Anal. Chem.
2002, 74, 2749-2762
Thermal Analysis
Sergey Vyazovkin
Department of Chemistry, University of Alabama at Birmingham, 901 South 14th Street, Birmingham, Alabama 35294
Review Contents
Method Development and Calibrations
Thermodynamics
Kinetics
Inorganics
Polymers
Energetics and Fuels
Pharmaceutical, Biochemical, and Biological
Applications
Literature Cited
Since 1988, the field of thermal analysis had been reviewed
by Professor David Dollimore, who passed away on August 4,
2000. This tragic event has been memorialized by dedicating the
special edition (1) of Thermochimica Acta that collects the papers
presented at the 27th NATAS Conference. David was a person of
truly encyclopedic knowledge and a great enthusiast of thermal
analysis. It is a great honor and responsibility to continue
reviewing the present topic in place of him.
The present review covers the years 2000 and 2001 and is
limited to 200 references. Thermal analysis is concerned with a
very wide area of applications described in a huge number of
publications. Suffice it to say that according to ISI Web of Science,
the most common thermal analysis technique “Differential scan-
ning calorimetry” was mentioned in around 4000 publications in
2000-2001! In this circumstance, an attempt to select 200 papers
that comprehensively cover the whole field would be futile.
Instead, the review covers the most popular applications of thermal
analysis as well as the recent developments of the method.
Over the past 2 years, one of the major events in the field of
thermal analysis was the 12th International Congress on Thermal
Analysis and Calorimetry that was held in Copenhagen, August
14-18, 2000. Over 300 presentations were made at the Congress.
The Congress proceedings have been issued as a separate volume
of the Journal of Thermal Analysis and Calorimetry (2) that
provides a representative collection of papers dealing with the
modern problems of the field. The break of the 21st century was
marked by a special issue (3) of Thermochimica Acta that
summarized the past progress and projected future developments
in the field of thermal analysis. Brown (4) published the second
edition of Introduction to Thermal Analysis, which makes an
excellent text for thermal analysis courses. Wunderlich stresses
(5) that thermal analysis courses are extremely important for
material sciences education and should be taught more widely;
that can, in part, be accomplished by creating and offering Internet
courses. Tanaka (6) emphasized the role of thermal analysis in
environmental chemistry education in the 21st century.
As an important source of emergency information on thermal
analysis, we should mention the list server “Thermal” (http://
10.1021/ac020219r CCC: $22.00 © 2002 American Chemical Society
Published on Web 04/19/2002
www.egr.msu.edu/mailman/listinfo/thermal) ran by Michael Rich
2749 at Composite Materials and Structures Center of Michigan State
2751 University. The list has a free access and includes dozens of
2751 thermal analysis experts who readily answer questions related to
2753 thermal analysis.
2755
2757 METHOD DEVELOPMENT AND CALIBRATIONS
2758 Parkes et al. (7) report the design and operation of a new
thermal analysis instrument that uses microwaves to simulta-
2760
neously heat and detect thermally induced transformations in
samples. Physical or chemical alterations in a material cause
variations in its dielectric properties that can be revealed by a
variety of means including changes in the sample temperature,
the differential temperature, or the shape of the power profile
during linear heating experiments. The decomposition of basic
copper carbonate is used to illustrate the sensitivity of the
instrument that shows a large temperature increase on the
formation of the strongly coupling oxide.
Smith and Shirazi (8) developed a sensitive method for
determining the enthalpy of gas-surface interactions. The method
combines a quartz microbalance with a microcalorimeter. The
calorimeter accommodates both sample and reference holders,
which are attached to a quartz crystal microbalance and are in
intimate thermal contact with a heat flow sensor. The sample is
coated with a thin polymer film capable of adsorbing or desorbing
vapors. The technique permits simultaneously measuring the
resulting change in the mass per unit area (to (0.25 ng cm-2)
and the heat flows (to (50 nW). A microcalorimetric method is
proposed by Gomez et al. (9) to determine the contact angle of a
nonwetting liquid within a mesoporous solid. It is based on the
simultaneous measurement of the heat and work of wetting, as
the pressure is raised. The method simply requires a previous
determination of the surface area to be wetted. Its utility is
illustrated for water in porous hydrophobic silicas.
Allen et al. (10) introduced a scanning calorimeter for use with
a single solid or liquid sample having a volume of a few nanoliters.
Its use is demonstrated with the melting of 52 nL of indium, using
heating rates from 100 to 1000 K s-1. The heat of fusion has been
determined to be within 5% of the bulk value, and the sensitivity
of the measurement is (7 µW. The heat of vaporization has also
been measured for individual water droplets from 2 to 100 nL in
volume. The measured value, 2250 ( 500 J g-1, is within 23% of
the bulk value for water. The use of high heating or cooling rates
(faster than 100 °C min-1) has been made in the method of high-
performance DSC (11). In addition to higher sensitivity and the
possibility of using submicrogram samples, the use of high heating
rates also allows one to practically eliminate slow phenomena such
as recrystallization of PE on melting or cold crystallization of PET
that simplifies interpretation of complex DSC signals.
Analytical Chemistry, Vol. 74, No. 12, June 15, 2002 2749
 Benoist and Le Parlouer (12) describe a new integrated circuit
detector that consists of a thermopile integrated in a silicon epitaxy
layer of a silicon wafer. This miniature detector is reported to have
a very short response time and about 10 times greater sensitivity
as compared to regular DSC instruments. The detector has been
employed in a portable single-pan DSC instrument. Dong and Hunt
(13) describe another new signle-pan DSC that is demonstrated
to have significant advantages over conventional heat flux DSC.
Tozaki et al. (14) developed a new method for simultaneously
measuring heat flow and thermal expansion at a temperature
resolution of millikelvins. The method has been applied to study
the thermal behavior of a single crystal of BaTiO3 that is known
to undergo a first-order tetragonal-to-cubic transition at around
404 K. This single transition has been detected on heating. On
cooling, both heat flow and thermal expansion have shown six
thermal events in the narrow region between 402 and 403 K. The
multiple events are explained by stepwise nucleation of the
tetragonal phase. Nakamura et al. (15) describe a newly designed
sample cell attached to TMA that enables swelling of polymer
hydrogels to be measured as a function of time. The application
of the cell is illustrated by studies of swelling of calcium alginate
dry film.
Riesen et al. (16) discuss a method of obtaining DSC informa-
tion from the measurements performed on a simultaneous TGA-
DTA instrument. A calibration enables the measured DTA signal
to be converted into a heat flow curve (DSC signal). Unlike regular
DSC, the method allows one to detect mass changes during a
process and, therefore, to account for heat losses associated with
sublimation and vaporization. The method has been validated by
correctly determining the melting enthalpy of anthracene and the
heat of phenol formaldehyde polymerization.
The use of modulated temperature programs has become an
integral part of various thermal analysis methods, including DSC,
TGA, and TMA. Among these, temperature-modulated DSC
(TM-DSC) attracts most attention. As compared to regular DSC,
the technique has a higher sensitivity and is capable of separating
some complex thermal phenomena by separating the DSC signal
into reversing and nonreversing components, which respectively
vary in-phase and out-of-phase with the temperature modulations.
The separation of the DSC signal is accomplished by using the
Fourier transform. However, Hu and Wunderlich (17) suggest
that similar information can also be obtained without the Fourier
transform from the imbalance in heat capacity, which is measured
by using sawtooth temperature modulations in regular DSC.
Although TM-DSC opens up exciting opportunities, it also
raises numerous concerns associated with the basic assumption
of the method that the response of the whole system (i.e.,
calorimeter and sample) to the temperature modulations is linear.
However, the response of kinetic phenomena such as glass
transition is clearly nonlinear. The violation of the linearity
condition results in measurement errors. Simon and McKenna
(18) presented quantitative analysis of such errors for the TM-
DSC measurements carried out in the glass transition region.
Simon (19) recently reviewed the theory of TM-DSC and its
applications to measuring heat capacity, the glass transitions, and
processes of crystallization and melting. Ozawa (20) recommends
that sound application of TM-DSC should at present be limited to
heat capacity measurements. Note that the reliability of these
2750 Analytical Chemistry, Vol. 74, No. 12, June 15, 2002
measurements is strongly dependent on the heat-transfer condi-
tions. The effect is explored in terms of mathematical models (21-
23). Merzlyakov and Schick (24) discuss the issue of optimizing
experimental parameters for TM-DSC measurements and suggest
numerical criteria for testing whether the DSC response is linear
and stationary.
Calibration of TM-DSC presents numerous challenges includ-
ing that of finding suitable standards. A proper calibration standard
should demonstrate a well-defined transition that does not disturb
the temperature profile within the sample during modulation (i.e.,
heat-cool cycle). As mentioned earlier, the response of the whole
system must be linear during modulation (25). This requirement
can be met when low-energy liquid crystal transitions are used.
It has been in particular demonstrated that the nematic-to-smectic
transition in a cyanobiphenyl liquid crystal (80CB) can be used
for temperature calibration of TM-DSC. Harkvoort et al. (26)
tested a number of compounds and reported that adamantane and
Zn have fast reversible transitions and can be applied both for
temperature and for heat calibrations. Because of its well-defined
liquid crystal-to-isotropic transition at 409 K, 4,4′-azoxyanisole can
be used for temperature calibrations. However, this substance has
a small heat effect that makes it not practically suitable for heat
calibrations. Other compounds such as NaNO3, In, Hg, and Pb
demonstrate noticeable supercooling and, therefore, are suitable
only for heat calibration. The problems of calibration in the cooling
mode have been examined by the working group “Calibation” of
the German Society for Thermal Analysis (GEFTA) (27). Because
of the general occurrence of supercooling for first-order phase
transitions, liquid crystals and substances with higher-order phase
transitions have been recommended for temperature calibration.
For heat calibration, they recommend using substances that show
a small degree of supercooling, and substances that have a known
temperature dependence of the transformation enthalpy.
Wunderlich et al. (28) studied the effects of the heat-
conducting paths from the temperature sensor to the sample and
from the sample-temperature to the reference-temperature sensors
on the determination of heat capacity by TM-DSC. The effects
were found significant and the relevant calibration procedures
were proposed. Using simulations, they (28) demonstrate that the
phase angle difference between the sample temperature and the
heat flow should be taken into account when determining heat
capacity. The results were experimentally verified for aluminum
samples of different masses in quasi-isothermal experiments at a
wide range of modulation frequencies. A great number of other
issues associated with calibration of various calorimeters are
discussed in a special issue of Thermochimica Acta (29).
There are no kinetic standards based on reactions of solid
substances. Sbirrazzuoli et al. (30) proposed an electronic solution
to the problem of kinetic standard for calibration of DSC. They
used a thermal resistor to generate the heat flow in accord with
a desired kinetic equation and a set of Arrhenius parameters.
Analysis of the obtained data suggests that for kinetic purposes
heat flow calibration should be preferred over the simple peak
area calibration.
The use of a modulated temperature program in TMA (TM-
TMA) allows for separation of the temperature-dependent (revers-
ible) expansion from the time-dependent (irreversible) stress
relaxation (31). By using TM-TMA, Riesen and Schawe (32) were
able to simultaneously determine the coefficients of thermal
expansion and shrinkage a drawn PET fiber. Kociba (33)
presented a new idea of calibrating temperature in TMA in the
temperature-modulated mode by using magnetic substances with
known Curie temperatures.
THERMODYNAMICS
Thermal analysis provides efficient tools for measuring fun-
damental thermodynamic properties such as enthalpies, heat
capacities, and temperatures of phase transitions. For instance, a
theory based on the Laplace equation of the surface and the
Gibbs-Duhem equation predicts a size-dependent melting tem-
perature depression. The phenomenon was studied by Allen et
al. (34), who applied the technique of thin-film differential scanning
nanocalorimetery to investigate the melting behavior of indium
films, consisting of ensembles of nanostructures. It was found that
the melting point of the investigated indium nanostructures
decreases as much as 110 K for particles with a radius of 2 nm.
Another size effect is reported by Toda et al. (35) for crystallization
and melting of ice crystallites confined in porous silica gel.
According to TM-DSC measurements, the processes occur at
temperatures 10-20 °C lower as compared to bulk crystals and
are explained by the effect of surface tension.
While widely used for detecting glass transitions, the method
of TMA finds very few applications in studies of first-order solid-
solid transitions (36, 37). However the method appears to be quite
advantageous in detecting phase transitions in decomposing solids.
For instance, heating of KH2PO4 results in the intensive dehydra-
tion that starts around 180 °C and causes anomalies in various
physical properties (e.g., heat absorption in DSC) that are
frequently mistaken for the tetragonal-to-monoclinic transition
(37). In this region, TMA demonstrates only the trivial thermal
contraction associated with decomposition. The transition occurs
in the temperature region 200-220 °C and clearly shows up as
an anomalous thermal expansion (37).
Price (38) discusses the use of TGA for determining the vapor
pressures and enthalpies of vaporization and sublimation. The
approach is based on the Langmuir equation for the rate of free
evaporation
-
dm
dt
) PR
x2πRT
M
(1)
where m is the mass, t is the time, P is the vapor pressure, R is
the vaporization coefficient, M is the molecular weight of the vapor
substance, R is the gas constant, and T is the absolute tempera-
ture. Equation 1 is rearranged as
P ) kν (2)
where k ) (2πR)1/2/R and ν ) -dm/dt(T/M)1/2. A plot of P versus
ν follows the same trend for different compounds regardless of
their chemical structure that allows compounds with known vapor
pressure to be used for estimating the calibration constant, k, and
thus the vapor pressure of unknown substances to be determined.
Combining eq 2 with the Clausius-Clapeyron equation gives
ln ν ) B - (∆H/RT) - ln k (3)
From the slope of a plot ln ν versus T-1 one determines the
enthalpies of vaporization and sublimation, ∆H that can be
corrected to a standard state by using empirical equations (38).
The method was extensively used by Dollimore and co-workers
to determine vapor pressures of various pharmaceutical com-
pounds (39-41). It should be stressed that the method assumes
the constancy of R, which is secured when the free surface area
does not change during the run. If this condition cannot be met,
Price (38) suggests determining the enthalpy by using temper-
ature jumps during which no significant change in the surface
may occur.
TGA and DSC can be conveniently used to study thermo-
dynamics of the surface processes of adsorption and desorption.
High-resolution TGA was employed by Li et al. (42) to measure
desorption of water, 1-butanol, and n-heptane from activated
carbons treated with oxidizing agents such as hydrogen peroxide,
perchloric acid, and nitric acid. Comparison of the themodesorp-
tion profiles for molecules of different polarities allows for studying
the surface properties of oxidized carbons. Eigenmann et al. (43)
demonstrate the potential of the method of pulse thermal analysis
for measuring adsorption. Pulse thermal analysis combines TGA
with a pulse device that injects a certain amount of a gas into the
carrier gas stream flowing through the TGA system. A series of
consecutive pulses at a constant temperature and atmospheric
pressure gives rise to an increase in the mass that may be
irreversible or reversible, being therefore associated with chemi-
sorption and physisorption, respectively. The method has been
validated by measuring adsorption of ammonia on zeolites. High-
pressure thermogravimetry was applied by Bentzen et al. (44) to
characterize a number of hydride-forming alloys in terms of
reversible storage capacity, working pressures, and temperatures.
The use of simultaneous TGA-DSC allows one to monitor both
the heat of adsorption and the mass of adsorbed substance. With
the help of this technique, Wang and Yeh (45) studied the
mechanism of adsorption of dioxygen and oxidation phenomena
on supported platinum metals (Pd, Pt, Rh) over a wide temperature
range. Pires et al. (46) found that microporosity of aluminum-
pillared clays correlated well the heats of adsorption measured
by TGA-DSC, which makes possible the use of this technique
for controlling the porosity.
KINETICS
The methods of thermal analysis make it possible to follow
the kinetics of various thermally stimulated processes such as
decomposition, oxidation, reduction, crystallization, and polym-
erization. The kinetics of these processes are most commonly
described by the following rate equation
dR/dt ) k(T)f (R) ) A exp(-E/RT)f (R) (4)
where R is the extent of reaction, k(T) is the Arrhenius rate
constant, A is the preexponential factor, E is the activation energy,
and f (R) is the reaction model. Equation 4 rests upon the concept
of a single-step reaction that was inherited by solid-state kinetics
from the kinetics of much simpler reactions in homogeneous
media. This concept as well as the two derivative concepts (the
concept of constant activation energy and the concept of reaction
model as a representative of the mechanism) is inconsistent with
the multistep nature of solid-state reactions (47). While contradic-
Analytical Chemistry, Vol. 74, No. 12, June 15, 2002 2751
tory to numerous experimental facts, these concepts are preva-
lently used in kinetic analyses. This situation is not very surprising
as the research area of solid-state decompositions presently lacks
an adequate theoretical framework (48). Some compromise
between the kinetic complexity of solid-state reactions and the
simplicity of their kinetic description is accomplished in the idea
that the overall rate of a multistep process can be represented by
a combination of single-step rate equations, each of which
represents a single step of the overall process. However, it is not
practically feasible to identify all single steps and describe their
rates by the respective rate equations. In practice, the overall rate
of a process is approximated by a combination of a few (usually
two to three) rate equations each of which holds for the whole
region of temperatures and extents of reaction. This approach is
implemented in several software packages (49). Another op-
portunity is to represent the overall rate by a set of rate equations
each of which holds for a given extent of reaction and a
temperature region that corresponds to this extent of reaction.
This approach is materialized in isoconversional methods and in
the closely related method of model-free kinetics (47) that reveal
the reaction complexity as a dependence of the effective activation
energy on the extent of reaction. This effect has inspired
introduction of new kinetic concepts of distributed reactivity (50)
and variable activation energy (47). Mention should be made of
the parallelism of these concepts with the concept of the time-
dependent energy barrier that is used in dispersive kinetics (51).
In addition to the conceptual issues, a great deal of kinetic
concern is associated with computational problems. Most of
kinetic data are collected under nonisothermal (usually linear
heating rate) conditions, for which eq 4 takes the form
dR/dT ) A/β exp(-E/RT)f (R) (5)
where β is the heating rate. Because a single nonisothermal run
provides information about both the temperature and conversion
dependencies (e.g., k(T) and f (R), respectively) of the reaction
rate, a large number of methods have been developed for
evaluating E, A, and f (R) from a single run. Such evaluation
obviously requires separating the temperature and conversion
dependencies that, however, cannot be accomplished experimen-
tally in a single run performed at a constant heating rate. The
single heating rate methods strive to accomplish the separation
computationally, by simultaneously adjusting E, A, and f (R) in
order to obtain the best fit of the data. However, the mutual
compensation of k(T) and f (R) gives rise to the fact that almost
any f (R) can satisfactorily fit data at the cost of drastic variations
in the Arrhenius parameters (47). For this reason, the single
heating rate methods tend to produce highly uncertain values of
Arrhenius parameters that cannot be used to characterize the
reaction kinetics (52).
The computational problems were largely sorted out in the
frameworks of the recent ICTAC Kinetics Project (49), the
participants of which were provided with isothermal and noniso-
thermal data on a hypothetical simulated process as well as on
the thermal decompositions of ammonium perchlorate and cal-
cium carbonate. The participants applied a variety of computational
methods. While comparing the results, special attention was paid
to the ability of the methods to handle multistep reaction
2752 Analytical Chemistry, Vol. 74, No. 12, June 15, 2002
mechanisms. The model-free isoconversional methods and model-
fitting methods that use multiple heating rate data were particu-
larly successful in correctly describing the multistep kinetics in
the simulated data. These methods also produced reasonably
consistent kinetic results for isothermal and nonisothermal data
and were identified as the most prospective techniques currently
available for kinetic analyses (49). By analyzing the results of the
project, several participants (53-55) concluded that the single
heating rate methods should be completely avoided. In any case,
the necessary condition for estimating reliable kinetic parameters
is the use of multiple heating programs, be they isothermal,
nonisothermal, or a mixture of the two (49, 53-55).
Unlike a single heating rate run, the use of multiple heating
programs allows for separating the temperature and conversion
dependencies of the reaction rate. For instance, the isoconver-
sional methods eliminate the conversion dependence (i.e., f (R))
by analyzing the rate data at a constant extent of conversion
d ln(dR/dt)R ER
-1
)- (6)
dT R
where the subscript R denotes values obtained at a given extent
of conversion. Evaluation of ER requires that the rate at a constant
extent of conversion should be determined at different tempera-
tures, which is accomplished by using multiple heating programs.
This requirement can be satisfied approximately within a single
experiment by using a series of heating or cooling steps during
which the extent of conversion does not change significantly. Then
the change in the reaction rate can be considered roughly as
occurring at a constant extent of conversion, and eq 6 can be used
for estimating the activation energy. The idea was first imple-
mented by Flynn (56) in his temperature jump method. A modern
commercial version of the method, known as modulated thermo-
gravimetric analysis (MTG), imposes a sinusoidal temperature
modulation on a linear hating rate program. In reality, the extent
of conversion changes even during a quick temperature step that
unavoidably introduces some systematic error in the values of
the activation energy determined by using MTG.
The activation energies obtained by MTG were compared with
the values that were obtained by the isoconversional method from
a series of linear heating rate runs (57, 58). For the thermal
degradation of several EPDM elastomers, Gamlin et al. (58)
reported that activation energies calculated from MTG are much
lower than those calculated from several runs by using an
isoconversional method. Schubnell’s data (57) show that for the
thermal decomposition of PTFE the values obtained by MTG are
somewhat greater than the values obtained from the isoconver-
sional analysis of multiple runs. However, for the thermal
decomposition of MnO2, the MTG values were significantly larger
than the values determined by the regular isoconversional method
and also demonstrated very strong fluctuations (57). Apart from
the possible systematic deviations, the reliability of an activation
energy obtained from a single experiment is always questionable
because the repeatability of such an experiment remains unknown.
Overall, extracting reliable values of the activation energy from a
single run is a tempting but rather impractical idea, regardless of
the temperature program used.
 Budrugeac and Segal (59) used sets of simulated and experi-
mental data to compare several isoconversional methods. They
demonstrate that the integral methods may yield a significant
systematic error for a process whose activation energy strongly
varies with the extent of reaction. It should be stressed that this
error does not invalidate the integral isoconversional methods in
general (60). It is unavoidable only in the simpler methods that
use integrated kinetic equations such as eq 7 used in the well-
ln (β) ) Const - ER/RTR (7)
known methods of Ozawa and Flynn and Wall. In this case, the
error results from the fact that eq 7 was derived by assuming the
constancy of the activation energy. The situation is, however,
entirely different for the methods that use integration as a part of
the procedure for estimating the activation energy. In particular,
Vyazovkin (60) demonstrated that the systematic error can be
practically eliminated in the integral isoconversional method that
evaluates the activation energy by minimizing the following
function
n n
J[ER,Ti(tR)]
Φ(ER) ) ∑∑ J[E ,T (t )]
i)1 j*i
(8)
R j R
where T(t) is the temperature program and J is integral of the
Arrhenius exponent with respect to time. The error in ER virtually
disappears when the integral is carried out over small time
segments, tR-∆R - tR as follows
∫
tR
J[ER,Ti(tR)] ≡ exp[-ER/RTi(t)] dt (9)
tR-∆R
The application of the Arrhenius equation for describing the
temperature dependence of the rate of solid-state decompositions
has been criticized by L’vov (61), who explores an approach that
is based on the theoretical treatments developed by Hertz and
Langmuir for vaporization of metals. The basic assumption of this
approach is that the primary step of decomposition of a solid is
its congruent dissociative vaporization. Although L’vov fairly
mentions that this assumption “might appear at first sight ... very
unusual”, he uses his approach to explain numerous experimental
values of the activation energies of reversible processes. Note that
comparison of theoretical values of the activation energy with the
experimental ones may itself present a considerable challenge as
the reported values tend to be widely differing (cf. an older paper
by Maciejewski (62), who analyzes 168 reported values of E for
decomposition of CaCO3). Such a discrepancy is usually explained
by the differences in experimental conditions and sample char-
acteristics. However, the method of computation of the activation
energy may also contribute to this discrepancy, which in the case
of single heating rate methods may be large enough to explain
dramatic differences in the reported values.
Attempts are also made to develop new reaction models
describing the conversion dependence of the reaction rate. The
fractal nature of heterogeneous processes involving solids is well
known. This stimulates ongoing efforts in applying the mathemati-
cal apparatus of fractal geometry to describing heterogeneous
reactions (63-65).
The experimental values of ln A and E are frequently found to
demonstrate a linear correlation, also known as a kinetic com-
pensation effect or an isokinetic relationship. A search for a
physical meaning of the effect remains a matter of inexhaustible
interest (66). A comprehensive review on isokinetic relationships
has been published by Liu and Guo (67). A compensation effect
is usually detected in the form
ln Aξ ) aEξ + b (10)
where ξ represents a factor that causes a variation in the values
of kinetic parameters, although a nonlinear form has also been
proposed (52). If ξ is a physical factor that can in principle affect
the activation energy barrier, this correlation may represent the
so-called “true compensation effect”. However, if ξ is a formal
factor associated with a model or a method of computation, the
correlation represents a “false” or “artificial compensation effect”.
False compensation effects indicate numerical instability of
estimating Arrhenius parameters. They are frequently found when
fitting single heating rate data to various reaction models. For
instance, such effects have recently been reported for thermal
decomposition of imido-phenilic-triazine resins and their phe-
nolic precursors (68) and dehydration of lanthanide 2,6-dihy-
droxybenzoates (69). On the other hand, compensation effects
were reported for a reaction of K2CO3 with various oxides (70),
for dehydration of formates, acetates, and propionates of various
metals (71), and for the thermal depolymerization of polysaccha-
rides at different values of pH (72). Because in the latter cases
(70-72) the observed variation in ln Aξ and Eξ may have been
caused by physical reasons, the compensation effects have been
interpreted in terms of reaction mechanisms. Note that reliable
detection of a true compensation effect may be challenging
because experimentally estimated Arrhenius parameters tend to
be strongly correlated due to mathematical reasons (i.e., false
compensation effect).
INORGANICS
Thermal treatment of inorganic substances has a great
synthetic potential as it may turn simple compounds into advanced
materials such as ceramics, catalysts, and glasses. The mechanistic
and kinetics studies of solid-state reactions are needed in order
to take advantage of this potential (73). Unfortunately, the
progress in this field has been rather slow (48). The mechanisms
are routinely identified in terms of simplistic reaction models that
were developed fifty and more years ago, and the concept of a
single-step reaction appears to dominate mechanistic and kinetic
analyses (47). The popularity of this approach can be explained
by the fact that its use affords creating mathematically simple and
logically attractive methods such as the well-known method of
reduced time plots when the reaction mechanism is identified by
visually comparing experimental data against the reaction models
in the coordinates of R against t/tR0 (tR0 is the time to reach a
given extent of conversion, usually 0.5 or 0.9). This method can
be used for analysis of isothermal data. The method was further
developed by Gotor et al. (74), who expanded its applicability to
virtually any heating program. The method can be used to analyze
solid-state reactions whose overall kinetics can be approximated
Analytical Chemistry, Vol. 74, No. 12, June 15, 2002 2753
by a single-step rate equation, or, in other words, whose Arrhenius
parameters and reaction model remain unchanged in a certain
region of temperatures and conversions. Processes of this type
are rather rare and may demonstrate the single-step behavior only
under some specific conditions. For instance, these criteria are
met for the thermal decomposition of ZnCO3 (smithsonite) under
high vacuum and at temperatures above 690 K (74). However,
this process demonstrates a complex kinetic behavior at lower
temperatures as seen from the application of an isoconversional
method that yields a variable activation energy (75). Note that in
general the procedures of identifying reaction models (mecha-
nisms) by selecting the best-fit models share one common flaw
that the models are selected from an unavoidably incomplete list,
which does not necessarily include the correct model.
The complex kinetic behavior is observed (47) for many
seemingly simple processes such as the thermal decomposition
of CaCO3 and dehydration of CaC2O4‚H2O that produce a single
gaseous product, and, therefore, often considered as a model or
standard single-step processes. It should be remembered that
these are reversible processes, and their kinetics are determined
not only by the temperature but also by the equilibrium and actual
pressure of the gaseous product (76). Maciejewski et al. (77)
convincingly demonstrated the complexity of an ostensibly simple
decomposition of CoC2O4‚2H2O. By applying a combination of
experimental techniques including TGA, DTA, DSC, XRD, TGA-
MS, and pulse thermal analysis, the process was demonstrated
to involve numerous reactions that occur in both solid and gas
phases. Similar results were reported by Vanhoyland et al. (78),
who applied high-resolution TGA, TGA-FT-IR, and high-temper-
ature DRIFT and XRD to follow decomposition of La2(C2O4)3‚
10H2O. All these data reflect a typical level of complexity
encountered in solid-state decompositions and can be used to
illustrate the point that fitting, say, mass-loss data to a single-step
reaction model and interpreting it in mechanistic terms may have
little value for learning reaction mechanisms.
Thermal decomposition of inorganic and metallorganic com-
pounds may provide simpler synthetic routes for many materials.
For instance, Diez et al. (79) obtained the metastable β-Bi2O3 by
decomposing hydrated bismuth oxalate in a CRTA apparatus
under air at ∼270 °C. Aono et al. (80) employ TGA-DTA to follow
the thermal decomposition of a heteronuclear La-Mn complex
that at relatively low temperatures (600-700 °C) yields single-
phase hexagonal LaMnO3 nanoparticles, which could not be
obtained by conventional sintering even at 1200 °C. The application
of thermal analysis in combination with XRD and FT-IR shows
(81) that the thermal decomposition of a mixture of barium
carbonate and tin tetrahydroxide results in the formation barium
stannate that has a cubic perovskite structure and can be used as
a sensor for the detection of liquefied petroleum gas. Tolochko
et al. (82) compare citrate and ceramic routes for preparation of
La2-xSrxNiO4 conducting oxide. The use of citrate mixtures leads
to fine powders and dense ceramics; it also reduces the temper-
ature by 150-200 °C as measured by TGA-DTA.
The thermal decomposition of polycarbosilane is a route to
Si-C ceramic materials. Simultaneous TG-DTA under argon flow
shows a weight gain and an exotherm at approximately 240 °C
that results from a reaction with oxygen present in the polymer
and suggests its high sensitivity to oxidation (83). The conversion
2754 Analytical Chemistry, Vol. 74, No. 12, June 15, 2002
of N-methylpolyborosilazane to Si-B-N-C ceramics occurs on
heating in three consecutive steps that are conveniently observed
and identified by a combination of thermal analysis and spectros-
copy as polycondensation (200-350 °C), fragmentation (580-620
°C), and elimination of residual hydrogen (1000-1300 °C) (84).
Weinmann et al. (85) used thermally induced hydrosilylation of
a mixture of oligovinylsilazane with tris(hydridosilylethyl)boranes
to obtain Si-B-C-N ceramics, whose yield and thermal stability
were evaluated by high-temperature TGA. Emanation thermal
analysis (86) proves to be an effective tool for in situ characteriza-
tion of microstructure changes that occur during the formation
of B-C-N ceramics produced by heating various precursors up
to 1100 °C.
Thermal analysis is conveniently used for characterizing
catalytic properties of inorganic materials. Lashdaf et al. (87) used
thermal analysis to test the suitability of volatile β-diketonato
complexes of Ru, Pd, and Pt for chemical vapor deposition and
atomic layer epitaxy methods of preparation of heterogeneous
catalysts. Jan et al. (88) synthesized new RuCl2(p-cymene)(ER2R′)
complexes and tested them as catalysts of the ring-opening
metathesis polymerization of cyclooctene. They found that for the
phosphane (i.e., E)P) complexes the catalytic activity correlates
well with the arene lability. The latter is estimated as the
temperature at which the p-cymene ligand is liberated as deter-
mined by TGA. Maciejewski et al. (89) applied pulse thermal
analysis to study the effect of calcination on the activity of TiO2-
and ZrO2-supported gold catalysts for CO oxidation. Pulse injection
of CO into an oxygen stream in TGA shows that the maximum
catalytic activity is obtained for the TiO2-supported catalysts
calcined at 500 °C and for ZrO2-supported catalysts at 560 °C.
Carabineiro et al. (90) use TGA to investigate the kinetics of the
reaction of NO, N2O, and CO2 at 450-900 °C with activated carbon
without catalyst and impregnated with a precursor salt of vanadium
(ammonium monovanadate). The addition of vanadium was found
to increase carbon reactivity and adsorption at lower temperatures.
Heating the silica samples (15-30 mg) in TGA at a rate of 5 °C
min-1 from room temperature to 1250 °C shows two mass-loss
steps respectively associated with dehydration (100-130 °C) and
dehydroxylation (91). Ek et al. (91) demonstrate that the second
mass-loss step can be used to estimate the OH group content,
which was found to be in a good agreement with NMR data.
Fernandes et al. (92) used TGA to study the kinetics of regenera-
tion of the alumina catalyst deactivated by coke that was formed
in the transformation of 1,3-butadiene in a fixed-bed continuous-
flow reactor. A special issue of Thermochimica Acta was dedicated
to the applications of calorimetry in catalysis (93).
Sestak (94) discusses history, present state, and prospects of
inorganic and polymeric glasses. The kinetics of crystallization
of inorganic glasses is widely studied by thermal analysis methods.
Malek (95) critically evaluates the limitations of the Johnson-
Mehl-Avrami nucleation growth model and points out that the
actual mechanism is difficult to explore within this model unless
some complementary studies are made. Suga (96) analyzes
thermodynamic and molecular aspects of transition phenomena
in solids, putting a special emphasis on the unique properties of
the amorphous (glassy) state. Atake et al. (97) performed heat
capacity measurements on the glassy and crystalline GeSe2 and
found that the heat capacity of the glassy state is smaller than
that of the crystalline state below ∼60 K, above which the values
transpose. The crossing phenomenon is explained by differences
in the density-of-states of the lattice vibrations that originate from
the different long-range ordering in the layered structures of
GeSe2. Heide et al. (98) applied TG-MS to analyze gaseous
products that are released from various industrial, laboratory, and
natural glasses heated under high vacuum in the temperature
region 800-1200 °C. The gaseous products contain several
hydrocarbons that appear to form as a result of a reaction between
carbon and hydroxide ion. The method has also been used in
analysis of antic glasses in order to determine the manufacturing
conditions (99). Stoch and co-workers (100) investigate correla-
tions between thermal and biochemical activity of the phospho-
silicate glasses used for medical purposes.
POLYMERS
Polymeric materials are one of the largest application areas of
thermal analysis methods. Thermal analysis is used to study the
physical processes of melting, crystallization, and glass transition
as well as chemical processes of polymerization and degradation.
Many of these applications are described in the recent book
Characterisation of Polymers by Thermal Analysis by Groenewoud
(101).
Processes that require large-amplitude cooperative motion of
large molecules (e.g., macromolecules) are unavoidably associated
with long relaxation times. As a result, nonequilibrium states can
be formed and studied in polymers by quickly changing the
temperature. For instance, Wundrelich (5) mentions 15 equilib-
rium and nonequilibrium phases that can be found in a one-
component polymer system. Because of the slow rates of ap-
proaching equilibrium, thermal response of such systems depends
on the time scale of an experiment that is determined by the
heating rate, the period of temperature modulation, or both. For
instance, Mathot (11) demonstrates that heating PET in DSC at
10 °C min-1 shows an exothermic peak followed by an endother-
mic one, which are respectively associated with cold crystallization
and melting. However, the use of the heating rate 100 °C min-1
results in suppressing cold crystallization, which does not have
sufficient time to occur in the short-time-scale run. Another
example is melting of PE crystals. The process is associated with
slow crystal perfection that on slow heating elevates the melting
of PE by as much as 10 K (5). The use of fast heating rates makes
it possible to outrun the process of crystal perfection and
determine the correct value of the melting point (5, 102).
In TM-DSC, the period of modulations determines the time
scale of experiment that allows one to separate and analyze
processes having different relaxation times. Among many interest-
ing phenomena, TM-DSC has helped in the observation of the
unusual phenomenon of reversible polymer melting that cannot
be explained in terms of classical theories of melting and
crystallization of polymers (103, 104).
DSC is widely used to study polymer crystallization kinetics
under isothermal and nonisothermal conditions. The isothermal
data are customarily analyzed in terms of the Avrami equation
(105, 106), which is also applied to nonisothermal data in the
form of Ozawa’s method (105, 107). The obtained values of the
Avrami exponent are routinely interpreted in mechanistic terms
(105-107). Because of the simplistic nature of the Avrami model,
such interpretations should be done with extreme care. The
Avrami exponents often have fractional values (108) and show
dependence on temperature and cooling rate (107). Noticeable
deviations of experimental data from the Avrami equation are
commonly reported (109, 110), and two equations may be needed
to fit actual crystallization data (111). The problems of the Avrami
analysis appear to become more profound for nonisothermal
crystallizations (110, 112). Martins and Pinto (113) attempt to
resolve the theoretical limitations associated with the Ozawa-
Avrami analysis of nonisothermal crystallizations. Cheng et al.
(114) stress that the two-phase crystallization model does not hold
for many polymers because of the presence of a metastable “rigid
amorphous fraction”.
As was shown by Toda et al. (115), TM-DSC can be used to
estimate the crystal growth rate, G, of polymer crystals in the
melt under quasi-isothermal conditions. The results are obtained
in the form of a dependence d(ln G)/dT on T. The method was
recently applied to study crystallization kinetics in poly(-capro-
lactone)-poly(styrene-co-acrylonitrile) blends (116) and in poly-
(4,4′-phthaloimidobenzoyldodecamethyoxycarbonyl) (117). Toda
et al. (35) employed this method for kinetic analysis of crystal-
lization and melting of ice crystallites confined in porous silica
gel. Note that after some rearrangements the aforementioned
dependence should afford an estimation of the activation energy
as a function of crystallization temperature
E ) RT 2[d(ln G)/dT] (11)
The resulting value would be a model-free estimate of the
activation energy, as it does not require assuming any kinetic
model such as that of Avrami.
Some polymeric and organic systems may exist in the liquid
crystalline (LC) state that is characterized by anisotropy of physical
properties in the absence of a three-dimensional crystalline lattice.
LC systems may form various mesophases, which are intermediate
between the isotropic liquid and ordered crystalline state. Transi-
tions between mesophases can be conveniently followed by DSC
as well as other techniques (118, 119). Yoshida et al. (118)
demonstrate the potential of the combined DSC-XRD technique
as applied to a LC phenanthrene polyester. On cooling from the
isotropic liquid state, the polymer shows three exothermic
transitions that, based on XRD data, have been associated with
successive formation of two mesophases and crystallization. A
combination of DSC with polarized light microscopy allows for
the study LC transitions and building phase diagrams of complex
systems that involve both LC and non-LC components (119).
The glass transitions can be detected by several thermal
analysis techniques. In DSC, the transition is observed as a change
in the heat capacity. Heat capacity is a thermodynamic property
directly associated with the intensity of molecular motions.
Heating glassy polymers above the glass transition temperature,
Tg, initiates long-range motion of polymer main-chain segments
that results in increasing the heat capacity as measured by DSC.
TM-DSC measures the so-called complex heat capacity, which,
unlike its equilibrium value, is time and frequency dependent. This
and other closely related topics were addressed in the special issue
of Thermochimica Acta (120). The frequency dependence of the
complex heat capacity in the glass transition region is treated
Analytical Chemistry, Vol. 74, No. 12, June 15, 2002 2755
theoretically by Hutchinson and Montserrat (121), who propose
a model based on the Kohlrausch-Williams-Watts equation. The
model helps to optimize the experimental conditions of measure-
ments and understand a correspondence between the Tg values
measured in conventional and temperature modulated DSC.
Park and McKenna (122) explored the glass transition behav-
ior of polystyrene solutions confined to nanometer-scale pores.
DSC shows two glass transitions, one of which is at a lower
temperature than the bulk-state Tg and the other is at a higher
temperature. The lower value is associated with the confined bulk
state, whereas the higher value is assigned to an interacting layer
at the pore surface.
The glass transition may occur during polymerization if the
glass transition temperature of growing polymer rises above the
actual temperature of the reaction system. This process is called
vitrification. Because of the dramatic decrease in the molecular
mobility, the reaction kinetics becomes controlled by slow diffu-
sion of the reaction species in the immobile glassy medium.
Vitrification is readily detected when resins are cured in TM-DSC
(123-128). Montserrat (123) comprehensively studied the effect
of various parameters on the values of Tg, heat capacity, and phase
angle determined by TM-DSC for isothermal epoxy cures. Van
Assche et al. (124) investigated the frequency dependence of the
vitrification phenomenon by using light heating TM-DSC that
affords measurements in the frequency range from 0.01 to 1 Hz.
TM-DSC and rheology data were compared (125) for cross-linking
copolymerization of an unsaturated polyester resin with styrene.
Schawe (126) reported that the phase shift signal measured by
TM-DSC is very sensitive to changes in the reaction kinetics and
can be used for evaluating the diffusion component of the curing
rate. Flammersheim and Opfermann (127) propose a diffusion-
control model of epoxy cure that is based on the WLF equation.
For curing of a dicyanate ester resin, Leroy et al. (128) use an
isoconversional method to determine a dependence of the activa-
tion energy on the extent of cure and then derive a kinetic model
that matches this dependence. Note that estimating of such
dependencies has been helpful in identifying complex mechanisms
of various curing reactions (129-132).
Vitrification is not the only reason for diffusion control in curing
reactions. The latter becomes operative if, for any reason, the
characteristic time of relaxation of the reaction medium exceeds
the characteristic time of a chemical reaction. On the basis of
kinetic analysis of DSC and rheology data, Vyazovkin and
Sbirrazzuoli (133) demonstrate that viscosity may induce diffusion
control in the initial cure stages. The phenomenon is described
by a kinetic model that predicts that qualitatively different
dependencies of the activation energy on the extent of cure should
be obtained respectively from the isothermal and nonisothermal
DSC data when an isoconversional method is used.
The usefulness of polymeric materials is largely determined
by their thermal, oxidative, and fire resistance. Crucial information
in this area is obtained from kinetic and mechanistic studies of
thermal degradation that presents a wide application area for
thermal analysis methods. By studying the kinetics and mecha-
nisms of thermal degradation of PMMA, Holland and Hay (134)
demonstrated the great potential of thermal analysis-FT-IR spec-
troscopy as a qualitative and quantitative kinetic tool. They
conclude that thermal degradation is initiated at chain ends as
2756 Analytical Chemistry, Vol. 74, No. 12, June 15, 2002
well as by random scission, which is attributed to preoxidation of
the polymer on storage at room temperature. Peterson et al. (135)
applied the isoconversional method (eq 8) to obtain reliable values
of the activation energy for the thermal and thermoxidative
degradation of PS, PE, and PP. The obtained data were compared
with numerous previously reported values and interpreted in terms
of reaction mechanisms. Note that the variable ER values deter-
mined by an isoconversional method correspond to nonlinear
Arrhenius plots. Nonlinear Arrhenius plots were reported (136)
for the kinetics of oxidative degradation of rubbers. Simon and
Kolman (137) propose a method that enables Arrhenius param-
eters of the oxidation induction period to be estimated from the
dependence of the oxidation induction time on the heating rate.
The application of the method to oxidation of PP, PE, and oils
yields the values of Arrhenius parameters that agree well with
the values obtained from isothermal data.
According to TGA and DTA, polyurethane decomposes in three
well-defined steps (138). The simultaneous use of IR data suggests
that the rupture of the weakest bond, C-NH, is the primary
degradation step, whose activation energy is about 98 kJ mol-1.
Vinylidene chloride-acrylate copolymers are excellent packaging
materials that provide an efficient barrier to small molecules such
as oxygen. However, at process temperatures, 150-170 °C, these
polymers undergo thermally induced degradative dehydrochlo-
rination that can be suppressed in the presence of multifunctional
amines (139) and high surface area magnesium hydroxide (140).
Howell et al. (139, 140) used TGA to study the effect of these
additives on thermal stability of the polymers.
The thermal degradation of the polyamides (6, 12, 66, and 612)
was studied (141) under air and nitrogen by means of thermal
analysis coupled with MS. The data allowed for identifying the
degradation products and evaluating the kinetic parameters.
Levchik and Weil (142) comprehensively review the combustion
and fire-retardant performance of aliphatic nylons. Addition poly-
imides based on bis(3-aminophenyl)methylphosphine oxide or tris-
(3-aminophenyl)phosphine oxide have excellent flame-resistance
properties (143). Varma (143) investigates the effect of weight
percent of phosphorus on thermal behavior and flame resistance
of these polyimides. The mechanism of the fire-resistant action
of inorganic tin additives on halogenated polyester thermosets
was examined by thermal analysis in conjunction with pyrolysis-
GC and other techniques (144). The residue analysis of sequen-
tially degraded samples suggests that the metal and halogen may
volatilize simultaneously, and therefore, both condensed and
vapor-phase mechanisms appear to be operating with the branch-
ing ratio dependent on both the halogen present and the
composition of the polyester.
Microthermal analysis combines the visualization power of
AFM with the characterization capabilities of thermal analysis that
is accomplished by replacing the tip of an AFM probe with a Pt
wire that can be controllably heated. Reading et al. (145) reviewed
the current state of development of microthermal analysis as
applied to polymeric materials. The discussion also involves new
techniques such as micropyrolysis-mass spectroscopy and pho-
tothermal IR microscopy, which combines microthermal analysis
with FT-IR spectroscopy. Hassler and zur Muhlen (146) discussed
the details and applications of this technique to the studies of
interfaces. The technique was applied (147) to study the role of
carbon and glass fiber reinforcement in an aerospace-grade
thermosetting resin. The results show the presence of a soft
interphase layer in the glass material and stress the importance
of fiber-matrix interactions during the formation of the inter-
phase.
Oulevey et al. (148) report a new form of microthermal analysis
that enables dynamic mechanical properties to be measured at
submicrometer scale. This is accomplished by mounting a sample
on a vibrating heating stage and observing the resulting amplitude
and phase of the motion of an atomic force microscope cantilever.
PS, PMMA, and PTFE respectively show primary relexations at
92, 118, and 138 °C. Secondary relaxations are detected at 60 °C
in PMMA and at 80 °C in PTFE.
ENERGETICS AND FUELS
Ammonium perchlorate remains a key energetic material for
rocket technologies. The substance is known to undergo a
transition from the orthorhombic to cubic phase at ∼240 °C. Rajic
and Suceska (149) used isothermal TGA to determine the kinetics
of the thermal decomposition of ammonium perchlorate in the
two crystalline phases. In both cases, the mass-loss rate was found
to obey the best-fit equation
dR/dt ) k(T)Rn(1-R)m (12)
The activation energies of the process are very close, being 146.3
and 153.3 kJ mol-1 for orthorhombic and cubic phases, respec-
tively. Note that the use of the single-step eq 12 is likely to disguise
the kinetic complexity that was detected (49) when more
sophisticated computational techniques were applied to the
thermal decomposition of cubic ammonium perchlorate studied
under isothermal and nonisothermal conditions. Waesche and
Wenograd (150) employed TGA and high-pressure DSC to
measure decomposition rates of ammonium perchlorate composite
propellants at pressures to 500 psi. The results were extrapolated
to give heat evolution rates at the surface temperatures of burning
propellants. A semiempirical condensed-phase combustion model
was used to calculate propellant burning rates from these heat
evolution rates and surface temperatures determined by equilib-
rium vaporization. Calculated and experimental burning rates are
found to agree within an order of magnitude.
Singh et al. (151) discuss the mechanistic aspects of thermal
decomposition of salts of perchloric and nitric acids and stress
that the proton transfer plays a major role in the process of
decomposition. Lurie and Chang (152) have shown that in the
presence of carbon black the decomposition rate of solid am-
monium nitrate may increase by more than 7 orders of magnitude.
They carried out kinetic studies in the temperature region 70-
150 °C and found that at lower temperatures the process proceeds
by a two-step mechanism with the first step absent at higher
temperatures. They also report that the process rate is proportional
to the amount of carbon black and that the activation energy of
the process is about 120 kJ mol-1 and does not vary during
transformation. Simoes et al. (153) examined the thermal decom-
position of phase-stabilized ammonium nitrate in its mixtures with
2-oxy-4,6-dinitramine-s-triazine by using DSC and TGA. The
process demonstrates a complex kinetic behavior that the authors
were able to describe only by an empirical equation of Sestak and
Berggren (eq 12).
Ammonium dintramide is considered as a halogen-free replace-
ment of ammonium perchlorate in solid rocket propellants. Tompa
(154) studied the kinetics of the thermal decomposition of
ammonium dinitramide by using the methods of TGA, DSC, and
high-pressure DSC. He found that under higher pressures (550
psi) the activation energy markedly decreases (from ∼170 to 120
kJ mol-1), indicating acceleration of the process in the presence
of decomposition products. Confining samples of explosives in
sealed glass capillary tubes allows regular DSC be used to monitor
the kinetics of thermal decomposition under elevated pressures.
(155, 156) The advantages of this approach are demonstrated by
Oxley et al. for decomposition of 3,6-substituted s-tetrazines (155)
as well as nitramines and difluoramines (156).
The methods of TGA and DSC were applied by Long et al.
(157) to study the thermal decomposition of liquid hexahydro-
1,3,5-trinitro-1,3,5-triazine (RDX) in open, pierced, and closed pans.
A comparison of the results suggests that in open pans evaporation
is a prevalent process with an activation energy of ∼100 kJ mol-1.
Confining the system in either a pierced pan or a closed pan
promotes liquid-state decomposition of RDX that occurs with an
activation energy of ∼200 kJ mol-1, which is consistent with the
energy of an N-N bond scission. Tompa and Bryant (158) studied
thermal decomposition of an admixture of RDX with ammonium
benzoate by using DSC and microcalorimetry. They report that
the presence of ammonium benzoate decreases significantly the
temperature and the activation energy (from 197 to 105 kJ mol-1)
of RDX decomposition. This is an indication of a reaction between
the two components which makes them incompatible in the
admixture. RDX-based metallized composite propellants were
studied by Divekar et al. (159). Kinetic analysis of DTA data shows
that the activation energy for the thermal decomposition of some
metallized propellants is similar to that of neat RDX, which
suggests that the thermal decomposition is the rate-limiting step
of the process. Jones et al. (160) examined the thermal properties
of a nanosized Al powder (Alex) by using a variety of thermal
analysis methods. They determined the specific heat capacities
of nano- and micrometer-size Al powders that are found to be
similar between 30 and 400 °C. They also determined the kinetic
parameters for the oxidation reaction of Alex, which was detected
at an onset temperature of 481 °C.
The thermal decomposition of a plastic bonded explosive
containing octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX),
binder, and plasticizer was examined (161) by using DSC and
TGA in order to obtain safety information for handling and use.
The obtained data allowed for estimating the critical temperature
for self-heating at various sample radii and the 500-day cookoff
temperature. Thermal conductivity, specific heat, and thermal
diffusivity were determined at the critical temperatures in order
to calculate the approximate time to explosion at these temper-
atures. Plastic bonded explosives were also studied by Campbell
and co-workers (162) in order to determine the glass transition
temperatures. Such measurements are of special importance as
the glass transition temperature appears to correlate with the
impact sensitivity of plastic bonded explosives.
A primer explosive, potassium 4,6-dinitrobenzofuroxan (KD-
NBF), was studied by Jones et al. (163), who applied the
techniques of TGA, DSC, and accelerated rate calorimetry. The
compound is found to decompose in the solid state via a multistep
Analytical Chemistry, Vol. 74, No. 12, June 15, 2002 2757
exothermic process. The first step is sufficiently rapid that ignition
occurs in large samples. Kinetic analysis was applied to both
nonisothermal and isothermal data and a range of activation
energies were obtained, depending on the experimental condi-
tions. Hydrazinium nitroformate (HNF) is considered as a very
promising ingredient for a new storable composite propellant. The
techniques of TGA-DTA, DSC, and microcalorimetry were
applied (164) to determine the purity, stability, and compatibility
of HNF with other materials. Nazin et al. (165) reviewed the
influence of molecular structure on the stability of high-energy
compounds. They discuss kinetic and mechanistic data on
decomposition of various energy-rich groups in monofunctional
compounds as well as in compounds with mixed functional groups.
Brown (166) describes the use and limitations of thermal
analysis and temperature profile analysis to the study of various
binary pyrotechnic systems. He discusses trends in burning
behavior and the factors that affect the combustion, such as fuel-
to-oxidant ratio. To accomplish fast heating rates and high
temperatures relevant to the processes of combustion, Brill et al.
(167, 168) apply the method of T-jump/FT-IR spectroscopy, in
which a small sample (100-200 µg) is spread onto the Pt ribbon
filament. The filament is heated in a pressurizable spectroscopy
cell at an effective heating rate around 800 °C s-1. The filament
temperature is calibrated by using melting point standards.
Decomposition products are detected spectroscopically as a
function of time and temperature. Thermal decomposition data
were collected for the hydrated Li+, Na+, K+, Cu2+, and Pb2+ salts
of 3-nitro-1,2,4-triazol-5-one (NTO), the Li+, Na+, K+, Rb+, Cs+,
Co2+, and Ni2+ salts of picric acid (167), and the hydrohalide (HCl,
HBr, HI) salts of 5-amino-1H-tetrazole (168).
Fuels are another energy-related area of application of thermal
analysis. TGA is widely used to simulate thermal processes
occurring in coal on its combustion. Zajdlik et al. (169) explored
the applicability of the shell progressive mechanism to combustion
of a single coal particle. They used TGA to monitor time
dependences of the particle mass and the temperature in the
particle and in the gas phase. The obtained experimental results
confirmed that the shell progressive mechanism can be applied
for the mathematical description of combustion of a single coal
particle. The oxidation of natural graphite particles was investi-
gated by simultaneous TGA-DTA (170). This process provides
a model reaction for examining the effect of the particle geometry
on process parameters. The reported results suggest that the
fraction of edge sites has a strong influence on such parameters
as ignition temperature, temperature of the maximum of the DTA
curve, and the temperature at which 15% carbon weight loss is
attained. Fan and Brown (171) applied TGA to 70 fly ash samples
obtained from diverse coals and boilers to determine that loss on
ignition (LOI) overestimates the amount of unburned carbon in
fly ash by at least 20% in 44% of the tested samples. As an
alternative to the LOI tests, they propose to measure unburned
carbon by using TGA.
The thermal deactivation of solid fuels can be investigated by
measuring the reactivity of chars prepared in TGA under well-
defined conditions. The obtained data permit estimating kinetic
parameters in an annealing model. Zolin et al. (172) report that
the annealing model predicts reasonably well the changes in
reactivity of chars prepared in different reactor environments at
2758 Analytical Chemistry, Vol. 74, No. 12, June 15, 2002
much higher heating rates and temperatures, and therefore, TGA
experiments can be used to capture the reactivity differences of
chars observed in combustion facilities. Burnham (173) demon-
strated that the Sestak-Berggren equation in its reduced form,
eq 12, is an excellent empirical kinetic law for describing
decompositions that have an initial acceleratory period. This
equation in particular fits both isothermal and constant heating
rate pyrolysis data for cellulose and kerogens. Activation energies
derived by nonlinear regression to multiple experiments are
consistent with those derived by simple isoconversional methods.
Conesa et al. (174) review kinetic models and methods for analysis
of TGA data from the standpoint of their application to the
pyrolysis of such energy sources as almond shells, olive stones,
and tire wastes. The discussion also covers choosing proper
conditions for a kinetic run, temperature calibrations, position of
the thermocouple, sample mass, and particle size.
A combination of TGA with evolved gas analysis techniques
such as FT-IR, MS, and GC/MS provides important insights into
the mechanism of pyrolysis of coals. For instance, combustion
and pyrolysis of the bituminous coals are known to produce
polycyclic aromatic hydrocarbons that pose potential health
hazards. The mechanisms of formation of these compounds were
significantly elucidated with the help of GC/MS (175). The
combined TG-MS method was helpful in identifying the alkali or
alkali earth chlorides as the sources of deposit formation in the
heat exchange tube of the fluidized-bed combustor (176).
A newly developed version of pVT-controlled scanning calo-
rimetry, scanning transitiometry, was applied by Stachowiak et
al. (177) to investigate the thermodynamic behavior of asphaltenic
fluids under in-well pressure and temperature conditions. As the
technique permits measurements over extended temperature and
pressure ranges, it is capable of detecting phase changes in
aliphatic systems during various scans of the three variables p,
V, and T. Performing successive compression-decompression
cycles shows that both flocculation and solubilization in an
asphaltenic fluid are governed by slow kinetic phenomena.
PHARMACEUTICAL, BIOCHEMICAL, AND
BIOLOGICAL APPLICATIONS
Pharmaceutical applications of thermal analysis were addressed
in a special issue of Thermochimica Acta (178). An overview of
the current pharmaceutical applications of calorimetric measure-
ments has been given by Thompson (179).
In the solid state, pharmaceutical compounds may exist in
various polymorphic, pseudopolymorphic (solvates), and amor-
phous forms, whose physical properties such as solubility, bio-
availability, processability, and stability may differ significantly.
The issue of polymorphic behavior of pharmaceuticals was
addressed by Giron (180), who emphasizes the role of thermal
analysis techniques in understanding transitions of different
polymorphs and solvates as well as glass transitions of amorphous
state. The discussion covers both thermodynamic and kinetic
aspects of polymorphism and is illustrated by numerous examples.
The recent advances in the area of prediction and characterization
of polymorphs and solvates were reviewed (181). Gu and Grant
(182) suggest using the transition and melting temperatures to
derive the thermodynamic stability relationships of the poly-
morphs (enantiotropes or monotropes). They used the reported
values of the heats of solution and solubilities (or dissolution rates)
to calculate the transition temperature of polymorphs for auranofin,
carbamazepine, chloramphenicol palmitate, cyclopenthiazide,
gepirone hydrochloride, lamivudine, MK571, premafloxacin, sul-
famerazine, sulfamethoxazole, sulfathiazole, and urapidil. The
resulting stability relationships are found to be in good agreement
with those reported using other methods, such as DSC.
The molecular mobility of amorphous pharmaceutical materials
is an important factor that determines their stability. The mobility
can be evaluated as relaxation times by using dynamic mechanical
analysis. Although relaxation times can be easily described by
the empirical Kohlrausch-Williams-Watts equation, Shamblin
et al. (183) demonstrated that knowledge of the parameters of
the equation is not sufficient for predicting stability of drugs. They
stress the importance of knowing the distribution of relaxation
times. Craig et al. (184) evaluated the use of TM-DSC as a means
of assessing the relaxation behavior of amorphous lactose via
measurement of the heat capacity, glass transition, and relaxation
endotherm. The use of this technique enabled separation of the
glass transition from the relaxation endotherm, thereby facilitating
calculation of the relaxation time as a function of temperature.
The mechanism and kinetics of thermal decomposition of solid
drugs are studied in connection with estimating their thermal
stability. Thermal analysis provides valuable tools for these studies.
The dehydration of nedocromil magnesium pentahydrate was
investigated (185) by TGA and DSC as a function of temperature,
particle size, sample weight, water vapor pressure, and dehydra-
tion-rehydration cycle. The two-step dehydration kinetics are best
described by the Avrami-Erofeyev equations with an activation
energy being markedly greater for the second step. The activation
energy decreased with increasing sample weight and decreasing
particle size. The dehydration rate increased with decreasing water
vapor pressure. Thermal analysis information in combination with
XRD and solid-state NMR has provided an insight into the
dehydration mechanism and the nature of solid-state phase
transformation during the dehydration. Rotich et al. (186) studied
thermal decomposition of substituted aminobenzoic acids. Most
of the substances sublimed well before melting, generally with
an increasing rate of mass loss beyond their respective melting
points. The processes of sublimation and vaporization were
extensively studied by Alexander and co-workers, who used TGA
to determine the vapor pressure as well as sublimation and
vaporization enthalpies for numerous pharmaceutical compounds
including several parabenes (39), derivatives of benzoic acid (40),
and allopurinol (41).
DSC presents a useful means of studying interaction of
excipients as well as of detecting their incompatibilities. Wissing
et al. (187) applied high sensitivity DSC to model mixes of aspirin
with magnesium stearate and stearic acid. The samples were
heated to temperatures between 45 and 70 °C and held for 1 h,
during which the heat flow to or from the sample was measured.
While no thermal events were detected for the individual com-
ponents or mixes with stearic acid other than melting of stearic
acid, 50% w/w mixes of magnesium stearate showed a marked
endothermic response at temperatures above 55 °C. Compacts of
magnesium stearate and aspirin were also studied, with consider-
ably more pronounced thermal events taking place compared to
the powder mixes. Giordano et al. (188) provide a comprehensive
review on the thermal properties of cyclodextrins and their
inclusion compounds. Special attention is paid to thermal analysis
studies of the hydrated forms of cyclodextrins and interactions
of cyclodextrins with water and drugs.
A great number of biochemical and pharmaceutical applications
are concerned with microcalorimetry. A review on isothermal
microcalorimetry was published by Wadso (189). Hansen (190)
reviewed the application of calorimetry to measurement of the
kinetics of slow processes, whose rate cannot be readily followed
by conventional chemical analyses. He also discusses instrument
selection and derivation of rate laws from calorimetric data. As
mentioned earlier, for solids there are no standard reactions whose
kinetics can be used for validation and calibration of kinetic
measurements. The situation appears to be different for liquid-
phase kinetics. The reaction of triacetin hydrolysis in an imida-
zole/acetic acid buffer system was analyzed by several microcal-
orimetric groups (191). Based on the analysis of the interlaboratory
data, this second-order reaction, performed at 298 K, occurs with
the reaction rate constant, k ) (2.80 ( 0.10) × 10-6 dm3 mol-1
s-1, and the enthalpy change, ∆H ) -91.7 ( 3.0 kJ mol-1.
However, notice should be taken of the earlier work by Guan and
Kemp (192), who demonstrated that the best fit for the hydrolysis
of triacetin is first order rather than the assumed second order.
Cuppo et al. (193) applied high-sensitivity differential scanning
microcalorimetry to study gelatin transitions in order to determine
the dependence of the kinetic and thermodynamic parameters
upon changes in composition and in temperature. Fitting data to
exponential functions shows that the characteristic time and the
fractional exponent of gelation are very sensitive to the concentra-
tion of gelatin chains and to the microscopic phase segregation.
Isothermal titration microcalorimetry and DSC were applied by
Barreleiro et al. (194) to study the interaction of DNA with vesicles
of cationic lipids mixed with varying amounts of a zwitterionic
lipid in dilute solutions. Analysis of reaction enthalpies as a
function of a charge ratio has helped in elucidating the interaction
mechanisms. The thermal behavior of triple helices of DNA was
examined by using DSC (195), which shows two independent
processes: the dissociation of the third strand from the target
duplex and the dissociation of tile double helix in two single
strands. Grasso et al. (196) conducted a DSC study of the
interaction of the human prion peptide with different artificial
membranes that helped them to detect a specific affinity of the
protein to a certain type of membrane.
The heat produced by animal cells in culture can be used as
the primary indicator of the kinetics of their metabolism. The
validity of the relationship between heat and metabolism is
demonstrated by Kemp (197) theoretically through the concept
of thermal advancement and in experiments by the use of
continuous cultures. This validation permitted the application of
heat flux as a probe of the metabolic state of cells in culture.
Morgan et al. (198) suggest estimating the efficacy of antimicro-
bial agents by using flow microcalorimetry instead of applying
traditional microbiological techniques, which are invasive and
destructive. They used the method to continuously monitor the
power output (bioactivity) of Streptococcus mutans in the presence
of antimicrobial agents and demonstrated good reproducibility,
precision, and accuracy.
Another exciting area of biocalorimetry is calorespirometry,
which combines measurements of metabolic heat and CO2
Analytical Chemistry, Vol. 74, No. 12, June 15, 2002 2759
production rates as a function of temperature. This technique
shows promise in matching plants to climate to optimize their
growth rate (199). Calorimetry is also used to study the behavior
of insects. Schmolz and Lamprecht (200) studied the metabolic
rates of insects during their different life cycles: larvae, pupae,
and adult. Larvae have high metabolic rates after hatching from
the egg. Prior to pupation, metabolism is strongly reduced. During
metamorphosis, the pupal instars typically exhibit a U-shaped
pattern of heat production. Insect adults have low resting
metabolic rates, close to the pupal metabolism. Metabolic rates
of active insects are up to 50 times higher than resting metabolism.
Professor Sergey Vyazovkin received his Ph.D. from the Byelorussian
State University in 1989. He then joined the Institute for Physical
Chemistry (Minsk) where he worked until 1993. Since 1993 he had held
visiting positions at the Technical University of Vienna, the University of
Toledo, and the Univerisity of Nice Sophia-Antipolis. Before joining the
University of Alabama at Birmingham, he worked in the University of
Utah as a research faculty and the deputy director of the Center for
Thermal Analysis. His research interests are concerned with the applica-
tion of thermal analysis methods to study thermally stimulated reactions
in polymeric, energetic, and pharmaceutical materials. He has authored
over 80 publications, including several invited review papers, and edited
a special issue of Thermochimica Acta on kinetics of thermally stimulated
reactions. He is a member of the American Chemical Society Analytical
Division, the North American Thermal Analysis Society, and the
International Confederation for Thermal Analysis and Calorimetry.
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