
Hi-Res™ TGA them. Of course, the atmosphere gases, the instrumental conditions and
the nature of the sample, plus the kinetics of the reactions occurring, will
affect the extent to which the reactions may overlap. Very small samples
will help, producing less interference between products and reactants, and
very low heating rates will help by allowing one reaction to finish before
the next begins. However, these conditions cause problems, either of
sensitivity, or of a very long time needed for the experiment, perhaps
several hours if isothermal or at a very slow heating rate.
Another method of improving the resolution is to control the rate of
reaction. This may be done by sensing the rate of mass loss [48] or by
sensing the evolution of a particular product gas [47] and using one of these
parameters to control the rate of heating. Generally these methods have
led to longer experimental times than for a conventional TG run.
Commercial equipment is now available [76] which achieves the benefit
of higher resolution of thermal events without sacrificially long experimen-
tal time. With microprocessor control, when no mass loss is occurring, it is
possible to have a high heating rate (for example, 50 Kimin), but when a
loss is detected the heating rate is reduced towards zero, and kept low until
the mass again becomes nearly constant. One analogy is with a video
recorder. If nothipg of interest is happening, we can 'fast forward' the
videotape. When an important event shows up, we can slow down or even
'pause' the tape.
For rapid sensing and control, it is necessary to have a thermocouple
close to the sample, plus a directed purge gas flow for rapid removal of
product gases and interchange with the sample, plus a thermobalance
system of high sensitivity to detect small mass changes and respond rapidly.
The commercial Hi-Res™ TGA system allows the operator to programme
in the resolution required, from a very high resolution where the experi-
mental time may be long, to a 'standard' experiment with a run giving
much higher resolution than a normal TG, but a comparable run time.
Applications of Hi-Re.,TM TGA have been reported for various materials,
from improved resolution for the dehydration and decomposition of
copper sulphate, to the analysis of fuel transport additives. Three examples
showing the improvements that may be obtained will be given.
2.7.1 Polymer blends
We have noted above the possibility of analysing ethylene-vinyl acetate

(EVA) copolymers by TG (see Figure 2.20). Although the steps are fairly
well resolved with conventional TG, Hi-Res™ TGA improves this
dramatically and gives better quantitative accuracy.
THERMOGRAVIMETRY 57
100
80
...... 60 Increasing
~ Vinyl Acetate
I/)
:a 40
:E
T
...!,..
20
0 '-
0 100 200 300 400 500 600
Temperature (0C)
Figure 2.26 Hi-Res™ TGA of ethylene-vinyl acetate copolymer blends. This figure
should be compared with Figure 2.20. (Courtesy TA Instruments Ltd.)
I-
32
'if A
.....
I/) ,\
.1
,\
~ rI
I \
CJ I
C. \
"C
0
50 100 150 200 250 300
Temperature I °C
Figure 2.27 Comparison of Hi-Res™ and conventional TG first derivatives for a polymer
derivative fuel additive. Solid line, conventional TG; dashed line, Hi-Res™ITG +4.
2.7.2 Fuel additives
Fuel and oil additives [77] may be subjected to an oxidative environment

and temperatures around 200 DC. They are designed to improve the
properties of the oil blend, especially the flow and oxidative stability.
Studies of their thermal stability are most important.
Conventional TG of a polymeric derivative used as an additive shows
a gradual, poorly differentiated mass loss. Figure 2.27 shows the TG first
derivative curves for conventional and Hi-Res™ TGA of this material.
The Hi-Res™ TGA gives a much clearer resolution of the mass losses into
three steps, after loss of low-boiling solvent. The mass losses can be
quantified more accurately, and the product gases identified by mass
spectrometry.
2.7.3 Drugs
The presence of water in both 'free' and 'bound' states in pharmaceutical

materials is most important. Estimation of the amounts of each type, and
the study of water bound in different ways may give better information
about the compatibility and action of the drug [78].
Figure 2.28 shows the conventional and Hi-Res™ TGA of a hydrated
drug substance, and the DTG curves enable a better separation of the
* 100
I.
<I
.....
III
~ 95
III
gj 90
:::!:
85
80
75
0 50 100 150 200 250
Temperature!'C
l-
I- 0.6
"C
0~ Free water
-;; 0.4
til· H:P
~ H2O
(!j
t:. Decomposition
"C 0.2
o.
0 50 100 150 200 250
Temperature/'C
Figure 2.28 Comparison of the Hi-Res™ and conventional TG and DTG of a hydrated
drug candidate (78]. Solid line, conventional TG; dotted line, Hi-Res™ index 4; dashed
line, Hi-Res™ index 5.
THERMOGRAVIMETRY 59
water present in various environments within the material, from the 'free'
moisture to two or more kinds of 'bound' water. The trace also shows
decomposition at higher temperatures.
2.8
1. Which of the following physical changes could NOT be detected by Problems
thermogravimetry? (Solutions on p. 273)
(a) loss of moisture; (b) sublimation; (c) melting; (d) gas adsorption.
2. Which of the following chemical reactions would NOT be detected by
thermogravimetry?
(a) CaC03 + SOz = CaS04 + COz
(b) CaC03 + SiOz = CaSi03 + COz
(c) CaC03 + NazS04 = CaS04 + Na zC0 3
Calculate the mass change in any of the reactions that could be detected.
3. You have decided to investigate a material using thermogravimetry.
Make a check-list of all the things you should do before attempting to
run the sample. If you are investigating the stability of the material,
what would you do as additional experiments?
4. Magnesium carbonate was dissolved in aqueous oxalic acid and a
crystalline product A obtained. When A was heated in air, 9.20 mg of A
lost mass in two stages only: 2.23 mg were lost up to 220°C and a further
4.49 mg by 500 °C. Write balanced chemical equations for the
preparation and decompositions of A.
5. An alloy containing silver and copper was dissolved in concentrated
nitric acid in a small ceramic TG crucible. When heated in air it gave the
TG curve of Figure 2.29. Observations showed the residue at the first
- - -.........._ _ _ _ _ _ _ _ _ 67%
Mass
_ _ _ _ _ _ 48%
200 500 900

Figure 2.29 TG curve of a silver-copper alloy after solution in nitric acid.
plateau was blue crystals, at the second a black solid and at the third a
mixture of black solid and metallic specks. Calculate the percentage
silver in the alloy.
6. Using the curves given in Chapter 2 as a guide, sketch the curves for
polyethylene (PE) and for poly(vinyl acetate) (PVA). If a copolymer of
these two (EVA) loses 15% of its weight in the first stage heating up to
390°C, calculate the percentage composition of the copolymer.
7. A colleague has performed a series of TG experiments on a sample of a
'pure' substance. He approaches you in some concern, because the
results are very different in. appearance and in temperatures of the
steps. What might he be doing incorrectly? If his results are correct,
what does this suggest about the sample?
References 1. AI. Vogel, Quantitative Inorganic Analysis (3rd edn), Longman, London, 1961,
p.104.
2. I. Barshad in Methods of Soil Analysis, Pt 1, C.A Black (ed.), No.9 in Agronomy Series,
American Soc. Agronomy, Madison, 1965, Ch. 50.
3. C. Duval, Inorganic Thermogravimetric Analysis (2nd edn), Elsevier, Amsterdam,
1963.
4. C.J. Keattch, D. Dollimore, Introduction to Thermogravimetry, Heyden, London, 1975,
Ch. 1.
5. W. Wendlandt, I. Chern. Educ., 1972,49, A571, A623
6. K. Honda, Sci. Rep. Tohuku Univ., 1915,4, 97
7. M.I. Pope, M.D. Judd, Educ. in Chern., 1971,8,89
8. P. Chevenard, X. Wache, R. de la Tullaye, Bull. Soc. Chim. Fr., 1944, 10,41
9. L. Cahn, H.R. Schultz, Vacuum Microbalance Techniques, Vol. 2, Plenum, New York,
1962, p. 7.
10. J.O. Hill, For Better Thermal Analysis and Calorimetry, III, ICTAC, 1991.
11. P.D. Gam, O. Menis, H.-G. Wiedemann, ICTA Magnetic Reference Materials Certifi-
cate, NBS GM-76, 1976.
12. J.M. Thomas, B.R. Williams, Quart. Rev., 1965, XIX, 239
13. F.W. Sears, M.W. Zemansky, H.D. Young, College Physics (5th edn), Addison Wesley,
Reading, MA, 1980.
14. W.L. de Keyser, Nature, 1962, 194,959.
15. W.-D. Emmerich, E. Kaisersberger, I. Thermal Anal., 1988,34,543; Netzsch TG 439
Brochure, Netzsch Mastermix Ltd.
16. T. Gast, E. Hoinkis, U. Muller, E. Robens, Thermochim. Acta, 1988, 134, 395.
17. Netzsch TG 449 Brochure, Netzsch Mastermix Ltd.
18. E.L. Charsley, A.C.F. Kamp, J.P. Redfern, Progress in Vacuum Microbalance Tech-
niques, Vol. 2, eds S.c. Bevan et al., Heyden, London, 1973, p. 97
19. D.A. Skoog, D.M. West, Fundamentals of Analytical Chemistry (4th edn), Holt-
Saunders, Philadelphia, 1982, Ch. 24.
20. F.W. Fifield, D. Kealey, Analytical Chemistry (3rd edn), Blackie, Glasgow, 1990,
Ch.12.
21. F. Brailsford, in Permanent Magnets and Magnetism, D. Hadfield (ed.), Iliffe/wiley,
London, 1962.
22. P.K. Gallagher et al., I. Thermal Anal., 1993, 40,1423
23. AR. McGhie, J. Chiu, P.G. Fair, RL. Blaine, Thermochim. Acta., 1983,67,241
24. E.L. Simons, A.E. Newkirk, Talanta, 1964, 11, 549
25. A.E. Newkirk, Thermochim. Acta., 1971,2,1
26. H.R. Oswald, H.G. Wiedemann, I. Thermal Anal., 1977, 12, 147
27. P.D. Gam, Anal. Chern., 1961,33,1247
28. M.L. McGlashan, Physico-Chemical Quantities and Units, RSC, London, 1968, p. 39.
29. J. Sestak, G. Berggren, Thermochim. Acta, 1971,3, 1
THERMOGRAVIMETRY 61
30. M.E. Brown, D. Dollimore, A.K. Galwey, Comprehensive Chemical Kinetics, Vol. 22,
Reactions in the Solid State, Elsevier, Amsterdam, 1980.
31. M. Reading, D. Dollimore, J. Rouquerol, F. Rouquerol, l. Thermal Anal., 1984,29,
775.
32. M. Arnold, G.E. Veress, J. Paulik, F. Paulik, Thermochim Acta, 1982, 52, 67
33. E. Urbanovici, E. Segal, l. Thermal Anal., 1993, 40, 1321
34. A.K. Galwey, Thermal Analysis, Proc 7th ICTA, Wiley, Chichester, 1982, p. 38.
35. K.H. Stem, E.L. Weise, NSRDS-NBS 30: Carbonates, 1969.
36. A. Bhattacharya, l. Thermal Anal., 1993,40, 141.
37. J.H. Sharp, G.W. Brindley, B.N.N. Achar, l. Am. Ceram. Soc., 1966,49,379.
38. L.K. Avramov, Thermochim. Acta, 1985, 87, 47.
39. M. Reading, Thermochim. Acta, 1988, 135,37.
40. C.D. Doyle, l. Appl. Polym. Sci., 1962,6,639.
41. A.W. Coats, J.P. Redfern, Nature, 1964,201,68.
42. M.E. Brown, Introduction to Thermal Analysis, Chapman & Hall, London, 1988.
43. T. Ozawa, Bull. Chem. Soc. lapan, 1965, 38, 1881.
44. J.H. Flynn, L.A. Wall, Polym. Lett., 1966, 4, 323.
45. Perkin-Elmer Analytical report, 1985, p. 16.
46. Netzsch Kinetics Software Brochure.
47. J. Rouquerol, Bull. Soc. Chim. Fr., 1964, 31.
48. F. Paulik, J. Paulik, Anal. Chim. Acta, 1971, 56, 328.
49. P.R. Hornsby, C.L. Watson, Polym. Deg. Stab., 1990,30,73.
50. K.A. Broadbent, J. Dollimore, D. Dollimore, Thermochim. Acta, 1988, 133, 131.
51. V.R. Choudhary et al., Thermochim. Acta, 1992, 194,361.
52. L. Erdey, G. Liptay, G. Svehla, F. Paulik, Talanta, 1962, 9, 489.
53. E.C. Roberson, Stanton Redcroft: Technical Information Sheet, No 18.
54. F. Rodriguez, Principles of Polymer Systems (2nd edn), McGraw-Hili, Singapore, 1983,
Ch. 11.
55. Stanton Redcroft TG750 Brochure.
56. R.H. Still, Brit. Polym. l., 1979, 11, 101
57. C.F. Cullis, M.M. Hirschler, Polymer, 1983, 24, 834
58. E.A. Turi, Thermal Characterisation of Polymeric Materials, Academic Press, New York,
1981.
59. H.T. Ellingham, l. Soc. Chem. Ind., 1944,63, 125
60. D. Dollimore, D.L. Griffiths, D. Nicholson, l. Chem. Soc., 1963, 2617
61. E.L. Charsley, S. St J. Warne, S.B. Warrington, Thermochim. Acta., 1987, 114, 53.
62. ASTM E1131-86: Compositional Analysis by Thermogravimetry, ASTM, Philadelphia,
1986
63. J. Chiu, in Thermoanalysis of Fibers and Fiber-Forming Polymers, ed. R.F. Schwenker,
Interscience, New York, 1966, p. 25.
64. M. Schnitzer, J.R. Wright, I. Hoffman, Anal. Chem., 1959,31,440.
65. B.D. Mitchell, A.C. Birnie, in Differential Thermal Analysis, Vol. 1, ed. R.C.
Mackenzie, Academic Press, London, 1970, Ch. 24, p. 695.
66. S. St 1. Warne, Proc 7th leTA, Toronto, 1982, Wiley Heyden, Chichester, 1982,
p. 1161.
67. C.M. Earnest, R.L. Fyans, Proc 7th ICTA, Toronto, 1982, Wiley Heyden, Chichester,
1982, p. 1260; and Perkin-Elmer Thermal Analysis Application Study, #32.
68. O. Kubaschewski, B.E. Hopkins, Oxidation of Metals and Alloys, Butterworth, London,
1962.
69. B.O. Haglund, Proc. 1st ESTA, Salford, 1976, Heyden, London, 1976, p. 415.
70. G. Baran, A.R. McGhie, Proc 7th ICTA, Toronto, 1982, Wiley Heyden, Chichester,
1982, p. 120.
71. Y. Shigegaki, S.K. Basu, M. Taniguchi, Thermochim. Acta, 1988, 133, 215.
72. J.P. Chilton, Principles of Metallic Corrosion, Royal Society of Chemistry Monographs
for Teachers, No 4 (2nd edn), RSC, London, 1973.
73. N. Pernicone, F. Traina, Pure Appl. Chem., 1978,50,1169.
74. S.D. Robertson, B.D. McNicol, I.H. de Baas, S.C. Kloet, J.W. Jenkins, l. Catal., 1975,
37,424.
75. J.G. Dunn, Stanton Redcroft Technical Information Sheet, No. 103, 1977.
76. TA Instruments Ltd, TGA 2950 System Brochure.
77. T.J. Lever, A. Sutkowski, J. Thermal Anal., 1993,40,257
78. A.F. Barnes, M.J. Hardy, T.J. Lever, J. Thermal Anal., 1993,40,499.
Bibliography Note The general thermal analysis texts given at the end of Chapter 1 have substantial
sections on thermogravimetry but are not listed again here.
C. Duval, Inorganic Thermogravimetric Analysis (2nd edn), Elsevier, Amsterdam, 1963.

C.J. Keattch, D Dollimore, Introduction to Thermogravimetry, Heyden, London, 1975.
Differential thermal
analysis and differential
3
scanning calorimetry
P.J. Haines and F.W. Wilburn
3.1
When an organic chemical is prepared, it is checked against known Introduction
materials for purity and stability. One of the easiest ways of doing this is to
determine its melting point! This cannot be done by TG, since it involves no
mass change! This also applies to solid-solid phase transitions and to some
solid-state reactions. We therefore need a technique that identifies these
transitions. Such a technique will give us a simple way of identifying and
assessing the quality of materials that may be applied across a large range
of substances, from polymers to metals.
The magnitude and direction of the heat change of the system is more
difficult to measure accurately and requires the more elaborate apparatus
of calorimetry. The techniques to be discussed in this chapter give an
interface between very sophisticated precision calorimetry and the qualitative
observations of melting points and heat changes.
3.2
The early work in studying the interplay of heat and chemical or physical Historical
changes was largely qualitative, but the experiments of Lavoisier and
Laplace around 1780 allowed the measurement of the quantities of heat
energy associated with changes of state and chemical reactions. Although
their apparatus required large quantities of sample, was slow to use and of
low accuracy, Lavoisier's work has earned him the soubriquet of 'the
grandfather of thermochemistry' [1]
During the same period, Fourier worked out mathematical descriptions
of transfer processes and he is responsible for many of the fundamental
ideas and equations that describe heat transfer. The idea for Ohm's law
defining resistance came from Fourier's work, and the compliment is
repaid in the use of the 'thermal analogue of Ohm's law' in some theories
of thermal analysis [2].
The work of Joule in the nineteenth century led to a greater understand-
ing of the relationship of heat and work, and of the laws governing
electrical heating, which now underly much of thermal analysis, both in
control of the furnaces and in some DSC apparati. Joule also pioneered the
use of twin calorimeter vessels, one containing a reference and the other
the substance under investigation [3]. Modern high-precision calorimetry
apparatus can be large and complex and the calculations involve many
corrections [4]. Nowadays, laboratories generally require the opposite of
these: small samples, rapid experiments, simplicity of use and ease of
obtaining results!
Le Chatelier is often credited with being the first to use a differential
thermal technique when he compared the temperatures shown by two
thermometers, one within a sample and one outside it, as they were all
heated in an oil bath. He was able to record melting transitions and the
behaviour of clay samples. He later worked with thermocouples and
characterised clay minerals into categories [5].
Roberts-Austen [6] pointed out that if the difference in temperature
Ts - TR = aT
is plotted against temperature or time, then a very sensitive method of
detecting changes and transitions is obtained. This identifies the technique
of differential thermal analysis (DT A)
Various theories were proposed to relate the DTA signals obtained to
the heat capacity and enthalpy changes of transitions and reactions
occurring during heating, but these were not entirely satisfactory. In 1964
Watson et al. [7] announced a differential scanning calorimeter (DSC) for
quantitative measurements. There are now two main types of DSC and the
distinction between the various sensors and apparati is given later. It is
recognised that DTA and DSC, properly used, can make accurate
measurements of the temperatures of thermal events, can detect the
exothermic or endothermic nature of the event, and that DSC can make
good measurements of the heat changes that occur.
3.3
Definitions The two techniques will be considered together, since they are frequently
used to study the same phenomena (see [8]).
3.3.1 Differential thermal analysis (DTA)
A technique in which the difference in temperature between the sample and

a reference material is monitored against time or temperature while the
temperature of the sample, in a specified atmosphere, is programmed.
DIFFERENTIAL THERMAL ANALYSIS AND DIFFERENTIAL SCANNING CALORIMETRY 65
1o
x
w
8z
w
Figure 3.1 Typical DTA or DSC curve, using the convention that endothermic peaks go
down. ~ indicates the differential signal for either temperature or power.
The DTA curve is generally a plot of the difference in temperature (a1)

as the ordinate against the temperature T (or occasionally, time) as the
abscissa. An endothermic event gives a downward 'peak' (Figure 3.1).
3.3.2 Differential scanning calorimetry (DSC)
A technique in which the difference in heat flow (power) to a sample (pan)

and to a reference (pan) is monitored against time or temperature while
the temperature of the sample, in a specified atmosphere, is programmed.
In practice, the heat is supplied to the sample contained in the pan, and
similarly, to the reference in its pan.
Two types of DSC are recognised:
1. Power-compensated DSC, where the sample and reference are
heated by separate, individual heaters, and the temperature differ-
ence is kept close to zero, while the difference in electrical power
needed to maintain equal temperatures (ap = d(aQ)/dt) is measured.
2. Heatflux DSC, where the sample and reference are heated from the
same source and the temperature difference aT is measured. This
signal is converted to a power difference aP using the calorimetric
sensitivity.
A constant calorimetric sensitivity is desirable, but not essential [9].
The DSC curve has aP as the ordinate and temperature (or occasionally,
time) as the abscissa. Since an endothermic peak involves the absorption of
more power by the sample, one convention plots endothermic peaks
Gast out
_1
R
~I
II
S
Furnace fo- bd bJ ,-- Recorder and/or
computer
1------------
fl 1
Programmer - Sensor amplifier
Figure 3.2 Schematic of a DTA or DSC apparatus. !J. indicates the differential signa\.
upwards (Figure 3.1). This does cause some confusion, and in this text, we
shall adopt the 'DTA' convention throughout, while indicating the sign of
heat flow on the y axis.
3.4
Apparatus The major parts of the system (Figure 3.2) are:
1. the DTA or DSC sensors plus amplifier
2. the furnace and its temperature sensor
3. the programmer or computer
4. the recorder, plotter or data acquisition device.
The range of designs for DTA and DSC is extremely wide, and shows a
gradation from qualitative DTA to power-compensated DSC, as shown in
Figure 3.3 [9].
3.4.1 The sensors
As shown in Figure 3.3, thermocouples are used as the sample and

reference sensors for many DTA and DSC units. For low temperatures,
copper--constantan or chromel-alumel have been used, while for higher
temperatures, or more aggressive environments, Pt-Pt/13%Rh has been
employed. Single thermocouples are in contact with the sample in «a),
(b)), but outside in types «c)-(e)). Some Mettler and Setaram DSC units
use multiple thermocouples or thermopiles «d),(e)) to increase the signal.
The 'Boersma' DTA, where the heat is conducted to the pans via a
conducting metal disc, is used in several apparati.
The exceptional case is the power-compensated DSC (f), where the
I (a) ~~ OTA To- T.=AT
~J L"J
~ (b) Quantitative OTA To- T.=AT
0
W
:T
: I (e) Heat-flux OSC or Boersma-type OTA To- T.=AT
: I
-I 0
(d) LU Heat-flux OSC dqt/dt
I(·I ~~
(f)
UU Heat-flux OSC
Power-compensated OSC
dqs Idt - dqR Idt = d(Aq)dt
dQs Idt- dQRIdt= d(A~t
Figure 3_3 The DTA-DSC series. 1\

, thermocouple;
vw-..
,thermopile; (T"l , heater [9].
Thermoelectric disc
(constantan)
Sample
pan
~~~~~~~1 Chromel
wafer
Alumel
wire
Figure 3_4 Heat flux DSC. (Courtesy TA Instruments Ltd.)
sensors are platinum resistors and the power is supplied to sample and
reference separately.
Where the dividing line should be drawn between DTA and DSC is
debatable [9], but several different manufacturers have shown [10] that
their instruments satisfy the requirements of DSC by determining calori-
metric data with good accuracy (Figures 3.4 and 3.5).
Pans and crucibles of many materials have been employed, but the
majority of low-temperature instruments use aluminium pans and lids,
provided they are not attacked by the samples and are only used well below
the melting point of aluminium, 660 OCt For more aggressive environ-
Pt
sensors
Individual
heaters
Figure 3.5 Power-compensated DSC. (Courtesy Perkin-Elmer Ltd.)
ments, platinum or ceramic crucibles may be used. The conductivity of the

crucibles and their contact with the sensors affect the thermal analysis
curves obtained.
A standard experiment might involve a sample of about 10-20 mg of
powder, or a disc punched from a polymer film, or a bundle of fibres being
placed in a weighed, lidded aluminium crucible, and the total mass
recorded. Sometimes an inner liner is placed on top of the sample to enable
the sample to make better contact with the base. The lid may be fixed to
the base using a simple press, and can give a sealed crucible capable of
withstanding about 2 atmospheres pressure. If vaporisation is not a
problem, small pinholes can be punched in the lid to allow escape of gas
products and reaction with the surrounding purge gas.
Special crucibles have been designed for containing higher pressures
[11], or for mixing liquids [12], or for observing the sample during heating
[13,14]. Liquids may be injected into the crucible using a syringe.
For the use of even higher pressures, the technique of pressure DSC
(PDSC) has been invented. The entire DSC cell is enclosed in a strong
stainless steel container capable of withstanding pressures from 1 Pa to 7
MPa (approximately 70 atm. ). This means that reactions that produce high
pressures of gases or react with gases under high pressure may be studied.
Additionally, vaporisations may be suppressed by running at higher
pressures. Uses of PDSC include the accelerated oxidative stability testing
of materials such as oils under high pressures of oxygen [15] and the
catalytic reduction of organic compounds with hydrogen [16].
3.4.2 The furnace and controller
Very similar comments can be made to those relating to TG (see p.28). For
high-temperature DTA, large ceramic-lined, electrically heated furnaces
are used with electronic control. Many small DSC systems use a resistance-
heated furnace enclosure of silver. The very high thermal conductivity of
silver ensures that there is a uniform temperature. For the simplest DTA
[17], a metal block, wound with an insulated heating element and having
two wells for sample and reference cells and thermocouples, gives a
satisfactory introduction to the principles of DTA.
Heating rates between 0 and 100 Klmin are used, but the normal rate is
about 10 Klmin.
One extra feature is the use of DTA or DSC below room temperature. A
cooling accessory or refrigeration unit is fitted around the cell and the whole is
cooled directly with liquid nitrogen or other coolants. It is essential that dry
purge gas is passed through the cell assembly during the cooling, since
condensation of water or ice onto the cells might otherwise occur.
3.4.3 The computer and display
The need for computer control and rapid data processing is paramount with
DSC, since the signal must be converted to the dP signal, using a calorimetric
sensitivity stored in software, and the curves that are obtained must be
analysed for thermal parameters by differentiation (to obtain onset tempera-
tures, for example) and by integration (to obtain peak areas).
3.4.4 The reference material
Both DTA and DSC are defined as differential methods, where the
behaviour of the reference material or pan is compared with that of the
sample and its pan. We must take account of ALL the thermal properties
that might be involved. For example, the emissivity of the sample may alter
if it changes phase, or reacts, or changes colour [18]. This is often avoided
by covering both sample and reference pans with snugly fitting lids, or by
sealing them. In many cases, small samples may be run on a DSC against
an empty pan as reference, but often better results are obtained by using an
inert reference material of similar thermal properties in the reference
crucible. For many applications, pure, dry pre-heated ('calcined') alumina,
A1 20 3 , is satisfactory. Carborundum, SiC, has also been used.
Occasionally, to make the thermal properties of sample and reference
more comparable, the sample may be diluted with the reference. It is
obviously important that they should not react, and this dilution sometimes
improves the baseline and peak shape in DTA experiments.
3.5
The shape and size of a typical DTA or DSC curve is determined as much Theory of DTA and
by the environment surrounding the sample and reference materials as by DSC (F.W. Wilburn)
0.1
0
Curve B
-0.1
----.
-0.2
-0.3
-0.4
hT
-0.5
-0.6 E
-0.7
-0.8
-0.9
-1
-1.1
300 350
Temperature °C
Figure 3.6 Typical DTAIDSC curves: A, practical curve; B, ideal curve.
the mechanism controlling the reaction and the sample material character-
istics. Figure 3.6 shows a typical DTA or DSC curve for a material which
melts (curve A) together with that (curve B) usually obtained in practical
situations. During a melt, the reaction should end at the peak and the
curve should then return abruptly to the baseline as in curve A. More often
the curve obtained is that of curve B showing a relatively slow return to the
baseline.
There are often further complications, in that the signal does not
necessarily return to the original baseline, but to some other arbitrary
baseline above or below this line, as shown in Figure 3.7. Indeed, the
situation may be even more complicated, as when the baseline not only has
a different value, but also a different slope. All these effects can be
explained from the theory of DTA and DSC.
A full discussion of the theory of DTA and DSC would not only require
this chapter, but this entire book, and even then it is questionable whether
such information would be of use in answering some of the more usual
questions asked when gaining information on typical DTA or DSC curves.
It is the intention here to explain some of the more common variations
seen in experimental curves in terms of theory and, where possible, to
suggest ways of reducing errors due to such variations.
We shall first consider the theory of DTA and of the closely related heat
flux DSC, and extend this to power-compensated DSC later.
Theories of DTA can usually be placed into one of two types.
0.4
0.2
/
0 I
\
-0.2
-0.4
AT
-0.6
-0.8
\ !
V
-1
-1.2
-1.4 ~......,...,..,rr-r-........".,rr-r-,.,..,......,~.,..,....,......,rr-r.,..,....,......,rr-r-,....,...,..,.,.,""""""""""-""""""""""""'''''''''''
~~~m~~~m~lli~m~~~~~
Temperature °C
Figure 3.7 Difference temperature measured by thermocouples in the test materials when
a change of sample thermal conductivity occurs.
In the first type, heat transfer equations such as the thermal analogue of
Ohm's law:
dq/dt = (Ta - Tb)/Rab
- where dq/dt is the heat flow between a and band Rab is their 'thermal
resistance' - are developed but no account is taken of the reaction
mechanism and the part it might play in the production of the peak.
Further, for simplicity, it is generally assumed that the different parts of
the apparatus (e.g_ the sample holder) have no thermal gradients within
themselves, which is not necessarily true.
In the second type, reaction equations such as those given by Brown [19]
and Keattch and Dollimore [20] are manipulated to develop various
relationships between the difference in temperature, !J.T, and the sample
temperature at a specific time, from which it is claimed that activation
energies and orders of reaction may be obtained. It is questionable
whether such relationships are valid when heat transfer is taken into
account. Some years ago, an electrical analogue of a DTA was developed
[21-24] and was followed with a computer program which allowed heat
transfer and reaction equations to be combined to show the influence of
heat transfer on the shape of DTA curves and its effect on peak area_
Borchardt and Daniels [25] developed heat transfer equations for a
system consisting of test tubes of liquid reactants within a stirred, heated
liquid. In such a situation the transfer of heat to the test materials would be
rapid. Their theory, of the first type, is only valid if a number of limiting
conditions are met:
1. The temperature in the holders must be uniform. While this would be
true for liquids, it is not the case for solids.
2. Heat transfer must be by conduction only.
3. The heat transfer coefficient must be the same for both holders.
4. The heat capacity of the test materials must be the same.
All these conditions are relatively easy to achieve for liquids, due to the
rapid transfer of heat within the system.
Coats and Redfern [26] adopted the second type of approach in that they
manipulated reaction equations to show that various relations exist
between the peak temperature and the heating rate from which it is
possible to derive activation energies and 'orders of reaction'. No account
was taken of heat transfer. Nearly all papers adopt one or other of these
approaches.
Many earlier pieces of DTA apparatus were made mainly of refractory
materials where heat transfer was comparatively slow. As might be
expected resulting DTA curves from different apparati differed widely!
One of the earliest papers on theory was that of VoId [27] who showed
mathematically that there is a relationship between the 'active area' of a
DT A curve and the heat involved. The 'active area' is that generated by
the reaction itself, while the remaining area is that produced as Ll T returns
to the baseline after the reaction has ceased (at point E in Figure 3.6). As
this return is governed by natural cooling or heating, which is dependent
on the thermal arrangement of the holder system, its form is exponential.
Thus, a plot of In(Ll1) vs time for that part of the DTA curve beyond the
peak becomes linear after point E. The area between the curve and its
baseline from the commencement of the peak to the point E is the 'active
area'. Further, VoId showed that the relationship between this 'active area'
and the heat of reaction is:
Heat = A .('active area')
where A is the slope of the linear part of the In(Ll1)-time curve. In this
theory it was assumed that the physical properties of the sample and
reference materials remained constant throughout the reaction. Thus, the
shape of a DTA peak, particularly that portion at temperatures above the
peak temperature, can be influenced by apparatus parameters. For
reactions other than meltings, the assumption that the reaction ends before
the DT A curve returns to the baseline is dependent on the type of reaction
under investigation. The 'active' part of the DTA curve for melts,
crystalline changes and zero-order reactions usually ends around the
maximum of the DTA peak, so that the return to the baseline is
exponential for a considerable portion of the DTA curve, and thus the end
of the reaction can be defined fairly accurately as well as the A factor
referred to above. However, if the reaction is controlled by other types of

mechanism then tl T is often close to the baseline before the reaction ends.
In this case it is difficult to determine the constant A. The high temperature
end of a DTA curve can comprise a mixture of reaction mechanism and
exponential return and can thus be different for different apparati.
The fact that this end of the DTA peak may not be a true representation
of the reaction can have other consequences if two reactions follow in
quick succession. In certain circumstances the two peaks may merge to
produce a single peak. Indeed, this was used some years ago to test the
discrimination ability of apparatus. A mixture of silica and potassium
sulphate has two peaks, one the result of the structural inversion in silica at
573 °e, the other at 583 °e owing to a crystal transition in potassium
sulphate. The ability to separate these peaks gave a measure of the
resolution of the apparatus.
Many of the theories developed for the examination of DTA traces
assumed that both before and after a reaction that produced a peak, the
physical properties remained the same and were independent of temperature.
On this assumption, the baseline remains the same across the DTA peak.
However, there are very few practical DTA (or DSC) curves for which this
is so. In older apparatus, the sample and reference temperatures were
measured using thermocouples in the centre of the test materials (Figure
3.3(a», which is the classsical DTA design. With such an arrangement,
theory indicates that the position of the baseline is influenced by the
relationship between the physical properties of the sample and reference
materials. In order to maintain a constant, near-zero baseline, the physical
properties such as the thermal conductivity k, heat capacity C and density p
of sample and reference had to be closely matched. However, if any of
these changed, either with reaction or with temperature, then the baseline
ofthe DTA curve varied from zero, as shown in Figures 3.7 and 3.8. It can
be shown that, for cylindrical samples of radius r, the equilibrium baseline
offset tlT is:
tlT = {~·,.z/4}·[(PR·CRlkR) - (Ps.Cs/ks)]
where ~ is the heating rate (K/s).
Usually the greatest change in any property of the sample material
occurs during a reaction, so that it is not uncommon for the greatest
baseline changes to occur during this period, i.e. during the production of a
DTA peak. This change in baseline level affects the calculation of the area
of the DTA peak. The magnitude of the error in calculation will depend on
the size of the peak, a large peak being less affected than a small one. The
error is compounded by not being able to define the 'true' baseline across
the peak. The simplest expedient of drawing a straight line across the peak
from the point where the DTA curve deviates markedly from the initial
curve to a point where the curve returns to a level baseline nearly always
results in an area that is too large, as shown in Figure 3.8. The baseline
0.8
0.6
0.4
0.2
o+-------------~~~~~
-0.2
4T
-0.4
-0.6
-0.8 Peak Area too large when joining by a straight line.

-1 Dotted line gives a better approximation.
-1.2
"..,...."........,,,..,....,,........,.......-'"T'"".,.,...,
-1.4 <-,-,.................T""'""T................T""'"""'"................,................,....,...,......................
~~~m~~~m~~~m~~~m~
Temperature °C
Figure 3.8 Difference temperature measured by thermocouples in the test materials when
a change in sample specific heat capacity occurs.
change in Figure 3_8 was computed from preset changes in the physical
constants occurring as the reaction was proceeding. It is sometimes
possible to define a baseline across the peak in the situation when the level
of the baseline is different before and after a peak, even if the true baseline
cannot be defined easily [28], and this is shown as the dotted line in Figure
3.8. Much depends on the type of reaction involved and no general rule can
be stated.
3.6
Heat flux DSC If the measurement thermocouples are positioned beneath the sample and
reference pans (Figure 3.3(c)-(e» we have the heat flux DSC designs_ The
shift in baseline is now only influenced by changes in the sample specific
heat capacity (Figures 3.9,3_10) and is not affected by the other properties
of the sample. Such a design of DSC may be used to measure specific heat
capacities. Unfortunately, the change in baseline is also dependent on the
characteristics of the pans holding the test materials so that the apparatus
has to be calibrated using known standard materials.
The area under the peak is directly proportional to the heat of reaction
[23,24,26].
I1H = K fl1T dt = K·(peak area)
The calibration constant K converts peak area into joules, and is a
thermal factor which may vary with temperature.
Problems of measurement of the area still arise owing to the difficulty in
0.6
0.4
0.2
o+------------------=~--
t.T
·0.2
-0.4
-0.6
-0.8
-1 ~~~~~~~~~~~~~~~~~~~~~~~~~
~~Bm~_~m~wBm~~~m~
Temperature °C
Figure 3.9 Difference temperature measured by thermocouples beneath the pan and test
materials when a change in sample specific heat capacity occurs.
0.2
o+---------------__~~--------~--------------
-0.2
-0.4
-0.6
~T
-0.8
-1
-1.2
-1.4 L.-,.-rr~TT"'.....,..~"._....,.,..~TT",...,..,.~...,......~.....,...,..,...,~,..,......,..,...,~,..,........,...,........,..,..,.........,
~-_m~ __ m~~~m~~~rn~
Temperature °C
Figure 3.10 Difference temperature measured by thermocouples beneath the pan and test
materials when a change in sample thermal conductivity or density occurs.
defining an accurate baseline. However, the DSC design does have some
advantages (not least the reduction in chemical attack) over earlier DTA
designs where the thermocouples were placed within the sample. Although
the sensitivity is greater with the thermocouples within the sample,
baseline shifts are often greater, being produced not only by changes in
specific heat capacity but also by changes in thermal conductivity and
density. In the DSC design, the positioning of the measuring thermo-
couples outside the test materials may reduce the sensitivity and overall
response and some small inversions may not be seen when using certain
types of DSC design.
3.7
Power-compensated In the other type of DSC, the sample and reference holders are insulated
DSC from each other and have their own individual sensors and heaters. The
electrical circuitry operates to maintain the holders at the same temperature,
within the electrical sensitivity of the circuitry, by varying the power
supplied to the heater in each of the holders [29,30]. The thermal energy
absorbed by the sample per unit time is exactly compensated by the
differential electrical power AP supplied to the heaters. Measuring this
power is equivalent to measuring the thermal power, and thus the baseline
is:
AP = dAqldt = ~·(Cs - CR)
and the peak area gives AH directly. In power-compensated DSC the
calibration constant required to convert peak area to joules is a constant
electrical conversion factor.
3.7.1 The effect of higher temperatures
Most DSC designs developed for the measurement of specific heat capacity
and AH are most suitable for temperatures up to around 700 °C. Above
this, radiation, which is always present but increases with temperature,
becomes significant. Most theories of DTA are based on heat transfer by
conduction and assume that radiation is insignificant, and so are only
relevant at lower temperatures. High-temperature cells tend to follow the
DSC design to avoid thermocouple contamination at temperatures up to
1500 0c. However, at high temperatures heat transfer from the source of
heat to the sample is rapid and if the measuring thermocouples are located
beneath the pans, the sensitivity may be relatively low.
3.7.2 Sample size
When a sample is undergoing a reaction, there is, of necessity, a

temperature gradient within it, as heat is abstracted (assuming an endo-
Table 3.1 Calibration materials for DTA and DSC [8, 30)
Temperature Enthalpy
Material (0C) (JIg)
Cyclohexane (t) -83

(m) 7
1,2-Dichloroethane (m) -32
Phenyl ether (m) 30
Biphenyl (m) 69.3 120.41
o-Terphenyl (m) 58
Polystyrene (Tg) 105
Potassium nitrate (t) 128
Indium (m) 156.6 28.71
Tin (m) 231.9 56.06
Potassium perchlorate (t) 300
Zinc (m) 419.4 111.18
Silver sulphate (t) 430
Quartz (t) 573
Potassium sulphate (t) 583
Potassium chromate (t) 665
Barium carbonate (t) 810
Strontium carbonate (t) 925
Note. (t) = crystal transition; (m) = melting; Tg = glass transition

temperature.
thermic change). To obtain meaningful calorimetric data, it is imperative

that the sample size be kept to a minimum in order to reduce such
gradients. However, if the sample consists of a number of materials, as
in a study of reaction processes, then it is usually difficult to obtain a small,
representative sample. In such a situtation, the ideal solution is to use a
larger sample with the thermocouple embedded in it and to recognise that
the apparatus is then only qualitative when used in this way.
3.8
For accurate work, it is essential to calibrate the temperature scale, and for Calibration
DSC instruments the apparatus must also be calibrated for calorimetric
sensitivity. ICTAC have approved a set of standard substances, which are
listed in Table 3.11 together with some other calibrants.
The particular instrument may have calibration factors already included
in the computer software, but these must be checked from time to time.
For a pure metal, such as 99.999% pure indium, the melting of which is
shown in Figure 3.11, the extrapolated onset temperature Te should
correspond to the correct melting point of the metal, 156.6 0c. The
integrated area of the peak As may then be used to calculate the
calorimetric sensitivity constant K:
K = flHs . msl As
where flHs is the enthalpy of fusion of indium (28.71 Jig), ms is the mass of
sample of indium (g), As is the peak area (cm 2) and K is the calorimetric
sensitivity (J/cm 2 ).
Note: If the area is calculated in K·s or W's then obviously the units of K
will change!
Calibration with several materials over the entire range of operation
should enable the temperature dependence of K to be found.
Example A sample of 6. 68 mg of high purity indium gave a peak of area
21.94 cm2 • Calculate the value of K at 156°C.
K = (28.70 x 6.68 x 10-3)1 21.94 = 8.74 x 10-3 J/cm2
Comparison of the calorimetric calibration for one instrument, using a
wide variety of materials over the range 0-660 °C [31], has shown that there
is good agreement, provided samples are of reasonable size, and the
heating rate is the same for calibration and measurement. The ICTAC
committees on standardisation are continuously checking and reviewing
the data and materials available for calibration [32].
A REMINDER!
The curves obtained for DTA and DSC will depend on the samples and
instrument conditions used:
Sample: chemical nature, purity, history.
Crucible: material, shape.
Rate of heating
Atmosphere: gas, static, flowing.
Mass of sample: volume, packing, distribution, dilution.
3.9
Applications There are such a large number and variety of applications of DTA and
DSC that readers should consult the journals or specialist texts for
particular examples. The selection given below is representative of the
range of uses of the techniques.
The applications may be divided roughly into two categories:
• Physical changes and measurements, such as melting, crystalline phase
changes, changes in liquid and liquid crystalline states and in polymers,
phase diagrams, heat capacity, and glass transitions, thermal con-
ductivity and diffusivity and emissivity.
• Chemical reactions such as dehydrations, decompositions, polymer
curing, glass formation and oxidative attack.
3.9.1 Physical changes and measurements
MELTING POINT AND Il.Hfusion OF MATERIALS
The determination of the melting point may be very easily done with
simple apparatus, but Il.H of fusion is much more difficult to measure.
~p
ENOO
150 156 160 170 Tfc
Figure 3.11 DSC peak for pure indium, showing the construction of the 'extrapolated
onset' (6 mg, 10 Klmin, nitrogen).
While DTA will give excellent qualitative measurements of Tm , we must

use DSC for tlH. Sharp melting peaks, similar to Figure 3.11, have been
obtained, with suitable apparatus, over a very wide range of temperature,
e.g. from n-heptane at -90°C to palladium at 1550 dc. The melting points
and tlH of fusion of these compounds determined by DSC or DTA as the
onset temperature are in good agreement with the literature values.
The crystallisation of pure materials can be awkward, since they often
supercool past their true freezing point by many degrees.
CRYSTALLINE PHASE TRANSITIONS
The crystalline form of a compound can greatly affect its properties, such
as solubility, density and electrical properties.
If a substance possesses two or more crystalline forms it is said to be
polymorphic. If the forms are stable over particular temperature ranges,
and have definite transition temperatures, the system is enantiotropic. If
one form is stable but the other metastable over the whole range of
temperature, then the system is monotropic and the less stable form will
always be tending to transform to the more stable.
POTASSIUM NITRATE, KN0 3
Potassium nitrate shows rather complex behaviour when heated and

cooled [31,32]. On first heating, there is an endothermic crystal transition
Heating
II-I I - Melt
ENDO
!
III-II I-III Melt-I
- - - - -...........- - - - - - - - - - - ' I I E - - - J ' - -
Cooling
100 200 300
Figure 3.12 DSC curves for potassium nitrate (4 mg, 5 Klmin, nitrogen).
(from form II to form I) at 128 °e with a !1H of about 5.0 kJ/mol and a
melting of form I at 334 °e with !1H ~ 10 kJ/mol. However, if the sample is
then cooled from about 150 °e, we obtain an exothermic peak at 120 °e
with !1H of only -2.5 kJ/mol. This must mean that it is forming a different
phase. form III. At lower temperatures it transforms slowly back to form
II. These transformations are shown in Figure 3.12.
Other nitrates also show crystal phase transitions, especially rubidium
nitrate [33], which has three transitions plus a melting, and ammonium
nitrate which has four before melting. Since NH4N0 3 is widely used as a
fertiliser, and occasionally as an explosive, these have been extensively
studied [34,35]. Figure 3.13 shows the DTA curve of ammonium nitrate.
First there is a small endotherm around 40 °e from form IV (rhombic II)
to form III (rhombic I), followed by a second small endotherm at 80 °e
transforming to form II (tetragonal). Two further, larger, endotherms
follow at about 120 °e to form I (cubic) and at 170 °e to the melt. These
transitions are very dependent on the treatment of the sample, and care
must be exercised, since the very large exotherm following at about 200 °e
represents explosion of the NH 4N0 3!
POLYMORPHISM IN FOODS AND PHARMACEUTICALS
Polymorphism is of particular importance in foods and pharmaceutical

preparations, since it can affect the solubility, stability, physiological
activity and bioavailability of the compound. As an example we shall
8z
w
100 200 300 T I "C
Figure 3.13 DTA curve for ammonium nitrate (powder, 10 mg, 10 Klmin, static air).
consider the glycerides, esters of glycerol (CH20H·CHOH·CH20H) and

long-chain aliphatic or unsaturated acids. They are present in fats, margarine
and chocolate, and are used in many pharmaceutical preparations.
The polymorphism of glycerides has been reviewed by Chapman [36],
who notes the use of microscopy, dilatometry, dielectric and X-ray
diffraction studies in addition to thermal work and spectroscopy, and
Aronhime [37] who concentrates on the applications of DSC. The
glyceride systems show at least three phases, distinguished by their spectra
and X-ray spacings. The highest melting 13 form is the most stable. The
lowest melting a form and the intermediate f3' form are metastable with
respect to the 13 form. Typical DSC traces are shown in Figure 3.14 for
tristearin (glyceryl tristearate). On first heating of a sample rapidly cooled
from the melt, we observe an initial melting of the a form at around 54°C
almost immediately followed by an exotherm due to the transformation
and crystallisation of the stable 13 polymorph. The 13 form then melts at
about 73°C. If the liquid is then cooled to a temperature a few degrees
above the melting point of the a polymorph, and held there until
crystallisation occurs, the f3' polymorph is obtained. Heating this form
produces a similar trace for the partial melting of f3', transformation to 13
and melting of 13, as shown in the dashed curve of Figure 3.14. DSC studies
have been made of the polymorphic changes in mixtures of confectionery
fats [38] and of the thermal characterisation of edible oils and fats [39].
Polymorphism of pharmaceuticals is discussed fully in the book by Ford
and Timmins [40] and by Hardy [41]. The forms ofnorfloxacin, a derivative
of 4-quinolone carboxylic acid, were studied by DSC, TG, X-ray diffraction
6P
I,
'I
/1
~~--------------~
1\
g I
I
\ I
\ J
"
r iii I I Iii I r I Ii, I lit I i I I I , i I I I

30 40 50 60 70 80 TloC
Figure 3.14 DSC curve for tristearin (4.3 mg, 5 K1min, nitrogen). Full line: first heat;
dashed line: reheat from 57 °C.
and spectroscopy [42], showing the need to use all available analytical
methods fully to characterise a material. Two different forms of this drug,
A and B, which show a wide spectrum of antimicrobial activity, were
obtained from different sources. The forms showed different X-ray
patterns and gave the DSC traces in Figure 3.15 when heated in dry
nitrogen at 10 Klmin. The form A had a melting point of 219.5 ± 0.2 °C
with a aH of 115 Jig, whereas form B also showed a broad transition at
195.6 ± 0.2 °C with a aH of 20 Jig which varied with heating rate. Since
this transition was not seen on re-running the sample after cooling, the
system is monotropic.
LIQUID CRYSTALLINE TRANsmoNS
The liquid crystalline state is of great importance in the preparation of

display devices. Many types of liquid crystal phases are formed from
molecules, often with polar end-groups, and with a rod-like structure. The
liquid crystals represent various degrees of 'order' within the liquid. From
a very ordered solid, we may progress to one of various smectic phases,
which have plate-like order, or to a nematic phase, which has rod-like
order, or to the cholesteric phase, which is a twisted nematic, and finally to
the isotropic, completely disordered liquid [43,44].
Considering the order changes in these transitions, the greater the
increase in disorder, the greater the entropy change as. Since
as = aHiT
o~---------------------------.
~------------------- ~
FonnA
1,-_ .. _ .. _-_ .. _ .. _ .. _ .. _ . _ .. _ .. _
.
.. ,., .. _ . ./:
Fonn 8 .
:e; solid-solid
..! 7.5 f-
~
u..
a;
G)
:r:
80 120 160 200 240

Temperature (0C)
Figure 3.1S DSC curves for two polymorphic forms of norfloxacin. (Redrawn from [42].)
120 140 Tf'C
Figure 3.16 DSC curve for p-azoxyanisole (15 mg, 16 Klmin, static air).
this means that aH will be large for a large change in order. Figure 3.16
shows the transformation of p-azoxyanisole
CH30·C6H4 ·N NO·C6H4 ·OCH3
The first transition at 119°C has a large aH because the material goes
1 _Smectic Phases - _.....Nematic- Isotropic Liquid -
100 185 200 250
Figure 3.17 DSC curve for OOBPD (9 mg, 10 Klmin, flowing nitrogen).
from ordered crystal to disordered, nematic liquid crystal. The second,

smaller, transition at 135°C goes to the true liquid phase.
Even more complex DSC curves are obtained for other systems, as
shown in Figure 3.17, for N, N' -bis(4-octyloxybenzylidene)-p-phenylene
diamine (OOBPD).
Exercise By examining the DSC trace of Figure 3.17, suggest probable

answers to the following:
1. What is the most likely phase below 100 °C?
2. Given that the phase stable above 205°C is a nematic liquid crystal,
suggest the type of phase changes that give rise to the peaks
between 120 and 205 0c.
3. On cooling this material to 80°C, after all the liquid crystal phases
have formed, two exothermic peaks are observed between 110 and
80 °C. What might be happening?
PHASE DIAGRAMS
When more than one chemical component is present, the thermodynamics

become even more complicated, and the melting behaviour more complex.
The traditional way of studying the phase behaviour of mixtures was by
cooling curves, plotting T versus time as a mixture cooled from the melt
[46]. DTA or DSC can give more information, more rapidly with smaller
samples, provided sensible conditions are used - that is, fairly slow heating
rates, preferably less than 10 Klmin.
When a pure solid substance A does not dissolve at all in pure solid B,
the freezing point of A is lowered by the presence of B, and the freezing
point of B is lowered by A, giving the diagram shown in Figure 3.18. The
Liquid
Liquid +
T Solid A Liquid
+ Solid B
P R
Solid A + Solid B
Pure A Composition Pure B
Figure 3.18 Eutectic phase diagram.
To,S
T
Liquid
Solid solutions
Figure 3.19 Phase diagram for a continuous series of solid solutions.
lowest temperature at which liquid can exist is called the eutectic tempera-
ture TE and below this we have various mixtures of crystals of A and
crystals of B.
When A and B are very similar in structure, for example, both form
cubic crystals, they may form solid solutions, where a mixed crystal
structure is obtained, having crystal lattice parameters intermediate
between those of A and B. This gives the phase diagram shown in Figure
3.19 [47] or the phase diagram of Figure 3.20.
The DSC or DTA curve of any of the mixtures in these systems generally
shows the phase changes.
When the temperature is higher than the solidus line, PQR, the mixture
will start to melt and an endothermic peak will be obtained, whose size will
depend upon the amount which melts at this temperature. The nearer the
mixture is to the eutectic composition Q, the larger the peak at TE • The
Uquid
Solid ex + Solid ~
Figure 3.20 Phase diagram for a system with partially miscible solids IX and ~.
TE
Figure 3.21 Eutectic phase diagram with superimposed DTA curves.
mixture will continue to melt, gradually, until the liquidus line VQW is
reached, when the final fraction will become liquid. This temperature is
given by the final peak of the trace.
Eutectic systems give two peaks, as shown in Figure 3.21. Solid solutions
give a single, broad peak, as shown in Figure 3.22. Partially miscible
systems give both sorts! When the components react to form compounds,
this gives more complex diagrams [47] which may still be studied by
thermal methods. The technique has been used extensively to study
metallurgical phase diagrams [48,49], mixtures of liquid crystals [50] and
pharmaceuticals [40].
Figure 3.22 Solid solution phase diagram with superimposed DTA curves.
COMPATIBILITY OF PHARMACEUTICAL MIXTURES
This term implies that two or more components of a pharmaceutical dosage

form may coexist without interaction during the whole shelf life of the
preparation. Often the dosage form contains the active drug component
plus other components or excipients to dilute, bind or disperse the drug. If
there is physical or chemical interaction, then the physical and pharmaceutical
properties of the mixture may be greatly affected. Jacobson and Reier [51]
studied stearic acid mixtures with penicillins and showed that DSC
methods correlated well with 8 week 50°C stability tests. If there is no
interaction, either physical or chemical, then the dosage mixture should
show the same thermal analysis features as the original pure components,
in the appropriate proportions. Any changes or new features indicate
interaction, as shown in Figure 3.23. Grant et al. [52] showed that a
mixture of glycerides showed eutectic behaviour, but that this was altered
considerably when therapeutic amounts of ketoprofen were added.
Giordano et al. [53] showed that although a simple physical mixture of
the drug trimethoprim (TMP) with the excipient cross-linked polyvinylpyr-
rolidone (PVP-XL) showed the same features as the original pure
components, grinding the materials together changes the behaviour, as
THERMOPLASTIC POLYMER PHASE CHANGES
Polymers which melt before they decompose may crystallise completely, or

may remain as irregular, amorphous solids or glasses [54]. On heating a
brittle 'glassy' polymer, the change to a more plastic material shows as an
increase in heat capacity, as discussed below. The polymer molecules are
~T
Pure A
Pure B
v
8z
w
1
1 :1 Mixture of
A+B
v-v-
Figure 3.23 Schematic DTA curves for compatibility of materials.
!
Endo
Temperature,OC
Figure 3.24 DSC traces of (a) PVP-XL (b) TMP, (c) physical mixture of 75% PVP-XU
25% lMP, (d) ground mixture of 75% PVP-XU25% lMP [53].
0.4
0.3
0.2
0.1
~
~
~ 0.0
~
.2
u. -0.1
'aiCD
J: -0.2
-0.3
-0.4
50 100 150 200 250 300
Temperature ee)
Figure 3.25 DSC curve for poly(ethylene terephthalate), PET, quenched from melt
(10 mg, 10 K/rnin, flowing nitrogen).
then freer to move and can rearrange into the more regular structure of a
crystal, giving an exothermic peak of 'cold crystallisation'. Finally, the
crystalline polymer will melt to a liquid often over a broad range. With
some polymers such as atactic polystyrene, this is difficult to detect. Figure
3.25 shows all these changes for poly(ethylene terephthalate), PET.
Some polymer samples can show multiple melting endotherms, indicat-
ing that portions of the sample have crystallised at different temperatures
during the previous thermal treatment.
Polymeric samples often do not crystallise completely. The area of the
melting peak of a partially crystalline sample may be compared to that of a
standard of known crystallinity, or a completely crystalline sample, to give
the percentage crystallinity [55].
%C t 11' 't - Area of sample melting peak x (% Standard)
o rys a 1m y - Area of standard melting peak
The components in polymer blends may melt separately and give evidence
of the materials present and their amounts. Mixtures of poly(propylene) and
poly(ethylene) have been analysed by DSC [56] and the components in
recycled polymer waste have been detected by DTA [57].
HEAT CAPACITY MEASUREMENTS
The amount of heat needed to raise the temperature of the sample by 1 K is

its heat capacity, Cp,s, in joules per Kelvin and:
Cp,s = (aqs / (1)p
No sall1lle baseline
Sapphire 133.6 "lI
400
I
415
I
425
J
435 445 455
! !
465 475
I
485
I
TJ1<
Figure 3.26 DSC curves for heat capacity measurement on molten polyethylene (PE).
On a DSC instrument, the calibrated y axis represents the differential

rate of supply of heat energy, or ~Power or (d~qldt). Since we are heating
at a constant rate, (d Tldt), the product of the y axis deflection ~y from the
baseline with no sample, divided by the heating rate, should give the
difference in heat capacity due to the sample.
Cp,s = K-~y I (dTldt)
where K is a calorimetric sensitivity, found by calibration.
Generally the calibration is done with sapphire, pure, crystalline A120 3 ,
whose heat capacity is well known.
Note: The higher the heating rate, (dTldt), the greater the deflection
obtained!
The 'no sample' baseline can be used to correct for the effects of the
reference side.
Exercise Given that the heat capacity of sapphire at 445 K is 0.997 JI (K g)

and the data in Figure 3.27, calculate Cp for PE. The heating rate is
20°C/min.
Cp (sapphire) = 0.997 x 133.6 x 10-3 = 0.1332 JIK
~y (sapphire) = 75.0 mm
Cp (sapphire) = (K x 75)/20 = 0.1332
Thus
K = 3.552 X 10- 2 J/(min mm)
For the polyethylene
dy = 34mm
so
Cp(PE) = (3.552 x 10-2 x 34)/ 20 = 0.0604 J/K
and since the mass of polyethylene is 23.14 mg,
Cp(PE) = 2.609 J/(K g).
This agrees quite well with literature values [59]. Wunderlich has published
considerable data relating to the heat capacity of polymers [60,61].
The heat capacity is a most important quantity to know for many
polymers, insulators and building materials [62].
GLASS TRANSITION TEMPERATURES
Below a certain temperature, known as the glass transition temperature Tg ,

the polymer segments do not have enough energy to rearrange or to rotate
themselves. Such a material is brittle and a glass. As the sample is heated,
there is a small increase in volume and energy, until at Tg the chains
become more mobile and the polymer more plastic or rubbery. Further
heating, as shown in Figure 3.27, allows the polymer to crystallise and then
melt. Cooling from the melt directly may cause some of the polymer to
crystallise at Tm. These changes are shown diagrammatically in Figure 3.27
and the Tg for various polymers is shown in Figure 3.28.
At the glass transition temperature, the heat capacity of the sample
increases, since the chains acquire further freedom of movement. There-
fore we observe a step and an increase dCp ' and also a change in the
expansion.
It must be clearly recognised that the Tg is a time-dependent phenomenon!
A polymer may slowly distort at a low temperature, but may behave in
a brittle fashion when bent rapidly. While the Tg bears a marked
resemblance to true second-order thermodynamic transitions [64] which
always occur over a fixed, equilibrium temperature range, the value
obtained for Tg depends greatly on the heating and cooling rates used in
the DSC run.
If the heating rate is very low, say 0.1 Klmin, the Tg may be low, say
80 °C, and this value is obtained again if the sample is cooled at the same
rate. However, if the same sample is heated and cooled at 20 Klmin the Tg
Figure 3.27 Schematic energy changes for material forming a glass.
PC
EP~
I ~~:s~ ~
.1P
EN DO ~
, SO. iii i 100. i i i I 150. i i i i T'oc
Figure 3.28 DSC curves showing the glass transitions for several polymers. All samples
about 20 mg as received, run at 10 Klmin in flowing nitrogen. PVC = poly(vinyl chloride);
PS = polystyrene; EP = cured epoxy resin; PC = polycarbonate [63].
rises to 85 °C or higher! What happens if the heating and cooling rates are
not the same? The sample that has been cooled slowly (say 0.1 Klmin) goes
through its Tg at 80 0c. If it is then heated at 20 Klmin it does not transform
till 85 °C. This means that the sample must absorb more energy to reach
the enthalpy of the rubbery state. This results in an endotherm, superim-
posed on the glass transition step. This is shown in Figure 3.29.
The heating and cooling rates must therefore be stated, and the Tg also
depends on molecular weight, degree of cure and amount of plasticiser
present [65,66].
&P
ENDO
90 100 110 T 1°C
FIgure 3.29 DSC curve for polystyrene cooled at 0.2 Klmin and then heated at 5 Klmin.
(After Wunderlich [65].)
PURITY MEASUREMENTS
The determination of the absolute purity of a material is of highest

importance for the characterisation of pharmaceuticals, insecticides, pure
organics and metals. The theory [67] assumes that there are two effective
components that give the eutectic phase diagram of Figure 3.30.
Thermodynamics shows that for a slightly impure A, containing XB
mol % of impurity B, the van't Hoff equation applies and the freezing point
is lowered from that TO,A of pure A to Tm [68). aT is given by:
aT=(To,A - Tm} = (R~,A/Mlfus,A}·XB
When the mole fraction of impurity is small, aT must also be small, but the
DSC peaks are found to be much broader for impure samples than for
pure. The reason for this involves the gradual melting of the impure
sample.
Consider the section of the eutectic diagram close to the pure A axis.
The lines may be regarded as approximately straight, and we may construct
similar triangles as shown. Since melting starts at the eutectic, the tie line
PQR may be divided so that the ratio of the liquid solid is
Fraction liquid/fraction solid = PQ/QR
or Fraction melted, F = PQIPR
From consideration of similar triangles, this may be put equal to the ratio
of temperature intervals on the y axis.
F = (TO,A - 1)/(TO,A - Tm) = (TO,A - 1)/aT
To,A
Tm
I
IQ R
T
I
'-
I "-
"-
Temp I "-
I
Figure 3.30 Section of eutectic diagram close to pure A.
Substitution into the van't Hoff equation gives:

(TO,A - 1) = (l/F)'(Rtij,A/M/fus,A)'xB
or, rearranging,
T = TO,A - (lIF)'(Rtij,A/aHfus ,A)'xB
This predicts that a plot of temperature versus (1/F) should be a straight
line of slope dependent on XB, TO,A' and aHfus,A- The temperature T may
be corrected for thermal lag, measured using the peak for the melting of
pure indium (Figure 3.11) or by the built-in software of the instrument
[69].
From a DSC trace (Figure 3.31) obtained at the slowest heating rate
possible, we may measure aHfus,A and TO,A approximately, and the fraction
melted at T °c from the ratio of the area a up to T, divided by the total
peak area A.
F= alA
Ideally this gives a good straight line. However, there are several factors
which combine to produce a curve:
• neglect of any pre-melting before the peak measured
• non-equilibrium conditions, due to dynamic heating
• solid-solution formation.
AP
ENDO
427 429 431 433 TIK
figure 3.31 DSC trace of an impure material showing partial area measurement and
temperature correction.
A correction for these factors that has been shown to be effective involves
the use of an add-on correction da
F = (a+da)/(A+da)
and
flHtus,A = K·(A+da)
This can be related to the modified van't Hoff equation for solid solutions
[70]
flT = (l-k)·(R'tfJ,AlflHtus ,A)·xB
where k is the distribution coefficient for the solid solution.
In a different approach to eliminating the non-equilibrium effects, the
use of discrete steps in heating has been suggested. If a step of less than 1 K
is used and the system is then allowed to equilibrate, the trace produced
shows peaks of equal area until melting commences. The peaks then
increase until melting is complete. The sum of the peak areas, corrected for
the heat capacity effect, gives values for a and A.
Plato and Glasgow [71] used the method to measure the purity of many
compounds and it forms the basis of the ASlM method E928--85.
Comparing the DSC and NMR methods of determining purity, Gam et al.
[72] have shown that solid-solution formation plays a large role in
determining the melting behaviour.
435
433
T/K
431
429
427
425~--~----------~~--~~~~----~------~
8 10
o 2 4 6
IIF
Figure 3.32 Plots of TIK versus lIF and corrected IIF: (a) uncorrected; (b) 5%
correction; (c) 10% correction; (d) 19% correction.
Example A 3 mg sample of an insecticide (RMM = 365) was melted on

a DSC at 1 Klmin and gave the following results:
TIK alcm2 F Total area, A = 10.5 cm2
427 1.78 0.170 K = 10.0 mJ/cm2
428 2.31 0.220
429 3.21 0.306
430 4.58 0.436
431 6.33 0.603
Calculate TO,A' tJ.Hfus,A and XB'
A straightforward plot of T against lIF gives a curve, intersecting the T
axis at about 434 K (Figure 3.32(a»
We may treat the data in three ways:
1. Continue adding small amounts to a and A until a straight line is
obtained;
2. Plot (1/(To,A - 1) versus F. The slope should give k.
3. Do a regression analysis of the curve.
1. Successive additions of 0.5 cm2 to the area give a best line when the
correction is about 2.0 cm2, and this gives a a corrected total area of 12.5
cm2, so that the corrected tJ.H is about 15.2 kJ/mol and the slope of - 2.2
gives an X B value of 2.1 mol% (97.9% pure A). This is shown in Figure
3.32.
2. If we rearrange the equations above, we find that a plot of 1/(To A

- 1) versus F should be a straight line of slope (!1HIRT~,A)lxB a~d
intercept related to the correction, k. If we assume that To A = 434 K and
make this plot, we get a value of XB of 0.028, or a purity of 97.2%.
3. Although this requires considerable time, or computation, it is
probably the best way ([19], Ch. 14). Regression analysis gives a
correction of 0.163 and a purity of 97.9%.
3.9.2 Chemical reactions
KINETICS OF REACTION FROM DSC TRACES
Chemical reactions, and some physical changes such as cold crystallisation,

occur at a temperature-dependent rate and involve an energy change, l1H.
We have seen how this may be related theoretically to the peak area and
we may make assumptions about the relationship between the rate of
supply of heat, which gives the !1P signal, and the rate of reaction. For the
heat capacity part of the change, which does not depend on the rate of
reaction but on the material present at a particular time, we can draw in a
proposed baseline. We must also use small samples and control the
instrument carefully so that the temperature gradients within the sample
are very small.
Provided we may make these assumptions, the peak that we obtain,
either for a scanning or for an isothermal run, may be divided into fractions
representing the fraction of reaction ex which has occurred.
The kinetic equations have been described in Chapter 2, and may be
very complex. The analysis of data is best done for a simple single-stage
process. If we are dealing with a multi-stage reaction, for example the
decomposition of a polymer, it is very difficult to assign kinetic parameters
to the stages of reaction. Additional information is needed for the separate
values of fl.H for each stage. The separate rates might be obtained by
combining DSC with other analyses of products, for example by infrared
spectrometry or evolved gas analysis.
Barrett [73] applied this method to the decomposition of free-radical
initiators like azobisisobutyronitrile (AIBN). The DSC of AIBN in dibutyl
phthalate at heating rates between 4 and 32 Klmin gave kinetic data
corresponding well to first order kinetics and an activation energy of about
125 kJ/mol in agreement with UV experiments.
Crystallisation rates of polymers have been measured [74, 75] using the
partial area to determine the percentage crystallized. The results often fit
an Avrami equation:
[- In(1-ex)]lIn = kt
where ex is the fraction of the final crystallinity developed at time t, and n
EXO
f
Total Area of Peak = A
At roc, a =aIA
aP Rate=da/dt ocay
300
Figure 3.33 DSC curve for exothermic reaction showing measurement of partial and total
areas.
EXO
f
~p
1-_..-::;
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __
5 10 15 20 25 tim in
FIgure 3.34 Isothermal DSC curves for polymer crystallisation.
depends on the mechanism of crystal growth, e.g. n = 3 for spherical

growth.
The assessment of thermal hazards by analysing kinetic data is a
standard ASTM method E698-79 [76]. The method recommended by this
committee is that of Ozawa [77], where samples are run at several different
heating rates, (3, the temperature corresponding to the peak maximum
Tmax is noted. Ozawa showed that if In«(3) is plotted versus liTmax a straight
line of slope approximately EIR is obtained, and the values may be refined
by using a correction factor.
3.9.3 Inorganic compounds and complexes
The dehydration, decomposition and other reactions that take place with
inorganic chemicals and minerals were among the first reactions studied by
DTA. We may obtain vital information about the endothenpic or exo-
thermic nature of the reactions, which may be compared with data from
thermodynamic tables. We can detect melting and other phase changes,
and the DTA (or DSC) trace itself is an effective 'fingerprint' of the
thermal behaviour of the compound under those particular conditions!
CALCIUM OXALATE MONOHYDRATE (Ca~04·H20)
Figure 3.35 shows the DTA curves of calcium oxalate monohydrate run
under flowing air and under flowing nitrogen. The endothermic peak
around 200 °C is due to the loss of the hydrate water, and is similar in both
gases. In nitrogen, the peak around 400 °C is also endothermic, and
corresponds to the breakdown of the oxalate with loss of carbon monoxide.
When the atmosphere is oxidising, however, the CO is oxidised as soon as
it is formed, and the peak becomes exothermic. The endothermic peak at
800 °C is due to the decomposition of the calcium carbonate, and is only
slightly affected by the change of gas.
II 0
,I I
I \
~ I
w
I
I
I
.1T
8z
w
Trc
Figure 3.35 DTA curves for calcium oxalate monohydrate: (a) in nitrogen; (b) in air.
Sample: 10 mg of powder, heated at 10 Klmin.
~T
8z
w
100 300 500 700 T/'C
Figure 3.36 DTA curves for copper sulphate pentahydrate: (a) unsealed pan; (b) sealed
pan with pinhole. Sample: 6 mg crystalline powder, 10 Klmin, flowing air.
The effects on the DTA curve of changes in heating rate, sample mass
and particle size, atmosphere and gas flow rate have all been thoroughly
investigated for this system [78].
COPPER SULPHATE PENTAHYDRATE (CuS04'5H20)
The dehydrations and decomposition of copper sulphate produce a series

of endothermic peaks on the DTA or DSC trace (Figure 3.36).
The initial loss of water may produce traces that seem different,
especially if different sample pans are used. A very open, flat pan will give
two broad, overlapping peaks of roughly equal area around 120°C. If the
loss of water is restricted - for example, by using a lidded pan with a small
pinhole only - then the water may be retained and boil off separately,
giving a triple peak. At higher temperature, the final molecule of water is
lost.
Calorimetric measurements on the dehydration peaks gives tJ.H values of
approximately:
CuS04'5H20 = CuS04'3H20 + 2H20 tJ.H (373 K) = 100 kJ/mol

CuS04'3H20 = CuS04'H20 + 2H20 tJ.H (400 K) = 104 kJ/mol
CUS04'H20 = CUS04 + H 20 ill (510 K) = 72 kJ/mol
The sample decomposes to the oxide at higher temperatures:
CUS04 = CuO + S02 + 1/202

8
z
UJ
Figure 3.37 DSC curve for cobalt pyridinium chloride (3.4 mg, 8 Klmin, flowing
nitrogen) [81].
METAL COMPLEXES
Very many complex compounds have been investigated by DSC [79, 80, 81
and general texts] and the effects of the metal and the ligand on the
reactions and the reaction enthalpies measured. The important factors are
the loss of the ligand, phase changes and decompositions of the sample and
of the products. For these complicated reactions, it is advantageous to use
simultaneous techniques which will be discussed in Chapter 5. One example
of the calorimetric use of DSC is cobalt pyridinium chloride, Co(CsHsN)2.CI2
[81], which gives four transitions up to 500 0c. At about 120°C, a small,
sharp endothermic peak with flH = 12.6 kJ/mol is obtained, but this
corresponds to no mass loss in the TG experiment. Three subsequent
peaks at 180, 280 and 350°C, show progressive losses on the thermoba-
lance, corresponding to loss of 1, 1/3, and 2/3 pyridine molecules respecti-
vely. The total flH for these reactions is about 120 kJ/mol(Fig. 3.37).
HIGH ALUMINA CEMENTS [82-85]
Ordinary Portland cement (OPC) is made by heating clays, which are

aluminosilicates, with calcium carbonate, and consists chiefly of mixed
calcium silicates. During their use, the cement is mixed with water which
hydrates the silicates and produces a good cementing material, which very
slowly develops its final strength over many months. The DTA curve of an
OPC is given in Figure 3.38, which shows the dehydration of the material
and also the peak due to the quartz transition at 573°C.
~T
lo.soc
100 200 300 400 500

Sample temperature °c
Figure 3.38 DTA curve for a Portland cement concrete sample (50 mg, 20 Klmin,
nitrogen).
High alumina cement (HAC) is made from bauxite and limestone, and is
mostly a mixture of calcium aluminates. These react with water and gain
strength more rapidly than OPC, and so they speed up the building
process. Unfortunately, under certain conditions, beams constructed of
HAC concrete collapsed catastrophically. A programme of testing was
undertaken at once in which DTA played a most significant part.
The material which is first produced in the hardening process is the
decahydrate
CaO·AI20 3 ·lOH20 abbreviated to CAHlO
This is not the most stable hydrate, and may gradually undergo a
'conversion' reaction to more stable compounds, such as the hexahydrate
and hydrated alumina or gibbsite.
3CaO·A120f6H20 (or C3AH6) and A120 3·3H20 (or AH3)
3(CaO·AI20 3·10H20) = 3CaO·AI20 3 ·6H20 + Al20f3H20 + 18H20
This conversion weakens the structure, because the products of reaction
are more dense and the reacted structure more porous, particularly if
conversion has taken place rapidly.
The decahydrate, the hexahydrate and gibbsite, plus several other
hydrates, all lose water over specific temperature ranges, as indicated in
Figure 3.39. All the dehydrations are endothermic, and the sample will
show these dehydrations clearly by DTA. It is also helpful to run to 600 °c
to show the silica peak, but also to show the dehydration peak of Ca(OH)2
at 500 °c which is characteristic of OPC.
The method of sampling is important, since high-speed drilling might
heat the sample above the dehydration temperatures. Plaster should be
removed, since the dehydration peaks of gypsum and plaster of Paris occur
in the region of interest for HAC. The slowly drilled out samples should be
(a) r------------_-_-=--=------
-- -- --
-_--=--------:==~-
100 200
Sample temperature °C
(b)
----------- -------~-;-~-~--,
0.5°C
100 200 300 400 500
Figure 3.39 DTA curves for HAC standards having conversions of (a) 50% and (b) 70%
[83].
sieved to remove large particles, and metallic particles from the drilling
should be removed with a magnet.
Samples of 10-100 mg are run in flowing nitrogen at heating rates
between 10 and 30 Klmin, and calibration standards run under the same
conditions. The 'degree of conversion', Dc, is calculated from the height of
the peaks measured, as shown on Figure 3.39.
D = 100· Amount of AH3

c (Amount of AH3 + amount of CAH lO)
or D = l00·a·(Height of AH3 peak)

c (a·Height of AH3 peak + b·Height of CAH lO peak)
or D = l00·(Height of AH3 peak)

c (Height of AH3 peak + K·Height of CAH lO peak)
where a and b are calibration constants and K=b/a.

Examples of the calculation of degree of conversion should not be
quoted to better than ± 5%
Calculation The calibration constant K was determined by running

standard samples with 50 and 70% conversion. For the 50%, the AH3
peak height was 3.5 cm and the CAH lO peak height 3.7 cm. Therefore:
50% = 100 x 3.5/(3.5 + K x 3.7)
Thus K = 0.95.
For an unknown HAC sample, the AH3 peak was 4.4 cm high, and the
CAH lO peak 2.6 cm high. Therefore:
Dc = 100 x 4.4/(4.4 + 0.95 x 2.6)
Dc = 64 ± 5% conversion.
CLAYS AND OTHER MINERALS
The literature describing applications of DTA on minerals is very large [82,

86-88], and only a few typical examples will be described here.
We have already seen from the HAC experiments that minerals give
characteristic DTA traces. Single component minerals, such as quartz,
show their phase transitions. Hydrated and hydroxyl minerals show
dehydration peaks, and carbonate minerals lose carbon dioxide. Typical
traces are shown in Figure 3.40.
Kaolinite, or china clay, is an important industrial mineral. The DTA
trace of Figure 3.41 shows a small, broad endothermic peak at about 100°C
and a much larger endotherm at 550°C. A sharp exotherm appears at about
1000 0c. These have been interpreted as loss of moisture at 100°C,
dehydroxylation by 700 °C and the reaction to form a new crystalline
material, chiefly mullite (3AI20 3· 2Si02).
Borate minerals have very complex structures and cannot always be
characterised by elemental analysis. For a series of minerals of general
formula M2B60 11 •xH 20, some containing discrete anions (Figure 3.42( a))
lose most of their water below 250°C while others which have linked chains
do not decompose until much higher temperatures (Figure 3.42(b)).
Mixtures of these two types may be analysed semi-quantitatively by
thermal methods [91].
3.9.4 Synthesis of compounds at high temperatures
The high-temperature reactions of inorganic compounds produce many

new materials, some of which are of special interest to the electronics
industry.
Montmorillonite
Illite
Mixed layer
Montmorillonite-
illite
Quartz
Dolomite
o 500 1000 1500
Sample temperature·C
Figure 3.40 DTA curves of some common minerals [89].
yxo
AT I
·C ENDO
500 1000 1300

Sample temperature ·C
Figure 3.41 DTA curve of kaolinite [89].

r
0
x
UJ
a
LlT
0
0
z
UJ
!
o 100 200 300 400 500 600 700 BOO
PC
Figure 3.42 DTA curves for triborate minerals: (a) Inyoite; (b) Colemanite. Samples of
about 20 mg, 10 Klmin, static air [91].
Heating together barium carbonate and iron(III) oxide in the molar ratio
1:6 gives the DTA shown in Figure 3.43.
When heated alone, barium carbonate shows sharp crystal phase
transitions at 810 and 970°C while iron oxide shows a transition at 675 dc.
Together, the mixture still shows the transition at 675 °C but now a large,
broad endotherm appears with a maximum at 870°C. X-ray analysis of the
final product shows it to be barium hexaferrite, BaFe12019' This material is
a valuable magnetic solid used as cores for inductive components.
Similar experiments can be conducted to produce a phosphor from
barium hydrogen phosphate BaHP04 heated with about 10% Ti0 2 to 1070
DC, when a material is produced which phosphoresces brightly in the visible
when illuminated with UV light [93].
3.9.5 Pyrotechnics
The reactions involved in pyrotechnics may be studied by DTA or DSC

since the small samples and programming allow good control of the system.
The reactions of 'black powder' (powdered sulphur, potassium nitrate and
charcoal) have been studied by DTA, TG and DSC [94]. The DTA in
nitrogen shows the phase transitions of sulphur and of KN0 3, vaporisation
of sulphur followed by the exothermic reaction between charcoal and
potassium nitrate between 390 and 550°C and the decomposition of
unreacted potassium nitrate (Figure 3.44). In air, there are two exotherms
4T
c
200 1000 T/oC
FIgure 3.43 DTA curves for (a) BaC03, (b) a-F~03' (c) mixture of BaC03:6F~03'
t
AT
~ ~~~~~~~~~~--~
o 100 200
Temperature (OC)
Figure 3.44 DTA of black powder in nitrogen at 20 Klmin (After [94]).

due to the oxidation of sulphur at above 190°C and then oxidation of
charcoal. A review of applications of thermal analysis to pyrotechnic
systems gives many other examples [95].
3.9.6 Superconductors
The discovery of the new materials whose superconducting properties

extended to much higher temperatures than before, has given a great
impetus to studies of high Tc superconducting ceramics. The synthesis of
yttrium barium copper oxide materials has been reviewed by Ozawa [96],
and Chen and Sharp report DTA studies on a high-temperature synthetic
method [97].
The reaction between Y203' BaOz and Cu metal in the proportions
0.5:2:3 on heating in oxygen is exothermic, as shown in Figure 3.45. They
showed that there is no reaction between YZ03 and copper when they are
heated alone, but that YZ0 3 and Ba02 reacted exothermically to produce
YZBa04' Copper and barium peroxide reacted very vigorously to produce
BaCuOz, and the ternary mixture gave a DTA which resembled a
combination of these two reactions, producing YBaZCU30y (y = 6-7) and
Y2BaCuOs detected by X-ray diffraction.
3.9.7 Organic compounds
The reactions of organic materials and of polymeric materials, both natural

and synthetic, have been widely studied by DTA and DSC. The effects of
the atmosphere are very important here, since oxidative degradation may
occur by a very different mechanism to non-oxidative changes.
OXIDATIVE DEGRADATION
Polymers and also oils degrade when heated in oxidising atmospheres. A

standard test for this has been devised and may be used to compare the
stabilities of polyolefins and of other oils and fats.
The sample may be heated in nitrogen to 200 °C and the atmosphere
then changed to oxygen, with the temperature held constant at 200°C. The
time for the onset of the exothermic oxidation is then noted. Alternatively,
the polymer may be heated in oxygen and the temperature at which the
onset of oxidation occurs noted.
The same type of test may be applied to lubricants, and to edible oils and
fats, and has been used to test the efficiency of anti-oxidants.
40
35 592
30
25
20
15
10
5
362
0
6
§'4
S
-
~
'ai
~
CD
2
100 200 300 400 500 600

Temperature (0C)
Figure 3.45 DSC curves for superconductor components: curves A to D 10 Klmin in

nitrogen; curve E 50 K/min in nitrogen [95].
A: 0.5YZ0 3 + 2BaOz B: 2BaOz + 3Cu
C: 0.5YZ0 3 + 3Cu D and E: 0.5YZ0 3 + 2BaOz + 3Cu
POLYMER CURE [100]
The reaction of small molecules to produce larger molecules with different

properties and more stability is generally exothermic. The average A.H of
polymerisation of unsaturated molecules like styrene and vinyl chloride is
about -100 kJ/mol. The reactions of thermosetting polymers, such as
epoxy resins and polyesters cross-linked with styrene, are also exothermic
and readily studied by DSC.
The reaction of the epoxy group with a curing agent, often an amine, is
the initial stage in the reaction and is followed by a further reaction of the
secondary amine with a further epoxy group.
(a)
EXO
r
AP
/
200 T/OC
100
(b)
EXO
r
AP
tim in
10 20 30 40
Figure 3.46 DSC curves for oxidation of polyethylene. The dashed line represents the
changeover from nitrogen to oxygen. (a) Scanning DSC for PE film, 10 Klmin; onset
temperature of oxidation = 220 ·C. (b) Isothermal DSC for PE film at 200 ·C; onset
time = 35 min.
OH
-+ R-NH-CH2-CH-R'
I
-+ R-N(CH2 -CHOH-R'h
This reaction occurs even at low temperatures, but is rapid above 100 °C,
1
a
~p
l ____
100 200
Figure 3.47 Schematic DSC for typical epoxy cure. Samples of 5 mg, 10 K/min, nitrogen.
(a) Initial run of uncured sample; (b) re-run of fully cured material.
giving the DSC trace of Figure 3.47. The initial Tg of the starting material is
followed by the large exotherm of the reaction. Re-running the cured
material shows a new Tg at a much higher temperature. Post-curing will
raise this Tg to even higher temperatures.
The kinetics of the reaction may be studied from scanning or an
isothermal experiment.
PROTEIN DENATURATION
Proteins may be classified as fibrous, with long thread-like molecules, for

example collagen, or globular, with compact 'spherical' shapes such as
insulin. Both types have well-developed structures involving folds, coils or
sheets and even a helix within a helix: a 'super-helix'. These structures are
destroyed by heating or denaturation at extreme pH, and this reaction is
endothermic.
Figure 3.48(a) shows the denaturation of collagen, a single material,
while Figure 3.48(b) shows the complex behaviour of mUlti-component
systems found in real animal muscle proteins. Note the large sample and
slow heating rate used here [102].
(a)
heatftow
Collagen
fexo
o LO
temperature °C
LO LO
(b) heat flow

'fish
beef
temperature °C
30 40 50 60 70 80 90
Figure 3.48 Micro-DSC curves for denaturation of proteins [102]. (a) 800 mg, 0.3%
collagen solution, sealed vessel, 0.5 Klmin; (b) 850 mg beef and fish muscle, sealed vessel,
0.2 Klmin. (Courtesy SETARAM)
POLYMER DEGRADATION [20,103]
The complex reactions that occur when polymers degrade in inert or

oxidative atmospheres have been discussed in Chapter 2. DTA and DSC
studies will give further information on the stages and enthalpy changes
involved.
The DTA curves for the oxidative decomposition of poly( vinyl chloride)
(PVC) and of polypropylene (PP) are shown in Figures 3.49 and 3.50.
PVC powder shows a small glass transition around 80 DC and then a small
endotherm near 300 DC, almost immediately followed by a very large
exotherm peaking at around 550 DC. These later stages correspond to the
Figure 3.49 DTA curve for poly(vinyl chloride). Geon powder, 20 mg, 15 Klmin, flowing
air.
Figure 3.50 DTA curve for unstabilised polypropylene film, 20 mg, 15 Klmin, flowing air.
degradation with loss of HCl and flammable volatiles, followed by

oxidation of the char which is formed.
PP decomposes in a single stage and the products are then easily
oxidised, so a single endothermic peak is obtained for the melt, followed
by a large oxidation peak.
3.10 3.10.1 Pressure DSC (PDSC)
Specialist DSC systems
By placing the entire DSC or DTA cell in a pressure-tight enclosure, it is
possible to work at pressures less than atmospheric, or more than
atmospheric.
A simple modification of DSC and DTA equipment [104] allowed
reasonably accurate determination of boiling points of organic liquids in
the pressure range 20--760 mm Hg. Seyler [105] investigated the parameters
affecting this type of measurement, especially the cell design and sample
size. Recent work [106] using hermetically sealed pans with 50--100 11m
laser-drilled holes gives vapour pressures within a few percent. Results for
the vaporisation of water at pressures up to 3.5 MPa gave excellent
agreement with literature data [107].
It should be noted that in raising the boiling point, or sublimation
temperature, any vaporisation which interferes with melting is suppressed,
and better melting point, purity and phase data will be obtained.
In predicting the oxidative stability of oils, polymers and foodstuffs, the
use of higher pressures of oxygen decreases the volatility of the material
(because the boiling point increases with pressure increase) and also
increases the concentration of reactant gas. Shorter test times are then
possible, and if any volatiles are lost at high temperatures, then lower test
temperatures and higher oxygen pressures may be used. These advantages
are discussed by Thomas [108]. Oxidation and ignition of oils under a high
pressure of nitrogen (8 MPa) with flowing oxygen was used to compare
new and used oil samples and anti-oxidants [107].
Reductions of organic compounds with hydrogen using metal catalysts
has been studied with PDSC. With platinum or palladium metal catalysts
on a silica substrate, the catalyst sample is heated to reaction temperature
in helium under pressure, and then the gas switched to hydrogen.
Chemisorption and catalytic reduction produce an exotherm on the DSC,
which can be related to the hydrogen consumed. If the desired ratio of
reactant to react with 2-3 mg of catalyst is put into the DSC cell, a similar
procedure produces an exotherm for the reduction of the reactant, for
example, m-dinitrobenzene using a 5% Pdlcarbon catalyst, as shown in
Figure 3.51 [109].
Phase diagrams and reactions for praseodymium oxides, reduction of
metal oxides, formation of a metal hydride and oxidation of charcoal [107]
all demonstrate the usefulness of a pressure DSC system.
3.10.2 Photocalorimetric DSC
Polymerisation may be initiated by ultraviolet light, and this is used in

many disciplines such as electronics, coatings and dental work. DSC cells
have been adapted to measure the polymerisation exotherm while the
m-D. NITROBENZENE ON 5"1. Pdl CARBON

AT 200 Psig Hz. 100· C
3.05 mgONB !Sdeg. C

2.73 mg PeIIC
o 30 60 90 120
Time (sec. from introduction of H2)
Figure 3.S1 Isothermal PDSC trace for the reduction of m-dinitrobenzene [109].
sample is irradiated with UV [110). The 'photocalorimeter' is made up of a

DSC and an accessory which illuminates the sample cell with UV light of
selected wavelength and intensity.
Tryson and Schultz [111) investigated the polymerisation of lauryl
acrylate and of 1,6-hexanediol diacrylate using a DSC illuminated by a
medium-pressure mercury lamp (Amax = 365 nm) through a heat filter filled
with de-ionised water and a manually operated shutter. The pans were
modified so that a uniform sample thickness was maintained. A typical
DSC cure curve is shown in Figure 3.52.
Manley and Scurr [112) used a DTA apparatus to study the UV curing of
surface coatings of methyl methacrylate plus azobisisobutyronitrile
(AIBN) and Hodd and Menon [113] investigated various initiators for the
photopolymerisation of acrylates.
3.10.3 Moduloted DSC (MDScrM)
The many changes that can be detected by DSC are both an advantage and
a disadvantage! If the primary purpose is to detect a glass transition, and a
second event such as a chemical reaction or crystallisation overlaps, how
may we separate them?
In a conventional DSC, a constant, linear heating rate is applied. If the
heating is 'modulated' by a small alternating amount of power supplied in
addition to the normal programmed heating, the temperature should
follow the profile shown in Figure 3.53 [114,115).
~l
w
AP
a 2 4 6 b tim in
Figure 3.52 Schematic photo-DSC curve for a photo-initiated polymerisation. (a) UV on;
(b) UV off.
112 - r - - - - - - - - - - - - - - - - . - 1 5 --c
6 " AMP +1· IOC/\ PERIOD /\ 1R 13 .•• O C/mln
'f
~ 111 I \ '30 SEC \ \ lOU /
~
:; \I I OI . 3 ° C!-
-
~110
~
~ 109
:
/ \
\
\
- 5
0 U
~
~
~ \ 0
~108 /lo8.eoc \ -5 ~
~
::I /lo7.eoc
\
\ \ /
/ \
\
-
Q)
'tI0 107 \ I -10 0
I " ~
:::i! I!ACKGROUND HEAT RATE loC/min ·11.54°C/mln T
106 -+-----,----.----..-----l--15..L
108.0 108.5 109.0 109.5 110.0
Temperature (Oe).
Figure 3.53 MDSC heating profile showing the overlaid ripple on the heating ramp.
When we have a heating programme such that

T = To + J3t + B sin(wt)
where w is the angular frequency (= 2Trf), To is the starting temperature
and B is the amplitude of temperature excursion, then the heat flow is
given by:
(dq/dt) = Cp[J3 + B·w cos(wt)] + f (t,1) + C sin(wt)
where Cp is the heat capacity, /(t,1) is the average underlying kinetic
-4+-----~----~----~----~----~~
25 75 125 175 225 275
Figure 3.54 MDSC trace for quenched PET before deconvolution.
response and C is the amplitude of the kinetic response to the sine wave
modulation.
The heat flow has a cyclic component which is made up of the sine and
cosine terms, the amplitude of which is determined by a Fourier transform
analysis. The underlying signal, which is equivalent to a conventional DSC,
is calculated by an averaging process. The value of C is often low, so that
the third term is negligible and the cyclic signal gives the heat capacity
directly. By multiplying this by the heating rate the reversing heat flow is
obtained. This is then subtracted from the underlying signal to obtain the
non-reversing heat flow.
The main component of the reversing signal is the heat capacity, and
thus the glass transition appears in this signal.
Other events which appear in the non-reversing signal are decompo-
sition, curing of polymers, cold crystallisation, and molecular relaxation at
T g• The total signal is shown in Figure 3.54 and the signals separated by a
discrete Fourier transform into the reversing and non-reversing parts are
The reversing part shows the glass transition and the melting as the main
events. The non-reversing shows the relaxation occurring at Tg plus the
cold crystallisation and the non-reversing component at Tm'
Because we may separate the events, each may be seen more clearly and
measured more accurately. Heat capacity may be measured directly, and
Tg separated from reactions occurring over the same temperature range, as
Applications to reversible and metastable transitions of liquid crystals,
or pharmaceuticals and polymers have been reported [116,117].
0.5 t· 1.0
1\ /\ a 0.0- a
.-..,..._._.1 \._._._._._.-...... \
. '-..-
~ ~
MDSCTM nonreversmg
i'
-m
0.0 component
0.5
~ -0.5 ..Q
iii
~ 1 0.0 .s::.
- -0.5
1i
:::t
-- ... ""
--------------------- ~
i: -1.0
~
a:
.-..
o
............. , :' __ 0
i z.-.. I
I
MDSCTM reversing'. - -0.5 ..L
-1.0
component ... :
I
I
,I
...... -1.5
50 tOO 150 200 250 300

Temperature (OC)
Figure 3.SS Resolved components from MDSC of PET showing the standard heat flow,
reversing and non-reversing heat flows.
1.0
MDSCTMReversing component
- - - - - - - - - - - - - ............ ~C glass transition
0.5 ... _------
Conventional DSC
Overlapping
0.0 transitions
MDSC™non-rev
-0.5 - component .I' - - " _
r------" ' .... _-...".-'
PET crystallization
-1.0 .-----t
+-------.,r-------.,r-----T""""
100 120 140 160 180
Temperature (OC)
Figure 3.S6 MDSC curves for a bilayer film of polycarbonate (PC) and PET. The overlap
of the Tg of PC and the crystallisation exotherm of PET is resolved.
3.11
Problems 1. Which of the following changes could NOT be detected by DTA: (a)
(Solutions on p. 275) loss of moisture; (b) sublimation; (c) desorption of vapour; (d) polymer
surface softening?
2. When the heating rate is changed on a DSC or DTA instrument,
without changing the sensitivity, what will be the effect on: (a) the
baseline; (b) any glass transition step; (c) an endothermic melting peak;
(d) an exothermic reaction peak?
3. Pure naphthalene melts at 80 0c. Pure I-naphthol melts at 123°C. All

mixtures of these two components show a single peak when heated and
a 50 mol% mixture shows a single broad peak around 100 0c. What type
of phase diagram does this suggest?
4. Pure phenacetin melts at 134.6 °C. From the DSC its heat of fusion is
53.3 kJ/mol. If the corrected fractions melted are 0.20 at 133.0 °C and
0.29 at 133.5 °C, estimate the purity of the phenacetin.
5. For the high-temperature reaction of copper sulphate:
CuS04 -+ CuO + SOz + IhO z
given the data below, estimate the !l.H for this reaction and comment on
the value with respect to the DTA trace given in Figure 3.36.
Compound !l.HlkJ/mol at 298 K

CuSOls) -800
CuO(s) -157
SOz(g) -297
°2(g) o
This estimate will be rather incorrect! Why?
6. A series of DSC runs were done on an epoxy coating material. The first,
run up to 100 °C only, showed a small endothermic step at 50°C. The
second, run up to 150°C, showed a large exothermic peak around
140 °C. The third, re-running the second material up to 200 °C, showed
a smaller exothermic peak around 140°C. The fourth showed no
exotherm, but only an endothermic step at about 100 0c. Please explain!
7. Without using a thermobalance, how would you distinguish between
DTA or DSC peaks that are due to structural inversions and those that
are due to chemical reactions with loss of mass?
8. A mineral felspar is reported to be suspect although its chemical
breakdown into Al 20 3 and Si02 reveals an ideal felspar. A DTA curve
shows three peaks: endothermic peaks at 600 °C and 750°C and an
exothermic peak at 990 °C. If the first and last peaks are characteristic of
kaolin, Alz0 3 ·2SiOz·2HzO, suggesting the felspar is contaminated, how
would you estimate the amount of kaolin in the suspect material, given
a 'pure' felspar which shows a peak at 750°C and a pure kaolin sample?
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Bibliography The general reference texts given in Chapter 1 all contain substantial sections on DTA and
DSC. In addition, the following are more specific to these techniques:
RC. Mackenzie, Differential Thermal Analysis (2 Vols) , Academic Press, London, 1970 and
1972.
W.J. Smothers, J. Chiang, Differential Thermal Analysis, Chemical Publishing Co, New
York,1958.
M.I. Pope, M.D. Judd, Differential Thermal Analysis, Heyden, London, 1977.
J.L. McNaughton, C.T. Mortimer, Differential Scanning Calorimetry, Perkin-Elmer, 1975,
Butterworth (Vol. 10 of IRS Physical Chemistry Series 2).
E. Kaisersberger, H. Mohler, DSC on Polymeric Materials, Netzsch Annual for Science and
Industry, Vol. 1,1991,
E. Kaisersberger, S. Knappe, H. Mohler, TA for Polymer Engineering: DSC TG DMA,
Netzsch Annual, Vol. 2, 1993, Netzsch, Selb.
Thermomechanical, 4
dynamic mechanical and
associated methods
M. Reading and P.J. Haines
4.1
The mechanical properties of materials are an essential guide to their Introduction
suitability for particular usage, and can indicate how the material has been
treated before testing. The molecular nature of the material will be most
important in determining the mechanical properties. For example, the
behaviour of plastics will be very greatly influenced by their chemical
structure, their blending and the way in which they have been fabricated.
The mechanical methods divide into two classes, depending on whether
the forces applied are constant or varied. Very often, the parameters and
properties which are measured are specific to the method, but can still be
extremely useful in comparing materials.
4.2
4.2.1 Thermomechanical analysis (TMA) Definitions
This is a technique in which the deformation of the sample under non-

oscillating stress is monitored against time or temperature, while the
temperature of the sample, in a specified atmosphere, is programmed.
The stress may be compression, tension, flexure or torsion, and if the
stress is too low to cause deformation, TMA monitors the dimensions of
the sample and this role can be called thermodilatometry.
If the stress is oscillating, the technique is called dynamic-load thermo-
mechanical analysis (DLTMA) [1].
4.2.2 Dynamic mechanical analysis (DMA)
This is a technique in which the storage modulus and loss modulus of the
sample, under oscillating load, are monitored against time, temperature
or frequency of oscillation while the temperature of the sample in a
specified atmosphere is programmed. The experiment is normally carried
out in such a way as to maintain the dynamic strain constant, although
constant stress experiments are also used sometimes. When constant strain
is used, the deformation is usually of the order of a few percent or less.
Certain specific methods, such as torsional braid analysis and torsional
pendulum studies may be incorporated into this definition, and dielectric
thermal analysis (DETA) gives results that may complement those of DMA.
4.2.3 Mechanical moduli
If any sample is subjected to a force, it may behave in a variety of ways

[2,3]. A large force, suddenly applied, will often break the material, but a
small force will deform it. Liquids will flow when a force is applied,
depending on their viscosity, 1]. Some solids may deform elastically,
returning exactly to their former shape and size when the force is
withdrawn. Others may behave viscoelastically, showing behaviour which
incorporates both flow and elastic deformation. With many materials,
there is an elastic limit above which the material undergoes plastic
deformation which is irreversible. Further increase in load eventually
causes fracture.
The parameters, symbols and terminology that will be used for studying
mechanical properties must be established [2,3,4). The symbols are
illustrated in FigWe 4.1.
The stress is the force applied per unit area. This may be :
a normal tensile stress: F/A
or a tangential, shearing stress: ,. = F/A
or a pressure change: ap F/A
All of these will have units of N/m 2 , or Pa.
This stress will cause a deformation measured by the strain, which is the
deformation per unit dimension, for example:
tensile strain or elongation: e alii
or shear strain: -y = llx/y
or volume or bulk strain: 6 = aVIV
Strain has no units.

For an elastic material, Hooke's law applies and strain is proportional to
stress, the constant being the modulus:
Modulus = stress/strain
Tensile, or Young's modulus: E = a/e
Shear modulus: G = ,./-y
Bulk (or compression) modulus: K = ap/(aV/V)
THERMOMECHANICAL, DYNAMIC MECHANICAL AND ASSOCIATED METHODS 125
(a)
/'
A
~--F
_Ax_
,;,;,;
,; - - - - -.---------
lr---
~::.......,~_F
~~------'
(b) yl
!:L-____________~V
(c)
, ,
'~
.'
Figure 4.1 Schematic of types of deformation: (a) tensile; (b) shear; (c) three-point
bending.
The distortion, where increasing the length I of a material also decreases

the breadth b, is measured by Poisson's ratio:
Poisson's ratio: v = (Ab/b)/(Al/l)
This is generally between 0 and 0.5.
The moduli are related to each other for isotropic materials:
G = E/(2(1 + v).
K = V3(EG/(3G + E» = E/(3(1-2v»
Penetration occurs when the applied stress causes the probe to sink
into the material, and a penetration modulus related to the depth of
(a)
F
~)KE_·F
Figure 4.2 Model components for viscoelastic behaviour: (a) spring or Hookean body;
(b) dashpot or Newtonian body; (c) sliding weight or Saint-Venant body.
penetration, the probe shape, the sample shape and the force may be
derived.
Three-point bending is shown in Figure. 4.1(c). If a bar of width band
depth a is supported by two knife edges a distance I apart, and loaded
centrally with a force F, it may be shown that the deflection y is given by:
y = FP/(4ba3E)
Viscous flow occurs when the shear stress T causes adjacent layers to
move relative to each other. The velocity gradient across the layers is given
by the rate of change of the shear strain, d'Y/dt. Ideal liquids show a
proportionality between these by Newton's law:
T = TJ (d'Y/dt)
There are several types of materiai which show 'non-Newtonian' behaviour,
and do not obey the above law. For example, paints may show an apparent
decrease in TJ as the shear stress is increased.
The more complex behaviour of materials can be represented by
combining the models above. We may represent the elastic part by a spring
(or 'Hookean body'), the viscous part by a dashpot (or 'Newtonian body')
and add another element provided by the sliding weight (or 'Saint-Venant
body') which will move when the frictional forces are overcome. These are
Combining the dashpot and spring in series gives a 'Maxwell body' which
THERMOMECHANICAl, DYNAMIC MECHANICAL AND ASSOCIATED METHODS 127
Stress
removed
SIope=- £
'f1
/
~
/
/
/
/
/
/ Set
/
/
/
/
<J,E /
o time o time
(a) (b) (c)
Figure 4.3 Viscoelastic behaviour: (a) the Maxwell body with spring and dashpot in
series; (b) creep behaviour; (c) stress relaxation.
will allow adequate quantitative explanation of viscoelastic phenomena.

Since the stress, CJ, is the same and the elongations, E, are additive,
de/dt = dEl/dt + dEidt = (liE) (dCJ/dt) + CJ/T)
Creep is the gradual, irreversible elongation of a sample when subjected
to a stress due to a combination of elastic behaviour and viscous flow. The
application of the initial stress will cause an initial elongation, Eo, which is
then increased by viscous flow. When the stress is removed, only the
deformation of the spring is recovered, and the dashpot flow gives a
permanent 'set', as shown in Figure 4.3(b):
E(t) = EO + CJotlT)
Stress relaxation may be analysed by considering a fixed elongation at the
start, and integrating the equation for the Maxwell body to see how the
stress changes with time. We find that:
In(CJ/CJo) = -EtlT)
This behaviour is illustrated in Figure 4.3(c)
In the case of an ideal elastic material, the deformations are exactly
reversible. If there is any viscoelasticity, however, the moduli become
complex and contain two parts. For example, in the case of the tensile
modulus, one is the storage modulus E', and the other the loss modulus E':
E* = E' + iE'
where i = V-I.
The ratio of these two moduli gives the loss tangent,
tan(8) = E'IE'
The thermal effects on materials may change all these parameters, and
also cause the material to expand. The coefficient of thermal expansion is
a = (dllf)/dT
This may also change with temperature, or with the nature of the material,
especially at such events as the glass transition.
4.3
Thermomechanical 4.3.1 Apparatus
analysis
While some equipment uses optical or mechanical measurements, many
modem TMA systems use a linear variable differential transformer
(LVDT) to produce an electrical signal from a linear movement [5]. This
consists of two mutual inductances with a common ferromagnetic core.
The magnetisation of the core by the primary coil induces a current in the
secondary coils. If a pair of symmetrically placed secondary coils connected
in series opposition are used, then equal but opposite signals are produced
when the core is at the centre point. When the core is displaced the net
signal increases. By using a phase-sensitive detector, a good linear
relationship between displacement and output is obtained.
The total equipment, shown in Figure 4.4, has the typical arrangement
I Foree
control
I
:g Sensor
~ifier
:g
LVDT ~
~
~
~ ~~
~
Probe
R800Ider
orOOfl1Uer
Programmer
SuppoII-t---t
Figure 4.4 Schematic of a TMA system.

Tension Mode
Tension Fiber Fiberlfilm
Dilatometry
Dilatometer
probe
Dilatometer
vial
Filling medium
Sample
Figure 4.5 Typical probes for TMA measurement [6].
of all thermoanalytical equipment. The L VDT is attached to a quartz

probe which rests on the sample, enclosed in a controlled atmosphere, and
a sample holder if necessary, and the whole assembly is enclosed in the
programmer-controlled furnace. For work below room temperature,
the assembly is cooled by placing a Dewar flask of liquid nitrogen around
it.
The force exerted on the sample by the probe will affect the thermo-
analytical results obtained. For that reason an additional unit is added
which can control the force, using mechanical or computer systems, so that
we may apply a compressive force, or tension, or a zero force for
dilatometry, or an oscillatory force for dynamic measurements (Figure
4.5).
PROBES
Probes of higher area will exert less pressure (since p=FIA) on the sample,
while those with a sharply pointed, small area or a rounded end will tend to
penetrate the sample. Special attachments will allow the same apparatus to
be used for flexural or bending measurements and with films. The probes
may be loaded manually or electromagnetically using the force control
system.
Dynamic or oscillating loads may be used and will often give further
information of thermal changes (DLTMA).
Viscosity measurements may be made using a parallel plate rheometer
(PPR) arrangement. This may be either an oscillating plate method, or a
method where the viscous behaviour is studied by measuring the approach
of two parallel plates moving towards each other with a viscoelastic
medium between them [7].
CALIBRATION
The calibration of the probe (Figure 4.6) for its response to length and
changes in length is generally carried out with standard length pieces of
metal or ceramic which have been measured independently.
Ic
.2
'"
c
t
.J:::
200 11m
&
c
.3
TI"C
Figure 4.6 Calibration graph for TMA. Steps correspond to the melting of tin (232 0q,
aluminium (660 0q and silver (960 0q.
Table 4.1
Coefficient of linear
Material expansion (axlWIK)
Fused silica 0.4

Pyrex glass 3
Aluminium 23
Epoxy resins 4~5
Polypropylene ~100
Calibration for temperature is complicated by the distance between the

sample and the measuring thermocouple in some larger apparati. Rep-
resentative samples may be 5 mm in thickness. A check may be carried out
using discs of ICfAC standards, such as indium, tin and lead, separated by
inert discs of alumina. When this 'sandwich' is placed on the holder and the
probe placed on top, the melting of each standard as the apparatus is
heated is shown by the penetration of the probe.
Recent work [8] and round-robin testing of the calibration with metals
and of measurements with standard polymers has shown reasonable
agreement, although Willcocks [9] has pointed out that the probe force
ought to be calibrated also.
4.3.2 AlppUc~ns
COEFFICIENTS OF EXPANSION
Strictly, this is 'thermodilatometry', since the probe force used should be

zero. Since the apparatus and techniques are similar to the other appli-
cations, both will be considered together. The probes and supports are
generally of fused silica whose coefficient of expansion is very low in
comparison with most other materials (Table 4.1).
For a single material, undergoing no transitions, the average coefficient
of expansion between two temperatures may be measured, as shown in
Figure 4.7. An 'instantaneous' value of a may be found from the slope of
the TMA trace, also called the 'DTMA'. Here we may use the equation:
dlldt = lo·a(dTldt)
For ceramics, the expansion of the glaze must be matched to that of the
body and this has been studied by dilatometry. The coefficient of
expansion of ceramics is also dependent on the quartz content, the firing
temperature and the quartz grain size [10].
Laminated electronic printed circuit boards are often checked for their
dimensional stability by TMA and the coefficient of linear expansion of
electrical insulating materials determined by TMA is a standard method
ASTM D3386--84 [11].
Dimension
Ilm
12
Figure 4.7 Coefficient of expansion of aluminium between 50 and 200 °C (5 mm sample,

10 Klmin, static nitrogen, 0.01 N load).
30
Dimension
20
10
50 150
Figure 4.8 Glass transition temperature by TMA. Sample: printed circuit board, 1 mm,
10 Klmin, static nitrogen, 0.01 N load.
GLASS TRANSmON TEMPERATURE
At the Tg (Figure 4.8) the heat capacity and coefficient of expansion

change abruptly. Under small load IX may be measured below and above
the Tg and the lines extrapolated back to give a single value. The heating
and cooling rates will affect this temperature, as well as the molecular
weight, degree of cure, plasticiser content and orientation.
Polysulfide
a
i i i
- 100 100 'C 100 200·C
Figure 4.9 Typical DLTMA curves of four elastomers (sealing compounds) in the
temperature range -90 to 200 DC. Sample thickness 2-3 mm, 10 Klmin alternating load of
0.00 and 0.04 N.
K
Expansion \
Length
I
I -
I
I
I
I
I
I
I
50 75 100 125 T/oe
Figure 4.10 Glass transition and softening in penetration mode. Sample of coated
material, 10 Klmin, 1 N load.
The oscillating load technique (DLTMA) is somewhat better for

detecting small changes, for example in plasticised elastomers (Figure 4.9)
[12].
If a higher force is used, particularly with the penetration probe a trace
similar to Figure 4.10 may be obtained. Below the Tg little penetration is
Table 4.2
VICATf'C DTULf'C
Sample ASTM TMA ASTM TMA
Unmodified PVC 84 86 75 73
Modified PVC 103 106 91 90
Impact modified PVC 85 84 73 73
shown, but above this temperature the polymer softens and the probe sinks
into the material. At the melting point, complete penetration occurs.
This experiment is particularly useful when the sample is coated onto a
substrate, for example an epoxy coating on a container; the Tg must be
selected by controlling the cure so that the coating will not crack in use nor
will the coating flow [13]. Similar experiments are used for a resin coating
on a wire.
SOFTENING TEMPERATURES
Standard ASTM methods are available for detecting the softening of a

polymer. The VI CAT test involves the measurement of the temperature at
which a particular penetration is obtained for a specified load on a
particular sample. The deflection temperature under load (DTUL) is
similar, involving the bending of a sample supported at its ends (Table
4.2). It has been shown by Yanai et al. [14] that by choosing suitable loads
and conditions these indices may be matched by TMA measurements.
The softening of other materials such as soaps and chocolate may also be
studied using TMA with the penetration probe.
SOLVENT SWELLING OF POLYMERS (FIGURE 4.11)
The sample and probe are immersed in a suitable solvent, for example, a
polystyrene-polybutadiene copolymer may be immersed in toluene. The
gradual uptake of the solvent causes the sample to swell, but also
contaminates the solvent, which may have to be renewed. The swelling
may be used to calculate the cross-link density using the Flory-Rehner
equation [15]:
n = -[In(l-v2) + V2 + 'Xl'v~/vl[V/3 - v2/2]
where n is the cross-link density (mol/cm3), V2 is the volume fraction of
polymer at equilibrium, VI is the molar volume of solvent and 'Xl is the
polymer solvent interaction parameter.
Solvent swelling of rubber

2P
Displacement
mm
1~ L -______________________________ ~
o 20 40. 60 80 100
time I minutes
Figure 4.11 Swelling of polyisoprene, immersed in toluene. Isothermal at 40 °C in static

nitrogen, 0.1 N load.
Upper clamp
Sample
thermocouple
Lower clamp
Figure 4.12 Film and fibre attachment for TMA [6].
The expansion, penetration and creep of the samples may all be studied
byTMA.
FILMS AND FIBRES
Film samples may be attached by small clamps or clips, and fibre samples
by hooks to a special attachment similar to that shown in Figure 4.12.
t
Contraction
ill
Extension
o 50 100 150 200 TI"C
Figure 4.13 Nylon fibre in extension mode, 10 Klmin [16] .
•
c:
0
~'E
Heating rate: 10°C/min
Mode: extension
Load:2g
X 138°C
8 Transverse direction
I
,
..J
<l
I Machine direction
c:
0 133°C'f.-
l
'iIl 134°C
c:
~
an
t
25 50 75 100 125 150 175
T(°C}
Figure 4.14 Blown polyethylene film. Film and fibre probe, 10 Klmin [16].
The sample is generally held under slight tension and the movement of
the probe will indicate stretching or shrinkage of the film or fibre. This is
especially useful to show transitions near the Tg• The shrinkage of fibres or
films often starts just above the glass transition temperature, as the
molecular arrangement is more free to alter. Figure 4.13 shows a nylon
fibre which shows slight expansion to Tg at 20 °e, then shrinkage to about
100 °e when there is a plateau, possibly due to moisture loss. Further
shrinkage continues until melt flow occurs near 250 °e.
Work on blown polyethylene film (Figure 4.14) [16] has shown the
effects of orientation, since there are distinct differences between samples
3oor-------------------------~
E
':;250 - -------'\
o
& \ -10 ~
~200 \ !
-5 \ -36.4°C -20 ~
g 150 \ 0
.iii I -30 .~
~ 100
is
\ /
II
Fiber tension
. -40
~
is
---I 50 d 1/ -50
.~
~
~ 0 -----I--.-70.2°C
~~~~~~~~~~~~~~-60
-140 -120 -100 -80-60 -40 -20 0 20 40 60
T
!.
Figure 4.15 Engine oil sample coated onto cotton fibre. The TMA curve (full line) shows
a glass transition at about -70°C and wax dissolution around -40 0c. The derivative
curve (dashed line) makes these events clearer. This experiment is run in tension mode,
which gives better sensitivity than the penetration mode [17].
cut from the 'machine direction' in which the film is travelling and the
'transverse direction' perpendicular to it.
One method of measuring transitions in liquids is to add them onto a
cotton fibre in the attachment (Figure 4.15) and study their combined
behaviour, rather as in torsional braid analysis (see p. 149).
PHASE TRANSITIONS
The molecular structure of different polymorphic forms means that they

have different densities, and different coefficients of expansion. This may
be detected using the normal expansion probe or a special 'dilatometric
attachment' where the expansion of the sample is transmitted to the probe
through an inert packing. Figure. 4.16 shows a trace for sulphur using a
normal probe. The expansion above 95°C is due to the a-13 phase change,
and the melting causes a contraction as the sample flows.
The phase transitions of sodium and potassium nitrates and of potassium
perchlorate as well as the polymorphic crystal transitions of organics give
TMA traces with a 'step' at the transition temperature.
The a-13 quartz transition at 573°C, which gives a clear peak on the
DTMA trace, was shown to be a suitable method for determining the
quartz content in ceramics [10].
SINTERING
The compaction and sintering of high-temperature materials may be

studied by TMA. Figure 4.17 shows the sintering of a refractory clay block
renroo J1ll1 .
a-p
transition
60 80 100 120 140 rrc

Figure 4.16 TMA of sulphur (5 Klmin, static air, expansion mode 0.01 N load).
expanaion % temperature "C deriv. %.mn-I I

1600
5 O.2~
T
1400
5
1200
-~j I
1000
-O.4J
-10
800
-o.aJ
-15
800 -0.8 !
-20 400
sample : refractory Clay
compression (load Sg) -1 1
-25 200
length: 12.42 mm
helium
-1.2.J
l
1800 3600 5400 7200 9000 10800 12600 14400 time s I
Figure 4.17 TMA, derivative TMA and temperature curves for refractory clay heated
under conditions to reproduce industrial furnaces [18]. (Courtesy SETARAM).
under conditions designed to reproduce industrial furnaces. Very little

change occurs up to 900 °C but a small shrinkage of 2.7% takes place at
about 980 °C, and a much larger one of 23.6% between 1100 and 1600 °C.
The derivative curve shows this most clearly.
A 'quasi-isothermal' approach has been used to study sintering of U02
powders [19]. The overall heating rate is controlled by the shrinkage rate.
When this rate becomes larger than a preset limit, the heating is stopped
and the shrinkage continues isothermally until the rate falls below the limit
again.
INORGANIC HYDRATES
Using a dilatometer adapted to record the electrical conductance of the

sample simultaneously with the dimensional change, Karmazsin et al. [20]
showed that the water losses from hydrated copper sulphate gave correspond-
ing shrinkages and increases in conductance.
An investigation of the uses of TMA as well as DSC and TG in the
selection of binding and construction materials [21] showed the distinction
between forms of calcium sulphate hemihydrate, and the effects of the
constituents of cement mortar (Portland cement, sand and water) on the
TMA curve.
POLYMER CURE
There are several ways of using TMA to study polymer cure. If the effect of
cure on the glass transition temperature has already been established,
TMA could be used to measure Tg after various cure times. As a polymer
cross-links, at a certain conversion it forms a 'gel' or network structure and
the viscosity rises considerably. The 'gel time' of a resin may be found
using the dynamic load technique (DLTMA). With the resin contained in a
suitable container, held isothermally, the probe force is changed between
about -0.05 and +0.05 N. Before the resin gels, the oscillations are very
large. When the sample gels, its viscosity suddenly increases and the probe
can no longer oscillate freely, so the trace becomes level [22].
Using the parallel plate rheometer (PPR) attachment, the gel time of a
prepreg material has been investigated. When heated at 10 K/min, the
material first expands slightly, then softens at about 70 cC and eventually,
after around 8 min at about 85 cC, gelation occurs and the probe stops
moving, as shown in Figure 4.18 [23].
4.4
If an oscillatory sine-wave stress is applied to a perfectly elastic solid, the Dynamic mechanical
deformation and the strain will be exactly in phase with the stress. When analysis
the same oscillatory stress is applied to a viscoelastic solid, the strain lags
behind the stress and is out-of-phase by an angle 8. The complex dynamic
modulus (E* in extension mode) must be used:
80 180
40 140
E
~
III 0 120
Ol
c: 6'
as
.t: ~
() -40 100 I!!
c:
e
::l
.2
'"
c:
III -80 80 III
E ,/' ~
is ~
I
-120 /" 60 T
//'"
....
I
-160 / Gelation process

, 40
-200 ,/ "
,-
20
"
0.0 2.0 4.0 6.0 B.O 10.0 12.0 14.0 16.0 18.0 20.0 22.0
Time (min)
Figure 4.18 Gel time of prepreg. 5 layers, 0.54 mm, 10 K/min, 10 g load.
E* = E' + iE"
where E' is the storage modulus, E" is the loss modulus and i = V-1.
The loss tangent is the tangent of the phase angle and
tan 8 = E"iE'
These are illustrated in Figure 4.19.
The values of the moduli will change with temperature as the molecular
motions within the material change. Chain and side-chain motions of
polymers and especially glass transitions will affect the moduli and tan 8
and the increase of frequency will also show a shift of the moduli and tan 8
up the temperature scale. These effects may be shown on a 3-dimensional
diagram, as in Figure 4.20.
The design of instrument may allow fixed frequency operation where the
frequency and amplitude are selected by the operator, or resonant
frequency operation, where the instrument allows the sample to oscillate at
its natural resonant frequency. Instruments like the torsional pendulum
and torsional braid analyser generally operate in this mode.
Several different types of dynamic mechanical analysers (or dynamic
mechanical thermal analysers) are commercially available, and their designs
vary considerably. Ideally, it should be possible to make measurements
with several different vibrational frequencies, with different clamping
arrangements, at different temperatures, and to apply the technique to
materials with a very wide range of moduli. The frequency range used is
generally between 0.01 and 100 Hz.
(a)
cr
Angle, WI
(b) E"
E'
Figure 4.19 (a) Sinusoidal stress and the strain response curve, showing the phase angle
lag, due to the viscoelastic behaviour. (b) The relationship between the complex modulus
E* and its real component E' and imaginary component Eft.
E' = storage modulus, Eft = loss modulus.
Figure 4.20 Effect of temperature and frequency on the moduli of a styrene-butadiene

rubber over the main Tg region. Note: 10 dyne/cm 2 = IN/m 2 [24].
4.4.1 Apparatus
One approach is to use a design similar to a TMA and to achieve the

necessary constant dynamic strain through computer control of the linear
induction motor. A second approach is to mount the mechanism responsible
for generating the cyclic deformation on a carriage that is moved in order
to accommodate changes in the overall sample size.
The furnace arrangement surrounds the mechanism and sample, and
cooling is achieved by pumping liquid nitrogen through the chamber
surrounding the furnace.
DMA CONFIGURATIONS
Modem DMA systems can operate in many modes, as illustrated in Figure

4.21(a) and (b).
Flexure may be measured by single and double cantilever bending and
three-point bending. Shear and extension modes may also be studied by
simply changing the clamping configuration. Torsion requires an instru-
ment dedicated to this mode. Flexure is preferred for high-modulus
materials, as measurable deformations may be achieved with comparati-
vely modest forces.
It is advisable to avoid the use of very high applied forces as these may
cause the clamping system to deform significantly and thus introduce
errors.
Extension is clearly preferable for fibres and thin films. To avoid
buckling, these sample types should be kept under a constant static stress
so that at no point in the deformation cycle does the instrument attempt to
compress the sample. If a constant dynamic stress experiment is being
carried out, the dynamic stress will change as the modulus of the sample
changes. The static stress must then change with the dynamic stress to
avoid buckling. Usually they are kept at a fixed ratio of 1.1-2 so that they
remain in concert.
CAliBRATION
There are a large number of unresolved problems with regard to accurate

calibration of DMA apparatus for temperature, storage and loss moduli.
The sample may be large, which presents problems with thermal transfer
and temperature monitoring. There are no universally accepted reference
materials for DMA calibration. Pure metals such as indium may be used
for temperature calibration but they have very different thermal con-
ductivities from polymer samples. It has been reported that it is rarely
possible to achieve agreement between instruments of better than 5 K
(a) ,----:::......::---------Vlbrator
~--T----- Displacement
Transducer
Liquid
--:).4IIIT-"" Nitrogen
(b)
I
f-~
I .
-Samplel
-Drive plate
~ ~
t-
COMPRESSION SHEAR TENSILE
Drive clamp oscillation

I
I
Q
d d Sample
/
Fixed clamp o 'Fixed
clamp
CANTILEVER BEND 3 POINT BEND TORSION
Figure 4.21 (a) Rheometric (Polymer Laboratories) DMTA. A bar sample is clamped
rigidly at both ends and its centre vibrated sinusoidally [24(a)). (b) The types of sample
clamping and stress possible with dynamic mechanical analysis [24(b)].
and when using the liquid nitrogen cooling accessory, and the same
reference standard (PMMA), differences of 10-15 K were sometimes
obtained [9]. The clamping of the material may also affect the properties
measured.
Currently, the best practice is to follow the manufacturer's calibration
procedures regularly to ensure calibration of the temperature sensor with
reference metals. This should then be checked using a suitable stable
reference polymer to detect calibration drift.
This should ensure that, while absolute values will have to be treated
with some caution, particularly with high-modulus materials, trends in
results from the same instrument under the same conditions can be
interpreted with confidence:
lana E'
,,---
E'
2 0.8 MPa
GPa
\
I"
\
\
,
I
1.5
I \ .--+ 0.6 150
I \ I
I \
I
I \ \
I
I \
I
.i \
0.4 100
I ). \
I .\ \
I I \
/
\
\
I \
0.5
/
/
\
\
, 50
,;
...
-_.---
".'
.~.,.
" ....
-20 0 20 40 60 80 T/oC
Figure 4.22 DMA curves for a fire-retardant PVC board. Sample 1.67 mm thick,
5 Klmin, nitrogen, 10 Hz.
4.4.2 Applications
GLASS TRANSITION TEMPERATURES
As a polymer passes through its glass transition temperature, Tg , the

storage modulus usually decreases by two or three orders of magnitude,
and the tan 8 goes through a maximum. Why should this be so?
The decrease in the moduli occurs when there is main chain molecular
motion and the maximum in tan 8 occurs when the frequency of the forced
vibration coincides with the frequency of the diffusional motion of the
main chain. An example of the DMA of a glass transition is shown in
Figure 4.22. DMA is very much more sensitive than DSC or other thermal
techniques for studying the glass transition.
BETA AND OTHER TRANsmoNS
For many polymers, in addition to the glass transition, there are also
secondary transitions observed at lower temperatures. By convention,
going down in temperature from the melt, the glass transition is also
referred to as the alpha transition, then at lower temperatures, the beta,
then gamma. This is illustrated in Figure 4.23.
For example, in amorphous poly(vinyl chloride) the alpha or glass
10 . 0.5
a
E' r'.1 tan I)
GPa
!;
8
,.
f'
• f
·I
0.4
~ i
6 I . 0.3
· I
I .
· I
4 0.2
I
I
2 0.1
_." .......... .,..._0_ ....... ___ ._._0'"

o
·100 o 100 200 TI"C
Figure 4.23 DMA of epoxy printed circuit board (5 Klmin, nitrogen, 7 Hz frequency).
transition is associated with relaxation of the main backbone chain and

occurs at about 88 DC at 1Hz, while the beta transition gives a broad tan
8 peak at about -35 DC and is due to motion of small groups, and the
gamma peak at -110 DC is also broad and due to motion of small chain
segments.
The effects of moisture on these transitions may be investigated by
DMA. For example, for nylon 66, a polymer with polar groupings, the
glass transition is shifted from 70 DC under dry conditions to about 0 DC
under 100% humidity.
The beta and gamma transitions are affected to a smaller extent.
RELAXATION KINETICS
DMA curves are affected by the frequency of the applied deformation, as

shown in Figure 4.24. These curves can be analysed using an Arrhenius-
type expression, taking the temperature Ttd at which the tan 8 reaches its
maximum over a range of frequencies:
In(f) = In(A) - EIRTtd
where f is the frequency, A is a constant and E is the activation energy for
the molecular motion.
An Arrhenius plot of In(f) against (1ITtd ) can thus yield the activation
energy for what is termed the 'relaxation process'. For beta and lower
Log E' (Nlm2)
Strain xl
1.0 TanS l°Clmin
0.33 1 3 1030Hz
0.5
Temp 50 00 70 00 90 100 110 l2O"C
Figure 4.24 DMA curves for a storage modulus E' and tan l) for a filled polymer. The
results for all the frequencies were obtained by multiplexing during a single scan at
1 Klmin.
temperature transitions this expression often provides a good model. Near

the Tg , however, the expression does not apply. Although over a small
interval it may appear to give a linear plot, over a broad range it can be
seen to be curved [25].
A more appropriate formula for the alpha process is the Williams-
Landel-Ferry (WLF) equation [26]. This requires the selection of a
reference temperature To:
log (a) = - CdT-To) / (C2 + (T - To»
where C1 and C2 are constants.
The data at other temperatures, T, are then shifted along the In(f) axis
by a shift factor, In(a), until a 'master curve' is produced (see Figures
4.25(a) and (b).)
In complex system including semicrystalline polymers, whether a particular
transition is a glass transition or a secondary transition can be investigated by
determining whether it exhibits Arrhenius or WLF behaviour.
(a) -6.5 I
log (ElPa) !
-7.0.
-7.5
-S.O
-S.5
-9.0
0 2 3 4
log (frequency/Hz)
(b) -6.5
log (ElPa)
Reference temperature 145°C
master curve
-7.0
-7.5
-S.O
-S.5
-9.0,
-2.5. o 2.5 5.0
log (frequency/Hz)
Figure 4_25 (a) A series of curves for E' as a function of frequency derived from
multiplexed DMA curves over a range of temperatures. (b) A master curve derived from
the data of Figure 4.25(a) using the WLF equation to shift the curves along the log
(frequency) axis to correspond with the 145°C reference curve.
POLYMER MISCIBILITY
DMA is often used to examine the degree of phase separation to be found

when two polymers are mixed together. Where two distinct Tg transitions
are found that have the same values as the pure materials, then complete
phase separation can be inferred. If a single glass transition peak is
observed at a temperature intermediate between the values for the two
pure materials, then the polymers are generally said to be miscible and
intimate mixing has occurred. A common expression that is used to relate
10.000
1.000
0.100
0.010 L--..J..---'---'-_'--...l.--:'
-150 -100 -50 0 50100150
Temperature(°C)
Figure 4.26 DMA curves showing the effect of adding different levels of rubber to a
cross-linked matrix [31].
the Tg of the blend to the composition of the blend and the values for the
components is the Fox equation [27]:
IITg,c = W AITg,A + WBITg,B
where Tg,c, Tg,A and Tg,B are the glass transition temperatures of the blend,
component A, and component B, respectively, WA is the weight fraction of
A and WB is the weight fraction of B.
RUBBER TOUGHENING
The inclusion of low Tg domains within a brittle matrix of higher Tg is a

well-established method of obtaining tough materials. Figure 4.26 illus-
trates how the amount of the rubber component influences the height of
the lower temperature transition for a cross-linked epoxy resin modified
with a carboxyl-terminated acrylonitrile-butadiene rubber. The strength of
the lower temperature transition can provide an indication of the fracture
resistance of the material [28].
CHARACTERISING CROSS-LINKING
An important feature of cross-linking systems is that of gelation, the point

at which a true network is first formed and causes the viscosity to rise
1.1
1
.. .. 0-
T"
o •
0.9 c
0
0
• 0
(!J
0.8 j 0
o 0
I
] 0.7 ~
I
.!!l 0.6 ~
..
1ii
E 0.5 ~
0
Z
0.4
0.3
~
0.5/ 2~1 5
0.2 /
J
0.1 )
0
0 50 100 150
Temperature(°C)
Figure 4.27 DMA results showing the cure of a cross-linking system at different heating
rates (squares) with results from a computer model (lines) [31].
towards infinity. This is then followed by a build-up in cross-link density

and consequently an increase in the storage modulus.
Prepregs are systems that comprise a reinforcing material, such as
carbon fibres, impregnated with a cross-linkable polymer. This type of
material can be formed and then heated to cure the system to make a light,
rigid product with excellent mechanical properties. DMA is well adapted
to subjecting a prepreg sample to a heating schedule, similar to that
encountered by the real system, and to following the cure performance.
Gelation is indicated not only by a rapid rise in the storage modulus, E' ,
but also by a peak in tan 8. As the cross-link density increases, the glass
transition temperature rises and may reach the cure temperature. When
this happens the sample vitrifies. This is also marked by an increase in
storage modulus and a peak in tan 8. In this way the transformation of the
prepreg from a pliable material to a rigid composite can be characterised.
DMA can be used to monitor the cross-linking of liquids by impregnat-
ing them onto an inert support such as a glass fibre braid. In this way, they
become similar to the prepregs described above and their cross-linking can
be followed in a similar way. The early work in this area was carried out
using a torsional braid analyser (TBA) developed by Gilham [29], but
modern instruments usually use a shear or flexural deformation. With this
kind of experiment, it is not generally possible to measure the absolute
modulus of the polymer as it is difficult to relate the modulus of the
polymer-glass fibre composite to that of the polymer by itself. Figure 4.27
shows some recent results from a study of the curing of an isocyanate-
hydroxy system at various heating rates. It can be seen that the DMA
results show the gel point clearly and the subsequent build-up in modulus,
and, therefore, cross-link density. From this type of experiment kinetic
parameters such as the activation energy may be calculated [30].
When a material is sufficiently cross-linked to form a solid with a
reasonable degree of mechanical integrity, then its modulus above the glass
transition temperature can be used to measure its cross-link density using
the formula:
G = pRT1Me
where G is the equilibrium shear storage modulus, p is the density, R is the
molar gas constant, T is the temperature (K) and Me is the average
molecular weight between cross-links. The dynamic storage modulus at
low frequencies will approximate to the equilibrium value (strictly the zero
frequency storage modulus). In this way, the mechanical properties
measured by DMA can be related to the polymer structure.
STUDYING 'PROBLEM SAMPLES'
Supported techniques can also be valuable for the investigation of

materials that pose difficulties when presented as an unsupported solid,
either because they creep too much to be securely clamped, or because
they are too brittle. Another advantage is that phase-separated materials in
which the matrix has the lower Tg can be investigated. In an unsupported
DMA experiment, as the matrix goes through its Tg the sample becomes
very soft and may simply flow out of the clamping system before the
response of the higher Tg occluded phase can be probed.
Using a supported technique this problem can be overcome. In general,
with supported techniques, however, care must be taken that there are no
very strong interactions between the support material and the polymer, as
these could distort the results, for example, by increasing the apparent
glass transition temperature of any strongly interacting component, or
causing it to be enriched at the polymer-support interface.
CHARACTERISING FILM FORMATION
Another type of supported technique is particularly useful for looking at

film formation based on coating a thin metal shim. A coating is spread on
the surface of the shim which is then placed in the DMA in a three-point
bending configuration [31].
Figure 4.28 shows the results of an experiment carried out on an
emulsion paint. The drying behaviour and solvent loss are followed by
close packing and coalescence of the latex particles. This can be followed
clearly on the storage modulus curve. The probe position indicates the
Stress measurements 1.00

-0.015 on latex paint 0.90
-0.020
I ,.-
C.SO ",-
-0.025
.......-------.-
Modulus 0.70 ~
x
.'".
c -0.030 0.60
.2
..
til
~
-0.035
i 0.50 !!:.
.2
-0.040 0.40
011
.c
2 -0.045 0.30 "
"C
0
D.. :::i!
-0.050 0.20
-0.055 Probe Position 0.10
-0.060 0.00
0.0 10.0 20.0 30.0 40.0 50.0 60.0
time I minutes
Figure 4.21 DMA results showing the drying behaviour of a latex paint, including the
build-up of internal stress [31].
degree of curvature of the coated shim, and therefore serves as a measure

of the internal stress building up within the coating.
This information is useful for studying the cracking behaviour or
adhesion loss in coating systems. The advantage over the braid technique,
in addition to the stress data obtained, is that it more nearly approximates
to the real world condition for coatings since the diffusion of solvents to the
surface may be impeded from a braid a few millimetres thick when
compared to a coating applied to a surface. The effects that might arise due
to interactions with the support are also minimised.
4.5
This method, known as DETA, is a complementary method to DMA, Dielectric thermal
where a sinusoidal oscillating electrical field is applied to the sample. The analysis
sample will behave as a dielectric, and instead of the complex mechanical
moduli, DETA measures the complex dielectric permittivity, E*. The
permittivity is the constant in the equation for electrical capacitance. For
example, with a parallel plate capacitor in which plates of area A are
separated by a distance d by a dielectric material, the capacitance C is
given by:
C = eAld = Er'eo (Aid)
where E is the permittivity of the dielectric material, eo the permittivity of
free space, and Er (= Eleo) is the relative permittivity (dielectric constant).
When the permittivity is measured with an a.c. field, it varies with the
frequency of that field. The permittivity is now complex:
E* = E' - iE"
where E' is identical with the relative permittivity and E" is the dielectric
loss.
As with mechanical moduli, this may be written in terms of the loss
tangent tan 8, where
tan 8 = E"iE'
This loss tangent corresponds to power dissipation within the dielectric
[32,33].
4.5.1 Definition of dielectric thermal analysis
DETA is a technique in which the dielectric constant (permittivity, relative

permittivity) and dielectric loss factor of the sample, in an oscillating
electric field, are monitored against time or temperature while the
temperature of the sample in a specified atmosphere is programmed. The
instrument is a dielectric thermal analyser.
4.5.2 Apparatus
The furnace, programming and computer control used in DETA are

similar to those in DMA and other thermal analysis techniques.
The sensors used in DETA may be parallel conducting plates between
which the sample, in the form of a thin disc, is placed. A small force is
exerted on the upper plate in order to improve contact with the sample. A
temperature sensor may be included in one plate.
An alternative is to use a single surface with an array of electrodes. This
may be placed onto the surface of the sample under slight pressure to
obtain good contact. This single-surface sensor may be connected by a
flexible lead for work remote from the main instrument [34].
It is also possible to adapt DSC or DTA systems to measure electrical
resistance or permittivity [35,36].
4.5.3 Frequency range
The advantage of DETA is that a far wider range of frequencies can be

used here than with mechanical perturbation in DMA, e.g. from about 1
Hz to 100 kHz, and several frequencies may be selected for measurement
during an experiment by multiplexing.
This means that DETA is ideal for studying the kinetics of relaxation
behaviour, as discussed above. High frequencies provide a fast data
collection rate, most suitable for looking at fast changes, such as a rapidly
curing polymer, where DMA would not be able to respond quickly
enough.
·0.02
f:'
tan Il
;2.5
/\ 0.01
I \
I \
\
,....--- I \
,/
/ "\ /
I \
\~
j
I
./ \
\ I
" '- //
0.00
:2.0
-100 0 100 200 Tf'C
Figure 4.29 DETA curves for poly(ethylene terephalate). The dielectric constant
increases with temperature and the tan /) curve shows two peaks, the strength of the
process showing that the dipole of the ester group is active in this motion.
4.5.4 Applications
The applications of DETA are similar to those of DMA, with the

advantages of an extended frequency range. It is important to recognise
that for DETA to detect a response, the sample must contain, or have
induced within it by the applied field, electrical dipoles. If these dipoles
have a very small dipole moment, j.L, then the effects observed will be
small. The value of e will vary during the relaxation process, from e Iu at the
beginning (unrelaxed) to e ' R at the end (relaxed). The strength of
the relaxation process (e R - e u) may be correlated with the strength of the
I I
molecular dipole [33]:

(e ' R - e' u) (2e ' R + e' u) = 41Tg<j.L2>
eIR(e ' u + 2) 3kT
POLYMER TRANSITIONS
The DETA curve for PET over a wide temperature range is shown in
Figure 4.29. The value of e' increases with temperature, but the tan 3 peaks
show the alpha (glass transition) and beta peaks clearly. The strength of
the beta process indicates that a large dipole, probably the ester grouping,
is active in this motion.
The complementary nature of DMA and DETA is seen from Figure
4.30, which shows the same relaxation process for poly(ethylene terphthalate)
• " ............ InPET .01HzI01OOkHz .02
DMTA DETA
-OA1Hz ...... - 411Hz
..... D.1Hz - 1kHz
. - 1Hz ..... 10kHz
- 100kHz
DMTA
LogE"
7.550±------..."ao.-------'....50-----~ZOOO
Figure 4.30 Comparison of the DMA and DETA results for PET. The low frequencies
(0.01-1 Hz) measured mechanically transfer smoothly into the higher frequencies (40 Hz
to 100 kHz) measured dielectrically (1 Klmin) [32].
at frequencies from 0.01 to 1 Hz by DMA and from 40 Hz to 100 kHz by

DETA, scanned in both cases at 1 Klmin. The DETA curves show an
upsweep at higher temperatures due to conductivity effects.
PHASE-SEPARATED MATERIALS [37]
The detection of the two phases in rubber toughened thermoplastic

polymer can be seen by either technique as two peaks in the tan 8 curve,
one at low temperature (e.g. -70°C) due to the dispersed rubber phase,
the other at higher temperature (e.g. +100 0c) due to the glass transition
of the thermoplastic.
Applications to coated materials, to natural fats and waxes and to
polymer cure have also been reported.
It is also possible to make measurements simultaneously by using a
remote DETA sensor embedded into the sample which is then clamped
into the DMA system. This has the advantages of all simultaneous
techniques, as outlined in Chapter 5, and allows a single experiment to
determine both DETA and DMA parameters.
4.6
Thermally stimulated Thermally stimulated current analysis (TSC or TSCA) is a technique that
current analysis and involves heating the sample to a temperature above the transition of
relaxation map analysis interest and then applying a static electric field E to induce polarisation P.
The sample is then cooled rapidly to a temperature considerably below the
onset temperature of the transition so that the orientation caused by the
polarisation is 'frozen' in place. The field is then cut off.
On reheating, the polarisation relaxes, generating a current which is
measured by a sensitive electrometer and gives a 'dynamic conductivity'
[38].
TSC and the related techniques of thermally stimulated luminescence
and depolarisation (TSL and TSD) applied to organic polymers were
reviewed by Fleming [39].
An interesting variant of this approach is called 'windowing'. Since
transitions normally occur over several tens of degrees Celsius, the sample
is heated to a temperature Tp within the transition range and the electric
field is applied for a known time. The temperature is then reduced by 5-10
degrees to Td , the field switched off and the sample held at that
temperature for a short time. The sample is then quench cooled. In this
way, only those motions corresponding to the narrow temperature interval
(or 'window') traversed while the field was applied are frozen in an
oriented manner. On reheating, the response measured is taken to arise
only from that part of the broad spectrum of relaxations of which the
transition is composed that were 'captured' by the windowing technique.
By varying the values of the temperature 'window' the transition can be
broken down into a large number of 'slices' which may be analysed
separately and used to construct the relaxation map analysis (RMA) of the
material [40]. In this way it is possible to gain a greater insight into the
complexities of relaxation phenomena.
4.6.1 Definition of thermally stimulated current analysis
This is a technique that monitors, against time or temperature, the current

that is generated when dipoles change their alignment in the sample, while
the temperature of the sample in a specified atmosphere is programmed.
4.6.2. Apparatus
The sample is contained between two electrodes within a furnace, with

cooling facility by nitrogen gas or liquid nitrogen, that can give cooling
rates up to -60 Klmin. The electric field is applied across the electrodes
and subsequently the current of 10- 17 to 10- 8 A is measured.
4.6.3 Applications
Besides the complementary nature of this technique to the other thermo-

analytical and thermoelectrical methods for the determination of glass
4X1013J (Alcm 2 )
>-
.~
c:
Polypropylene fl l\ \:
\ :'
,
\
\
~ ,.r,.
:; , '. I
/"'{ \
\... \
u/ \ '. ,:
! \ i
! \', :'
,./
!', I
,!/.,---"",<~----
,
\l
\ ",
-13 f "--._--- ..-
10
-100°C O°C 100°C

Figure 4.31 TSC curves for drawn (full line) and undrawn (dashed line) polypropylene,
showing the polarisation recovery as the sample is heated [40].
transitions and beta and gamma transitions of polymers and composites

and curing processes, TSC and RMA have been used to investigate the
glassy state of amorphous polymers such as polystyrene, and the relaxation
behaviour of different regions in semi-crystalline polymers. Figure 4.31
shows the TSC curves for drawn and undrawn polypropylene, and Figure
4.32 shows the RMA for the undrawn polypropylene. The relaxation
component at lower temperatures is attributed to the inter·spherulitic
regions, and that at higher temperatures to the chains whose ends are
under constraint from the crystallites [40].
A study of PEEK [41] has shown the existence of two amorphous
phases.
TSC has also been used for the investigation of bone [42]. Analysis of the
fine structure of the complex TSC of bone and of products from the
de mineralisation of bone and comparison of the organic and mineral
phases and the pure components have shown the importance of the
interphase.
4.7
Problems 1. Suppose you wished to design a TMA system that used an optical
(Solutions on p. 276) sensor to detect the movement of the probe. What type of sensor
might be suitable? Sketch the whole apparatus and mention any
disadvantages of this type of system.
2. A metal rod 3.00 mm long expands by 7.5 "",m when heated from 0 to
100°C. Calculate the coefficient of linear expansion. If a block of the
same metal measuring 3.0 x 5.0 x 10.0 cm was heated over the same
-40 -30 -20 -10 0 10 20 30 40 50 60 708090
sec
3
-1
4.4 4.2 4.0 3.8 3.6 3.4 3.2 3.0 2.8
Figure 4.32 Relaxation map analysis (RMA) for undrawn polypropylene. The lines show
three types of behaviour: straight Arrhenius, WLF curvature and lines obeying a
compensation law. The lines converging in the low-temperature region may characterise a
glassy phase under stress [40].
temperature range, how much would its volume increase and what is
the coefficient of volume expansion?
3. A sample of polyamide film of thickness 1.00 mm at 30 °e expanded by
5 f.Lm when heated to 80 °e, by a further 5 f.Lm up to 120 °e and by 7.5
f.Lm more up to 150 °e. Estimate the glass transition temperature of
this polyamide.
4. A penetration probe with a hemispherical end of radius R = 2 mm
rests on a rubber material held at 54°C. With a load of 20 g, the
penetration depth, d, was 0.113 mm. Given the approximate formula:
F = 1.778E-Ro. 5 ·d1. 5
where F is the applied force, calculate the modulus E and compare it to
the Young's modulus for this rubber of 2.3 x 106 Pa. What sort of TMA
curve would this give?
5. Describe the difficulties associated with carrying out constant strain
experiments on thin films and fibres. How are these difficulties
overcome? Sketch the changes that would occur in the dynamic force
as a fibre is heated through its glass transition. Illustrate how any other
applied force would also change.
6. Two polymers are mixed together in solution and the solvent is then
allowed to evaporate to form a solid. If this solid proves impossible to
clamp in a DMA because it is too brittle, what alternative approach
could you adopt? What would be the disadvantages of this approach?
G' mn6
-50 o 50 100 150 Trc

Figure 4.33 DMA curve for Problem 8.
How would you be able to tell if the polymers were miscible or

immiscible?
7. Suggest ways of looking at the cross-linking behaviour of a polymer
system that, before cross-linking occurs, is a low-viscosity liquid. What
type of feature would you expect the DMA to show as the system
cures? What important information about the properties of the fully
cured system could you establish by DMA and how would you go
about obtaining these data?
8. If you were given the DMA results shown in Figure 4.33 and are told
that the sample consisted of only one polymer, how would you assign
the peaks and the molecular motions from which they arise? If told
that the sample consisted of two polymers, what other explanation
might there be for the results?
9. For a particular sample of polycarbonate the storage modulus curves
were determined at a series of temperatures and frequencies. In order
to plot a 'master curve' referenced to 145°C, the individual curves
needed to be shifted along the log (frequency) axis by the amounts
listed below.
Temperature ("C) Shift factor (log(a))
135 3.36
140 1.57
145 o
150 -1.38
155 -2.60
(a) Show that these values may be fitted to a WLF equation with
C1=22.9 and C2=78.1
THERMOMECHAN ICAl, DYNAMIC MECHAN ICAl AN D ASSOCIATED METHODS 159
(b) If the lowest measured frequency is 10-2 Hz, calculate the lowest
frequency that could be found from the master curve.
10. A sample of polyisoprene which was originally a cube of side 1.65 mm
was allowed to swell in toluene and the dimensional change measured
by TMA. The final dimension was 2.83 mm. Given that the polymer-
solvent interaction parameter Xl = 0.391 for this combination and that
the molar volume of toluene is 106.3 cm3/mol, calculate the cross-link
density using the Flory-Rehner equation.
1. J.~. Hill, For Beuer Thermal Analysis and Calorimetry III, ICTA, 1991. References
2. F.W. Sears, M.W. Zemansky, H.D. Young, College Physics (5th edn), Addison-Wesley,
Philippines, 1980.
3. F. Rodriguez, Principles of Polymer Systems (2nd edn), Ch. 8, McGraw-Hill, Singapore,
1983.
4. ASlM D4092-9O, ASTM, Philadelphia.
5. B.K. Jones, Electronics for Experimentation and Research, Prentice-Hall, London, 1986.
6. TA Instruments Ltd, TMA 943 Brochure.
7. RB. Prime, Proc. 7th ICTA, Wiley, Chichester, 1982, p. 984.
8. T. Ozawa, 1. Thermal Anal., 1993, 40, 1379.
9. P.H. Willcocks, 1. Thermal Anal., 1993,40, 1451.
10. K.-H. Schuler. R. Sladek, P. Huse, Thermochim. Acta, 1988, 135, 333.
11. ASlM D3386-84, ASTM, Philadelphia.
12. R Riesen, W. Bartels, Proc. 7th ICTA, Wiley, Chichester, 1982, p. 1050.
13. W.P. Brennan, Perkin-Elmer Application Study, #26, 1978.
14. H.S. Yanai, W.J. Freund, O.L. Carter, Thermochim. Acta, 1972,4, 199.
15. R.B. Prime, in Thermal Characterisation of Polymeric Materials (ed. E.A. Turi) ,
Academic Press, New York, 1981, p. 507.
16. W.P. Brennan, Perkin-Elmer Application Study, #23, 1977.
17. M.Y. Keating, Dupont Application Brief, TA-96, 1985.
18. Setaram, lMA 92, File 12: Applications Brochure.
19. M. EI Sayed Ali, O.T. Slilrensen, L. Hiilldahl, Proc. 7th ICTA, Wiley, Chichester, 1982,
p.344.
20. E. Karmazin, M. Romand, M. Murat, Proc. 2nd ESTA, Aberdeen, Heyden, London,
1981, p. 562.
21. H.G. Wiedemann, M. Roessler, Proc. 7th ICTA, Wiley, Chichester, 1982, p. 1318.
22. R Riesen, H. Sommerauer, Amer. Lab., 1983,30.
23. P.G. Fair, P.S. Gill, J.N. Leckenby, Dupont Application Brief, TA-9O.
24. (a) R.E. Wetton, Developments in Polymer Characterisation, Applied Science, 1986, Ch.
5; (b) R.E. Wetton, J.S. Fisher, K.E. Pettitt, A. Evans, J.e. Duncan, Amer. Lab.,
January, 1993, 25, 16.
25. F. Biddlestone, A.A.S. Goodwin, J.N. Hay, G.A. Mouledons, Polymer, 1991,32,3119.
26. M.L. Williams, R.F. Landel, J.D. Ferry, 1. Amer. Chem. Soc., 1955, 77, 3701.
27. T.G. Fox, Bull. Am. Phys. Soc., 1956, 1(2), 123.
28. D.J. Lin, J.M. Ottino, E.L. Thomas, Polym. Eng. Sci., 1985,25,1155.
29. A.F. Lewis, J.K. Gilham, 1. Appl. Polym. Sci., 1962,6,422.
30. M. Claybouro, M. Reading, 1. Appl. Polym. Sci., 1992,44,565.
31. M. Reading, in Thermal Analysis- Techniques and Applications (ed. E.L. Charsley, S.B.
Warrington), RSC, Cambridge, 1992.
32. RE. Wetton, M.R. Morton, A.M. Rowe, Amer. Lab., 1986, 70.
33. (a) H. Frohlich, Theory of Dielectrics, OUP, London, 1958; (b) V.V. Daniel, Dielectric
Relaxation, Academic Press, New York, 1967.
34. S.T. Eckersley, A. Rudin, 1. Coat. Tech., 1990,62,89.
35. A.K. Sircar, T.G. Lombard, J.L. Wells, Thermochim. Acta, 1980,37,315.
36. K. Rajeshwar et al., Thermochim. Acta, 1979, 33, 157.
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1986, 21, 443.
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863.
Bibliography The general reference texts given in Chapter 1 should be consulted.

Simultaneous techniques 5
and product analysis
P.J. Haines
5.1
The previous chapters have concentrated on single techniques and their Introduction
applications. However, we should remind ourselves that thermal methods
often require complementary analysis by other techniques for a more
complete understanding of the processes occurring. Even with the simplest
decompositions - for example, when heating hydrated copper sulphate -
we cannot be sure of the stages of reaction unless we confirm the products,
both solid and gaseous, by other analyses. It would be useful to start by
combining the thermal methods themselves, since they follow similar
regimes of heating and atmosphere control, and should show the thermal
events in a complementary manner.
The dynamic nature of thermal methods affects the results we obtain.
Remembering SCRAM, we must consider the sample, the crucible or
holder, the rate of heating, the surrounding atmosphere and the mass of
sample. It would therefore be an advantage to use the same sample, the
same heating rate and other conditions, but to sense the properties
simultaneously. This saves both in time, since one run does the work of two
or more, and on sample, if we have only a small amount to investigate.
Most importantly, it gives results for two or more techniques under
precisely the same experimental conditions.
It is only when two techniques are used on the same sample in the same
run that the term 'simultaneous' should be used. When separate amounts
of the same sample are run on different instruments, or even on different
arrangements of the same instrument, then the term 'combined' or
'consecutive' should be used [1].
The products of thermal analysis may be analysed by any standard
analytical method [2]. Gases can be separated by gas chromatographic
columns and may be analysed by infrared or mass spectrometry, or by
specific gas detectors, for instance. Solids can be examined by X-rays or by
spectrometry, or taken through the regimes of separation and chemical
analysis. It is also important to observe the nature of the change as it
occurs, and running a sample on a heated stage under a microscope allows
this to be done as well. As discussed above, it is a further advantage if these
methods can be run simultaneously with the thermal analysis.
Ultimately, it might be possible to combine many analytical techniques,
both conventional and thermal, together in a single, thermoanalytical
system. One example of such a system was used in space exploration and
produced data on the nature of the surface of Mars [3]. Uden and co-
workers [4] have combined thermal analysers, pyrolysis furnaces, gas
chromatography, vapour phase IR, mass spectrometry and elemental
analysis into a single, complex system. They used the apparatus for the
characterisation of oil shales, for polymers and organometallic compounds.
5.2
Simultaneous thermal Definition [1] Simultaneous techniques refers to the application of two or
analysis more techniques to a sample at the same time. A dash is used to separate
the abbreviations, e.g. simultaneous thermogravimetry and differential
scanning calorimetry is TG-DSC.
5.2.1 Simultaneous TG-DTA and TG-DSC
As these are the most frequently used thermal methods, it is especially

important to have a simultaneous technique incorporating both. The early
work by the Pauliks and Erdey [5] used the derivatograph and allowed measure-
ment of TG, DTG, DTA together. Many other designs have followed, and
are often based on a thermobalance modified to weigh both sample and
reference and to measure the temperature of each. A typical modern
assembly for simultaneous TG-DSC (or 'STA') is shown in Figure 5.1.
The sample and reference materials are contained in crucibles, located
on and supported by a heat-flux DSC plate. The leads to the temperature
sensors below the crucibles go through the alumina support rod to the
balance and detector systems. This system operates from -120 to 1500 °C,
being cooled by a liquid nitrogen chamber for subambient operation. For
temperatures from -160 to 2400 °C, a slightly different TG-DTA assembly
may be used.
The SETARAM TG-DSC 111 uses symmetrical twin furnaces each with
a Calvet microcalorimeter [7] while the T A Instruments SDT 2960 has a
dual-beam horizontal design in which ceramic beams support the DTA
sample and reference holders and dual meter movements are used to
monitor the weight changes in sample and reference [8].
5.2.2 Applications
Many of the applications detailed in Chapters 2 and 3 may be carried out

using the TG-DSC system. Some new examples will be used here.
SIMULTANEOUS TECHNIQUES AND PRODUCT ANALYSIS 163
I gas outlet (MS-GC-FTIR)
~
/----"'\
I \
DSC sample carrier ( . ~.. \
\ I
_--_...
\ I
\
\ ' .... ;/
/
t - - t - - - - - furnace
-- ,
/ ..... ....
TG sample carrier (~_\

\
' ..... _
..../
I
J-I--+----sample carrier
't-+---- radiation shield

thermostatic control f-+---- protective tube
~~~-"-~
~--- vacuum seal
_ -('J<)- - - reactive gas
-[)I<]- - - protective gas
:--+t----
inductive displacement
evacuation system transducer
InE __-++--_ _ electromagnetic
compensation system
+---- vacuum tight casing
Figure 5.1 Netzsch STA 409 Simultaneous Thermal Analyser for TG-DSC. Note the
facility for evolved gas analysis.
CALIBRATION MATERIALS [9]
Since it is quite difficult to calibrate the temperature with a conventional

thermobalance system, and is much easier with DTA materials with well-
characterised melting points, the use of simultaneous TG-DTA in a
magnetic field allows the two calibrations to be performed in the same run.
Figure 5.2 shows the melting endotherms of lead at 327°C and of zinc at
419 °C which show only on the DTA, plus the Curie point transition of
nickel which shows only on the TG. Thus, an accurate value for the
temperature of this transition could be found as 358.1 ± 0.4 °C when a
heating rate of 10 Klmin was used.
SODIUM TUNGSTATE DIHYDRATE [8]
The decomposition of inorganic salt hydrates has been studied by single

thermal analysis techniques, and the STA will give the TG and DTA
information on the same sample at the same time. For example, the three-
stage decomposition of calcium oxalate run on STA shows both the TG of
Figure 2.15 and the DTA of Figure 3.35.
The dehydration of hydrated sodium tungstate Na2W04.2H20 is shown
in Figure 5.3. This material is used to standardise moisture analysis systems
(see p. 170) and shows a single mass loss on the TG at around 100 °C of
about 11 % due to the loss of hydrate water, which should theoretically be
l
0
NICKEL
01 >
::l.
E .2 .......
....... TG
-.J
C/)
«
z
g.4
C/)
~
DTA C/)
C/)
C/) «
« I-
~ ENDOTHERMIC 0
LEAD
ZINC
-30
300 350 400 450
SAMPLE TEMPERATURE / °C
nickel using
Figure 5.2 Determination of an accurate value for the Curie point of
simultaneous TG-DTA in a magnetic field.
100~~\--------------------------------~4
,...'1 (----.--..-.-.-..-.-..~~5l0C r'l69~:~~_ ~

81°C
98 2
i i i 0
i
:
i i
I .,. I-
, Ii
I .2 <l
Impurity
Water loss
I i" Melting
-4
92 \\ :i
:j
\ -6
90
8R8.I-__ __---,r-_ _ _--r-_ _ _-::-:~-----:::±"-8

o 200 400 600 800
Temperature (0C)
Klmin, nitrogen at
Figure 5.3 STA of sodium tungstate dihydrate. Typical conditions: 10
100 cm /min, 10
3 mg powdere d sample.
first
10.9%. The DTA curve shows three endothermic events. Since the
coincides with the TG loss, it must represent the endoth ermic dehydr ation
585
to anhydrous Na2W04 • The two sharp DTA endotherms with onsets at
the
and 697°C must be phase transitions and are a crystal transition and
sodium tungsta te, respectively, in agreem ent
melting of the anhydrous
with the literature.
More complex behaviour is shown by the decomposition of salts such as
magnesium nitrate hexahydrate, Mg(N03h-6H 20 [to]. This initially melts
at about 90°C and simultaneously starts to lose water. The DTA and TG
curves are most uneven, since the sample loses more water with consider-
able bubbling. The final water is lost by 350°C (42% loss) and the
anhydrous salt melts at 390 °C before decomposing to the stable oxide (600
0c) leaving a residue of 15.7% of the original material. This complex
behaviour needs additional techniques such as thermomicroscopy to sort
out the stages.
FIRE-RETARDED WOOD [11]

The complex pattern of decomposition of wood is shown by the TG-DTA
trace of Figure 5.4. The stages of combustion of cellulose have been
identified [12,13] as dehydration and decomposition to laevoglucosan,
followed and accompanied by production of flammable volatiles, tars,
carbon and gases such as water vapour and oxides of carbon. Treatment
of the materials with fire retardants such as borates, phosphates, or
aluminium salts alters the temperatures and stages of decomposition. This
may be observed very readily on TG-DTA. The small initial drying peak is
little affected by the additive, but both the magnitudes and temperatures of
the subsequent peaks are considerably changed. Tang and Neill [14] have
compared the TG and DTA traces for a number of fire-retarded cellulose
materials.
POLY(VINYL CHLORIDE) [15]
The thermal properties of polymers used as dielectric materials can be

determined by STA. For example, filled PVC used as a cable sheathing
gave the STA curves shown in Figure 5.5 in both nitrogen and air. The
glass transition often shows on DTA at around 80°C, and the dehydro-
chlorination reaction at around 270°C is weakly endothermic, but shows a
large weight change of over 50%. The subsequent loss of volatiles is very
exothermic in air but less so in nitrogen. Small peaks are due to the
additives present as fillers, fire retardants, heat and UV stabilisers, acid
acceptors and char promoters [16]. The residue of around 10% in air comes
from mineral additives and the larger residue in nitrogen is due to the
uncombusted material and fillers such as carbon black.
PHARMACEUTICALS [17]
The nature of pharmaceutical materials, the water they contain and their
thermal stability is often studied by TG-DSC. Figure 5.6 shows the loss of
100
mass %
50
'\
'- --
o-
EXO
1
.1T
.1
ENDO
'\
\
\.
Figure 5.4 STA of poplar wood. Untreated (full line) and fire retarded (dashed line).
Derivatograph trace after [11]; 10 Klmin, air.
water from a hydrated pharmaceutical, followed by the melting of the

anhydrous material at about 170°C without decomposition, and lastly the
start of an endothermic change above 250 0c.
REACTIVE ATMOSPHERE EFFECfS [7]
If the atmosphere above the sample is reactive, we may study the

oxidation, reduction, catalytic and adsorptive reactions and corrosions.
These all require an STA system that will not be adversely affected by any
reactant or product materials. Figure 5.7 shows the reduction of a nickel
oxide catalyst supported on silica by hydrogen. The water produced is
detected by an attached mass spectrometer (see p. 171) and the three stages
100
mass %
50
EXO
1
dT
1
ENDOr-----
100 300 500 700 TIDe
Figure 5.5 STA of poly(vinyl chloride) insulation sample; 20 mg sample,S Klmin, air
(full line) or nitrogen (dashed line) at 60 cm3/min (After [15]).
correspond to loss of adsorbed water around 100 °C and the reduction of

the nickel oxide by the hydrogen around 500 0c. The DSC shows the
endothermic nature of the desorption and the exothermic nature of the
reduction.
5.3
In interpreting the mass losses in TG, or the peaks in DTA, we could not Evolved gas analysis
identify the products from that technique alone. Those thermal analysis
techniques were not capable of differentiating between an endothermic
loss due to solvent, or a decomposition reaction, or a physical process such
as vaporisation. We very often need to identify the gases or vapours
involved in the thermal process, but we must be most careful that they are
not changed by further reaction or delayed by condensation or transfer lag.
23.5 15
23.0
10
22.5
5
22.0
Cl
E
21.5 0 &l
Ul
rn 21.0 -5 ~
~ 20.5 -10
20.0
-15
19.5
-20
19.0
18.5 -25
0 50 100 150 200 250 300

TrC
Figure 5.6 STA of pharmaceutical compound (22.6 mg, 10 K1min, nitrogen at

50 cm 3/min).
heat flow (mW) mass loss (mg)

NiOlSi02 -8
2
-7
o
--.-
evaporation --.-.-.~-;;.....
of absorbed H20, -5
-2
-3
-2
-4
-1
o
roc
Figure 5.7 STA-EGA of the reduction of a NiO/Si02 catalyst in hydrogen; 30.1 mg, 10
K1min, 80% N2 , 20% H 2 • Note: mass loss is here shown upwards. (Courtesy SETARAM).
Definition Evolved gas analysis (EGA) is a technique in which the nature

and/or the amount of gas or vapour evolved from the sample is monitored
against time or temperature while the temperature of the sample in a
specified atmosphere is programmed [18].
Where the gases are detected, but not analysed, the technique can be
referred to as evolved gas detection (EOD).
5.3.1 Instrumentation
There are many ways in which the evolved gases may be detected and
identified. For general thermal decomposition work, a large sample of
several grams may be heated in a furnace in a flowing gas stream, using a
controlled temperature programme. The products can be collected by
passing the gas through an absorber, or through a cold trap, or through a
series of specific gas detectors.
McNeill has developed the technique of thermal volatilisation analysis
(TVA), where the sample is heated in vacuo, and the products are
progressively condensed. The products are differentiated as the involatile
residue, remaining in the oven, the high boilers, like waxes and less volatile
oils, condensing on the walls, and the volatiles, passing on to the traps for
condensation at lower temperatures [19,20]
For example, a copolymer of poly(vinyl bromide) (PVB) and poly-
(methyl methacrylate) (PMMA), with 19% PVB, was shown to decompose
in three stages by TO experiments. In a TVA experiment, the products
from the first stage were volatile under vacuum at -100°C and the product
composition changed at 220 °C and again at 325°C. By separation, the
products contained CO2 , HBr, CH3Br, CH30H and MMA monomer.
Infrared examination of the residue showed lactone rings.
5.3.2 Apparatus
It is an advantage to control the conditions by using a thermal analysis

technique to provide the heating. Thermogravimetry has been widely used
for this, and the gases evolved from the thermobalance are conducted away
into other analytical devices. A typical arrangement is shown in Figure 5.8.
5.4
We may classify the methods used for detection and/or identification under Detection and
three headings: identification of evolved
gases
1. Physical methods: conductivity, density.
2. Chemical methods: reaction, colour indication, electrochemical.
3. Spectroscopic methods: mass spectrometry, infrared.
We should add to this list the separation of mixtures of evolved materials

by chromatographic techniques.
Heated gas line
Sensor
Carrier
gas in
Figure 5.8 Schematic of TA-EGA system. The evolved gases are carried through the
heated line by the carrier gas to the sensor (e.g. conductometric, pH, colorimetric) and/or
the absorbent container.
5.4.1 Physical methods
The sensitive detectors of gases used for gas chromatography are often
added to thermal analysis units to detect evolved gases. The DSC
instrument could be fitted with a thermal conductivity detector to show
changes in the gas streams. Flame-ionisation detectors (FID) have been
used to detect gases evolved directly from heated plastic materials as well
as gases separated by GC, but they will not, however, detect water vapour
or carbon dioxide.
The gases evolved may be absorbed into a suitable solvent - for
example, water vapour into dioxane or an organic vapour into an oil. The
change can be followed by monitoring the electrical conductance or the
capacitance of the solution or the solution may be analysed by chromato-
graphic methods.
These methods often have the disadvantage that they are non-specific.
Any gas which changes the physical properties will be detected.
In the moisture evolution analyser (MEA) [21], the moisture evolved
from the heater is transferred by nitrogen carrier gas into the electrolytic
cell detector where it is absorbed by phosphorus pentoxide coated onto
platinum electrodes. The water is electrolysed to hydrogen and oxygen
which are carried away by the gas stream. The electrolysis current is
integrated and gives the amount of water directly. The system may be
calibrated using water or a hydrate such as sodium tungstate dihydrate
which has a theoretical water content of 10.92%. The technique forms the
basis for the ASTM method D4019.
The capacitance moisture probe [22] has metal electrodes surrounding a
hygroscopic dielectric layer which rapidly reaches equilibrium with the
water vapour pressure, and changes the capacitance of the cell. A dew-
point instrument has also been used to detect water [23). There may be
difficulties with these due to a slow, non-linear response to the moisture
and lack of reversibility.
5.4.2 Chemical methods
The chemical reaction of gases with reagents or detectors specific to their

chemical nature is a simple method of detecting single types of gases. The
evolution of acidic gases, such as HCI from heated PVC, or of phthalic
anhydride from polyester resins, can be detected and quantified by
absorbing the evolved gas in a solvent such as aqueous alkali and
measuring the change in pH, or the colour of an indicator or by eventual
titration. For example, carbon dioxide evolved from heated concretes was
dissolved and reacted with dilute, aqueous barium hydroxide and the
reaction followed by conductance measurements [24].
Similar techniques can be used for the evolution of alkaline gases, such
as ammonia, and McGhie et al. [25] report a simple pH method for
measuring pH of a constantly renewed solution containing gases evolved
from an ammoniumlhydronium beta alumina:
(NH4·H30)1.67 MgOo.67 A110.33 0 17
The TG showed unresolved, multiple weight losses, but the pH trace
clearly showed that most of the NH3 is evolved below 400 °C, while the
water evolved has little effect on the pH.
Many gases may be identified by the use of Draeger tubes. These contain
reagents specific to particular gases, which change colour when they react.
A semi-quantitative measurement of the gas concentration may be made.
Electrochemical detection using pH electrodes has been mentioned
above, but electrodes sensitive to other species, such as metal ions,
chloride, fluoride and cyanide ions, and gas-sensing membrane electrodes
for such gases as CO2, N02, H 2S, S02 and NH3 are available [2]. The gas-
sensing electrodes operate by establishing an equilibrium between the gas
in the solution outside the electrode and the electrode membrane, which
then equilibrates with the internal solution and internal electrode system.
A coulometric detector was used by Brinkworth et al. [26] to monitor
sulphur dioxide evolution during coal combustion studies. The coal was
burnt in a TG apparatus connected through an oxidation furnace to a
coulometric cell. Any sulphur compounds evolved were oxidised to S02
which was then titrated [27] with iodine generated automatically. Figure
5.9 shows the weight loss and sulphur evolution profiles of three coals.
5.4.3 Spectroscopic methods
MASS SPECTROMETRY (MS) AND SIMULTANEOUS TG-MS
Mass spectrometry is a very good technique for identification of evolved

gases and vapours. If a sample in the vapour state is introduced into the
mass spectrometer under high vacuum, usually better than 10-5 torr, the
100
0___0--';':\0. . . fc BOOr
BO
~
~ 60 \\ :I
8
600
"#. 40 ~.\ -; 400

~
c:
20 . .2 200
.~~
0 --I.F
100 200 300 400 500 600 700 200 400 600 800 100
(a) Temperature °C Temperature °C
(b)
Figure 5.9 (a) Weight loss profiles and (b) sulphur evolution profiles for three coals
heated in air: (i) high volatile C bituminous, 3.2% pyritic, 0.3% organic S (full line);
(ii) semi-anthracitic, 0.1 % pyritic, 0.6% organic S (dotted line); (iii) medium volatile
bituminous, 1.0% pyritic, 0.7% organic S (dot-dash line) [26].
molecules M may then be ionised in various ways, for example by high

energy electron impact using electrons accelerated by a potential differ-
ence of about 70 V:
M + e* = M+ + 2e
The species M+ is the molecular ion and generally a radical cation with an
odd electron.
With such a high energy, there is a high probability that the molecular
ion, M'+, may fragment into a lower mass fragment ion and a neutral
fragment, for example, the molecular ion of propanone [CH3·CO·CH3l+
with a mass/charge ratio m/z = 58 readily fragments either to CH3·CO+
(mlz = 43) or to CH3+ ions (mlz = 15). The fragmentation pattern is
characteristic of the molecule being studied.
Using other 'soft ionisation' techniques, such as chemical ionisation,
fragmentation effects may be reduced.
The positive ions are accelerated through magnetic and/or electric fields
which separate them according to their mass/charge ratios (m/z), and the
ions are then detected by an electron multiplier [2].
The mass spectrometer operates in a high vacuum, which sets a problem
of interfacing this spectrometer to any thermo analytical system. The
evolved gas is extracted from the thermal analysis instrument through a
heated capillary leak at a suitable temperature. Methods such as jet or
orifice separators have been used [28,29] to reduce the pressure before the
mass spectrometer. The sampling capillary is set as close as possible to the
sample and may be heated up to around 250°C. A second stage reduction
using a fine frit as a molecular leak may be added. This arrangement
reduces the transfer time between the TG and the MS to less than 1 second
[30,31,32]. A modern system is shown in Figure 5.10.
The software available with modern MS systems allows us to select
Silica-lined
stainless steel connector
H TGA furnace
~ I
capillary
~e~n9 c::r;I
Sample pan
connectIon I
1mmgap
.--J '~TO mass spectrometer
_ quadrupole
~ Molecular leak
Teflon seal I! (silicon carbide frill
To second stage
(a) of rotary pump
shut-off molecular
valves leak
carrier gas
analyser + and
head products
aU-glass
jet separator
rotary
(b) backing pump
Figure 5.10 (a) TG-MS system; (b) dual inlet system for STA-MS.
several mass numbers and monitor them continously throughout the run,
or to perform a rapid scan over a range of masses to obtain full mass
spectra of the gases evolved. With proper materials and pumping there is
little retention of the gases in the capillary or spectrometer, and so there is
no 'memory' effect.
The 'total ion current' (TIC) shows the sum of all ionic species at a
particular time, and may be compared to the thermal analysis curve.
CALCIUM OXALATE MONOHYDRATE (FIGURE 5.11)

This compound should be familiar by now! The TG trace shows .three steps
over the temperature range up to 100 DC, and by examining the evolution
of the molecules of water (mlz = 18), or carbon monoxide
(mlz = 28) and carbon dioxide (mlz = 44), we can say most certainly what
the changes represent. The run was performed in argon (mlz = 40), which
was subtracted from the spectra as background. The evolution of water
corresponds exactly with the first DTG peak at 200 DC, the evolution of CO
with the second at 480 DC, and of CO2 with the third around 770 DC. Note
that there is also some CO2 at the second stage, possibly due to the
disproportionation of CO [33], and that the mlz = 28 trace also peaks
during the third stage, due to the fragmentation of the CO2 ions.
o TG
Mass
loss% IOTA
20
EXO
40
T , 1
60J,.lV
1
II ' \ l
:I .
I I
I \
ENDO I
60 nVz 18
-
I \
~z_~_ \ /
nVz 28
200 400 600 800
Sample temperature I °C
Figure 5.11 TG-DTA-MS curves for calcium oxalate monohydrate (15 mg, 15 Klmin,
argon).
POLY (ETHYLENE OXIDE) (FIGURE 5.12) [34]
Polymer decompositions may be extremely complex, and many products

may be evolved simultaneously. The TG curves in air show a DTG peak
with several overlapping parts. Monitoring of the prominent mass spectral
peaks at mlz = 73 (probably a C3H 50 2 species) and mlz = 88 (p-dioxane,
C4Hg0 2) shows how they are evolved as a function of temperature.
Different samples from different suppliers gave very different traces, and
performing the experiment in nitrogen also altered the scans.
Studies on PVC [31,35] (see also p. 179) have shown that the stages of
that decomposition may be monitored by TG-MS and that the first stage
correspends to evolution of HCI, low molecular weight hydrocarbons,
especially benzene, and vinyl chloride monomer, while later stages
produce higher molecular weight materials and finally a residue.
BRICK CLAYS [31]
A sample of an Oxford clay used in the manufacture of common bricks

gives the TG curve shown in Figure 5.13 when heated at 20 Klmin in air.
The evolution of water (mlz = 18) occurs below 200 °C while at 300 °C
combustion of the organic material produces several volatiles. Higher
temperature processes involving the reactions of clays, carbonates and
pyrites produce the complex patterns of evolution of CO2 (mlz = 44) and
S02 (mlz = 64).
10.1
10.1
·1
10 ~----~~--~--~~------~~--~~
o 100 200 300 . 400 0 100 200 300 400 500
Temperature (0C) Temperature (0C)
Figure 5.12 TG-MS curves for poly(ethylene oxide) Mw = 5 x Hr, from two suppliers
(10 Klmin, gas flow 100 cm3/min). Top curves show the TG under air (full line) or
nitrogen (dashed line) and the lower curves the mass spectral response curves.
il~~
8J 15 "
~ 20 '--
25
!
x50 A!\. ------~
amu
'i' A !\
~~V~44
~18
o 200 400 600 800 1000
Temperature I °C
Figure 5.13 TG-MS curves for an Oxford clay (40 mg, 20 Klmin, air) [31].
5.4.4 Simultaneous thermal analysis - gas chromatography - mass

spectrometry
Although it is possible to obtain separate responses for several molecular

species by thermal analysis - mass spectrometry, pyrolysis of samples such
as polymers may give many products. It is an advantage if these can be
Figure 5.14 Vibrational motions of H 20 molecule. (a) Symmetric stretch 3652 em-I;
(b) Antisymmetric stretch 3756 em-I; (c) Bending 1596 em-I.
separated between the thermal analysis unit and the mass spectrometer by
gas chromatography. It is possible to do this by freezing the products in a
cooled trap [36,37], but it is better to take the sample directly to avoid
secondary reactions. Combined systems have been described [38,39] where
this may be done, and important information has been obtained on the
decomposition of polymer systems.
5.5
Infrared and Infrared spectrometry measures the absorption of light in the region of 2.5
simultaneous to 50 j.1m (or 4000 to 200 cm- I ) due to its interaction with molecular
TA-infrared vibrations. The number of fundamental frequencies of a molecule with n
atoms is (3n - 6), or, if linear, (3n - 5). Not all of these may be active, since
a condition for infrared absorption is that the molecular dipole must
change during vibration.
Typical infrared bands with simple molecules involve the fundamental
vibrations. For example, with the molecule H 20, which is non-linear, the
vibrations are shown in Figure 5.14.
In more complex molecules, the infrared spectrum is often interpreted in
terms of the 'group frequencies', that is, vibrational frequencies typically
observed for functional groups within the molecules. For example, in the
molecule of propanone, CH3 • CQ·CH3 , we may assign the main infrared
spectral bands as follows:
Group Vibration Wavenumber (cm -1)
C=Q stretching 1720
CH3 stretchings -2900
CH3 bendings -1400
C·CQ·C -bend -1200
In gaseous samples, the molecular rotations also interact to give a
complex 'ro-vibrational spectrum' with spectral bands. It should be noted
that gaseous IR spectra often appear very different to the condensed phase
spectra of the same chemical. For example, hydrogen-bonding effects are
much less in the gas phase.
The spectra of many gaseous products may be measured by infrared
spectrometry. The exceptions are homonuclear diatomic gases (e.g. N2 ,
02) whose molecules have no dipole. Although the spectra are often
complex, there are advantages in using IR, particularly if a Fourier
transform instrument is available. The infrared spectrum of a mixture of
gases may be interpreted for each gas. The evolved gases may be carried
from the furnace or thermal analysis system at atmospheric pressure in
nitrogen or dry CO2-free air or an inert gas. A long path-length through the
gas is required, since the concentrations are low, and condensation of
volatiles, especially water, should be avoided. Alternative methods con-
dense the evolved material either in an argon matrix onto a cooled,
reflective surface [40] which then moves into the path of the spectrometer
or into a tube packed with a chromatographic absorbent such as Tenax for
subsequent desorption, separation and detection.
5.5.1 Apparatus
While it is not intended to discuss infrared instrumentation fully here, it is

essential to point out the main components and sampling methods used in
infrared [2].
In a dispersive IR spectrometer, the infrared radiation from the IR
source (e.g. a heated filament) is focused by mirror optics onto the sample.
Since the container should absorb as little IR as possible, the sample is
usually kept between windows of ionic solids, such as NaCI or KBr plates
(or AgCl or CaF2 plates if water may be present). The radiation is then
dispersed by a grating or prism, and detected by thermocouple, pyroelec-
tric or other detector.
Sample cells which may be heated (or cooled) are available and have
been used to study the thermal behaviour and kinetics of reaction.
Fourier transform infrared (FTIR) spectrometers use similar sources,
sampling devices and detectors, but work through the interference of two
IR beams controlled by a mirror system. The interferogram is then
converted by the Fourier transform software into a spectrum of transmit-
tance against wavenumber. FTIR has several advantages over dispersive
systems, particularly in time saving, in improved resolution and accuracy
and in its ability to work over a greater range of infrared intensities.
Software allows the integration of the spectral intensity as a function of
time to give the total evolution profile as shown by IR (Gram-Schmidt
reconstruction) .
Non-dispersive infrared analysers using an infrared source compare the
IR intensity passing through a reference cell filled with a non-absorbing gas
with that passing the sample cell through which the evolved gas flows. The
detector cells are filled with the gas to be detected. The difference in
absorption of IR relates to the concentration of IR-absorbing gas, e.g.
CO 2. Their use for EGA has been discussed by Morgan [41] and also their
application, with mass spectrometric and other EGA techniques to mineral
sciences [42].
Reflection techniques, such as attenuated total reflection (ATR), where
the sample is in contact with a prism of high refractive index, are useful and
Heated gas line Infrared

spectrometer
Furnace
Sample Heated
IR
cell
I"
Carrier
gas in
Figure 5.15 Schematic of a thermal analysis-infrared system.
minimise sample preparation. Thermal ATR units are now available so

that the sample spectrum may be measured as a function of temperature.
Diffuse and specular reflectance attachments have been adapted for
heating experiments.
The general arrangement of a thermal analysis unit combined with
infrared is shown in Figure 5.15.
5.5.2 Applications
AMMONIA EVOLUTION FROM MINERALS [43]
The evolution of gaseous ammonia from natural and synthetic ammonium-

containing minerals has been carried out by non-dispersive IR. The
minerals, in which the NH+ 4 ion has substituted for K+, were heated in a
furnace at 50 Klmin and the gases carried over to the IR by a carrier gas
stream flowing at 300 cm3/min.
Figure 5.16 shows the EGA traces for ammonia and water evolved from
NH4-illite up to 1000 °C in both pure N2 and mixed N 2/0 2 atmospheres.
The synthetic ammonium illite would have an ideal formula
NH4AIlSi3,AI)OlO(OHh- The decomposition profile shows that there are
two major losses, the first around 550°C where both H 20 and NH3 are
evolved, and the second, around 750°C, where the gas evolved is mostly
H 20.
This corresponds with the expected decompositions of the silicate-bound
ammonium:
V2[(NH4)2-0-] = NH3 + 0.5H2 0
followed by the hydroxyl water release:
[AI2(Si3,AI)OlO(OHh] = [xA1 20 3 + ySi0 2] + H 20
A word of caution should be noted here. The amount of NH3 detected
NH 4-ILLITE
...
2500,...------------, 2500-v------------,
'.··'...
n
{2OOO .. ·-
oS
§ 1500
~ E :
8
B1000 ·· ..
··- ..
..
~
f·······.. ............
~5OO .: ....
........... ........ ........
."
O+-~~+-~r-r-r-~~ O+-,...-,...-~~r-~~~~
o 100 200 300 .ao 500 &00 700 800 goo 1000 o 100 200 300 400 500 &00 700 800 goo 1000
r ....peI.lUt. ('C) T.mperatur. !'C)
Figure 5.16 Evolved gas profiles for ammonium illite; 20 mg samples, in N2 (left) and
N2/02 atmospheres. NH3 (full line) and H 2 0 (dotted line) [43].
by integrating the EGA peaks is sometimes less than the theoretical, while
the amount of H 20 is higher. It is likely that partial oxidation of the
evolved NH3 to nitrogen and water is responsible for this discrepancy.
POLY(VINYL CHLORIDE) (FIGURE 5.17 a-e)
The detection of HCl and other gases from heated PVC by TG-FTIR
confirms the evolution of HCl and of benzene over the first peak of the
DTG (Figure 5.17). The infrared spectrum in the region ofthe second peak
suggests a complex mix of hydrocarbons and carbonyl compounds. The
final weight loss around 800 °C gives a spectrum corresponding chiefly to
carbon dioxide with some carbon monoxide. Since the run was performed
in nitrogen, oxidation would be minimal, and the temperature, weight loss
and residue suggest that there may be a considerable amount of inorganic
filler, possibly calcium carbonate.
For a blend of copolymer of vinyl chloride and vinyl acetate, the TG-
FTIR shows the evolution of HC1, of ethanoic acid (acetic acid) when
heated in nitrogen and the production of CO2 due to combustion in air at
high temperatures (Figure 5.18).
POLYESTER RESINS
Polyester resins of the general formula:

-[-O-RI-O-CO-R2-CO-O-RI-O-CO-R3-CO-]n-
I
[R4]m
I
105.7 TGAlIR
100.0
10.3 ~ __ ~ ____ ~ ____ ~
49.0 200.0 400.0 597.0

Temperature (C)
(a) weight loss versus temperature for PVC pipe
(b)
~
~
0
]
0.003 Evolved gases
-ti
'E
~
I
E
I!! 0.000
~ 0.0 20.0 30.0
(c) Scan time
Fig 17(aHc)
derived from a glycol HO-RcOH, an unsaturated diacid or R 2(COOHh,

and a saturated or aromatic diacid R 3(COOHh and cross-linked, generally
with styrene (R4), are widely used in construction, marine and engineering
applications, especially when reinforced with glass fibre. Their thermal
behaviour and fire-retardant properties are of great importance [45,46,47]
and the gases,evolved have been studied by trapping at low temperature,
by mass spectrometry and pyrolysis.
In a study of a polyester resin prepared from a brominated glycol, maleic
anhydride and phthalic anhydride and cross-linked with styrene, with 8%
of a zinc stannate fire-retardant additive, the TG was run with analysis of
the evolved gases by FTIR. The integrated (Gram-Schmidt) IR trace
followed the TG and DTG curves closely, and the collected IR spectra
showed the stages of decomposition. Figure 5.19 shows the TG and EGA
(Gram-Schmidt) curves and Figure 5.20 shows part of the infrared spectral
0.02
0.00
3300.0 3000.0 2500.0

(d)
Wavenumbers
0.01
Q)
g
i
.:( o.oo~"""'..,...'",.....
3300.0 3000.0 2600.0
(e) Wavenumbers
Figure 5.17 TG and FfIR curves for PVC degra . ''1. The rate of weight loss curve (b)
is mirrored by the evolved gas profile (c) and thr 'If HCI at 370°C (d), and the
hydrocarbon band at 3000 cm~1 at 515°C ··'red. (After [44aJ.)
record. The peak at 2350 cm- I is c N temperatures (or

times) an ester is evolved, probabl T used in the catalyst.
Between 200 and 320°C the rna' .alic anhydride, while
above 320 °c styrene is evolved Ie HBr, CO, CO2 and
other products. It is also possiblf mdow' and observe how
the evolution of carbonyl COT ,ear 1700 cm- I ) changes
during the analysis and to cop rum with reference library
spectra.
A study of the pyrolYf flame-retarded cotton and
polyester-cotton fabrics useD ~ A-EGA infrared analysis to
mass% TG
dm/dt
.. _-----,
DTG (a)
\ .... , ..-- --, ,..----
"
"._
\ \,/ '- , /
I t
'/
IJ i":
.~. \
,.... i
I
Gram-
Schmidt
(b) 1\
•• _ . _. __ J' ., ....... ..,.J"-'--___ . _.;
;
'\ ._.-.
200 400 600 600 1000 TI"C
(c)
T%
4000 3000 2000 1500 1000

-1
Wavenumber I em
Figure 5.18 TG-FTIR trace for PVC/PVAc copolymer. The DTG curve (a) and the
'infrared thermogram' (b) show the events clearly. The infrared spectrum (c) of the
gaseous products at the first TG loss (around 300 DC) shows the spectra of ethanoic acid
(acetic acid) and the HO band. (After [44b).)
study the profiles for evolution of CO, CO2 and H 20 heated in nitrogen
[48].
5.5.3 Gas chromatography and pyrolysis GC-FTIR
In many cases the gaseous products from heating real samples contain
many chemical species: for example, on heating a polyester resin (Figure
5.21), up to 20 major peaks and 160 minor ones! It is sometimes possible to
collect samples by trapping in a cold trap, or by adsorption on a suitable
solid (e.g. 'Tenax') and to desorb onto a gas chromatographic column.
'-. \
I
I
,
"
I \
/
~"-
mass % r I
\
Gram-
I r Schmidt
I \
I \
\
\
,
"
\
-'
I "-
/ "-
/
150 300 450 600 T/oe

Figure 5.19 TG and Gram-Schmidt plot for degradation of a polyester resin; 20 mg, 25
Klmin, nitrogen 100 cm 3/min (TG, fuJi line; Gram-Schmidt, dashed line).
Abs
0.03
0.02
0.01
-0.003\-_ _ _ _.--_ _ _ _ _ _ _ _- ._ _ _ _ _ _ _---'

3161.0 2000 858.3 Wavenumber / em-1
Figure 5.20 Stacked plot of part of the set of FTIR spectra recorded during the run of
Figure 5.19.
Another alternative is to pyrolyse the sample for a few seconds at a

selected temperature on a heated coil or ribbon and to sweep the products
immediately onto a GC column using the carrier gas. By using a series of
increasing temperatures the thermal degradation may be studied, although
r
temperature °C
400 1 .1
J~ A lJ,l II
II
i I II
3501 IL I dl
1
.1
300 1 1 GC response
250 j l J a
34 30 26 22 18 14 10 6
retention time: minutes
Figure 5.21 Pyrolysis gas chromatograms showing the effect of temperature on the
distribution of degradation products from a brominated polyester resin [46].
it is necessary to point out that there is a very great difference between a

retention time of a few seconds in a carrier gas stream and a time of several
minutes under thermal analysis conditions. This method has been com-
bined with FTIR and MS identification to give temperature-resolved
separation of products or simulated thermal analysis. The books by Jones
and Cramers [49], Irwin [50] and Vorhees [51] give many examples of the
applications of pyrolysis techniques.
5.6
Infrared product The examples quoted above illustrate that IR may be of great use for
analysis evolved gas analysis. The products or intermediates of a reaction may be
analysed by infrared spectrometry also. Modern FTIR instruments can
work well in both transmission and reflection modes. Samples may be
collected during a reaction and prepared for IR analysis in the usual ways
in order to follow the course of the reaction. Alternatively, the IR spectra
may be measured at various temperatures as the sample is heated in
a thermally controlled IR cell using either transmission or reflection
techniques.
5.6.1 Application to polymer samples
Mirabella [52,53] used an FTIR microscope to measure the transmission

IR spectra of polymer samples simultaneously with their DSC curves. He
2.5
<1>
g 1.5
~o
1:\
~
0.5
O'0i===~-=.--=::::;:::===;::=:::::~----r-
4000 3500 3000 2500 2000 1500 1000
Wavenumber
Figure 5.22 A series of transmission IR spectra at various temperatures during the

heating of an epoxy sample containing 100 parts resin and 35 parts of activator [54].
showed that the IR intensities may change during heating through a

physical change such as melting, and that degradation of a poly(vinyl
alcohol) sample could be studied isothermally and showed a reduction in
the hydroxyl band. Johnson et al. [54] measured the transmittance FTIR
spectra at various temperatures for an epoxy resin system using a similar
DSC-FTIR microscope system, and their results are shown in Figure 5.22.
Another technique is to reflect the IR from the surface of the sample in a
metal DSC pan and record the reflectance spectrum, although under
certain conditions this may give a reflectance IR spectrum that has a
different appearance with distorted band shapes. However, this may be
corrected using the Kramers-Kronig transformation [54].
The kinetics of polymerisation of epoxy resins have been studied by
FTIR and the results compared with the DSC cure [55,56,57].
5.6.2 Polymorphism
Some endothermic changes detected by DSC could be due to a chemical or

a phase change in the sample. In a comprehensive study of a pharmaceutical
precursor, p-hexadecylaminobenzoic acid (HABA), Reffner and Ferrillo [58]
used DSC, thermomicroscopy and FTIR microscopy. The first DSC trace
showed endotherms at 90, 105 and 123°C, but on second heating the first
peak appeared at 71 dc. Thermomicroscopy and IR showed that there
were three crystalline polymorphs, I, II and III. Form I changed to form III
at 90°C while form II changed at 71 DC, and form III melted to a liquid
crystalline material at 104-105 dc. The liquid crystal became a true liquid
at 123-124 DC. The IR spectra were measured at the temperatures at which
each form was stable, and although the spectra were very similar, minor
spectral differences could distinguish each phase.
5.6.3 Metal complexes
The changes that occur when metal complexes or metal organic com-
pounds are heated are often followed by IR. The disappearance of
characteristic IR bands, or the appearance of others, is a guide to the
decomposition.
For example, in a study of the low-temperature synthesis of BaBi0 3
using citrate complexes of barium and bismuth nitrates [59], the IR spectra
showed the ester formation around 185°C, loss of organics and BaC03
formation by 380°C and BaBi03 after prolonged heating at 850°C.
Similarly, the thermal decomposition of hydrated thallium(l) oxalates used
TG, DTA, X-ray and infrared to clarify the stages in the decomposition
[60].
5.7
Thermomicroscopy It is often true that analysts may ignore the microscope as a tool, but it is
also true that they may ignore heated stages and their methods [61]. It is
frequently easy to identify the course of reactions and the nature of
changes in physical properties by observation during heating.
Definition [18] Thermoptometry is defined as 'a family of thermo-

analytical techniques in which the optical property of the sample is
monitored against time or temperature, while the temperature of the
sample, in a specified atmosphere, is programmed'.
The observation of the sample under a microscope is thermomicroscopy,

which will be our chief concern in this section. If the light intensity is
measured, we can call it thermophotometry and if the method measures the
light emitted from the sample, the technique is thermoluminescence.
It is very useful if the light intensity transmitted through the sample and
system, or reflected from the sample, is monitored. Other refinements such
as image analysis, video recording of the images, spectrometry and DSC
have all been added to the basic hot-stage microscope, as shown in Figures
5.23 and 5.24.
The sample in the heated stage may be illuminated by plane polarised
light using a polarising filter. If the sample is the same in all directions - for
example, an isotropic liquid or a cubic crystal - it will not alter the
polarisation.
Liquid crystals and solids of other crystalline systems will convert the
light into elliptically polarised light due to differences in refractive index in
the different directions and produce interference colours, characteristic of
the sample. At a phase transition temperature, a change in the polarisation
,---,------,- - - - - - - - - I
~
We®
e.
Monit FP90
Tape recorder
Flgure 5.13 Mettler thermo-optical station including 1, microscope; 2 and 3, video

cameras; 4, photomonitor; 5, camera; 6, handset [62].
(a)
~
~
r ! Microscope objective
,l;)TAlDSC sensor with glass pans
SMa fumaoe ..... Pt100
Heat protection filter
Inner casing. warm
Cooling air
/ Outer casing. cold
~'ZZZZ2:zzzz:<1===/l~rp::t~
~ . rOTA/OSC signal
:}.".z.::7,; . ",,,,~J.J~
I ~. - - - - - - Protection glass
(b) 0--- Light sourCe of microscope
F1gure 5.24 (a) Linkam THMS 600 series heating and freezing stage, showing sample
preparation [63]; (b) Mettler FP 84 DSC hot stage [62].
will occur. The colours observed and the light intensity will also change at
the transition. If the eyepiece has a polariser set at 90° to the polarising
direction of the first filter ('crossed polars'), the changes may be seen most
easily. Before melting, most crystals show as a regular, coloured pattern.
After melting, the liquid appears black, since the light is completely cut off
by the crossed polars.
r------+I amplifier
CdS
photoconductive
cell
microscope
modified 3 - channel
cover
recorder
Perkin Elmer
DSC 1- B -
controller
.......- - - - - amplifier
Figure 5.25 Combined DSC-reflected light intensity apparatus.
Thermomicroscopic equipment is available to work from -180°C to well

above 2000 DC. Polarised light hot-stage microscopy work is designated
by several sets of initials: thermal depolarisation analysis (TDA) [64], de-
polarised light intensity (DU) [65], or thermo-optical analysis (TOA) [66].
Charsley et al. [67] have described a reflectance unit which has been used
to study pyrotechnic reactions. Haines and Skinner [68] modified the
Perkin-Elmer DSC 1-B to record the light reflected from the sample cell,
as shown in Figure 5.25.
The use of thermomicroscopy simultaneously with DSC or DTA adds
significantly to both techniques [69,70]. Rapid progress has been made in
microspectrometry, and both Fourier transform IR (FTIR) and Raman
microscopes incorporating heating or cooling stages are now widely used
[71,72,73].
5.7.1 Applications
The applications of thermomicroscopy cross the entire range of materials

from alloys, ceramics and minerals through foods, biomaterials and liquid
crystals to pharmaceuticals, plastics and pyrotechnics. Examples will be
chosen here to highlight the use of simultaneous thermomicroscopy-DSC/
DTA.
5.7.2 Phase equilibria
The melting behaviour and purity of materials has been discussed in

Chapter 3, but direct observation of the nature and extent of the melting
may be made by thermomicroscopy. An estimate of the fraction melted
may be made visually, or from measurements of the transmitted light trace,
to complement the DSC measurements. Wiedemann and Bayer [74]
describe an interesting application to azobenzene, which gradually trans-
formed from the cis-isomer to the trans-isomer under illumination. Simul-
taneous thermomicroscopy-DSC has also been used to show that the
double peaks on the DSC trace for tetratriacontane (~H7o) are due to a
solid-solid transition at 69 °C followed by melting at 73 °C.
Barrall and Gallegos [75] used depolarised light intensity and DTA
separately to record the phase behaviour of ammonium nitrate and
polymers and compared the traces. Later workers have confirmed this
behaviour using simultaneous measurements. The glass transition behaviour
and stress relaxation of polymers and their blends has been studied by
TOA and DSC [66] and considerable work has been done on the
crystallisation rates of thermoplastic polymers [76,77]
Liquid crystals need to be studied by both DSC and thermomicroscopy,
and the combined technique gives the greatest benefit [78]. A compound
having a single nematic phase, such as p-azoxyanisole has two transitions.
The crystal-nematic change gives a large DSC peak, but a small change in
transmitted light (Figure 5.27). The nematic-isotropic change gives a small
DSC peak, but a much larger optical change, as shown by the photograph
in Figure 5.26.
Wiedemann [79] used this method to study the more complex phase
behaviour of OOBPD (N,N' -bis(4--octyloxybenzylidene)-p-phenylenediamine)
and Haines and Skinner [68] have shown that DSC with reflected light
measurement can be used for phase studies.
Welch described the adaptation of the thermocouple as a sample holder,
as well as a temperature sensor and heater [SO], and Miller and Sommer
[SI] incorporated this principle into a DTA unit, using it to study the
polymorphism of lithium and sodium sulphates.
High-temperature applications to inorganic compounds are described by
Schultze [S2] who recorded the DTA curve and simultaneously observed
the congruent melting behaviour of LiBi(P03)4 and the subsequent
formation of a glass on cooling.
The application of thermomicroscopy to pharmaceuticals is discussed
fully in an excellent, well-illustrated book by Kuhnert-Brandstatter [83].
Polymorphic changes within crystal systems mean that the crystal dimen-
sions, types and structures change, and each different form interacts with
polarised light in a characteristic way. A change from one crystal form to
another is observed as a spread of altered shapes and colours of crystals
across the field. Enantiotropic forms show distinct crystal habits. It is also
(a) (b)
(c)
Figure 5.26 Polarised light microscope photographs of p-azoxyanisole heated to (a) 9O·C
(crystal), (b) 130°C (nematic) and (c) 135 °C (nematic going to isotropic liquid).
possible to investigate eutectic formation and refractive index by thermo-

microscopic methods.
Wiedemann and Smykatz-Kloss [84] used the whole range of thermal
analysis techniques (TG, DTA, TMA, TOA and MS) to study the phase
transitions and losses of thenardite, Na2S04, from various sources, and
show the effects of sample composition, previous treatment and heating
and the importance of thermomicroscopy in recognising the phase changes.
The light intensity transmitted or reflected by the sample may be recorded

continuously during heating. This has the advantage, shared with TG, that
l
EXO
Heat
Flow
ENDO
!
t ,i-- -" - "
Increase
- -- ---- _...' ,
I
Light I
intensity
\_-------
150 T/oC
Figure 5.27 DSC (full line) and transmitted light intensity curves with crossed polars, for
p-azoxyanisole (15 mg, 16 Klmin, static air).
such changes are additive, and may indicate small, low-energy changes too
small to register on DSe. In studies of reactions where the samples may be
opaque, or may become so during reaction, there are advantages to using a
reflected light system. Wendlandt describes a full system for dynamic
reflectance spectroscopy [85] and surveys the applications, particularly to
complex compounds. He points out that 'unlike TG or DTA, dynamic
reflectance spectroscopy can be used to monitor only a single reaction at a
time, thus eliminating the effect of reactions occurring simultaneously'.
5.7.4 Hydrated salts
Using simultaneous DSe and reflected light intensity (RLI), Haines and
Skinner [68] showed how the decomposition behaviour of manganese
formate dihydrate, Mn(OOe.H)2·2H20, may be followed. Figure 5.28
illustrates the changes recorded. Loss of hydrate water around 130°C
changed the crystals from translucent to opaque, and decomposition to
manganese oxides, mostly brown MnO, occurs around 300 °e. The extra
change shown by a decrease in RLI at 200 °e was shown by electron
microscopy to be due to the cracking of the anhydrous formate.
Similar traces may be obtained for copper sulphate pentahydrate and for
gypsum [86]. The dehydration of magnesium nitrate hexahydrate is more
complex since initially the sample becomes liquid on heating to about
100 °e, and then the water bubbles off giving 'spiky' DTA and RLI traces,
t
EXO
Heat
Flow
ENDO
!
t
~-"-,
I ,
____ I '_,
Increase "
"
Reflected
light
intensity
\
\
,,
\
\
\
\
\
.... _---
150 250 350 T/OC
Figure S.28 DSC (full line) and reflected light intensity curves for manganese formate
dihydrate (5 mg sample, 16 Klmin, static air).
until the anhydrous solid is formed around 250 DC. Fusion and decompo-
sition to the oxide follow above 400 DC [87).
The ability to observe reactions and simultaneously to record the
thermal traces has been important in the study of pyrotechnics [88], glasses
and ceramics [89,90] and in elucidating the mechanism and kinetics of
processes.
5.8
X-ray methods The analysis of solid products may be carried out by chemical methods, but
this does not reveal the structures - crystalline or otherwise - of the
material. Polymorphic forms of the same material may give the same
chemical analysis, but have very different structures and properties. X-ray
analysis will reveal those structures and hence aid in the identification of
the stages of reactions studied by thermal methods.
The diffraction of X-rays by a regular crystal lattice obeys the Bragg
equation:
nA = 2d sin 9
where n is an integer, Ais the wavelength of the X-rays, d is the spacing of
the crystal planes and 9 is the angle of diffraction.
, (313)Fe:p4
(400)Fe :P4
(110)a-Fe (333) Fe :P4 (440)Fe:p4 (200)a-Fe
/ T/oC
550
510
470
430
20 A....- 390
350
O~~~~ __- J_ _ ~_ _ - L__~__~__~__~__~___
~
27 31 35 39 43 47 51 55 59 63 67
28. grad
Figure 5.29 Selected X-ray diffraction patterns of the high-temperature corrosion of steel.
Copper-Ka radiation.
The technique of X-ray powder diffraction [27] is particularly suited to

the small samples used in thermal analysis techniques, and the powder
diffraction patterns are indexed in a comprehensive set of tables [91].
Typically, the pattern is produced by the use of a collimated, monochromatic
X-ray beam striking a powdered sample and producing a diffraction
pattern, recorded photographically or electronically, which shows a series
of sharp lines of characteristic intensity as a function of the angle 6, as
The lines may be indexed according to the Miller indices of the crystal
planes and/or the chemical species producing them, as shown in Figure
5.29. The X-ray pattern may be obtained using the reactant and products
isolated after the reaction, or, as in Figure 5.29, the diffraction patterns can
be obtained while the samples are heated and cooled in a programmed
way. The X-ray diffractometer may be combined with a low- or high-
temperature device to give a temperature resolved X-ray diffraction
(TRXRD) unit [93].
Wide angle X-ray diffraction (WAXD) or wide angle X-ray scattering
(WAXS) can be used in a similar way to powder diffraction to obtain a
radially symmetrical, one-dimensional diffraction pattern from which the
structure may be indexed according to Bragg's law.
X-rays are more strongly scattered by atoms of high atomic mass, and
many applications involve inorganic reactions. Modem techniques also
allow the study of organic and polymer systems. In small angle X-ray
scattering (SAXS) the X-rays are scattered by regions with different
electron densities. This provides a very good technique for studying the
morphology of multiphase polymers, and it is often used in combination
with DSC.
5.8.1 Applications
CORROSION OF STEEL [92]
The oxidation of steel in air is a complex solid/gas reaction, and layers of

Fe203, Fe304 and FeO may grow on the Fe surface. The reactions should
be studied as they occur and TRXRD gives the series of X-ray diffraction
patterns shown in Figure 5.29. The patterns show that the main bulk of
product at temperatures up to 550°C is Fe304 and the formation of Fe203
and FeO is negligible. The kinetics of the reaction may be studied by TG
and fit a parabolic oxidation law.
SYNTHESIS OF TOPAZ [94]
The reaction of Al20 3 and Si02 in the presence of ammonium fluoride will
produce topaz AI2(Si04)(OH,F)z under certain conditions. The thermal
analysis curves for a mixture of corundum (natural AI20 3), quartz (Si0 2)
and ammonium fluoride (NH4F) in the ratio 1 : 1 : 6.4 are shown in Figure
5.30(a), and the X-ray diffraction patterns of the products at various
temperatures are given in Figure 5 .30(b). This complicated synthesis is
shown to occur in at least four stages.
1. About 150°C: Endothermic reaction of the corundum and quartz
with the ammonium fluoride to produce complex fluorides:
Al20 3 + Si02 + 18NH4F ~ 2(NH4)3AIF6 + (NH 4hSiF6 + 10NH3
+ 5H20
2. About 230°C: Endothermic decomposition of the complex aluminium
fluoride:
(NH4hAIF6 ~ NH4AIF4 + 2NH3 + 2HF
3. At 340°C: A sharp decomposition of the complex fluorides and
volatilisation of products:
(NH4hSiF6 + NH4AIF4 ~ SiF4 + AIF3 + 3NH3 + 3HF
Figure S.30 (a) Thermal analysis curves for the reaction of corundum-quartz-ammonium
fluoride mixture of ratio 1:1:6.4. 500 mg, 10 K1min. (b)-(d) X-ray diffraction patterns of the
products of the above reaction at (b) 155°C, (c) 240 °C and (d) 800 °C. Cu-Ka radiation. A =
NH4A1F4, B = (NH4)zSiF6, C = (NH4hA1F6' T = topaz, Q = quartz, Cor = corundum.
(a)
CB
NaCI
(3
(b)
20
B
NaCI
B
!
(e)
!
60 65
A1F3
T T
T
T
T A1F3
A1F31 T A1F3
TrTJ.'TTTT 'TT
,
w.J , .... JII..JJ..
, I
50 55 60 65
Fig 3O(a)-(d) (d)
29
4. At 800°C: A broad endotherm corresponding to the reaction of
excess quartz to form topaz:
Si02 + 2AIF3 + 4H20 --7 AllSi0 4)(OH,Fh + 4HF + H2
At higher temperatures, the topaz may dissociate to corundum and lose
SiF4 •
FIRE-RETARDANT REACflONS [95]
Fire retardants (FR) for polymers may act in several ways. The additive
itself may be the chief fire retardant, for example by vaporising into the
flame and quenching it or by undergoing endothermic decomposition to
cool the reaction. Reactive monomers, such as halogen-containing diacids
in polyester resins, may be both part of the polymer and also the chief
producer of flame-quenching species. Other additives, particularly in-
organic oxides such as Sb20 3 and Mo03, may act by intermediate reactions
with the polymer to produce less flammable products or flame-quenching
species. Investigation of the behaviour of molybdenum trioxide in polyester
resin systems showed that it acted as an excellent FR, especially in the
presence of halogen-containing species. Thermal analysis showed that in
air, the Mo03 remained after degradation of the polymer, until it sublimed
at around 750°C. Evidence of reduction to Mo0 2 was found in air above
300 °C, and in nitrogen the residual carbon in char reacted to give
molybdenum carbide (see Figure 5.31).
POLYMER STRUCTURE
The powder diffraction pattern of polymers may be used in their identifica-

tion; for example, the two crystalline forms of polyethylene can be
distinguished by their patterns and polymer crystallinity can be estimated
[96].
Conventional methods of obtaining small angle X-ray scattering (SAXS)
and wide angle X-ray diffraction (WAXD) data may require long exposure
times to obtain good results, and are limited to materials that are stable
over this time scale. To get good X-ray patterns over a range of
temperatures requires special apparatus capable of containing the sample
and allowing passage of X-radiation. In order to combine X-ray methods
with DSC a high flux of radiation and a fast detector must be used.
Koberstein and Russell [97,98] used synchrotron radiation as the X-ray
source and a Mettler DSC modified to allow transmission of X-ray
radiation plus a fast, position-sensitive electronic detector to obtain DSC/
SAXS and DSC/wAXD results. They studied low-density polyethylene
and thermoplastic copolyurethanes and found that there were semi-
crystalline segments and amorphous soft segments.
1001--........
, ,,
,,,
,,
,,
, I
f- 50 I
!
I
I
,,
I
I
,
\
900C
----------------t
'- 10% Br 4.8%Mo 0
o - - - - - - - 10% Br
100 300 800
(a)
(a) Residue in air above 550°c
M003
IT
(b) Residue in N2 above 550°c

Mo02
(c) Residue in N 2 above 900°c
(b) 20 30 40 50 60
Figure 5.31 (a) TG curves for a brominated polyester, alone (full line) and with added
Mo03 (dashed line). 10 mg, 10 Klmin, nitrogen at 6 cm 3/min. (b) X-ray diffraction curves
for the molybdenum-containing residue from heating the polyester in air and nitrogen.
Cu-Ka radiation.
~
curved detector-WAXD qUadra: deltector_sAXS
-- -- --
Be ------:-
I _---
' ' 'boom

) -- 'I' >
beam-stop I
Linkam hot-stage
Figure 5_32 Schematic of the arrangement used for simultaneous SAXS and WAXD (99).
Ryan [99] has used synchrotron radiation monochromated to give a pinhole

beamline of wavelength 0.152 nm and a quadrant detector for SAXS and a
curved detector for WAXD covering 7(1' of arc, as shown in Figure 5.32.
Recently, this has been combined with a DSC of single specimen design so
that simultaneous SAXS-WAXD-DSC information may be obtained.
The measured scattered intensity I(q) is a function of the scattering
vector q, which has units of (lengtht\ and is defined by
q = (4-rr/'A)·sin(eJ2)
where E is the scattering angle. The Lorentz correction may be applied to
the intensity data because of the lamellar nature of a sample such as
polyethylene to give the function Iq2. The peak obtained on the curve of
Iq2 against q curve will give the domain spacing, d, from Bragg's law:
d = 2-rrlqpeak
The intensity may be converted to the invariant Q by the equation:
Q = f I(q)·q2 dq
or to a 'relative invariant' from Q' from the area under the Iq2 vs q curve
between the first reliable data point (q= 0.01 A. -1) to the region where Iq2
becomes constant, that is at q= 0.20 A.-\ as shown in Figure 5.33.
The W AXD patterns of high-density polyethylene (HDPE) are given in
Figure 5.34 as a function of temperature. They show the sharp diffraction
due to crystallites in the region 8(}-120 °C which broadens as the melting
point is approached, until at 2 K above the melting point the pattern
becomes that of an amorphous liquid.
The relative invariant Q' and its differential with respect to time (dQ'Idt)
are shown in Figure 5.35 along with the DSC curve obtained simultaneously.
The Tg is not observed in the SAXS patterns, but the temperature
correlation of the crystallisation and melting events between the SAXS and
DSC data is readily observed.
5.9
Electron microscopy The very high magnifications possible with transmission electron micro-
and associated scopy (TEM) and the excellent depth of field that can be achieved with
techniques scanning electron microscopy (SEM) make them most useful tools for
o 0.1 0.2
o
alA
Figure 5.33 Plots of the intensity I and the Lorentz connected intensity Iq2 for a
semicrystailine sample of HDPE plotted versus the scattering vector q [99].
./'
~
_----
...........
Temperature
Figure 5.34 WAXD patterns of HDPE as a function of temperature. Numbers next to

the lowest curve correspond to the Miller indices of the orthorhombic crystal [99].
examining the solid products from thermal analysis experiments. If the

electron microscope is also equipped to analyse the X-ray spectrum
produced from the sample by the electron impact - for example, by energy
o o
o
Q'
dQ'/cIt
-.••
• •• "",.~ .
.................. .". • ....
DSC •• •
•
•
••
50 100 150 200 250 300

T /oC
Figure 5.35 Combined SAXS patterns of the DSC for poly(ethylene terephthalate). The
relative invariant Q' (open circles), its derivative with respect to time, dQ'/dt (filled
circles) and the DSC plot are compared [100].
dispersive analysis of X-rays (ED AX) - then this will give an elemental
analysis of the sample [2].
These techniques have been widely used as complementary methods to
thermal analysis; for example, Galwey [101] has used SEM to characterise
the kinetics and mechanism of solid-state reactions, and Reller et al. [102]
have investigated the morphological changes in jadeite, NaAl[Si20 6] and
nephrite, Caz(Mg,Fe )5[(OH,F)Si40 11 h.
5.10
Conclusion Thermal analysis techniques may be combined together with great advan-
tages in time, sample and interpretation, but it is most necessary to use
other analytical methods to confirm the identity of the intermediates and
products that occur during the thermal processes.
5.11
Less common thermal Several other techniques of thermal analysis are used to measure particular
analysis techniques properties as a function of temperature or time. The definitions are given
below and the references give a description or review of these methods and
some of their applications, and additional information may be found in the
general reference texts listed at the end of Chapter 1. A special edition of
Thermochimica Acta (1987, volume 110) was devoted to reviews of less
common methods.
EMANATION THERMAL ANALYSIS (ETA)
A technique in which the release of trapped (usually radioactive) gas from

the sample is monitored. [V. Balek, Proc. 7th ICTA, Wiley, Chichester,
1982, p. 371; Thermochim. Acta, 1987, 110, 222.]
THERMOLUMINESCENCE (TL)
A technique in which the light (thermoluminescence) that is emitted from

the sample is monitored. [T. Calderon et al., Thermochim. Acta, 1988, 133,
213.]
THERMOMAGNETOMETRY
A family of thermoanalytical techniqes in which a magnetic property of the

sample is measured. [R. Moskalewicz, Thermochim. Acta, 1979,28,229;
S. St J. Warne, P.K. Gallagher, Thermochim. Acta, 1987, 110,269; P.K.
Gallagher et al., 1. Thermal Anal., 1993,40,1423.]
THERMOSONIMETRY
A technique in which the sound emitted by the sample is monitored. [K.

L0nvik, Proc. 4th ICTA, Budapest, 1974, Vol. 3, p. 1089; Thermochim.
Acta, 1987,110,253; S. Shimada, 1. Thermal Anal., 1993,40,1063.]
5.12
1. You are presented with a VERY small sample of material and asked to Problems
characterise it. What methods would you choose? If thermal data (Solutions on p. 280)
were required, which simultaneous thermal methods might be most
appropriate?
2. A sample of polymer was analysed by simultaneous TG-DTA. The
thermal changes that might occur are: (a) glass transition; (b) plasticiser
loss; (c) residual curing; (d) crystallisation; (e) melting; (f) oxidation;
and (g) degradation. Which of these would be detected by DTA and
which by TG?
3. A sample of an impure brick clay was heated in air to 900 °C and the
evolved gases analysed by an infrared method. If the sample contained:
(i) a clay (AI 20 3)x'(Si02)y'(H20)z
(ii) gypsum, CaS04·2H20
(iii) calcite, CaC03
(iv) organic matter and
(v) pyrite, FeS2
account for the EGA peaks due to H 20, CO2, CO and S02.
4. A sample of calcium hydrazidocarbonate, Ca(N2H3COO)2·H20, was
heated in argon to 950°C and the evolved gases studied by mass
spectrometry. The losses corresponded as follows:
(a) at about 100 °C to a peak in the mlz = 18 trace;
(b) at about 350°C to large peaks for mlz = 17,28, and small peaks for
mlz = 44 and 18;
(c) at about 850°C to peaks for mlz = 28 and 44.
Suggest explanations for these observations.
5. During microscopic observation in a DSC run, a sample of a crystalline
inorganic salt was found to undergo the following changes:
(a) at 55°C there was a colour change from blue to green and a sharp
endotherm appeared on the DSC;
(b) at 110°C the crystals became opaque green and a broad DSC
endotherm appeared peak;
(c) at 180°C the colour changed again to brown and a large DSC
endotherm.
Are these changes consistent with each other? Suggest an explanation
for each observation. Would TG help?
6. Tristearin was studied by DSC in Chapter 3. A parallel thermomicro-
scopy study showed that using polarised light with crossed polars, the
depolarised light intensity during heating
(a) decreased nearly to zero around 56°C then
(b) increased to more than its initial value at 62°C and
(c) decreased again to zero at 75 °C.
Explain these observations, using the comments in Chapter 3.
7. (a) The decomposition of zinc oxalate dihydrate, ZnC20 4·2H20, was
shown by TG and DTA to occur in two stages with a loss of mass of
about 19% by 200 °C and a total loss of 57% by 400 °C. If we
suggest the reactions as:
(i) ZnC20 4·2H20 ~ Zn~04 + 2H20 and
(ii) ZnC20 4 ~ ZnO + CO + CO2
how could we identify both gaseous and solid products?
(b) An oxide gel formed by precipitation gave only a diffuse pattern on
X-ray diffraction. On heating on a DTA it gave an exothermic peak
at 640°C and the product from heating gave a series of sharp lines
on the XRD. Why?
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2. F.W. Fifield, D. Kealey, Principles and Practice of Analytical Chemistry (3rd edn),
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12. F. Shafizadeh, Adv. Carbohydr. Chem., 1968, 23, 419.
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14. W.K. Tang, W.K. Neill, J. Polym. Sci. (C), 1964,6,65.
15. G. Stevens, Fire & Materials, 1983, 7, 173.
16. J.J. Pitts, Flame Retardancy of Polymeric Materials, Vol. 1 (ed. W.C. Kuryla, A.J.
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17. J. Hider, Int. Labmate, 1990, XVII (VI), 9.
18. J.O. Hill, For Better Thermal Analysis and Calorimetry (3rd edn), ICTAC, 1991.
19. I.e. McNeill, J. Polym. Sci., Polym. Chem. Edn., 1977, 15, 381.
20. I.C. McNeill, European Polym. J., 1970, 6, 373.
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22. A.J. Diefenderfer, Principles of Electronic Instrumentation, Saunders, Philadelphia,
1979.
23. P.K. Gallagher, E.M. Gyorgy, W.R. Jones, J. Thermal Anal., 1982,23, 185.
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25. A.R. McGhie, J.D. Denuzzio, G.e. Farrington, Proc. 14th NATAS Cont, 1985.
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27. D.A. Skoog, D.M. West, Fundamentals of Analytical Chemistry, Holt-Saunders, New
York, 1982, p. 453.
28. E. Clarke, Thermochim. Acta, 1981, 51, 7.
29. E. Kaisersberger, W.-D. Emmerich, Proc 7th ICTA, Wiley, Chichester, 1982, p. 279.
30. P.A. Barnes, Proc. 1st ESTA, Heyden, London, 1976, p. 31.
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Oxford, 1981, p. 144.
36. J. Chiu, Thermochim. Acta, 1970, 1, 231.
37. J.A.J. Jansen, W.E. Haas, H.G.M. Neutkens, A.J.H. Leenen, Thermochim. Acta.,
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38. L.F. Whiting, P.W. Langvardt, Anal. Chem., 1984,56,1755.
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41. D.J. Morgan, J. Thermal Anal., 1977, 12, 245.
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43. S. Inglethorpe, D.J. Morgan, J. Thermal Anal., 1993,40,29.
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45. P.J. Haines, T.J. Lever, G.A. Skinner, Thermochim. Acta, 1982,59,331.
46. G.A. Skinner, P.J. Haines, T.J. Lever, J. Appl. Polym. Sci., 1984,29,763.
47. P.A. Moth, PhD Thesis, Kingston University, CNAA, 1992.
48. D. Price, A.R. Horrocks, M. Akalin, Anal. Proc., 1990,27,148.
49. e.E. Jones, e.A. Cramers (eds), Analytical Pyrolysis, Elsevier, Amsterdam, 1977.
50. W.J. Irwin, Analytical Pyrolysis, Marcel Dekker, New York, 1982.
51. K.J. Vorhees (ed.), Analytical Pyrolysis, Butterworth, London, 1984.
52. F.M. Mirabella, Appl. Spectr., 1986,40,417.
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54. D.J. Johnson, D.A. Compton, P.L. Canale, Thermochim. Acta, 1992, 195, 5.
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57. J.M. Barton, Adv. Polym. Sci., 1985,72,111.
58. J.A. Reffner, R.G. Ferrillo, J. Thermal Anal., 1988,34,19.
59. G.K. Chuah, S. Jaenicke, K.S. Chan, S.T. Khor, J.O. Hill, J. Thermal Anal., 1993,40,
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60. S.R. Sagi, M.S. Prasada Rao, K.V. Ramana, Proc. 7th ICTA, Wiley, Chichester, 1982,
p.499.
61. W.e. McCrone, Proc. 1st ESTA, Salford, Heyden, London, 1976, p. 63.
62. H.G. Wiedemann, J. Thermal Anal., 1993,40,1031.
63. Linkam Scientific Instruments, THMS 600 Brochure.
64. G.W. Miller, Analytical Calorimetry, Vol I, Plenum, New York, 1970, p. 397.
65. E.M. Barrall, J.F. Johnson, Appl. Polym. Symp., 1969,8,191.
66. A.J. Kovacs, S.Y. Hobbs, J. Appl. Polym. Sci., 1972, 16, 301.
67. E.L. Charsley, A.C.F. Kamp, Proc. 3rd ICTA, Davos, Birkhauser-Verlag, Basel, 1972,
1,499.
68. P.J. Haines, G.A. Skinner, Thermochim. Acta, 1982, 59, 343.
68. H.G. Wiedemann, G. Bayer, Thermochim. Acta, 1985,85,271.
69. E.M. Barrall II, J.F. Johnson, Thermochim. Acta, 1972,5,41.
70. G. Arneri, J.A. Sauer, Thermochim. Acta, 1976, 15, 29.
71. D.A. Clark, G. Nichols, Anal. Proc., 1990,27,19.
72. M. Bowden, D.J. Gardiner, G. Rice, D.L. Gerrard, J. Raman Spec., 1990, 21, 37.
73. B. Cook, Analytical Applications of Spectroscopy II (A.M.C. Davies, C.S. Creaser,
eds), RSC, Cambridge, 1991, p. 61.
74. H.G. Wiedemann, G. Bayer, Thermochim. Acta, 1985, 92, 399.
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76. F.L. Binsberger, B.G.M. de Lange, Polymer, 1970, 11,309.
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79. H.G. Wiedemann, Mettler Application No. 805.
80. J.H. Welch, J. Sci. Inst., 1954, 31, 458.
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82. D. Schultze, Thermochim. Acta, 1979,29, 233.
83. M. Kuhnert-Brandstatter, Thermomicroscopy in the Analysis of Pharmaceuticals,
Pergamon, Oxford, 1971.
84. H.G. Wiedemann, W. Smykatz-Kloss, Thermochim. Acta, 1981,50,17.
85. W.W. Wendlandt (ed.), Modern Aspects of Reflectance Spectroscopy, Plenum, New
York, 1968, p. 53.
86. K. Heide, Thermochim. Acta, 1972, 5, 11.
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The general reference texts given in Chapter 1 contain much material. One other text is very Bibliography
relevant to this chapter:
W. Lodding (ed.), Gas Effluent Analysis, Arnold, London, 1967.

6 Problem solving and
applications of thermal
methods
Introduction In industry and in academic research and teaching, thermal methods are
used most frequently to solve problems, or to aid in their solution together
with other analytical techniques. It is the aim of this chapter to illustrate
typical problems and to suggest the thermal methods that may help in their
solution or in the understanding of the phenomena that cause the problem.
Many of the problems have arisen in the course of recent research in
chemical and engineering laboratories. Some occurred in industry or
consultancy where the problem had to be solved as quickly and as
completely as possible.
Table 6.1 An overview of some of the papers presented at 10th

ICfAC, Hatfield, England, August 1992
Environmental
Agricultural residues Ancient mortars
Carbonate minerals Coal and other fuels
Conservation Fly ash
Geological materials Oil recovery
Zeolites
Polymers
Aromatic polymers Bismaleimide resins
Copolymers Degradation of polymers
Epoxy resins Flame-retardant polymers
and many more!
Pharmaceuticals and fine organics

Dextran Erythrocytes
Fatty acid esters Liquid crystals
Organoplatinum anti tumour agents Proteins
New materials
Carbide synthesis Catalysts
Ferro-electric polymers Lithium germanate glasses
Pyrochlores Semi- and super-conductors
Thin films
PROBLEM SOLVING AND APPLICATIONS OF THERMAL METHODS 207
The range of application of thermal methods is now enormous! A survey

of the papers presented at the 10th ICfAC Conference in 1992 shows how
widely these techniques are now applied (Table 6.1).
In some cases, the thermal method has been well enough established
that it is now used as a standard test method - for example, as one of the
ASTM test methods. Several of these will be illustrated.
For comparison purposes, the problems have been grouped according to
the materials being studied. The problems are presented in sequence and
are followed by the suggested solutions. While these solutions are con-
sidered as the most probable answers in view of the evidence presently
available, it is, of course, possible that later work will reveal that a
different interpretation should be used. The original references should be
consulted wherever possible.
The conditions used for the thermal analysis runs are stated in each case,
and where a change in sample mass, atmosphere or rate of heating is
known to make a difference to the interpretation, this is noted.
Section 6.1 Inorganic materials List of examples

6.1.1 Tin(II) formate decomposition (TG, DTA, EGA, HSM)
6.1.2 Mixtures of carbonates (TG)
6.1.3 Strontium nitrate decomposition (TG-MS)
6.1.4 Calorimetry and phase transitions of potassium nitrate (DSC)
6.1.5 Decomposition of barium perchlorate (TG, DTA)
6.1.6 Solid-state reactions (DTA)
Section 6.2 Polymeric materials

6.2.1 Characterisation of a polymer (DSC, TG, DMA)
6.2.2 Polymer blend analysis (DSC)
6.2.3 Kinetic studies of polymer cure (ASTM 698)
6.2.4 Polymer decomposition studies (TG-MS)
6.2.5 Oxidative stability of polymers (DSC)
6.2.6 Studies of an epoxy-glass composite (DMA)
6.2.7 Characterisation of a thin adhesive film (DETA)
Section 6.3 Fine chemicals and pharmaceuticals

6.3.1 Purity determination (DSC)
6.3.2 Phase diagrams of organic chemicals (DSC)
6.3.3 Liquid crystal studies (DSC, TO A)
6.3.4 Stability and polymorphism of pharmaceuticals
6.3.5 Dynamic mechanical analysis of foods products
Section 6.4 Other materials

6.4.1 Carbon oxidation (TG)
6.4.2 Proximate analysis of coals (TG)
6.4.3 Oil testing (DSC, thermomicroscopy)
6.4.4 Soil analysis (TG)
6.4.5 Catalyst studies (TG, DSC, etc.)
6.4.6 Survival of Antarctic micro-arthropods (DSC)
Problems
Caution In the solutions to all the following problems, and in the many
other areas for which thermal methods have proved so useful, there are
certain 'Cautionary Notes' that should be taken into consideration on
every occasion.
1. The history of the samples and their preparation are very important.
Ground samples, especially if they are mixtures, may behave very
differently from 'chunky' samples.
2. The run conditions are most important for reproducibility and interpre-
tation. SCRAM!
3. The computing methods used may be a great help, but we should also be
aware of the pitfalls they can present:
(a) A noisy trace may be a suggestion of instrumental problems which
should be investigated. Excessive computer smoothing will not only
remove the noise, but also any small signals!
(b) Using the computer to increase the sensitivity may be overdone.
The onset temperature for, say, an oxidation of an oil could be per-
ceived as lower than before, simply because smaller changes are
detected. A threshold value for the change might be a better approach.
(c) Computers will do exactly what you tell them! If we propose that a
certain change is an 'nth order' reaction, the computer will sort out
the data to give a best fit, and tell you that 'n = 4.321' even though
this may be a meaningless figure!
6.1
6.1.1 Tin(II) formate decomposition Inorganic materials
(For solutions, see p. 245 and Reference 1)
Tin(II) formate (or tin methanoate) was prepared by reftuxing
tin (II) oxide with aqueous formic acid under a nitrogen atmosphere
for several hours, and then crystallising the product. The salt is
unstable and oxidises to give tin (IV) oxide in air and sunlight.
The salt was analysed by quantitative chemical analysis, infrared
spectrometry and X-ray powder diffraction, and was shown to have
the composition: Sn(HCOO)2.
The decomposition was studied by TG and by DTA in the first
instance and gave the traces shown in Figure 6.1.1.
TG and DTA
Sample: tin(II) formate, polycrystalline powder
Crucible: Pt dish
100
TG
---·3O%1oss
Mass%
_ _ _- - - - - - - - - - - 36% loss
50
t
EXO
OTA
ENDO
200 400 600 8000 TI"C
Figure 6.1.1 Thermal analysis curves for tin (II) formate.
Rate: 2-10 Klmin

Atmosphere: static air
Mass: approx. 10 mg
Questions
(a) What are the stages of decomposition?
(b) Why does the DTA show two endotherms around 200 DC?
(c) How would you confirm the products of reaction?
6.1.2 Mixtures of carbonates

(For solutions, see p. 246 and References 2-4)
Mixtures of metal carbonates can occur in nature, or as products of

chemical reactions. Their decompositions are well characterised and
distinct in temperature and mass loss. For mixtures of metal carbonates, is
it possible accurately to measure the amount of each carbonate in a
mixture?
100
Mass% -- - - .... '\ I

.------ _, , - - - -
...
'\
I
DTG
\ I
I
,
\
I
I
I loss = 27.0%
I
I , loss 29.2%
70
I ,
II
I'
JI
I'
II
./
200 400 600 Tre 800
Figure 6.1.2 TG and DTG curves for mixture of copper and calcium carbonates.
An artificial mixture of calcium carbonate and 'copper carbonate' was

made from laboratory reagent-grade chemicals by weighing and thorough
mixing. The samples were analysed by TG only in flowing nitrogen (Figure
6.1.2).
TG
Samples: mixed calcium and copper carbonates, powder
Crucible: Pt dish
Rate: 10 Klmin
Atmosphere: nitrogen, 30 cm 3/min
Mass: 10 mg
Questions
(a) The sample contained exactly 5.0% by weight of calcium carbonate. Is
this confirmed by the TG trace?
(b) Several 'copper carbonates' are reported in the literature:
CuC03 , CuC03'Cu(OH)2' 2CuC03'Cu(OHh, etc.
Which, if any, of these does the TG suggest is present?
(c) If silver carbonate, Ag2C0 3 , were added to the mixture, could all three
components be detected accurately?
6.1.3 Strontium nitrate decomposition

(E.L. Charsley and S.B. Warrington, TACS, Leeds)
Strontium nitrate can be made by the usual methods, for example:

strontium carbonate plus nitric acid, and also by double decomposition
reaction of strontium chloride and sodium nitrate. It is used to produce the
'red fires' in pyrotechnics.
As part of a fundamental study of alkali metal and alkaline earth nitrates
and nitrites and of pyrotechnic formulations containing them [5], a
combined TG-MS study of the behaviour of strontium nitrate was
performed.
The sample was shown to be Sr(N03)2 by conventional analytical
methods. Small sample masses and a helium atmosphere were used to
remove the gaseous products efficiently from the reaction and prevent
complications due to any reversible reactions.
TG-MS (Figure 6.1.3)

Sample: strontium nitrate, Sr(N03)2, crystalline powder
Crucible: Pt boat
TG
2 m!Z32
m/z30
m/z46
500 600 700
Sample temperature °C
Figure 6.1.3 TG-MS curves for strontium nitrate.

Rate: to Klmin
Atmosphere: He, 15 cm 3/min
Mass: 4.4 mg
Interface: jet separator
Questions
(a) What do the TG and MS traces suggest as the most likely course of
decomposition of the strontium nitrate?
(b) Is there any evidence for the formation of strontium nitrite Sr(N02)2?
(c) What causes the dip in the mass spectrometric traces around 590°C?
How might you confirm your answer?
6.1.4 Calorimetry and phase transitions of potassium nitrate

In contrast to the previous examples, this is a problem in quantitative

calorimetry. Potassium nitrate is easily obtained in high purity and is used
as a standard ICTAC calibration material [9]. However, the phase behaviour
is complex, and measurements of the thermodynamic parameters show a
wide variation!
Potassium nitrate shows several phase changes [11], particularly a
crystalline transition from Phase II (orthorhombic) to Phase I (rhombo-
hedral) at 128°C. On cooling, a third form (Phase III, also rhombohedral)
appears.
A sample of ICTAC reference potassium nitrate, purified by recrystal-
lisation and drying, was studied between the temperature limits 67°C
(340 K) and 197°C (470 K) on a DSC. Calibration of the DSC was
performed with a sapphire disc and with indium metal [to] and the
temperatures were corrected. The traces are shown in Figure 6.1.4(a) for
sapphire and for KN0 3 .
DSC
Samples: (a) calibrant: sapphire disc, 24.08 mg
(b) KN0 3 powder, 33.11 mg
Crucibles: aluminium
Rate: 8 Klmin
Atmosphere: static nitrogen
Questions
(a) Calculate the molar heat capacity of KN0 3 at at least two tempera-
tures below the transition (Phase II) and at least two temperatures
-
V
.,.. Empty pan
-10
Sapphire, 24.08 mg
IL
KN03 , 33.11 mg
-30
-so l
300 350 400 450 500
TI"K
Figure 6.1.4{a) Heat capacity of potassium nitrate.
above the transition (Phase I), given that the heat capacity of sapphire
in this range may be calculated from the equation [14]
Cp (sapphire)/(J/(K g)) = 1.4571 - 3.355 x 10-5 x (TIK) - 200.17/(TIK)
(b) The value of the enthalpy change for the transition from crystalline
form II to crystalline form I was found to be IlH = 5.35 kJ/mol and the
corrected temperature of transition 401 K (128°C). Calculate the
entropy change IlS for this transition.
Using the values of the molar heat capacity found in (a), correct the
value of IlH (transition) to the value at 298 K, and hence find the value
for IlHf (I, 298 K) for the high-temperature form I, given that for the
stable low-temperature form II,
IlHf (II, 298 K) = -497.1 kJ/mol
What errors could affect this answer?
(c) Measurements of the enthalpy of transition of another crystalline form
of KN03 , form III to form I, have been made and it was found that IlH
(III-I) was 2.66 kJ/mol, about 400 K. The enthalpy of fusion of form I
at 334°C is about 11 kJ/mol. Estimate the enthalpy change for form III
changing to form II at 400 K and the (hypothetical) enthalpy of fusion
of form II.
Note Values of the thermodynamic parameters show a considerable

variation, e.g. values of IlH (II-I) are quoted from 4.9 to 5.7 kJ/mol [10].
100
mass%
""--------c - - - - 13.8% loss
'---- - - 46.6% loss
t
EXO
aT
ENDO
100 200 300 400 500 600 T/'C
Figure 6.1.5 Thermal analysis curves for barium perchlorate hydrate.
6.1.5 Decomposition of barium perchlorate

The decomposition of barium perchlorate, Ba(CI04)z·3H20, was studied

in order to see what effect semiconducting oxides (Mn02 and EU203) had
on the kinetics and mechanism of the reactions [15].
The TG, DTG and DTA traces for the barium perchlorate trihydrate are
shown in Figure 6.1.5.
Samples: barium perchlorate powder

Crucible: Pt dish or multiplate holder
Rate: 10 Klmin
Atmosphere: nitrogen, lOcm 3/min
Mass: approx. 50 mg
Questions
(a) Explain, as far as possible, the features of the TG, DTG and DTA
curves and suggest the nature of the products at both 300 °C and 600 °C.
(b) What other techniques could be used to confirm the identity of the
products suggested above?
(c) When the pure hydrated barium perchlorate is mixed with Mn02 in a
molar ratio ofl:l, the thermo analytical behaviour changes. Two
molecules of water are lost first, then the final one. The temperature of
216 THERMAL METHODS OF ANAL VSIS
the final decomposition is lowered from about 460 DC to about 310 DC
and takes place in a single, smooth step. Suggest reasons for these
effects.
6.1.6 Solid-state reactions

Mixtures of barium salts with potassium salts sometimes give very interest-
ing thermal analysis curves. On cooling and re-running the products, the
curve is sometimes quite different! The reaction between solid hydrated
barium hydroxide and solid potassium nitrate [19] has been suggested as a
means of solar energy storage.
Ba(OHh·8H20 + 2KN03 = Ba(N03)2 + 2KOH + 8H20

The endothermic forward reaction around 80 DC (aH = 226 Jig) is partially
reversed on cooling below 60 DC but only gives out 138 Jig.
An investigation of the reaction of barium chloride and potassium nitrate
gave the curves shown in Figure 6.1.6 [20,21).
Samples: solid BaCl2 + solidKN03 in molar ratio 1 : 2

large grains of mean radius = 0.5 mm
Crucible: platinum
Rate: 2 Klmin
First Run 1 2 3__- - - -

t
EXO
dT
ENOO Second Run
100 200
Figure 6.1.6 DTA curves for mixtures of 1 HaC)2; 2 KN03 •

Atmosphere: air, static

Mass: 0.5 g
Questions
(a) The TG shows small losses at::::::: 100°C on the first run, but not on re-
running. Peaks 1-4 on the DTA also disappear when the product from
heating to 350°C is re-run, but Peak 5 still appears. Suggest an
explanation. Would this reaction be suitable for solar energy storage?
(b) If the relatively large crystals used in this run are ground to a fine
powder, Peaks 1-3 and 5 change very little, but Peak 4 is much
sharper. Propose an explanation for this, and a method of testing.
(c) Peak 2 does not correspond to any change on the TG trace, nor does it
appear in re-running the sample. Is this peak characteristic of either
reactant?
6.2
6.2.1 Characterisation of a polymer Polymeric materials
While spectroscopic methods of identification of polymers, especially

infrared spectrometry, are extremely powerful and selective, with some
samples it may be difficult or impossible to prepare a sample suitable for IR
analysis, especially if that sample is highly filled!
The characteristic thermal behaviour of polymers does depend greatly
on their nature, preparation and treatment. However, compilations of the
typical properties of polymers are available [24] and we may measure many
of these by thermal techniques.
The ASTM D3418 method [25] requires very specific treatment for the
polymer in order to measure the glass transition temperature, melting
temperature and crystallisation temperature. In summary, the method is as
follows:
For a first-order transition
1. The sample is loaded into the pan, making sure there is good contact
between the sample and the pan.
2. The sample is heated under nitrogen at 10 Klmin to 30°C above the
melting point and held for 10 min to erase thermal history.
3. The sample is cooled to 50 °C below the peak crystallisation tempera-
ture at a rate of 10 Klmin. The sample is next heated at 10 Klmin and
the heating (DSC or DTA) curve recorded.
4. After holding at the higher temperature for 10 min, the sample is cooled
at 10 Klmin and the freezing curve recorded. The temperatures Tf , Tm ,
Tc and Te are recorded as shown in Figure 6.2.1(a) and a note is made if
there are multiple meltings.
Heat
Flow
ENDO
I
,
\1
I
Tm2
Temperature (OC)
Figure 6.2.1(a) ASTM definitions of melting and crystallisation temperatures.
___'~, .~ ("i!
Heat
Flow
EN DO
I
Temperature (OC)
Figure 6.2.1(b) ASTM definitions of glass transition temperatures.
For the glass transition

5. A fresh sample is taken and treated as in 1, 2 and 3 above, heating at 20
Klmin. It is then quench cooled to 50°C below the transition
temperature and held for 10 min.
6. The sample is then heated at 20 Klmin and the curve recorded. The
temperatures shown in Figure 6.2.1(b) are reported.
The characterisation could be extended further by recording the TG curve

of the material. This is the subject of ASTM D3850 [26], which relates to
solid electrical insulating materials. Briefly, the standard test involves using
a suitable calibrated thermobalance with a flow of dry air of 40-100 cm31
min, heating at 5 Klmin and recording the TG trace.
Characterisation using TMA and DMA is also very useful [27]. These
will give additional information about the glass transition temperature and
other low-temperature changes, plus the moduli of the polymer.
Sample
The sample provided was a white solid. This was prepared for analysis
according to the directions given in the ASTM methods. A mass of about
10 mg was used for each technique and the samples were run in air at 10
cm 3/min (Figure 6.2.1(c».
Questions
(a) Record the transition temperatures from the DTA trace as detailed
above and identify the polymer present in the sample.
(b) Comment on the TG trace obtained.
6.2.2 Polymer blend analysis

A blend of polymers was submitted for analysis, and it was considered

possible that the material contained a proportion of recycled polymer
produced by 'Post Consumer Reclaim (PCR)'.
A very widely recycled polymer is poly(ethylene terephthalate), PET,
used for the majority of soft drink plastic bottles. The major impurity in
the recycled product would be the caps, made from polypropylene, PP.
Many other bottles for household chemicals and shampoos are mainly
high-density polyethylene, HDPE, and these too could contain PP as
impurity.
The DSC traces for two samples of 'plastic' are given in Figure 6.2.2
together with typical thermal data for the constituents (Table 6.2.2). For
pure PP, the melting peak at around 160°C has an area of 100 JIg, under
the same scanning conditions.
Samples: plastic granules

Crucible: aluminium
Rate: 10 Klmin
Atmosphere: nitrogen, 6 cm 3/min
Mass: (a) 10.5 mg; (b) 17.1 mg
1 0 0 , - - - ' -_ _ _ _ __ . _ _ _ _ 4~'O'loss
Mass 0/0
50
o L _____________--.:::==::-I0/0 residue
100 300 500 TI"C
t
EXO
Heat
Flow
1\ - Cooling
ENDO
~ Heating_
Figure 6.2.1(c) Thermal analysis curves for unknown sample.
Questions
(a) Calculate the enthalpy of each peak in mJlmg (or Jig) of mixture.
Hence calculate the percentage of polypropylene in each sample and
suggest what further thermal studies might be done to assist in
quantifying the quality of the polymers for their end use.
(b) What further analysis would you suggest as confirmation of the
composition of the blend?
Sample 1
Area
126 rnJ
Heat
Flow
ENDO
Area
1
154 mJ Area
622mJ
100 150 200 250 T;oC
Figure 6.2.2 Samples 1 and 2 of polymer blends.
Table 6.2.2
Polymer
HDPE -120 130 180

PP -20 176 100
PET 80 250 40
6.2.3 Kinetic studies of polymer cure

Epoxy resins are used for many purposes, for example as matrix resins for
advanced aerospace composites. It is important that the curing process and
the relationship of resin structure to properties is well understood.
The sample studied here is a trifunctional epoxy compound:
together with a hardener, 4,4'-diaminodiphenylsulphone (DDS).

Calorimetric curing experiments were paralleled by both IR and rheo-

logical measurements. The fraction reacted was calculated from the
infrared peaks of the epoxy and amine groups.
To investigate the most appropriate kinetic equation and f(a), iso-
thermal runs were conducted at a series of temperatures between 125 and
225°C. The product after a long cure was re-run to obtain a baseline
correction. A typical co"ected isothermal run is shown in Figure 6.2.3(a)
and the data for one run are given in Table 6.2.3(a).
The data may then be used to interpret scanning DSC runs, as shown in
Figure 6.2.3(b). Data from runs at several different scan rates are given in
Table 6.2.3(b).
1.25
Heat
Flow
1.00
.75
.50
.25
0
0 20 40 60 time/min
Figure 6.2.3(a) Isothermal DSC of epoxy cure at 150°C.
Table 6.2.3(a)
Time(s) 1000xrate a
90 4.87 0.05
180 5.35 0.10
300 5.51 0.15
390 5.57 0.20
480 5.57 0.25
582 5.46 0.30
660 5.20 0.35
750 4.92 0.40
960 4.20 0.50
t
EXO
I
Heat
Fbw
50 100 150 200 250 TI"C
Figure 6.2.3(b) Scanning DSC run of epoxy resin cure (6.1 mg, 10 Klmin, nitrogen).
Table 6.2.3(b)
Peak
Rate (Klmin) temperature (K)
1 431.3
5 467.9
10 485.7
20 504.9
Sample: XD-DDS
Crucible: aluminium
Rate (a)O (isothermal at 150°C); (b) 10 Klmin
Atmosphere: nitrogen, 30 cm3/min
Mass: about 6 mg
Questions
(a) An equation used by several workers to describe cure kinetics [35,36]
is:
Rate = (Kl + K 2·am)·(1 - a)n
By plotting [Rate/(1 - a)n] against am, we can obtain Kl and K 2• Try
this with m = 1 and n = 2 and m = 1, n = 1 (autocatalytic reaction).
(b) Ozawa [38] has shown that for runs at different scan rates 13, for the
same fraction a reacted:
10glO 13 = constant - 0.4567EIRT
Plotting 10glO 13 against lITo. gives an approximate value of E.
Corrections can be applied to refine the value of E, as shown in the
ASTM 698. Calculate E.
6.2.4 Polymer decomposition studies

(E.L. Charsley and S.B. Warrington, TACS, Leeds)
The curing and subsequent degradation of phenol-formaldehyde novolaks

cross-linked with hexamethylene tetramine (hexamine, HMT) is important
and affects the properties of the finished products.
1. Novolaks are commonly prepared [39] by the reaction under acidic
conditions of a molar excess of phenol with formaldehyde (methanal),
usually about 1.25 : 1. The initial intermediate methylol phenols react
rapidly to form linked, substituted phenols with the elimination of
water. A general structure for this product is shown in I.
2. Novolaks may be converted into cross-linked networks by the further

reaction with an agent, most often hexamethylene tetramine, HMT (see
II).
II
3. The reaction of HMT with phenols alone has been studied [40] and two
crystalline products characterised by X-ray analysis. The curing and
Mass %
100
TG
so
DTA
60
\
lSamu ",--,'-""
I
I ' .... _----- ......
'"
________ J
I
------
"
~~!~~
29amu
100 300 500

Sample temperature / °C
Figure 6.2.4 STA-EGA curves for phenol-formaldehyde-HMT.
degradation of novolak-HMT systems was investigated by TG, DTA

and mass-spectrometric EGA [40,41] and the curves are shown in
Figure 6.2.4.
Sample: phenol-formaldehyde novolak-HMT resin

Crucible: platinum
Rate: 10 Klmin
Atmosphere: argon
Mass: 15 mg
EGA: mass spectrometric system
Questions
(a) Explain as far as possible the mechanisms of curing and degradation of

the resin as shown by these curves.
(b) How might the cure kinetics be followed?
(c) If a fully cured and moulded sample of a filled novolak-HMT resin was
run, what type of TG, DTA and EGA traces would you expect to
obtain?
6.2.5 Oxidative stability of polymers
The widespread use of polyolefins for sheeting, for bottle caps, for
electrical insulation and for plastic water piping requires a method of
testing the thermal and oxidative stability of the polymer material. These
tests are specified in the ASTM methods D3350-84 for polyethylene plastic
pipes and fittings, and in D3895-80 for copper-induced oxidation of
polyolefins [44].
The problem here concerns the degradation of water piping under
natural conditions. The surface of a pipe with an outside diameter of 180
mm, coloured blue for coding, appeared to have deteriorated after use
under normal conditions for 9 months [46].
There are two methods of testing of the oxidative stability of polyolefins
by DSC: either scanning in air, or isothermal in oxygen. Both were used
for these samples [45].
(a) Oxidation induction temperature
Samples of about 5 mg were cut, without using heat, from the inner, outer,
surfaces of the pipe. These were placed in unlidded aluminium pans in the
DSC. As a check a small sample of pure indium was used as calibration.
Sample: polyethylene blue water pipe

(i) outer; (ii) inner.
Crucible: aluminium
Rate: 10 Klmin
Atmosphere: oxygen, 50 cm 3/min
Mass: ::::=5 mg
(b) Oxidation induction time (OfT)

Larger samples weighing about 15 mg obtained as above were placed in the
DSC and heated in nitrogen to 200 0c. After equilibrating for 5 min, the
gas was switched to oxygen and the timing started.
Sample: polyethylene blue water pipe

(iii) outer; (iv) inner
Crucible: aluminium
Rate: isothermal at 200 °C
Atmosphere: nitrogen, 50 cm3/min then oxygen, 50 cm 3/min
Mass: ::::= 15 mg
Questions
(a) Compare the stability of the samples as measured by each test.
(b) Suggest what other tests or techniques might help to investigate this
problem.
6.2.6 Studies of epoxy-glass composite

The dynamic mechanical measurements on plastics are the subject of

ASTM D4092 [48].
While the addition of any filler to a polymer will affect the chemical and
mechanical properties of the material, the reinforcement of a polymer
matrix with fibre material, such as glass fibre or carbon fibre, gives greatly
increased strength. One glass fibre type frequently used is 'E-glass', which
has a tensile modulus, E :::::: 100 GPa, and a tensile strength around 2 GPa.
It is not surprising that a polymer, such as nylon 66, which has E :::::: 1-2
GPa and tensile strength around 70 MPa, is greatly increased in strength
[49,50,51].
The polymer component may be a thermoplastic, such as nylon, or a
thermoset such as a cross-linked polyester or an epoxy resin. The
reinforcement can be of glass, carbon, mineral or metal fibres. The use of
pre-impregnated materials or 'prepregs' makes the fabrication simpler, and
often it is these materials which must be investigated for their cure kinetics.
As the curing process proceeds, the glass transition temperature of the
composite increases. The presence of glass fibre may affect the thermal
stability of the material.
At temperatures below the glass transition the cured composite behaves
like a glass. Above Tg , the composite is viscoelactic.
Sample: epoxy-glass composite

Holder: 3-point bending platform
Rate: 2 Klmin
Atmosphere: nitrogen
Size: 23 mm x 3 mm x 0.9 mm
Frequency: 10Hz
Static stress: 11 MPa
Questions
(a) What temperature is the glass transition? What other transitions may
be observed?
(b) Given the values of the storage modulus E' and tan 8, calculate the loss
modulus E' at 100 and 150°C.
(c) If this sample were only partially cured, what would happen to the
moduli and to the temperature of the glass transition?
6.2.7 Characterisation of a thin adhesive film
(T.J. Lever, T.A. Instruments Ltd)
Coloured polyethylene terephthalate (PET) films are often coated on car

windows to reduce heat build-up inside the car during exposure to strong
sunlight. These films are typically 25 Il-m thick and are affixed to the glass
using a thin (4 Il-m) layer of adhesive. Since the satisfactory performance
and longevity of these films is obviously related to their ability to remain
adhered to the glass, the glass transition temperature, Tg, of the adhesive is
important, particularly where the windows will be exposed to harsh winter
temperatures.
The characterisation of the adhesive sets a problem since it is a small
component of the bulk material. It is not possible to find the Tg by DSC or
TMA, or even DMA, since the effect is swamped by the thicker PET film.
Even extracting the adhesive with a solvent was not suitable, since the
solvent was an effective plasticiser!
Many adhesives contain polar groups - for example, epoxies, silicones or
cyanoacrylates [55]. Since dielectric thermal analysis (D ET A or D EA)
detects relaxation processes at the molecular level, especially for polar
groups, this technique should provide a higher sensitivity for this problem.
6.3
Fine chemicals and 6.3.1 Purity determination (ASTM E928)
pharmaceuticals (For solutions, see p. 257 and References 58-{j1)
Background and method

As discussed in Chapter 3, the presence of impurities in a sample will cause
the melting peak measured by DSC to broaden and to shift to lower
temperatures. For pharmaceuticals, insecticides and fine chemicals, the
assessment of purity is very important.
The ability to perform the experiment, together with the calculations,
allows the analyst to check that the purity is within acceptable limits or to
suggest the remedies needed.
In many cases, the purity measurement may be controlled by the
computer attached to the DSC system but the corrections that must be
made to the 'raw' data must be appreciated.
1. The apparatus is calibrated by running a suitable standard, such as high-
purity indium (Tm = 156.6 °C, aHfus = 28.7 Jig) under the same
conditions as we shall use for the sample (for example, 0.5 Klmin).
2. The sample pan is cleaned with a solvent (CH 2C1 2) and dried at 700 K
for 1 min. A sample of 1-3 mg is weighed into the pan, which should
then be sealed to avoid mass loss. It has been found that placing an
inner liner to keep the sample in good contact with the base of the pan
A
G D B
Heat
Flow
ENDO
394.5 395.0 T/K
Figure 6.3.1(a) DSC curve for purity determination on benzoic acid sample.
improves reproducibility. The sample is then heated in flowing nitrogen

through the melting transition at a low heating rate and the DSC curve
recorded. A rate of 0.3-0.7 Klmin is recommended, but higher rates are
sometimes used. The pan is re-weighed to check that no loss has occurred.
3. The total area ABCA under the curve in Figure 6.3.1(a) is measured as
well as the fractional areas such as ADEA for several cases in the range
10-50% of the total area.
4. The leading edge of the indium DSC peak has a definite slope. Each
sample temperature recorded should be corrected by transposing a line
of this slope through the point E to the baseline at G. At temperature G
the fraction represented by the area ADEA has melted:
F = ADEAJABCA
5. It is probably as well to check that the sample has not decomposed
during the melting! If this is suspected, it is sometimes possible to try a
short purity determination with the lower temperature points.
6. Corrections to the measured purity curve are estimated in order to
produce a straight line plot of T versus lIF. This may be done by
successsive additions, or by computer. The ASTM method advises
working with fractions between 0.1 and 0.5 of the total area.
Problem
A sample of benzoic acid was thought be be slightly impure. A purity
determination was carried out using the standard ASTM procedure, and
Table 6.3.1(a)
Corrected TIK Fraction area/units F lIF
394.39 35.8 0.101 9.90

394.46 43.9 0.124 8.06
394.53 50.2 0.142 7.05
394.61 61.6 0.174 5.75
394.65 70.4 0.199 5.03
394.73 87.8 0.248 4.03
394.80 113.1 0.319 3.13
394.93 175.2 0.495 2.02
curves (Figure 6.3.1(a)) and results (Table 6.3.1(a)) were obtained.
Sample: benzoic acid (C6H 5COOH, RMM 122)

Crucible: aluminium
Rate: 0.5 Klmin
Mass: 2.40 mg
Total peak area: 354.0 units
Calibration constant: 0.904 mJ/unit
Questions
(a) Plot T against 1/F for the data given above. Attempt corrections by
adding 10 or less to the fractional area and to the total area to linearise
the graph.
(b) Calculate the corrected IlHfus per mole of benzoic acid. As a rough
guide, enthalpies of fusion are of the order of 10-35 kJ/mo!.
(c) Calculate the percentage purity of the sample.
(d) Suggest what methods might be used
(i) to check the percentage purity and
(ii) to identify the chemical nature of the impurities.
6.3.2 Phase diagrams of organic chemicals

The phase behaviour of mixtures of chemicals is very important in the

fields of pharmaceuticals [62,63,64], fine organics [65] and in metallurgy
[66]. In industrial situations, the interaction, solubility and crystallisation
may govern the processing method to be used.
Urea (CO(NH 2)2, RMM 60) and phenols are known to form compounds
[62,64]. The problem here is to investigate the phase behaviour and to find
any compound formation with m-nitrophenol (m-N0 2·C6H 4·OH, RMM
139).
o mol% MNP
38.5%
45.8%
55.1%
Heat
Flow
63.3%
ENDO
1 79.6%
974%
100%
60 80 100 120 140

Tre
Figure 6.3.2(a) DSC curves for mixtures of urea and m-nitrophenol.
Table 6.3.2(a)
Tube U/g MNP/g Tube Ulg MNP/g
1 0.500 0.000 5 0.100 0.400

2 0.194 0.285 6 0.050 0.450
3 0.144 0.282 7 0.003 0.248
4 0.100 0.285 8 0.000 0.500
Mixtures of urea and m-nitrophenol were made up by accurately

weighing into small glass tubes amounts of each to give a total mass of
about 0.5 g. The components were mixed thoroughly and then melted by
gentle heating. After cooling, samples of about 4 mg were run on the DSC
(Figure 6.3.2(a) and Table 6.3.2(a)).
Samples: mixtures of urea (U) and minitrophenol (MNP)

Crucible: aluminium
Rate: 8 Klmin
Mass: = 4 mg
Questions
(a) Measure the extrapolated onset temperature, Tl and the final tempera-
tures of any subsequent peaks, T2 , etc.
(b) Plot the phase diagram and label as fully as possible.
(c) If a third component were added, would it still be possible to
determine the phase diagram? What other thermal techniques could
be used here?
6.3.3 Liquid crystal studies

(J.W. Brown, Kingston University)
Introduction
Liquid crystals possess a degree of molecular order intermediate between
the three-dimensional order of a crystal and the complete disorder of a true
liquid [67,68]. Liquid crystals may be 'thermotropic', that is, they are
formed by heating certain crystalline materials such as p-azoxyanisole (see
p. 189), or 'lyotropic', formed by treating certain compounds, such as
soaps, with a suitable solvent.
Considerable interest has been shown in these materials recently
because of their potential use in opto-electronic devices and also for ftat-
screen displays for computers and televisions [69]. New compounds are
being synthesised and tested for liquid crystalline properties by many
techniques, especially DSC and thermomicroscopy [70]. The effects of
chemical structure on their transition temperatures and on the phase
behaviour of pure compounds and mixtures must be investigated. The
molecules are often elongated systems with a fairly rigid, polar structure -
for example, a molecule with linked, p-substituted aromatic rings.
Three broad types of liquid crysta1line phase are identified. The highest
degree of order, after crystals, is shown by the smectic phases, which have a
layered structure with molecules aligned at a common angle, parallel to
each other within the layers. The many different polymorphic smectic
phases may have different alignment angles and order within the layers,
and show different optical, X-ray and thermal behaviour.
If the molecules have their long axes parallel, but are randomly
arranged, we get the nematic phase, with a characteristic optical texture of
lines and brushes. Cholesteric phases have a sequence of nematic layers
with a progressive change in the direction of the axis in going from one
layer to the next, 'like a pack of cards, twisted about an axis normal to the
plane of the cards' [67].
Problem
A new material (III) was synthesised with p-di-substituted aromatic rings.
III
R' = C;H190; R = C3H7

When run on the hot-stage polarising microscope it gave the photographs
shown in Figure 6.3.3{a) from which the textures may be observed, and on
the DSC the curves (Figure 6.3.3{b».
Sample: new material 'APPPP', crystalline

Crucible: aluminium (DSC); glass (HSM)
Rate: 5 Klmin
Mass: =1 mg
Questions
(a) Does this material show any liquid crystalline behaviour?
(b) If so, what types of phases are present?
(c) What other techniques might be used to confirm the phases?

The stability, and hence the shelf-life, of pharmaceutical drugs and of

dosage mixtures is highly important since the product may become less
effective or even produce by-products which are less beneficial or cause
side-effects.
In section 6.3.1 we examined a method of testing the purity of the
sample. Clearly this could be applied to actual samples that have been
stored for extended periods at a specified temperature (e.g. 80°C) and this
is often a legal requirement. The time taken for the assay to fall to 90% of
its initial value is called to.1' This type of test takes a considerable time.
In this section we shall try to set up suitable thermal analysis tests to aid
in testing of pharmaceutical products.
ii
iv
LIWIC.AM SCIEt.lTIFIC ItUiT LTD
Figure 6.3.3(a) Hot-stage microscope photographs of APPPP. Linkam hot-stage, crossed

po\ars. (i) 90°C; (ii) 109°C; (iii) 127°C; (iv) 172 °C; (v) 182°C.
Questions
(a) How could we estimate the stability of a drug compound in a shorter

time?
(b) How could we determine whether the sample degrades at melting, or
has polymorphic forms?
(c) What methods could be used to study the loss of water or of solvent
from the sample?
(d) How much sample shall we need for each of these tests?
Heating-
Heat
Flow
ENDO
~ I
~ l_....JL----"'-------A "-Cooli"9
50 100 150 200 T/'C
Figure 6.3.3(b) DSC curves for the heating and cooling of APPPP sample. 5K1min,
1 mg, static air.
6.3.5 Dynamic mechanical analysis of food products

(Courtesy TA Instruments)
Samples of food materials may deteriorate unless they can be kept under
'ideal conditions'. The absorption of water, or its loss, will alter the
texture, appearance and the appeal of the product. Samples of food with
the wrong rheological or mechanical characteristics may be unsuitable for
some purposes.
While such thermal processes as protein denaturation and starch
gelatinisation may be studied by DSC [77,78,79] and loss of moisture could
be followed by TG, the small changes that these cause in mechanical
properties of the food are best studied by DMA [80,81].
Sample: Commercial white bread, exposed to atmosphere, 23°C,
70% relative humidity; compressed from 14 mm thick to
2mm
Clamping: vertical clamps; strip 8 mm x 13 mm x 2 mm
Rate: 2 Klmin
Atmosphere: air
Questions
(a) What happens to the bread samples?
(b) What would be the next test you might do?
6.4 6.4.1 Carbon oxidation
Other materials (D. Dollimore, Department of Chemistry and College of
Pharmacy, University of Toledo, Toledo, Ohio, USA)
Introduction
Carbons may be prepared by heating certain organic compounds in the
absence of oxygen. If the compounds have a low molecular mass, e.g.
methane, then a carbon black results. If, on the other hand, the organic
compound is a macromolecule, then the action of heat in the absence of
oxygen may either break down the polymer by chain scission to produce
monomers or fragments of lower molecular mass, or cause the polymer to
degrade by chain stripping to produce a carbon skeleton. In the latter case,
the carbon product may be produced and retain the solid state throughout
to give a char or charcoal. In other instances, carbonisation is accompanied
by a fluid transformation, and in this case the product is termed a coke.
Both cokes and charcoals may be 'activated' to produce a high-area
activated carbon by thermal treatment in air, oxygen, carbon dioxide or
water vapour. The activation process involves the gasification of a few percent
of the material to develop a high-area, porous structure. Chemical activation
with metal oxysalts produces extremely high surface area carbons.
The gasification of carbons in air occurs with the formation of carbon
monoxide, carbon dioxide and traces of other gases due mainly to
impurities. There is a correlation between the activity and surface area
which may be investigated by following the loss of mass of the solid phase
[82]. The correlation is seen most easily in carbon blacks where all the
surface is an 'external surface' with no surface residing in pores.
A temperature jump method was used because of its simplicity. A
sample is placed in the thermobalance and heated to the starting tempera-
ture. The temperature is held for a given time, is then increased by 10 K,
and held constant for the same time interval as before. The process is
repeated until six good plots of mass against time have been completed.
The time interval (20 min in this case) was chosen carefully so that in this
time a linear plot of mass against time was recorded, which greatly
simplifies the evaluation of the Arrhenius parameters. Experimentally, we
note that zero-order kinetics apply:
do./dt = kT
and 0. = krt
where 0. is the fraction decomposed, t is time and kT is the specific reaction
rate at temperature T K.
Experimental (Figures 6.4.1 (a) and (b))

To complement the kinetic measurements, the surface area of each sample
of carbon black was determined by nitrogen adsorption.
N774WITCO
107.00
93.00
79.00
65.00
51.00
37.00
23.00
9.00
o 20 40 60 80 100 120 140 160 180 200 220
TIME (Min)
Figure 6.4.1(a) Temperature jump plot for carbon black Witco N774 oxidised in air using
20-min periods at each temperature.
N774 F CABOT
104.00---.--_ _
92.00
80.00
68.00
56.00
44.00
32.00
20.00
470 480 490 SOO 510 520 530 540 550 560 570 580
TEMP (DEG C)
Figure 6.4.1(b) A typical plot of mass loss vs temperature for carbon black Cabot N774
oxidised in air using the temperature jump method using 20-min periods at each
temperature.
Table 6.4.1 Typical results of the
oxygen jump method applied to carbon
black Witco N683 of surface area
36 m2 /g
Mass loss % T/K 103 k/s- 1
4.13 763 3.44

5.74 773 4.78
8.4 783 7.00
11.62 793 9.68
15.61 803 13.0
20.02 813 16.7
Samples: carbon blacks, dried for 1 h at 100 °C

Crucible: platinum
Rate: combined: isothermal steps and rising temperature
Atmosphere: aIr
Mass: 10 mg
Questions
(a) Figure 6.4.1(a) appears as a curve! Explain why this is so and how the
rate constant could be calculated from the plot.
(b) From the data of Table 6.4.1, construct an Arrhenius plot and
determine the activation energy for the carbon black Witco N683
(c) If a series of carbon blacks from different sources and with different
surface areas were run, how could the results be correlated?
6.4.2 Proximate analysis of coals

The composition of a complex natural material like coal was formerly done
by a series of tests to determine the moisture content, the volatile matter,
fixed carbon and ash contents. These establish the grade or rank of the coal
and are reported as the 'proximate analysis' (Figure 6.4.2(a)). The ASTM
method D3172 reports the procedure for performing these measurements,
but it has been shown that thermogravimetry can give a good proximate
analysis in rather less time [90,91].
The procedure is to measure the thermogravimetric curve while heating
to 110°C in nitrogen for 5 min and then heating rapidly to 900°C in
nitrogen. After holding for a few minutes in nitrogen at 900 °C, the gas is
switched to oxygen.
Sample: anthracite coal, coarse powder

Crucible: platinum
Rate: as above; 50 Klmin
Atmosphere: nitrogen, 50 cm3/min, then oxygen at 50 cm3/min
Mass: 25.0 mg
Questions
(a) Measure the moisture content by the mass loss at 110 0c.
(b) Measure the volatile content by the mass loss between 110 and 900°C.
(c) Measure the fixed carbon by the mass loss at 900 °C after switching to
oxygen.
(d) Measure the ash content as the residue at 900°C.
6.4.3 Oil testing

Introduction
The thermal and oxidative stability of mineral oils affects their perform-
ance and lifetime as lubricants and, in a similar way, the thermal and
oxidative stability of edible oils affects their performance, taste and
interaction with other foods. In either case, anti-oxidants may be added to
prolong the lifetime of the oil.
In addition to the oxidative stability, thermal methods may be used on
mineral oils to look at the wax content and its dissolution, the effectiveness
of any additives [94,95] and could also be used to investigate the volatility
of low-boiling oils. Analysis of oil shales has been carried out by DTA and
TG [96,97].
The oxidative stability of edible oils and fats may be treated in a similar
way. Burros [98] has reviewed the applications of thermal analysis in food
chemistry, and Hassel has compared the 'active oxygen method' (AOM)
with TG and DSC techniques [99].
Pressure DSC will have the advantage of allowing operation under
higher pressures of oxidant, while restricting the volatilisation of the
material. If no PDSC is available, it may be more suitable to run in pure
oxygen at 1 atmosphere pressure.
Problem
Samples of mineral oil were provided and their comparative oxidative
stabilities required for comparison with a micro-oxidation test which also
investigated deposit formation during the oxidation [100].
The effect of contact with metals, such as carbon steel, was important.
Samples: lubricating oils

Crucible: aluminium
Rate: 8 Klmin to 400°C
Atmosphere: oxygen, 25 cm 3/min
Mass: about 2 mg
Method To investigate the oil oxidation and simultaneously the deposit

formation or discoloration, the simultaneous DSC-reflected light intensity
apparatus described in Chapter 5 was used (Figure 5.2.5, Figure 6.4.3).
EXO
Heat
Flow
- - - - - - - - - - - - - ' ......... ,
'\
\
Reflected \
light \
\
Intensity \
DECREASE
I 100 200
Figure 6.4.3 DSC and RLI traces for oxidation of an oil sample.
300 TfOC
Note A problem arose immediately, since the oil became much less
viscous as the temperature was raised and flowed into the edges of the
crucible. This was solved by containing the oil on a small mat of glass fibre
punched from a GF filter paper.
Questions
(a) Does the method detect onset of oxidation and of deposit formation,
and are they different?
(b) What other techniques should be used to investigate this?
6.4.4 Soil analysis

Soil samples must be analysed for their components, and classical methods
require several independent tests, taking a considerable time. It has been
claimed that analysis for moisture, organic content and mineral. content
may be carried out by thermogravimetry (Figure 6.4.4).
Samples: soils collected from forest area of Surrey, England, sieved
through a 2 mm sieve and kept in sealed containers until
used
100
2.
mass%
50
1.
o~----~------~----~----~----~
200 400 600 800 1000
Figure 6.4.4 TG of two soil samples (100 mg, 6 Kimin, static air).
Crucible: alumina
Rate: 6 Klmin
Mass: about 100 mg
Questions
(a) Besides thermal analysis, what other tests should be performed on the
original sample?
(b) Estimate the moisture content, organic matter and mineral residue of
these samples.
(c) Is it possible to identify the minerals present? What other methods
could be used, and what problems would occur if the soil had a high
clay content?
6.4.5 Catalyst studies

Catalyst preparation by heating a suitable precursor in an active atmosphere

was mentioned in Chapter 2. A DTA apparatus adapted to allow gas flow
through a sample has been used to investigate the effectiveness of V20 5
catalysts for the oxidation of S02 [104] and a combined DSC-MS system
using the Setaram Cal vet microcalorimeter was employed to study the
catalytic reduction of NO with NH3 [105]. A flow-through TG system could
be used with open or gauze crucibles.
The effects of the catalyst surface are very important, and measurements
of the surface area paralleling the thermal and compositional analysis
should be considered.
Adsorption of the starting materials onto the catalyst surface and
desorption of the products may be investigated by thermal methods [106].
Chemisorption is generally an exothermic process, and desorption endo-
thermic.
For the methanation of carbon monoxide:
CO + 3H2 = CH 4 + HP
a nickellalumina catalyst is used [107]. The performance depends on the
nickel particle size and the mechanism of reaction at lower temperatures
could be hydrogenation of adsorbed CO, followed by dehydration, or, at
higher temperatures, CO dissociation followed by hydrogenation of the
surface carbon. The reaction is highly exothermic (AH = -206 kllmol) and
could be investigated by DSC.
Samples: reduced Ni-A1203 catalyst
Crucible: aluminium
Rate: 10 Klmin
Atmosphere: H 2, with CO added 40 cm 3/min
Mass: 1-10 mg
Questions
(a) Discuss the shape of the DSC curves (Figure 6.4.5).
(b) How would the metal of the DSC cell affect the results?
(c) How could the kinetics of the reaction be studied?
6.4.6 Survival of Antarctic micro-arthropods

(W. Block and M.R. Worland, British Antarctic Survey,
Cambridge)
The Antarctic environment presents the local popUlation of mites and

collembolans with a severe survival problem. Freezing temperatures and
drying conditions may not occur together [110]. They survive by using two
processes to improve their cold-hardiness. Firstly, they evacuate food and
water from their guts to reduce the probability of heterogeneous nuclea-
tion. Secondly, they accumulate polyhydric alcohols such as glycerol to
enhance their supercooling [110, 110a]. Antifreeze proteins inhibit the
growth of ice below the equilibrium freezing point, and give a differential
between the melting and freezing points [llOa].
r
EXO
Heal
Flow
baseline
100 200 300 TfOC
Figure 6.4.5 DSC curves for Ni-A1203 catalyst. The baseline was run after reduction in
100% hydrogen. The reaction curves were then obtained in (a) 0.2% and (b) 0.5% CO in
hydrogen.
f
EXO
Heat
Flow Area 466 JIg
-Cooling
·20 ·10 o +5 TfOC
Figure 6.4.6 DSC curve for Cryptopygus antarcticus cooled at 1 Klmin. (Data courtesy
British Antarctic Survey and TA Instruments Ltd.)
The water loss could be studied by a modified isothermal TG experi-

ment, where the species are maintained at constant temperatures in the
range -to to 45°C over a desiccant and their mass loss measured [110].
For example, the species Cryptopygus antarcticus lost 5% water per hour at
-to °C (Figure 6.4.6).
The freezing studies could also be conducted using DSC [110a-112].
Using a cooling rate of 1 Klmin, a freezing-intolerant mite froze about 80%
of its body water, whereas a freezing-tolerant midge only froze 57% of its
water.
Sample: whole insect Cryptopygus antarcticus

Crucible: sealed large aluminium
Rate: 1 Klmin cooling
Atmosphere: He, 30 cm 3/min
Mass: 0.06 mg
Questions
Discuss the observations of the DSC curve (Figure 6.4.6).
Solutions
6.1
6.1.1 Tin(lI) formate decomposition Inorganic materials
(a) The TG shows clearly that there are two main stages of reaction:
(i) a loss of about 35% near 200°C and
(ii) a gain of mass starting near 600°C.
These could represent the decomposition of the formate to oxide:
Sn(HCOOh = SnO + HCHO + CO2
which gives a calculated loss of 35.5%, followed by the disproportion-

ation and oxidation of the tin (II) oxide:
2SnO = Sn0 2 + Sn (I)

2SnO + O 2 = 2Sn02 (II)
Sn + O 2 = Sn02 (III)
A residue of tin (IV) oxide would correspond to a final mass loss of

around 28%, but in practice it is about 29-32%. It is not possible to
detect the disproportionation reaction by TG.
DT A confirms these changes, giving an endothermic (double)
reaction near 200°C and a broad exotherm near 600°C.
The value of !J.H for the disproportionation reaction (I) calculated at
298 K is -9.1 kJ/mol, and the oxidation reactions are both very
exothermic.
(b) The double DTA peak near 200°C corresponds to a change in slope of
the TG, but no definite intermediate could be detected by X-rays.
However, examination in a hot-stage microscope showed that the
sample melted during the first endotherm. This is the fusion of the
original salt, which then decomposes more rapidly in the molten state.
Unusually, at a slower heating rate, a single peak is obtained because
the salt may decompose completely before it can melt.
(c) The products of reaction have been confirmed by several methods:
(i) The gaseous products released around 200°C were studied by
mass spectrometry and shown to be HCHO, HCOOH (by
oxidation of the methanal) and CO2.
(ii) The solid product was studied by scanning electron microscopy
(SEM). It was seen that metallic tin formed first on the surface of
the tin (II) oxide matrix and was then oxidised to tin(IV) oxide.
(iii) X-ray analysis showed that only the formate and oxide were
produced in the first stage and only tin metal, tin(II) oxide and
tin(IV) oxide in the second stage.
6.1.2 Mixtures of carbonates
(a) As reported in Chapter 2, calcium carbonate decomposes above

600°C, and so the high-temperature loss of 2.2% must be due to the
CaC0 3 . This corresponds to the reaction:
CaC0 3 = CaO + CO2 Calculated loss: 44%
Thus a loss of 2.2% corresponds to 2.2 X 100/44 = 5% of the mixture.
(b) The amount of copper carbonate must therefore be 95% of the original
mixture. The loss at the lower temperature of about 200°C was about
27%. The calculated losses from the possible 'carbonate' formulae are:
CuC03 = CuO + CO2 Calculated loss: 35.6%
CuC03 ·Cu(OH)2 = 2CuO + CO2 + H 20 Calculated loss: 28.0%
2CuC03 ·Cu(OH)2 = 3CuO + 2C02 + H 20 Calculated loss: 30.8%
The closest agreement is for CuC0 3·Cu(OHh. This is generally
reported as the usual copper carbonate [2] although it may be
hydrated. X-ray data confirm that this is the solid present.
Note that the DTG curve shows only a single loss, so both carbon
dioxide and water vapour are lost simultaneously [4]
(c) Silver carbonate has been reported to decompose in two stages:
Ag2C03 = Ag20 + CO 2 = 2Ag + 11202 + CO2
The temperatures of these decompositions are about 230 and 400°C,
so that the first reaction would almost coincide with the copper
carbonate decomposition, but the second would be 'in the clear'. The
decompositions might be expected to be simple, but have been shown
to depend upon the mode of preparation, and the conditions used [3].
Although a reasonably good calculation of the amounts of silver,
copper and calcium carbonates can be made from the TG curve, the
results are rather variable.
6.1.3 Strontium nitrate decomposition
(a) The TG run shows a single mass loss of 51 %, which suggests that the
nitrate goes eventually to the oxide:
Sr(N03)2 = SrO + (NO, N02, O2)
These three gases are all detected by the mass spectrometer:
nitric oxide, NO, mlz = 30
nitrogen dioxide, N0 2 , mlz = 46
oxygen, O2 , mlz = 32
(b) Since the oxygen is evolved at a lower temperature than the other
gases, showing the very high sensitivity of the MS system, it is possible

that there is a tendency to form the nitrite:
Sr(N03h = Sr(N02h + O2
However, the evidence is inconclusive and there is no plateau or even
a dip in the TG curve. The evolution of NO follows soon after the
production of oxygen, so that the decomposition is continuous.
(c) The dip in the MS curves for NO and O 2 at around 590°C was found by
observation of the reaction on a hot-stage microscope to correspond to
the bulk fusion of the partially decomposed nitrate [7]. This will affect
the kinetics of decomposition. DTA studies show that strontium
nitrate melts around 600°C and decomposes endothermically with
considerable bubbling with a second DTA peak at 730°C [8].
Note 'The rate of decomposition was found to be strongly dependent on

the thickness of the molten film and the efficiency of product gas removal.
This extreme dependence upon experimental conditions has generated
confusion in the literature regarding the mechanism of reaction. The use of
mUltiple simultaneous techniques is proving extremely helpful in the
resolution of these anomalies' [5].
6.1.4 Calorimetry and phase transitions of potassium nitrate
(a) The deflections must be corrected for the 'empty pan' baseline, so that
ay(sample)= (y(sample)-y(empty»
The calculation of the heat capacity at temperature T for samples run
under the same conditions as calibrants, especially the same heating
rate, may be done using the formula:
ay(unknown,1) x Cp (calibrant,1) x m(calibrant)
C (unknown,1) = --'--"----------'----"-"-------'------'-----'-
p ay(calibrant,1) x m(unknown)
Some values at specific temperatures are tabulated in Table 6.1.4. The
method used is specified in ASTM E968.
Table 6.1.4
T(K) Cp (J/(K g»
Sapphire KN0 3 KN0 3
350 0.873 0.973 98.4
370 0.904 1.018 102.9
380 0.918 1.039 105.1
390 0.931 1.060 107.2
410 0.955 TRANSITION
440 0.987 1.240 125.4
450 0.997 1.245 125.8
470 1.015 1.258 127.2
2500
2000
1500
10 x cp .......
1000 ---
500
Cp
o
350 400 450
T/K
Figure 6.1.4(b) Heat capacity curves for potassium nitrate.
These are in reasonable agreement (± 1%) with the results of

Carling [10] over this range and are plotted out in Figure 6.1.4(b).
(b) Given the data for aH and T for the transition,
LlSt = LlH/Tt
= 5350/401
= 13.3 J/(K mol)
Literature values range from 12.4 [11] to 13.8 [10]. On average, we
may write the molar heat capacities over this range of temperatures for
KN0 3 (RMM 101.1) as:
Cp (Phase II) = 21.4 + 0.220 x (T/K) J/(K mol)
Cp (Phase I) = 99.0 + 0.060 x (T/K) J/(K mol)
and LlH (II-I) = 5.35 kJ/mol at 401 K Using Kirchhoff's equation,
(aaHla7)p = acp and integrating, we get:
aH (Tz) = aH (T1) + Jacp dT

= aH (T1) + aa(T2 - T1) + ab/2 x (T~ - TD
From the above:
aa = (99.0 - 21.4) = 77.6 J/(K mol)
ab = (0.060 - 0.220) = -0.160 ll(K mol)
Thus, for 298 K:
aH(II-I, 298 K) = 5350 + 77.6 x (298 - 401) - 0.080 x
(298 2 - 401 2)
= +3117 llmol = + 3.12 kllmol
The probable error in this value is about 1%. Therefore,

aHf (I, 298 K) = -497.1 + 3.1 = -494.0 kllmol
(c) (i) Using Hess's Law,
aH (III-II) = aH (III-I) + aH (I-II)
= 2.66 + (-5.35)
= -2.69 kllmol
(ii) Again, using Hess's law:
aH (II-I) = aH (II-I) + aH (I-I)
= 5.35 + 11.0
= 16.35 kllmol
Note! Errors will certainly be present since we have not measured Cp

down to the required temperature. Also, it should be noted that strict
calorimetry using DSC really requires much more sophisticated calcula-
tions [13].
6.1.5 Decomposition of barium perchlorate
(a) (i) The loss of hydrate water takes place in two stages.
Ba(CI0 4h-3HzO (solid) = Ba(CI04h·2H 20 + HzO
Ba(CI0 4h·2H 20 = Ba(CI0 4h + 2H20
The total RMM = 390.4, so that the first reaction should show a
loss of 18 x 1001390 = 4.6%, and the second a total loss of 3 x 4.6
= 13.8% of the original mass. This behaviour is echoed by the
DTA curve which shows two peaks, the second being a 'doublet',
which might indicate three different environments for the three
water molecules.
(ii) The DTA curve alone shows two sharp endotherms between 250
and 400°C. These have been reported [16] as phase transitions of
anhydrous barium perchlorate and have been used as a 'finger-
print' for the presence of barium perchlorate.
(iii) Both DTA and TG show a broad, double peak for the exothermic
decomposition, in some cases preceded by a small endotherm and
corresponding to a total mass loss of 46.6%
There is some evidence of a discontinuity in the traces, but this
was found to disappear when a multiplate sample holder was used
allowing free loss of product gases.
The product could be barium oxide or barium chloride:
Ba(CI04)2·3H20 = BaO + Cl2 + 3.502 + 3H20Totaiioss 60.7%
Ba(CI04)2·3H20 = BaCl2 + 402 + 3HP Total loss 46.6%
Obviously, the chloride is the more likely product.
(b) The loss of water could be confirmed by specific water detectors (see
Chapter 5), by IR or MS. The phase changes and the final barium
chloride are confirmed by X-ray studies.
(c) The effect of Mn02 and other semiconducting oxides is catalytic. The
water is lost in a different manner, suggesting different environments.
The first stage of the final decomposition was found by kinetic analysis
[15] to have an activation energy of 110 kJ/mol in the presence of
Mn02. When run alone Ea was 225 kJ/mol. The mechanism of reaction
was also changed.
6.1.6 Solid-state reactions
(a) The mass losses around 100 °C may be attributed to irreversible loss of
moisture from the reagents. They correspond to the endotherms 1 and
3 on the DT A trace. The only exothermic peak, Peak 4, might be due
to a solid-state reaction:
This is not reversible, and consequently does not appear in re-runs.

Calculation of ilH for the reaction from published data [22] gives a
value of about -20 kJ/mol corrected to 270°C.
The large, sharp, endothermic Peak 5 does appear in the re-run, and
must be due to the fusion of the mixture of products at 320°C.
The products are confirmed by X-ray diffraction studies, and also
by running a 1 : 2 mixture of Ba(N0 3)2 and KCl, which only shows
Peak 5.
Since the reactions are (i) at high temperature and (ii) not rever-
sible, they would perhaps not be suitable for solar energy storage.
Suitable systems are discussed in [23].
(b) Grinding the reactants together improves the surface contact, reduces
the particle size, and 'mechanically activates' the solid-state reaction.
Fatu [21] has made measurements of the enthalpy and of the activation
energy of the reaction.
(c) Peak 2 corresponds to the solid-solid phase transition of KN0 3 , at 128
DC, which was discussed in Problem 6.1.4. Since the potassium nitrate
disappears in the reaction, this peak too will disappear.
6.2.1 Characterisation of a polymer 6.2

Polymeric materials
(a) While the scale of the figures does not allow highly accurate measure-
ments, the temperatures during the melting and crystallisation peaks
and the glass transition are approximately:
MeltingrC CrystallisationrC Glass transitionrC
Tf 185 Tf 163 Tf 50
Tm 200 Tc 143 Te 63
Te 210 Te 131 Tm 58
Identification using a suitable transition range eliminates many
polymers, but gives as possibilities nylon 6 or nylon 6/10 which have
melting ranges around 200°C and Tg values around 50°C.
Measurement of the heat capacity might give additional confirmation,
as might the study of the crystallisation behaviour [27,28].
(b) The TG trace shows a mass loss of about 5% at low temperature,
which is probably moisture. This suggests a polymer having polar
groups, such as a nylon. The decomposition temperature for 1% loss is
around 350°C, which is in accord with reports for nylon 6 [29].
Note DMA experiments on this material gave a storage modulus value of

about 1 GPa at 25°C, a tan 3 peak around 50 °C for the glass transition and
a broad beta transition around -50°C.
Conclusion The most probable identification of this material is nylon 6

without plasticiser or filler. It does not show any multiple melting peaks in
this case. Further analysis (for example, by IR) would be most useful.
6.2.2 Polymer blend analysis
(a) Sample 1 has a majority of HDPE, melting at around 125°C and the
small peak at 160 °C is due to the PP impurity. The peak areas given
show that:
for HDPE = 1663/10.5 = 158.4 J/(g mixture) and
for PP = 126/10.5 = 12.0 J/(g mixture).
Since pure PP has a IJ.Hm of 100 J/g, this sample must have a PP content
of 100 x 12.0/100% PP = 12.0% PP by weight.
Note: Calculating on the PE (IJ.Hm = 180 J/g) we find a PE content of
100 x 158.4/180 = 88% by weight.
Sample 2 is mainly PET, and does show the glass transition peak
around 80°C as well as the main melting at 250°C. The minor peak at
170 °C is PP, and the percentage is calculated as above:
For PP: Peak = 154/17.1 = 9.0 J/(g mixture) and so

PP = 100 x 9.0/100 = 9.0% PP
For PET: Peak = 622/17.1 = 36.4 J/(g mixture) and so
PET = 100 x 36.4/40 = 91% PET.
For a series of samples, it is probably better to establish a calibration
graph of %A versus peak area.
The mechanical properties of the samples are of prime importance
in their recycling and re-use. Measurements of the DMA curves and
comparison with standard material would be useful.
The presence of additives in the recycled material possibly from the
'impurity' polymer such as PP may have a deleterious effect on the
moulding characteristics because it affects the crystallisation rate. This
rate may also be studied by DSC.
(b) Analysis by other thermal methods might be possible, but complemen-
tary techniques, such as JR, might be more quantitative.
6.2.3 Kinetic studies of polymer cure
(a) Figure 6.2.3(c) shows the plots obtained for the different values of m
and n. Reasonably good agreement is obtained for m = 1, n = 2 over
the range of a = 0.05---0.40. Evaluating the constants from this plot
gives Kl = 0.42 X 10- 3 S-l and K2 = 2.28 X 10- 3 s-1.
20
15
10 m=1,n=2
"' ____ Er--- -{)---------

-.()----"""
_e----'O----- e- -- m=1,n=1
4 5
o 2 3
alpha
Figure 6.2.3(c) Plots of rate function against alpha.

1.5
log ,p,
1.0
.5
o~ ____________________ ~~ ____ ~
1.9 2.1 2.3
Figure 6.2.3(d) Ozawa plot for epoxy cure.
A good test of the validity of the equation used is to plot a 'reduced

time' graph of (X against tltO•5 for several temperatures (to.5 = t where
(X = 0.5). For this reaction there is good fit over the temperature range
150--200 dc.
Once the kinetics are established, it is possible to analyse an
isothermal or a scanning DSC trace more fully.
(b) The plot oflog10 13 against liTpeak is shown in Figure 6.2.3(d). The slope is
-3850 K. Therefore, E = -R x slope/0.4567 giving a value of E =
70.1 kJ/mol. This may be refined by using the Flynn and Wall method
to give a better value of about 66 kJ/mol.
Note ASTM method D5028 uses similar procedures to study the cure
properties of pultrusion resins by thermal analysis.
6.2.4 Polymer decomposition studies
(a) The TG curve shows a small weight loss of 1.3% around 100 °C which
is due to water evolved [42,43] during the initial reaction being trapped
in the novolak. This gaseous product is confirmed by the mlz = 18
trace on the EGA. There is also a melting or glass transition reported
below 100°C [40,41]. These two events may be differentiated by
running the DTA in sealed or high pressure cells to restrain the loss of
water.
The major sharp mass loss around 140°C accompanied by an
exotherm on the DTA and a large peak at mlz = 17 on the EGA
corresponds to the curing reaction shown in Scheme 6.1.
The accompanying loss of water and of a little formaldehyde
.--&-rn --&.
OH OH
-.~, + 2
Scheme 6.1
(mlz = 29) could be due to release of further trapped or lightly bound

material.
Degradation, accompanied by further cross-linking, goes on in
stages from about 250°C. The release of more ammonia, and later of
water and formaldehyde, is complementary to the mass loss shown by
TG and the broad DTA peaks.
(b) The curing and kinetics have been studied [43] by using isothermal TG
at various temperatures between 140 and 240°C and by scanning TG.
The release of ammonia could also be monitored by EGA, either mass
spectrometric [41] or chromatographic [40].
(c) A fully finished product would not be expected to show the initial
water loss, or the sharp curing reaction. However it would show the
later, post-cure stages, and it has been found that release of water,
ammonia and formaldehyde causes cracking of the sample and spikes
on DTA and DTG traces due to very rapid losses. At temperatures
above 400°C, phenol (mlz = 94) was detected in addition to other
products.
6.2.5 Oxidative stability of polymers
(a) The temperature scanning traces (Figure 6.2.5(a» show that the outer
sample (i) has a much lower induction temperature, Tind , of 211 °C
compared with the inner sample (ii) which has not been exposed to UV
and has a Tind = 245°C. The indium melting peak occurs at the correct
temperature. Specifications for piping set a satisfactory value of 'lind at
220°C.
The same behaviour is found for the isothermal traces (Figure
6.2.5(b», where the outer sample (iii) starts to oxidise after 15 min,
but the inner (iv) does not do so until 55 min. The times may vary, but
'good samples' generally show an OIT over 30 min.
1
Heal
Flow
Inner sample
.,-----_01"';_,r__
,245°C
Outer sample
~---.,-I--
k211 °C
50 100 150 200 250 TfOC
Figure 6.2.5(a) Scanning DSC runs for blue water pipe.
I---------------------------~T---
, I =55min
iii Outer
00 10 20 30 40 50 60 tlmin
Figure 6.2.5(b) Isothermal DSC runs at 200 °C.

(b) Other information may be obtained from the DSC scan such as the
melting peak of the polyethylene. The degree of crystallinity is found
from the enthalpy of melting. For 100% crystalline material, ARfus =
290 Jig. Since we have values here of 170 Jig for (i) and 180 Jig for (ii),
the outer, degraded sample is slightly less crystalline. This is discussed
further in ASTM D3417.
The other tests that could be used to quantify the degradation of this
polymer are many. Thermal methods such as TG, TMA and DMA will
give additional information. Spectroscopic techniques such as IR to
look at the carbonyl peak near 1700 cm- 1 and UV to examine the
formation of any conjugated structures have been used [46].
Notes 1. The catalytic effects of copper and copper salts require that
polyethylene in contact with copper (e.g. in electrical wiring) should
contain stabilisers to protect against copper. If such stabilisers are not
present, OIT values as low as 0.5 min at 190°C are reported [45].
2. In the recycling of polymers, the oxidative stability is important. The
onset temperatures of blended recycled polymers showed that a fresh
sample gave an onset at 291 °c, but with 45% recycled content, the onset
was 293.7 °C. The rate of oxidation increased with recycled content [47].
6.2.6 Studies of epoxy-glass composite
(a) The glass transition of this material occurs between 120 and 175°C
(Figure 6.2.6). If we accept the mid-point of the major change as the Tg
[48], then we would estimate it as 150 ± 5 0c.
Below the Tg we observe another peak, more clearly in the tan B
curve, due to the beta transitions at about -20°C [52,53].
(b) Since tan 8 = E"IE', we may calculate:
At 100°C: E' = 12.3 GPa, tan 8 : : : : 0.018,
so E" : : : : 0.22 GPa.
At 150°C: E' = 3.1 GPa, tan 8 : : : : 0.33,
so E" : : : : 1.02 GPa.
(c) As the sample is cured, the modulus and the Tg both increase.
Isothermal curing shows an increase in modulus with time, and
increasing the post-cure time increases Tg •
6.2.7 Characterisation of a thin adhesive film
The film sample was placed between the parallel plates of the DEA
apparatus and under slight load to maintain good contact. The samples
were heated from -100 to +50 °C and the multiplexed DEA curves
E'
lano
GPa
(1 0.30
!\
15
!\
10 / \, 0.20
\,
5
\, 0.10
\,
-100
--- ---------_/
o~~----~~~--------~----~~~~~
o 100 200 300
,
------
\
T/"C
Figure 6.2.6 Dynamic mechanical analysis for epoxy composite.
recorded at freqllencies between 1 Hz and 1 kHz. The results are shown in

Figure 6.2.7.
Figures 6.2.7 (a) and (b) show the dielectric loss factor e" as a function of
temperature for the polyester with and without adhesive coating. The PET
substrate showed a broad, frequency-dependent transition, designated as a
beta transition with a peak between about -90 and -20 DC. The PET
adhesive sample, on the other hand, exhibited the PET beta transition, but
also showed a higher temperature transition at about -20 DC at 1 Hz,
which is the Tg of the adhesive.
Figure 6.2.7(c) presents the dielectric permittivity e' of the coated film
which shows an inflection point at the Tg of the adhesive which is not seen
in the trace for PET alone. Either of these parameters could be used to
characterise the adhesive.
6.3
6.3.1 Purity determination (ASTM E928) Fine chemicals and
pharmaceuticals
(a) The plot of Tagainst l/Fis not linear, so must be corrected. Normally,
we should use computer software provided by the instrument manu-
facturer, but here we wish to check the method manually.
Attempts to straighten the line by adding successive increments
equivalent to a fraction of 0.025 should allow a reasonable number of
calculations. In this case 10 units is 0.028 of the total area. The graph
(Figure 6.3.1(b» and Table 6.3.1(b) show the results of successive
additions of 10 units or less.
10000.,300., 10.0,
3000., 100.,3.00,
1000.,30.0,1.00 Hz
::-0.05
Tg of ADHESIVE -->
~
o
onI
LL
In
In
o
..J
0.00
-100 -SO -60 -40 -20 0 20 40
(a) Temperature (0C)
0.02
10000.,300., 10.0,
3000., 100.,3.00,
0.02 1000., 30.0, 1.00 Hz
\Y0.01
0
0
nI
~0.01
In
0
..J
0.005 ~ - Relaxation
(b) -100 -SO -60 -40 -20 20 40

Temperature (0C)
3.
~ 2.9
Z.
~ 2.S
I~
...
~ 2.7
2.6
2.5
(e) -100 -SO -60 -40 -20 0 20 40

Temperature (0C)
Figure 6.2.7 Dielectric analysis of coated thin film: (a) polyester with adhesive, E";
(c) polyester with adhesive, E'.
396 r-------------------.
T/K
395
394
393
0 5 10 15
1/F
Figure 6.3.1(b) Plots of lIF (corrected) against T.
Table 6.3.1(b) Correction of lIF
Addition/units:
0 10 20 30 35 37.5
9.90 7.95 6.70 5.84 5.49 5.34

8.06 6.75 5.85 5.20 4.93 4.81
7.05 6.05 5.33 4.79 4.57 4.46
5.75 5.08 4.58 4.19 4.03 3.95
5.03 4.53 4.14 3.82 3.69 3.63
4.03 3.72 3.47 3.26 3.17 3.12
3.13 2.96 2.81 2.68 2.63 2.60
2.02 1.97 1.92 1.87 1.85 1.84
The plots become more linear, and that with an addition of 37.5
units (fraction 0.106) is a good straight line.
Slope = - 0.1530 K
Intercept = 395.2 K = To
(b) The correction of 0.106 gives a corrected total area of:
Area = 1.106 x 354.0 = 391.5 units
and thus
IlRfus = Sensitivity x Area x RMMlmass
= (0.904 x 103 x 391.5 x 122)/(2.40 x 10-3)
= 17 995 J/mol
(c) Since the slope is -(RTo2/IlHfus)xB' where XB is the mole fraction
impurity, then:
Table 6.3.2(b)
Tube U/g MNP/g mol% MNP TlrC T2f'C
1 0.500 0.000 0.0 133

2 0.194 0.285 38.5 79 112
3 0.144 0.282 45.8 79 91
4 0.100 0.285 55.1 67 80
5 0.100 0.400 63.3 67 77
6 0.050 0.450 79.6 66 74
7 0.003 0.248 97.4 65 94
8 0.000 0.500 100.0 96
XB =
0.1530/(8.314 X (395.2)2/17995)
= 0.00212 or
Purity = 99.79 %
(d) The purity could be checked by chromatographic or spectroscopic

methods which could also identify the impurity after suitable calibration.
6.3.2 Phase diagrams of organic chemicals
(a) The temperatures measured from the curves with an accuracy of ±1 °C

and assumed to be corrected for any thermal lag are given in Table
6.3.2(b).
(b) The phase diagram (Figure 6.3.2(b» is typical of systems forming a
compound with an incongruent melting or peritectic point. From the
limited number of runs reported here, it seems probable that the com-
ponents form a 1: 1 compound, with a peritectic point of79±1 °C and
that this compound forms a eutectic with m-nitrophenol at 67±1 °C at
a composition of 72 mol % MNP.
These results are in good agreement with those reported in the
literature [63]. Other excellent examples of phase equilibria studies are
given by Ford and Timmins [64].
(c) Three-component phase diagrams can be studied by DSC, but care is
needed in their interpretation. Thermomicroscopy is most useful in
discovering the phases present.
6.3.3 Liquid crystal studies
(a) Since there are several transitions on the DSC and different textures
on the hot-stage microscope, there are probably liquid crystalline
phases. The supercooling of the lowest transition from 92°C on
r
1300~ Liquid
Tf'C ~
'0.
110
SolidU +
;:
Liquid
90 -
- - - - - - - -........-r-
SolidC + • MNP
70 SolidU + Liquid
Solid C + Solid MNP

o mol%MNP 100
Figure 6.3.2(b) Phase diagram for the urea-m-nitropheno! system.
heating to below 75 DC on cooling strongly suggests liquid crystalline

behaviour.
(b) The images from the hot-stage microscope show a considerable degree
of order. This suggests that the phases are smectic. The crystallisation
from the melt forms a 'fan-like' texture characteristic of Smectic-A.
The transition around 138 DC has a very low aH and shows very little
optical change. It is probable that the phase below 138 DC is a Smectic-
B (hexagonal). Another small DSC peak at 122 DC is accompanied by
the 'banding' of the fan texture. This is typical of Smectic-E. The
crystalline compound melts to Smectic-E at 92 DC on heating. The
phase behaviour is thus:
Crystalline ~ Smectic-E ~ Smectic-Bhex ~ Smectic-A ~ Liquid
(c) X-ray diffraction techniques were used to confirm the structures.
(a) Since increasing the temperature will increase reaction rate in accord-
ance with the Arrhenius law, we could heat the drug sample from
ambient until decomposition occurs. Hardy [72] points out that if the
decomposition is exothermic then we could use the ASTM E698
method for evaluating hazardous materials, or use Ozawa kinetics.
From the reaction rate equation, it is possible to estimate the time to
10% reacted (to.I) at various temperatures and then to test it by
isothermal runs at elevated temperature, for example:
100 TG
mass%
DSC
Aged
-----"'"
New \
\ I
\ I
Heat \
Flow \
ENDO
! Acetic acid
EGA
100 200
Figure 6.3.4 Thermal analysis curves for aspirin sample: 7.3 mg, 10 Kimin, static air
(TG, DSC), flowing nitrogen (EGA).
Ergocalciferol: In k = 27.7 - 13930/(T/K)

Therefore at 150°C, k = 5.46 X 10-3 min-I
Assuming first-order kinetics,
to.1 = 19.2 min
This was close to the value found.

(b) If the sample degrades during the endothermic melting, then the purity
will be reduced. This will have two effects: the peak temperature will
be lowered and the peak will be broadened or lowered depending on
the reaction [76].
A simple experiment with aspirin (acetylsalicylic acid) showed that
keeping the sample in air at room temperature changed the peak shape
[73]. Running the TG simultaneously with the DSC showed that
immediately after the melting at 140°C, an endothermic decompo-
sition takes place with a mass loss of about 35% (Figure 6.3.4). EGA
analysis of the gaseous product identified it (by FTIR) as acetic acid
from the reaction to salicylic acid [74].
Polymorphic forms could be detected by DSC or thermomicroscopy
[75]. Their interconversion should involve no mass loss on TG.
(c) Loss of solvent would certainly involve a mass loss on TG [73].
Thermomicroscopy often shows water or solvent loss, and this could
be identified by a suitable EGA method.
(d) DSC purity experiments need only a few milligrams, and the STA run
used 7.4 mg.
6.3.5 Dynamic mechanical analysis of food products
(a) The DMA of the bread samples (Figure 6.3.5) clearly shows the
changes that occur in samples as they are kept. Three things change:
1. The storage modulus E' measured at -40°C decreases from 1 GPa
in the fresh sample to a few MPa in the 'overnight' sample.
2. The storage modulus E' measured at +25 °C increases very slightly
from 2 MPa in the fresh sample to 16 MPa in the 'overnight'.
3. tan 8 peaks decrease, or disappear!
Possible reasons for these effects are that they are due to the removal
of both tightly and loosely bound water. In the fresh sample, the
crystalline water increases the subambient modulus and tan 8. The
increase in room temperature modulus may be due to the 'plasticising
effect' of water on the bread starch.
(b) As a follow-up experiment, many possibilities exist. The reference
paper studied pasta material as a function of immersion time.
Other bread samples or other storage conditions could be investi-
gated. If the effects are due to water loss, isothermal TG might be used
under the same storage conditions.
6.4
6.4.1 Carbon oxidation Other materials
(a) Figure 6.4.1(a) on p. 237 consists of linked straight line segments for
each 20-min plot. The rates can be considered as zero order and the
rate of reaction calculated from the percent mass loss over a given
time.
(b) Figure 6.4.1(c) shows the Arrhenius plot for the example given. The
slope is -2.05 x 10-4 and thus the value of E is calculated to be 171
kJ/mol and A = 1.57 x 1Q4 S-I.
(c) A plot of the specific reaction per unit area against the surface area for
20 carbon black samples with areas between 30 and 141 m2/g shows a
general trend for low surface area carbon blacks to have faster rates
per unit area than the high surface area carbons. Figure 6.4.1(d) shows
the collected data at 773 K, with the rate data normalised to Cabot
N774 as unity. There is considerable scatter but the trend is clear at
this temperature and also at 793 and 813 K. The full data are given in
[82].
For a particular series of reactions there is frequently a relationship
1.0 120
0.8
~r~,
100
0.8
Jg
;F Q) 80 IV
a..
0 0.6
~ 0.6 ~
--UJ ~
c:
60 ~
A
I 0.4 ./1I
I I
I
T 0.4 40
I
1 0.2
~
0.2
\\ 20
..----- ---- 0
0.0
(a)
·60 ·40 ·20 0 20 40 60
Temperature (OC)
120
1000
0.8 100
800 til IV
IV ::: 80 a..
'" !\0---
a.. Q)
0 0.6 ~
-~
UJ
600
~
c:
60 UJ
T
~
I 400 ',\ 0.4

40 ~
200 \
1 0.2 20
\
'-.- 0
0
(b) -60 ·40 ·20 0 20 40 60
Temperature (0C)
120
1000
0.8
100
800
Jg
IV
a.. 0
Q)
0.6 80 l
~ 600 c: :E
-UJ ~ 60=~
UJ
I 400 T 0.4 40
~
1 0.2
_.c:----.---.--.-.--.----
~
200 20
0
0
0 20 40 60
(e) -60 -40 -20
Temperature (DC)
Figure 6.3.5 DMA of bread samples: (a) fresh; (b) 3 h; (c) overnight.
WITCO N683
6
4 M=
fa
R 4
=2.0Sx10
fa =171 !!!.
Ink 3 mol
Figure 6.4.1(c) Arrhenius plot for oxidation of carbon black Witco N683.
KlS.A. vs SA AT 773.1SK
S.A. OF CABOT N774
1.40
e
1.30
e
1.20
1.10
•e
1.00 e e
.90 me
Comparative
reaction .80 e
rate
per .70
unrt
•e
,
area .60
e e
.SO
a a
e
.40 e
.30
.20 e
.10
2030 40 SO 60 7080 90100110120130140
Surface area m2 9- 1
Figure 6.4.1(d) Plot of specific reaction rate per unit area against the total surface area
for the oxidation of carbon blacks at 773 K.
34
32
30
28
26
24
22
InA
20
18
16
12
14
12
140 160 180 200 220 240 260
120
kJ
iiiOI
Figure 6.4.1(e) Compensation plot for oxidation of carbon blacks in air.
between the pre-exponential factor A and the activation energy E, called

the 'kinetic compensation effect' [83]. If In(A) is plotted against E, a
straight line graph is often obtained although the individual data may seem
to be rather random. This compensation effect plot is shown as Figure
6.4.1(e).
According to Grisdale [84] and Smith and Polley [85] the rate of
oxidation is about 17 times faster in the direction parallel to the basal
planes (along their edge, atoms described here as 'edge atoms') than
perpendicular to them. The low-area carbons show a preponderance of
'edge atoms' at the surface available for oxidation leading to a faster rate of
oxidation per unit area.
This interpretation has some implications for the reinforcing action of
carbon blacks in elastomers. Reinforcement is clearly seen in elastomer-
carbon black composites with carbon blacks of high surface area, suggest-
ing in the light of the above results that interaction between the elastomer
and the basal carbon atoms is a feature which imparts reinforcing action.
6.4.2 Proximate analysis of coals (Figure 6.4.2(a»
(a) The loss to 110°C is 0.70 mg, or 2.8%. This low value for the moisture
content is typical for an anthracitic coal.
(b) Loss in nitrogen between 110 and 900 °C is 3.63 mg, or 14.5%, which is
the volatiles content.
(c) After switching to oxygen when all the flammable volatiles had gone,
the mass decreases by 18.02 mg or 72.1%. This is the fixed carbon.
(d) The residue of 2.65 mg or 10.6%, stable at 900 °C in oxygen, is the ash
content.
Values for anthracitic and other coals have been shown to agree well with
the ASTM values for the same coals [91(a)].
The calorific value can be estimated by the use of the Goutal equation,
or a modification thereof. For anthracitic coals, the equation may be
written [91(b)].
P = 343(C+V)
where C is the percentage fixed carbon on a moisture-free basis and V is
the percentage volatile matter on a moisture-free basis.
For the above, C = 74.1%, and V = 14.9%, therefore
P = 30 527 Jig = 13 133 BTU/lb
Other thermal techniques used for coals include DSC to determine the
calorific content. Figure 6.4.2(b) shows the DSC of a coal similar to the one
used above, where a small coal sample is run in oxygen and the exothermic
peak between 200 and 600 °C measured. The area corresponds to 20.67 J
for 0.6881 mg coal, or 30 kJlg or 12 924 BTU/lb.
'--_...1-_.---- ______ _
mass
18.02 mg loss
Nitrogen
o 2.65 mg Residue
T/OC 200 400 600 800 900 time
Figure 6.4.2(a) TG proximate analysis of a coal.

t
EXO
Heat
Flow
200 400 600 T/oe
Figure 6.4.2(b) DSC of a coal sample (0.688 mg, 20 Klmin, O2),
6.4.3 Oil testing
(a) The traces clearly show that the onset of oxidation and the onset of
discoloration and/or deposit formation occur at the same temperature
and time.
The volatilisation of the oil in an open pan is slightly troublesome. If
the system could be operated under pressure, or in a crucible
constructed for observation under pressure, this could improve base-
lines.
The temperature of oxidation onset is 510 K (237 Qq, which is in
reasonable agreement with other data.
Comparison of four other oil samples showed a rather poor
correlation of the AOM test with both DSC onset time and DSC/RLI
onset temperature.
(b) Other techniques used to investigate oxidation of oils, both mineral
and edible, include infrared and UV spectrometry, gas chromatography
and electron spin resonance (ESR) spectrometry.
The onset of oxidation often gives a better indication of the start of
reaction than, say, IR since the concentration of product species is
very low at this point.
6.4.4 Soil analysis
(a) The measurement of soil pH, of particle size and mineral microscopy
should all be carried out on the original sample as heating will destroy
the texture. Removal of organic matter by peroxide oxidation would
also be carried out at this stage.
(b) Sample 1
Moisture loss (to 150°C) 18%
Organic matter (150--550 0c) 35%
Mineral content at 600 °C 47%
Mineral breakdown at 750°C, residue 30%
Sample 2
Moisture loss (to 150°C) 12 %
Organic matter (150--550 0c) 5%
Mineral content at 600 °C 83%
Mineral breakdown (not observed)
(c) It is not possible to identify the minerals present from thermal analysis
alone. X-ray diffraction or geological chemical analysis would be
needed.
In Sample 1, the decomposition with a mass loss of some 36% near
800 °C might suggest that calcium carbonate is present and this should
be investigated. Chemical tests did not confirm the presence of
carbonates.
Clay contents higher than around 40% cause problems owing to the
de hydroxylation of the clays in the same range as the other reactions.
Neither sample here showed evidence of high clay content by other
tests.
6.4.5 Catalyst studies
(a) The formation of methane causes a strong exotherm which reaches a

maximum value at around 250°C due to the almost complete reaction
of the carbon monoxide with the hydrogen. With large amounts of
catalyst, there may be some 'overheating' due to the thermal lag within
the sample.
(b) The presence of catalytic centres on the DSC cell surface will certainly
affect the reaction. The cell must be kept clean and the surface area of
the catalyst high in comparison with the cell surface.
(c) Kinetic studies on the catalysed reaction could be conducted by
varying the CO concentration supplied, and also the hydrogen pres-
sure, or by measuring the partial pressures of the components
independently.
6.4.6 Survival of Antarctic micro-arthropods
Two events occur during cooling. At around -5 DC, activity slows, but this
is hardly detected on the DSC curve. At -14°C there is freezing exotherm.
This is well below the equilibrium freezing point expected, but fairly
typical for this species.
The enthalpy change of about 466 Jig may be compared with that of
water (at 0 0c) of 2257 Jig. This suggests a water content of about 20%,
assuming complete freezing (or only 20% of the body water froze).
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Appendix
Solutions to problems in
Chapters 1-5
Chapter 1
1. Substance is low melting, and probably covalent. It burns in air with no Introduction to thermal
residue, so is possibly an organic (C,H,O) compound. The melting methods
could be studied by DSC or TMA under nitrogen to prevent burning.
The burning could be studied by TG in air. (Example: naphthalene.)
2. The colour change, residue and brown fumes suggest a hydrated
transition metal nitrate. (Example: cobalt nitrate hydrate.)
3. Thermodilatometry. This is a special case of thermomechanical analysis.
4. 'Thermoelectrometry is a family of techniques in which an electrical
property is measured against time or temperature while the tempera-
ture of the sample in a specified atmosphere is programmed.'
5. (a) The sample formula or source is not specified.
(b) The apparatus (DSC, TG, etc.) is not specified.
(c) The rate, atmosphere and mass of sample are not given.
6. Thermomicroscopy could be used to study the changes and evolved gas
analysis to study the gaseous products. The solid products could be
analysed by X-ray diffraction or wet chemical methods.
Chapter 2
1. Moisture loss, sublimation and gas adsorption all involve a change of Thermogravimetry
mass. Melting does not, and is not detected by TG.
2. (a) Would be detected since the gases are not weighed, but the solid
increases in mass; (b) would be detected, since CO2 gas is lost;
(c) would not be detected, since the double decomposition involves no
mass change.
3. As always, remember SCRAM!
S check the provenance, formula and state of the sample
C select an inert crucible, suitable to the temperatures to be used
R select a heating rate and start and end temperatures
A set the purge gas and flow rate
M decide what mass of sample you wish to run
For stability testing, you may have to perform several runs under
different conditions, e.g. in air and nitrogen.
4. Carbonates usually react with acids to give off carbon dioxide and yield
a salt:
Mg C0 3 + H 2C20iaq) = MgCP4'xH20 + CO2
A
The loss 2.23 mg (24.2%) to 220 °C could be of the hydrate water. The
RMM of the compound A is (112 + x x 18). If x = 2 then the loss
would be [2 x 18/148] x 100 = 24.3%
MgC 20 4·2H20 = Mg~04 + 2H20
As we have seen with calcium oxalate, the decomposition may go
through the carbonate to the oxide. Since there is only one stage here,
it is probable that the oxide is formed directly, since the residue is
27.0%, compared with the calculated residue of 27.0% for the total
loss.
The second reaction must be:
MgC20 4 = MgO + CO + CO 2
5. The final residue must be silver metal plus copper oxide, totalling 48%
and with a loss from the previous stage, copper oxide plus silver
nitrate, of 67%. Thus, a loss of 19% for loss of 'N03" RMM 62, in the
reaction:
AgN0 3 = Ag + N02 + 1/202
corresponds to a silver (RAM 108) content of 33.1%. Since the
AgN0 3 (RMM 170) would then be 52.1 %, the CuO must be
(48.0 - 33.1) = (67.0 - 52.1) = 14.9%
The copper (RAM 63.5) must be 11.6% of the original salts, or the
original alloy has
100 x [33.11(33.1 + 11.6)] = 74.0% silver
6. The initial loss is chiefly due to the breakdown of the poly(vinyl
acetate) with loss of ethanoic acid (acetic acid). A loss of 15% due to
ethanoic acid (CH3COOH, RMM 60) means that the vinyl acetate
moiety,
-[-CH2-CH(00C.CH3)-]-' RMM 86,
must make up 21.5% of the copolymer.
7. Suggest to your colleague that his or her procedure should be more
rigorously standardised! (SCRAM!) Are similar masses of sample
being used each time? Are the conditions the same? If the heating
APPENDIX SOLUTIONS TO PROBLEMS 275
rates are different, temperatures will be different too. If all rules have
been obeyed, it is probable that your colleague's sample is not pure, or
that it is not homogeneous. This actually happened with samples of
magnesium hydroxide that were damp!
Chapter 3
1. (a) Loss of moisture is endothermic and would be detected. Differential thermal
(b) Sublimation is endothermic. analysis and differential
(c) Desorption is endothermic. scanning calorimetry
(d) Polymer softening, unless at a glass transItion, may not be
detected since it is a mechanical, more than a thermal transition.
DMA would detect it.
2. As always: SCRAM! In this case the heating rate will have the effect of
changing the appearance of all the observed events, since:
(a) Ay= ~'CP' the baseline shift will double each time the heating rate
is doubled;
(b) AH = fAP dt = KfAT dt, the integration must be conducted with
respect to time. If we change the time by heating more rapidly, we
shall change the area.
3. This system forms a continuous series of solid solutions.
4. The fractions melted may be plotted versus temperature, remembering
that T should be in Kelvin!
T/K 1/F
407.8 0.00 The slope of the plot = - 0.32
406.7 3.45 = - (RT1/AH).x B
406.2 5.00 = - (8.314 x 407.82/53 300)'x B
Thus X B = 0.0123, or the purity of the phenacetin is 98.77%.
5. AH = -157 -297 - 0 - (-800) = 346 kJ/mol. This indicates an
endothermic reaction, as found. This is an estimate at 298 K, but the
reaction actually occurs around 1000 K. Data on the heat capacities
would be needed to correct the value.
6. The first run shows the Tg of the initial material. The second shows the
curing reaction and the third only the Tg of the cured sample.
7. Peaks due to mass loss occur only on first heating whereas inversions
usually appear 'inverted' on cooling curves. If cooling is not possible, a
second heating should reproduce an inversion but not a peak due to
loss of mass.
8. A mineral of 'ideal' composition is quite unusual. Mixtures of kaolin
(K) and felspar (F) are made by weighing out various proportions of K
and F and mixing them well. Each mixture, and the suspect material, is
subjected to both DTA and TG runs. The mass loss at 600°C is noted,
and a graph of mass loss versus kaolin content is plotted. The %K of
the suspect material may then be read from the graph. The height or
area of the peak at 600°C may also be correlated with %K.
Expansion
1
m
15
10
o
112°e
50 100 150 200 T/oe
Figure A.I Expansion plot of a polymer.
Chapter 4
Thermomechanical, 1. A simple system might involve a light source and photocell to sense the
dynamic mechanical movement of a shade across a light path due to the expansion of the
and associated methods sample. Disadvantages could arise from optical interference, heat
distortion, or the non-linear response of the detection system.
Such systems are described in B.K. Jones, Electronics for Experi-
mentation and Research, Ch. 8, Prentice Hall, London, 1986.
2. From the laws of expansion:
al = cx·l·aT = cxx3.00xlO- 3x100

cx = 2.5xlO- 5 K- 1
This is approximately the value for aluminium. The volume expansion
may be calculated from:
VT = Vo(1 +cx·b,.\T)3 = 150(1 + 2.5xlO- 5 xlOO)3
VT = 151·128 cm 3
The coefficient of volume expansion is then
or approximately 3 cx.
3. A simple plot of al versus T gives two lines intersecting at about
112°C. Note that with this small amount of data, the full characterisa-
tion of the glass transition is not possible (Figure A.1).
4. Substituting the values in the given equation:
F = 0.020x9.81 = 0.1962 N
R = 2.0xlO- 3 m, d = 0.113xlO- 3 m
Expansion
1
m Tg
Temperature
Figure A.2 Penetration TMA for rubber sample.
Thus E == 2.05x106 Pa. This compares well with the Young's modulus
value of 2.3x106 Pa.
The TMA curves might have the appearance of Figure A.2.
5. Normally for thin film or fibre samples, the most appropriate mode of
operation is in tension. The first difficulty is that of avoiding buckling
the sample. This is achieved by applying, in addition to the dynamic
force, a constant tension sufficiently large to prevent the total force
becoming compressive, but not so large as to cause excessive creep!
Typically it is 1.1 to 2 times the dynamic force. An additional problem
is encountered when the modulus of the sample changes. As this
happens, the force required to maintain a constant dynamic strain
changes. During a glass transition, this may change by three orders of
magnitude, so the constant tension must change too. This can be done
by holding the ratio of the dynamic and constant forces at the same
value throughout the experiment. The variation of these forces is
shown in Figure A.3.
6. If the sample prepared is too brittle to be clamped in the normal way as
supported technique may be used. A convenient technique is to
impregnate a glass fibre braid with the solution and then allow it to dry
before mounting the braid in the DMA. This relates to 'torsional braid
analysis', TBA. One disadvantage of this approach is that it is not
possible to measure the absolute value of the polymer modulus.
Another is that the sample may interact strongly with the glass fibre
braid which could distort the results by, for example, increasing the
apparent Tg or by the enrichment of a component of the sample at the
sample-support interface.
In this case the sample is a mixture. Experiments must be performed
on each component to establish their Tg values. If they are different
-----" - - - - Tensio
""-
----- \
\
- - - Dynarr
Force
- TgRange_
Temperature
Figure A.3 Forces during operation with a thin film or fibre.
then the results for the mixture provide clues for whether the two
polymers are miscible. If there are two peaks in the tan 8 plot that have
the same values as the pure component polymers, then they are
completely immiscible. If a single Tg is seen at an intermediate value,
then they are miscible.
7. Dynamic mechanical analysers are rarely adapted for making measure-
ments on liquids as they require that the sample be clamped into
position. A convenient way of investigating cross-linking behaviour is
to mount a glass fibre braid in the DMA (as in Problem 6) and then
impregnate it with a known volume of liquid sample. If heating is
required to initiate cross-linking then an appropriate heating pro-
gramme is used.
The storage modulus will begin to rise when the gel point is reached,
also marked by a peak in tan 8. As cross-linking proceeds the Tg of the
sample will increase and may rise to meet the cure temperature. When
this happens the sample will vitrify. This is also marked by an increase
in storage modulus and a peak in tan 8. The cure cycle can be said to be
complete when the temperature programme, which may be imitating
the environment in a real industrial process, has ended, or when the
storage modulus reaches a plateau. After this stage, the Tg of the
sample and any residual cure can be measured by cooling the sample
and performing a temperature scan in the normal way. After the Tg the
modulus may rise if the cure reaction is pushed further.
The cross-link density of the cured material can be found by
measuring its modulus above the Tg • This cannot be done on a support,
as the modulus of the polymer-braid composite is difficult to relate to
the modulus of the polymer. Consquently, a cured sample must be
prepared before running in the DMA. Different frequencies should be
tried to gauge the effect of this variable, but a plateau value should be
reached at low frequencies equivalent to the equilibrium storage
modulus. The cross-link density may then be calculated using the
equation in the text.
8. If the two peaks arose from a single sample, then the upper tempera-
ture transition, involving such a large drop in modulus, would be
assigned as a glass transition (or 'alpha transition') caused by large-
scale cooperative motions that involve the main polymer chain. The
lower temperature transition would then be assigned as a beta-
transition. Such secondary transitions are caused by localised motions
which involve little motion of the main polymer chains. These include
side-chain motions, or in-chain events such as rotations and large angle
torsionallibrations.
If the sample were composed of two components then the upper
temperature event would still be assigned as a glass transition, but the
lower temperature event might now be due to a second phase that has
a lower Tg • Whether the lower temperature event is due to a secondary
transition or a second Tg may be investigated by measuring the
relaxation kinetics as a function of temperature. If it follows a WLF
expression, then it should be a Tg , whereas a secondary transition
normally follows an Arrhenius equation.
9. (a) The value of log(a) may be compared with the calculated value
from the given WLF constants:
Trc log (a) [obs.] log(a) [WLF]

135 3.36 3.36(2)
140 1.57 1.56(6)
145 o o
150 -1.38 -1.37(8)
155 -2.60 -2.59(9)
We could also perhaps show the agreement with the Arrhenius
expression. If the temperature of maximum tan I) for 1 Hz is taken
as 145°C (418 K), then the maxima occur at other temperatures
when the frequency is shifted, e.g. using a frequency of 398 Hz,
the maximum will be at 155°C (428 K). A plot of In if) against
IITtd gives a smooth curve. This suggests that the transition studied
may be an alpha transition.
(b) The lowest frequency will be 10- 2 Hz lowered by 10- 2.6 Hz, that is
10-4 .6 Hz.
10. Using the dimensions given, the fraction of polymer in the final
solvent-swollen material will be:
V2 = (1.65)3/(2.83)3 = 0.198
With the given data:
-[In(l - 0.198) + 0.198 + 0.391 (0.198)Z]
n=
106.3[ (0.198)113 - (0.198)/2]
n = 1.469 x 10- 4 mol/cm 3
Chapter 5
Simultaneous 1. With modern instrumentation, even very small samples may be
techniques and product analysed quite easily. As a first attempt, we should choose non-
analysis destructive methods, such as IR or microscopy. If thermal data are
needed, DSC and thermomicroscopy should provide information on
polymorphism, melting, purity and thermal stability. With a very small
sample, simultaneous DSC-thermomicroscopy and/or DSC-FTIR
could be very informative.
2. If the appropriate traces in Chapter 2 and Chapter 3 are studied, it
should be clear that in normal circumstances, the detection will be as
follows:
Event DTA TG
(a) glass transition Yes No
(b) plasticiser loss Yes Yes
(c) residual curing Yes Possibly
(d) crystallisation Yes No
(e) melting Yes No
(f) oxidation Yes Yes
(g) degradation Yes Yes
3. The evolution of gases may be resolved by temperature or time or by

spectral dispersion.
(a) H 2 0 from (i), (ii) at about 100°C and from (ii), (iv) between 200
and 700°C.
(b) COz from (iii) around 800°C and from (iv) between 200 and
600°C.
(c) CO from (iv) between 200 and 500°C.
(d) SOz from oxidation of (v).
[Reference: D.J. Morgan, S.B. Warrington, S. St J. Warne,
Thermochim. Acta, 1988, 135,207.]
4. The reaction at about 100°C might correspond to loss of hydrate
water, which would give a mass spectrometric peak at mlz = 18, as
found.
Peaks due to ammonia (mlz = 17) and nitrogen (mlz = 28) or carbon
monoxide (also mlz = 28) occurring at 350°C suggest decomposition
of the anhydrous material, with some loss of COz and water.
The final loss at 850°C is the decomposition of the calcium
carbonate to calcium oxide with loss of COz (mlz = 44). The peak at
mlz = 28 could be due to the fragmentation to CO or to chemical
reduction of the dioxide. We may write the equations:
At about 100°C:
Ca(N 2H 3COOh·Hp = Ca(N2H3COOh + HP

with a loss of 8.4% against a calculated loss of 8.6%.
At about 300°C:
Ca(N2H3COO)2 = CaC0 3 + 2NH3 + N2 + CO

with a loss of 42.0% against a calculated loss of 43.3%.
At about 800°C:
CaC0 3 = CaO + CO2

with a further loss of 21.8% against a calculated loss of 21.1 %.
Chemical and X-ray analyses confirmed the products, but some
unidentified material was present.
[Reference: B. Novosel, J. Macek, V. Ivancevic, 1. Thermal Anal.,
1993,40,427.]
5. Obviously we should know a great deal more about the sample, its
history and composition before we can give proper answers, but the
evidence presented suggests:
(a) The colour suggests a transition metal salt or complex, possibly
containing chromium, copper or cobalt or iron. A colour change at
55°C suggests a phase change or a decomposition. TG would help
here.
(b) At 110°C the crystals became opaque. This is frequently asso-
ciated with hydrate or complex decomposition. The TG should
show a mass loss if this is correct. Such a decomposition would be
endothermic.
(c) A colour change to brown might indicate a further decomposition
(to oxide?). This could well be endothermic, and would be shown
byTG.
Additional information is required here!
6. Tristearin was noted in Chapter 3 to exhibit polymorphism. The low-
temperature ex form melts at about 56°C, and this would decrease the
light transmitted through crossed polars. Recrystallisation to form 13
restores the light intensity, since the crystals will depolarise the light.
Melting of the 13 form at 75°C takes the intensity back to zero,
characteristic of an isotropic liquid.
7. (a) The mass losses correspond closely to the suggested reactions, but
we must note that all intermediates and products should be
checked by independent analytical methods.
For (i), the water evolution could be checked by EGA, either
MS or IR or a specific detector. Similarly the evolution of CO and
CO2 simultaneously in (ii).
The nature of the solids in all cases should be checked by X-ray
diffraction and/or chemical analysis. All these checks were carried
out in the reference below.
[Reference: D. Dollimore, D.L. Griffiths, D.Nicholson, J. Chern.
Soc., 1963, 2617.]
(b) The original gel is clearly amorphous and has no regular crystalline
structure. On heating, it either crystallises (or possibly reacts) to
form a crystalline compound.
[Reference: J.A. Navio et al., J. Thermal Anal., 1993,40, 1095.]
Index
abbreviations 5 copper sulphate pentahydrate 45,

activation energy 9, 224, 238, 253 100
ammonium nitrate 80-1, 189 corrosion 55, 194
Antarctic micro-arthropods 242,269-70 coulometric titration 171
antifreeze proteins 242 creep 127
apparatus 9 cross-linking 148
area of peak 73-8 crucible 15,29,67-8,78
Arrhenius equation 9,34, 145 crystallinity 89
atmosphere 16, 31, 166 crystallisation 97, 218
Avrami kinetic models 33,39 Curie point 30
azoxyanisole 190
data processing 13
balances 24--7 DEA, DETA see dielectric thermal
barium hexaferrite 106 analysis
barium perchlorate 215,249 definitions 3-5
baseline 73-6 dehydration 42, 44, 45, 58, 139, 163,
beta transitions 144, 153 191
borate minerals 104, 106 denaturation 111
bread 235 derivative techniques 4
brick clays 174 derivative thermogravimetry 4, 23
building materials 139 dielectric materials 151
bulk modulus 124 dielectric thermal analysis 151-4, 228,
buoyancy 26 256
differential kinetic methods 36
calcium oxalate monohydrate 44,99, differential scanning calorimetry 63
173-4 et seq., 209, 213, 217, 219, 221, 226,
calibration 30, 77, 130, 142 228, 230, 232, 233, 239, 242
calibration materials 30, 77, 163 apparatus 66
calorimetry 64, 213 calibration 77
carbonates 17,49, 51, 106,210,246 definition 65
carbons 236,264 history 63
catalysts 54, 166,241,269 sensors 66
cellulose 48 theory 69
cements 101, 139 differential techniques 4
clays 104, 174 differential thermal analysis 63 et seq.,
coals 53,238-9 209,215,216,224,241
coefficients of expansion 131 see also differential scanning
compensation effect 268 calorimetry
complementary techniques 18 diffusion models 33
complexes 101, 186 DMA, DMTA see dynamic mechanical
complex moduli 127 analysis
complex permittivity 151 drugs 58
computers 11-13 DSC see differential scanning
constant rate methods 41 calorimetry
controlled rate TG 56 DTA see differential thermal analysis
controller 68 DTG see derivative thermogravimetry
copper carbonates 211 dynamic load thermo mechanical
copper, oxidation 55 analysis 123, 133, 139
dynamic mechanical analysis 139,227, infrared spectrometry 176
235 integral kinetic methods 38
dynamic mechanical thermal analysis see International Confederation for Thermal
dynamic mechanical analysis Analysis and Calorimetry (ICTAC) 3
isothermal methods 222, 226
EGA see evolved gas analysis
EGD see evolved gas detection Journal of Thermal Analysis 21
electrochemical detection 171
electron microscopy 198 kinetics
Ellingham diagrams 49 equations 8, 33
emanation thermal analysis 201 from DSC 97-9,225,252
endothermic change 7 from TG 32-42
enthalpy 6 linear variable differential
entropy 8 transformer 129
epoxy resins 109, 145, 185, 221, 227
liquid crystals 82, 185, 189, 232, 260
epoxy-glass composite 227, 256
liquid samples 137
equilibrium 7
loss modulus 127, 140
ethylene-vinyl acetate copolymer 50, 56
loss tangent 127, 140, 152
eutectic 85-6
low temperature operation 69, 129
evolved gas analysis 167 LVDT see linear variable differential
evolved gas detection 169 transformer
exothermic change 7
expansion 128, 131 magnesium hydroxide 42
magnesium nitrate hexahydrate 165, 191
fibres 135-6, 142, 150 Mampel kinetic equation 37
films 135-6, 142, 150, 228, 256 mass 18
fire retardants 144, 165, 196 mass spectrometry 171-6
Flory-Rehner equation 134 MDSC see modulated DSC
flow rate 17 melting points 63, 78, 218
foods 80, 114, 235, 263 melting wire calibration 30
Fourier transform infrared 176-7, 183 minerals 104, 178
Fox equation 148 mixtures, analysis by TG 48-54
free energy 8 modulated DSC 115
frequency effects 140-1, 145, 152 moduli 124
FfIR see Fourier transform infrared moisture effects 145
fuel additives 57 moisture evolution analysis 170
furnaces 28, 68 MS see mass spectrometry
fusion 78
nomenclature 4-6
gas chromatography, 170, 182 non-dispersive infrared 177
geometric kinetic models 33, 37 novolaks 224
gelation 139, 148-9
glass transition temperature 91-2, oils 57, 114,239,268
132-3, 144, 153, 218 OPC see Portland cement
glycerides 81 order of reaction 33
gravimetric analysis 22 oxalates 49
oxidation 54, 236
HAC see high alumina cement oxidation induction temperature 226,
heat capacity 7,89-91,116-17,213,247 254
heat, effects of 2 oxidation induction time 226, 254
heat flux DSC 65, 74 oxidative degradation 108, 226, 239
heat transfer 63, 71 Ozawa kinetic treatment 39,98,224
heating rate 15
high alumina cement 102 paint 151
Hi-Res TGA 56 parallel plate rheometer 130
high temperature synthesis 104 PDSC see pressure DSC
history 1 penetration 125, 133-4
hot -stage microscopy see permittivity 151
thermomicroscopy pharmaceuticals 58,81,87, 165, 189,
hydrates 191 228, 233, 261
INDEX 285
phase diagrams 84,230, 260 sample holder 15
phase separation 148, 154 samples 10, 14, 18, 28, 68
phase transitions 79, 137, 189, 213 SAXS see small angle X-ray scattering
phenol-formaldehyde resins 48, 224 self generated atmosphere 31
phosphor 106 sensors 10
photocalorimetric DSC 114 shear modulus 124
Poisson's ratio 125 simultaneous techniques 19, 161 et seq.
polyester resins 48, 109, 179 simultaneous TG-MS 171,212,225
polyethylene 47, 90--1, 136, 226 simultaneous TG-GC-MS 175
poly(ethylene oxide) 174 simultaneous thermal analysis 162
poly(ethylene terephthalate) 89, 118, sintering 137
153, 200, 219, 228 SI units 6
polymers small angle X-ray scattering 193, 196-9
blends 50, 56, 219, 251 sodium tungstate dihydrate 163
characterisation 217, 251 softening temperature 134
crystallinity 89, 115 soils 52, 240, 268
curing 109, 139, 212, 252 solid solutions 85-6
degradation 47, 112, 185,224,253 solid state reactions 216, 250
glass transitions 91, 132, 133, 144, solvent swelling 134
153, 218 ST A see simultaneous thermal analysis
miscibility 147 steel 194
phase changes 87 storage modulus 127, 140
structure 196 strontium nitrate 212, 247
transitions 153 sulphur 137-8
poly(methyl methacrylate) 47, 169 superconductors 108
polymorphism 80, 185, 189, 233 supported techniques 150
polypropylene 47, 112-13, 156,219 symbols 4-6
polystyrene 47, 93 synthesis 104
poly( tetrafluoroethylene) 47
poly(vinyl chloride) 48, 112, 144, 165, temperature programmed reduction 54
174, 179, 181 tensile modulus 124
Portland cement 101 TG or TGA see thermogravimetry
potassium nitrate 79, 213, 247 TG-MS see simultaneous TG-MS
power-compensated DSC 65, 76 theory of DSC and DTA 69
pressure DSC 68, 114 thermal analysis 4
product analysis 161 et seq. thermal expansion 128, 131
programmer 28 thermal lag 15
proteins 111 thermally stimulated current
proximate analysis of coals 53, 238, analysis 154-6
266 thermal volatilisation analysis 169
purity 93,228,257 thermobalance 23-7
pyrolysis gas chromatography 182-4 thermodilatometry 123
pyrotechnics 106 thermodynamics 5-8
thermogravimetric analysis 23
quartz 104, 137 see also thermogravimetry
thermogravimetry 22 et seq., 209, 211,
rate-jump techniques 41 215, 236, 238, 240
rate of heating 15 apparatus 23
reaction kinetics see kinetics calibration 29
reactive atmosphere effects 54-5, 166 history 22
reduced time plots 38 kinetics 32
reduction 54, 114 thermoluminescence 201
reference materials 69 thermomagnetometry 201
reflected light intensity 188, 191, 240 thermomechanical analysis 123
reflection techniques in lR 177 apparatus 128
relaxation kinetics 145 thermomicroscopy 186-92, 232, 239
relaxation map analysis 154-6 thermomolecular flow 26
RMA see relaxation map analysis thermoptometry 186
rubber 52-3 thermosonimetry 201
rubber toughening 148 three-point bending 125-6
tin formate 209, 245 viscous flow 126
TMA see thermomechanical analysis
topaz 194 WAXD see wide angle X-ray diffraction
torsional braid analysis 149 WAXS see wide angle X-ray scattering
TSC see thermally stimulated current wide angle X-ray diffraction 193, 196-9
analysis wide angle X-ray scattering 193, 196-9
TVA see thermal volatilisation analysis Williams-Landel-Ferryequation 146-7
wood 165
units 6
X-ray methods 192 et seq.
vaporisation 114 X-ray powder diffraction 193
vapour pressure 114
viscoelasticity 124, 127 Young's modulus 124

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Thermal Methods of Analysis

Principles, Applications and Problems

M. Reading T.J. Lever

SPRINGER-SCIENCE+BUSINESS MEDIA, B.V. I~n

The wide range of applications of thermal methods of analysis in measuring

Professor E.L. Charsley TACS, Leeds Metropolitan University, Calverley

Professor D. Dollimore Department of Chemistry, University of Toledo,

Mr P.J. Haines 38 Oakland Avenue, Weybourne, Farnham, Surrey GU9

Dr T.J. Lever TA Instruments Ltd, Europe House, Bilton Centre, Cleeve

Dr M. Reading Physics Section, Research Department, ICI Paints,

Dr. F.W. Wilburn 26 Roe Lane, Southport, Merseyside PR9 9DX

The authors wish gratefully to acknowledge permissions to reproduce

1 Introduction to thermal methods 1

3 Differential thermal analysis and differential scanning

4 Thermomechanical, dynamic mechanical and associated

5 Simultaneous techniques and product analysis 161

6 Problem solving and applications of thermal methods 206

Appendix: Solutions to problems in Chapters 1-5 273

Table 1.1 The effects of heat on solid materials

Effect Possible conclusion Example

Thermal analysis (TA) is defined [17] as:

EXAMPLES OF SYMBOLS USED IN THERMAL METHODS

Technique Abbreviation Property Uses

1. Thermogravimetry TG Mass Decompositions

Less frequently used techniques

Glass transition temperature K

When a substance is heated, its physical properties and sometimes its

Quantity Symbol Unit(s) and abbreviation(s)

equations and by thermodynamic functions showing the properties of the

standard enthalpy change 6.W, generally expressed per mole of substance.

Most reactions tend to proceed to an equilibrium state. This may be almost

may be applied to physical equilibria, such as solution, adsorption or

Chemical reactions occur at particular rates, defined by the rate of change

1.3.3 General apparatus

Almost all thermal methods use a similar arrangement of apparatus, as

Figure 1.1 Schematic diagram of thermal analysis system.

system and, after processing, are displayed on a screen or recorder as a

1.4.1 The computer as an instructional tool

There are several 'computer-aided learning' schemes available for analytical

1.4.2 The computer as a data gatherer

The earliest commercial thermal analysis instruments produced signals that

1.4.3 The computer as a data processor

The software available with computer-linked thermal analysis instruments

1.4.4 The computer as a research tool

The design and operation of thermal analysis equipment, even more so

1.5.1 The sample

1.5.2 The crucible

The material of the sample holder or crucible should be stated, together

1.5.3 The rate of heating

Experiments may be carried out at heating rates (dT/dt) from 0 Klmin -

where Te is the observed, uncorrected temperature at heating rate [3, Te 0 is

Te = 303.56 + 0.074'[3 - 0.2 = 304.10 K

Ti,fast > Ti,slow

1.5.4 The atmosphere

Gas at 1 atm Thermal conductivity at 373 KI(1O-2 J/(smK)

then Le Chatelier's Principle tells us that the presence of a large

1.5.5 The mass of the sample

Such a scheme might also involve a thermogravimetric experiment from

A. Blazek, Thermal Analysis, Van Nostrand, London, 1972.