Polymer Degradation and Stability 96 (2011) 974e981

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Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

Constant rate thermal analysis for thermal stability studies of polymers

Pedro E. Sánchez-Jiménez*, Luis A. Pérez-Maqueda, Antonio Perejón, José M. Criado
Instituto de Ciencia de Materiales de Sevilla, C.S.I.C.-Universidad de Sevilla, C. Américo Vespucio no. 49, 41092 Sevilla, Spain

a r t i c l e i n f o a b s t r a c t

Article history: This paper explores the relationship between the shapes of temperatureetime curves obtained from
Received 31 August 2010 experimental data recorded by means of constant rate thermal analysis (CRTA) and the kinetic model
Received in revised form followed by the thermal degradation reaction. A detailed shape analysis of CRTA curves has been per-
12 January 2011
formed as a function of the most common kinetic models. The analysis has been validated with simulated
Accepted 28 January 2011
data, and with experimental data recorded from the thermal degradation of polytetrafluoroethylene
Available online 26 February 2011
(PTFE), poly(1,4-butylene terephthalate) (PBT), polyethylene (PE) and poly(vinyl chloride) (PVC). The
resulting temperatureetime profiles indicate that the studied polymers decompose through phase
Keywords:
CRTA
boundary, random scission, diffusion and nucleation mechanisms respectively. The results here presented
Kinetic models demonstrate that the strong dependence of the temperatureetime profile on the reaction mechanism
Thermal degradation would allow the real kinetic model obeyed by a reaction to be discerned from a single CRTA curve.
Kinetics Ó 2011 Elsevier Ltd. All rights reserved.
Random scission

1. Introduction controlled in such a way that the reaction rate is kept at a constant
predefined value along the entire process [1,2,22e24]. If the
Thermal analysis techniques are routinely used in many scien- selected reaction rate is low enough, the mass and heat transfer
tific and industrial laboratories for studying the thermal decom- phenomena that accompanies thermal decomposition processes
position of polymeric materials. Among them, thermogravimetry can be minimized significantly, thereby yielding results which are
(TG) is one of the most common since the mass of a sample is easy much more representative of the forward reaction [1,15,25,26]. This
to measure accurately and valuable information regarding the advantage is especially useful in thermal degradation of polymers
nature of the process can be extracted from a mass loss against time because many volatiles are usually evolved and may influence the
or temperature plot. While most TG studies are carried out under evolution of the reaction [25]. Additionally, polymers have gener-
isothermal or linear heating rate conditions, constant rate thermal ally a low thermal conductivity and heat transfer phenomena can
analysis (CRTA), formerly introduced by Rouquerol, constitutes play a significant role in thermal degradation if experimental
a promising alternative [1,2] that has already proven its usefulness conditions are not carefully controlled. Furthermore, the enhanced
in sintering and preparation of materials [3e14]. While several control over the decomposition process provided by CRTA makes it
papers dealing with the application of this method to the study of a much more effective tool than conventional methods for the
the kinetics of solid state reactions have been published [15e17], discrimination of overlapping processes. An additional feature of
this approach has rarely been extended into thermal degradation of CRTA experiments is that the a-T plots are strongly dependant on
polymers [18,19]. the reaction mechanism. This property of CRTA methodology
The main differences between CRTA and conventional methods constitutes an important advantage over conventional TG. It has
are summarized in Figs. 1 and 2. Fig. 1 has been adapted from the been well established that it is impossible to discriminate among
one originally published by Reading [20,21] and shows the different kinetic models from a single TG curve when obtained under linear
trends the temperature, conversion and reaction rate follows heating conditions since thermal degradation curves thus recorded
with time under isothermal, linear heating and controlled rate are all sigmoidal in shape regardless of the reaction mechanism
methods. Alternatively, Fig. 2 illustrates the different setups needed [27e30]. On the other hand, due to the close relationship between
for running conventional (isothermal and linear heating) and the temperatureetime profile of CRTA curves and the reaction
CRTA experiments. During a CRTA experiment, the temperature is mechanism, it should be possible to unambiguously discern the
kinetic model from a single CRTA curve.
Several kinetic models for the description of solid state reactions
* Corresponding author. Tel.: þ34 954489548; fax: þ34 954460665. have been proposed during the last decades, with diffusion, phase
E-mail address: [email protected] (P.E. Sánchez-Jiménez). boundary controlled and nucleation and growth of nuclei being the

0141-3910/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2011.01.027
 P.E. Sánchez-Jiménez et al. / Polymer Degradation and Stability 96 (2011) 974e981 975

reactions. Such work would be very illustrative of the power of the

technique for discriminating the real kinetic model of the reaction
from a single experimental curve. The shape analysis will be vali-
dated by a set of experimental CRTA curves obtained from the
thermal decomposition of four commercial polymers: polytetra-
fluoroethylene (PTFE), poly(1,4-butylene terephthalate) (PBT),
polyethylene (PE) and poly(vinyl chloride) (PVC).

2. Materials and methods

Commercial Poly(butylene terephthalate) (Aldrich, product

number 435147), polytetrafluoroethylene (Aldrich, product
number 182478), polyethylene (Aldrich, product number 332119,
medium density d ¼ 0.940) and poly(vinyl chloride) (Aldrich
389323, average Mn w47,000; average Mw ∼80,000) were used in
this work. Thermogravimetry measurements were carried out
with a homemade TGA instrument that uses a CI Electronics Ltd
electrobalance connected to a gas flow system to work in inert
atmosphere (70 cc min1 N2). Small samples (9 mg) were used in
order to minimize heat and mass transfer phenomena. They
were placed on a 1 cm diameter platinum pan inside a low thermal
Fig. 1. Trend of temperature, mass lost and reaction rate during a thermal decompo-
sition reaction under different heating methods. This figure has been adapted from the mass homemade furnace. The instrument allows working either
one first published by Reading [20,21]. under conventional linear heating conditions or under sample
controlled conditions. A description of the experimental set-up is
shown in Fig. 2b and can also be found in more detail in references
most usual ones [31,32]. These kinetic models account for the [22,40,41].
relationship between the reaction rate and the conversion a by
assuming certain ideal geometrical conditions and reaction driving
forces. Nevertheless, when studying polymer degradation reactions 3. Shape analysis of CRTA curves
most authors tend to ignore these models, resorting instead to
empirical first or n-order models that have no physical meaning The reaction rate, da/dt, of a solid state reaction can be described
and, even more important, give no guarantee they are actually by the following equation:
representative of the studied process. However, recent works have
da
demonstrated that those ideal models can often describe the ¼ AexpðE=RTÞf ðaÞ (1)
thermal degradation of polymers much more precisely than “n- dt
order” laws [33e38]. Furthermore, a new kinetic model for random where A is the Arrhenius pre-exponential factor, R is the gas
scission, a mechanism to which the degradation of a wide range of constant, E the activation energy, a the reacted fraction, T is the
polymers is attributed, has recently been developed [39]. process temperature and f(a) accounts for the reaction rate
The aim of this work is to carry out a detailed shape analysis of dependence on a. The kinetic model, f(a) is an algebraic expression
CRTA curves as a function of the different kinetic models and which is usually associated with a physical model that describes the
extend it to the recently proposed model for random scission kinetics of the solid state reaction [32]. Table 1 shows the functions
corresponding to the most common mechanisms in literature.
In the case of experiences carried out under constant rate
conditions, the reaction rate, da/dt, is maintained at a constant
value, C, during the entire experiment. Hence, Eq. (1) could be
rewritten as:

C ¼ A eE=RT f ðaÞ (2)

3.1. Diffusion, Avrami-Erofeev and “n-order” models

As it was mentioned before, the shape of the CRTA curves is

strongly dependant on the reaction mechanism. The shape analysis
for the different kinetic models in Table 1 has been performed by
means of determining the existence of minima, maxima or inflec-
tion points in the temperature versus a plots, and by locating at
what a values those effects appear. From Eq. (2), after taking
logarithms and rearranging terms we get:

A E
lnf ðaÞ ¼ ln  (3)
C RT
Fig. 2. Scheme showing the differences between a conventional heating control The first and second derivatives of the temperature with respect
system (a) and the more sophisticated controlled rate thermal analysis (b). to a result in the following expressions, Eqs. (4) and (5):
976 P.E. Sánchez-Jiménez et al. / Polymer Degradation and Stability 96 (2011) 974e981

Table 1
f(a) kinetic functions for the most widely used kinetic models, including the newly proposed random scission model.

Mechanism Symbol f(a) f0 (a) f00 (a)

Phase boundary controlled reaction (contracting area) R2 ð1  aÞ 1=2 1 1
2ð1aÞ1=2 4ð1aÞ3=2
Phase boundary controlled reaction (contracting volume) R3 ð1  aÞ 2=3 2 2
3ð1aÞ1=3 9ð1aÞ4=3
Random nucleation followed by an instantaneous growth of nuclei. F1 ð1  aÞ 1 0
(Avrami-Erofeev eqn. n ¼ 1) 11=n
nlnð1aÞþn1 nþ1þlnð1
Random nucleation and growth of nuclei through different An nð1  aÞ½lnð1  aÞ11=n aÞ
½lnð1aÞ1=n ð1aÞ½lnð1aÞ1=n
nucleation and nucleus growth models. (Avrami-Erofeev eqn s1.)
2lnð1aÞ
Two-dimensional diffusion D2 1=lnð1  aÞ 1
ð1aÞ½lnð1aÞ2 ð1aÞ2 ½lnð1aÞ3

3ð1aÞ2=3 1=2ð1aÞ1=3 aÞ1=3 ð1aÞ2=3 1

Three-dimensional diffusion (Jander equation) D3 ð3ð1 Þ
2½1ð1aÞ1=3  ½1ð1aÞ1=3 2 3ð1aÞ2=3 ½1ð1aÞ1=3 3

ð1aÞ4=3 2½ð1aÞ1=3 1þ1

Three-dimensional diffusion (Ginstling-Brounshtein equation) D4 ð1  2a=3Þ  ð1  aÞ2=3
2½ð1aÞ1=3 12  3ð1aÞ8=3 ½ð1aÞ1=3 13

Random Scission L ¼ 2 L2 2ða1=2  aÞ 1

a1=2
2 1
2a3=2

Random Scission L > 2 L>2 No symbolic solution No symbolic solution No symbolic solution

dT RT 2 f 0 ðaÞ Out of the kinetic models listed in Table 1, only diffusion ones
¼  (4)
da Ea f ðaÞ present a solution to Eq. (8). Consequently, the temperature versus
a CRTA plots of diffusion driven reactions are expected to show an
"  2 00 # inflection point at ai values.
d2 T RT 2 2RT f 0 ðaÞ f ðaÞf ðaÞ  f 0 ðaÞ2 Finally, “n-order” mechanisms yield neither minima nor maxima
¼   (5)
da2 Ea Ea f ðaÞ f ðaÞ2 nor inflection points.

The first and second derivatives of the considered kinetic

models, f’(a) and f’’(a), have been listed in Table 1 together with the 3.2. Random scission models
corresponding f(a) functions. For a plot of T against a to show
a maximum or a minimum, a certain am at which dT/da ¼ 0 must A random scission mechanism implies a random cleavage of the
exist. Therefore, at the maximum/minimum the following condi- bonds along the polymer chains, producing fragments of progres-
tion must be fulfilled: sively shorter length that will eventually evaporate when the size is
small enough. A mathematical model for depolymerisation
f ’ ðam Þ ¼ 0 (6) processes was developed by Simha-Wall [42] but it has rarely been
used because the resulting f(a) kinetic equations cannot be
The above equation has solution only for Avrami-Erofeev
expressed directly as a function of the reacted fraction, thereby
models when n > 1. In such cases, a maximum/minimum appears at
making them very difficult to apply to the kinetic analysis of
an am value which is given by the following equation:
experimental TGA data. A recent work addressed the problem by
  reformulating the Simha-Wall model and proposing the following f
1n
am ¼ 1  exp (7) (a) function for the degradation reactions governed by random
n
scission mechanisms [39]:
According to Eq. (7), am depends only on the Avrami-Erofeev
order. Therefore, from Eqs. (5) and (6) is easy to deduce that d2T/ f ðaÞ ¼ LðL  1Þxð1  xÞL1 (9)
da2 > 0, indicating that the temperature versus a CRTA plots of
where x and L are the fraction of bonds broken and the minimum
reactions fitting an Avrami-Erofeev law must yield a minimum at
length of the polymer that is not volatile, respectively. Unfortu-
the reacted fraction am. The values of am found for each Avrami-
nately, Eq. (9) presents a symbolic solution only when L ¼ 2. The
Erofeev model have been included in Table 2.
problem can be sorted out by calculating numerically the f(a)
On the other hand, the appearance of an inflection point at am
functions for L s 2, just by giving values to both L and x. Alterna-
would require that d2T/da2 ¼ 0. Hence, according to Eq. (5), the
tively, a symbolic expression can be obtained by the use of a fitting
following expression must hold true:
function:
 
RT
½f ’ ðai Þ þ 1  f ðai Þ f ’’ ðai Þ ¼ 0 (8) f ðaÞ ¼ cð1  aÞn am (10)
2Ea
The equation above is a modified form of the SestakeBerggren
equation [43], and it is fully capable of fitting every kinetic model in
Table 1, effectively working as an umbrella that covers the different
Table 2
Position of the minimum on the temperature- a plots for the case of Avrami-Erofeev
kinetic models, by merely adjusting the parameters n, m and c [44].
and random scission models together with the values the parameters c, n and m The fitting of the numerically calculated f(a) functions to Eq. (10) was
have to take in order to make Eq. (10) match the corresponding ideal models. done by means of the maximize function of Mathcad software. Table 2
Symbol am n m c
lists the values that the cited n, m and c parameters have to take in
order for Eq. (10) to match the random scission f(a) functions [39].
A2 0.393 0.807 0.515 2.081
A3 0.486 0.751 0.695 3.204 The first derivative of Eq. (10) becomes zero at am ¼ m=ðn þ mÞ .
A4 0.528 0.725 0.787 4.340 Therefore, as d2T/da2 > 0, the CRTA temperature versus a plots
L2 0.250 1.119 0.400 1.204 for reactions driven by random scission models would show
L3 0.273 1.057 0.396 2.080 a minimum like the Avrami-Erofeev models, but at lower am values
L4eL8 0.275 1.039/1.017 0.394/0.386 2.93/6.24
as is shown in Table 2.
 P.E. Sánchez-Jiménez et al. / Polymer Degradation and Stability 96 (2011) 974e981 977

In order for the curves to have an inflection point, the second

derivative of Eq. (4) should be equal to zero, so that Eq (8) holds
true. As there is no a value that fulfils that condition, no inflection
point should appear in the CRTA curves.

4. Simulation of CRTA curves for different kinetic models

The analysis above has been validated by a set of simulated a-T

curves constructed taking into account the different kinetic models
in Table 1. Fig. 3 shows a series of curves constructed assuming
CRTA conditions at a constant reaction rate of 0.01 min1, an acti-
vation energy of E ¼ 150 kJ mol1 and a pre-exponential factor of
1015 min1. The simulation was carried out by means of the Runge-
Fig. 4. Scheme illustrating the initial steps of polymer decomposition by a random
Kutta method using the Mathcad software. The curves in Fig. 3 scission mechanism.
confirm the shape analysis performed in Section 3. The curves
simulated considering a diffusion kinetic model (Fig. 3a) show
clearly the appearance of an inflection point while the curves stages of the reaction, the temperature raises until the pre-
drawn according to (1-a)n laws (Fig. 3b) present neither tempera- determined reaction rate is attained. At that point, the reaction rate
ture minimums nor inflection points. It is worth noting that (1-a)n suddenly accelerates and the system has to cool down in order to
laws comprise both the empirical “n-order” models that lacks any maintain the conversion rate. In Avrami-Erofeev models, the
physical meaning and the ideal models that were proposed segment previous to the acceleration can be attributed to the
assuming phase boundary controlled reactions such as the F1, R2 formation of nuclei. Once the nuclei start growing, the increase in
and R3 models that are included in Table 1. On the other hand, the the reaction surface induces a steady raise in the reaction rate, thus
curves simulated assuming random scission and Avrami-Erofeev making the temperature decrease accordingly. After the tempera-
models (Fig. 3c and d) feature a temperature minimum at the am ture minimum, the coalescence that happens due to the nuclei
predicted in Table 2. The minimum appears because at the initial growth provokes a reduction on the reactive surface, and the

Fig. 3. T-a plots corresponding to simulated CRTA curves (reaction rate 0.01 min1) constructed by using the following kinetic parameters: activation energy of 150 kJ mol1, a pre-
exponential factor of 1015 min1 and (a) diffusion, (b) phase boundary contraction, (c) random scission; and (d) Avrami-Erofeev kinetic models.
978 P.E. Sánchez-Jiménez et al. / Polymer Degradation and Stability 96 (2011) 974e981

consequent diminution in the reaction rate has to be compensated Fig. 4. The minimum that appears for nucleation and random
by an increase in temperature [15,23]. scission driven decomposition reactions is a very noticeable
A similar reasoning can be followed in the case of random feature, what can be very useful for a quick identification of these
scission mechanisms. The mass loss that occurs during a degrada- mechanisms from a single CRTA curve. However, it should be taken
tion reaction via random scission is ascribed to the evaporation of into consideration that this procedure for determining the kinetic
short fragments, which are most probably released after breakages model can only be used if the investigated process is a single step
close to the chain endings. The chances for those events are much one (that is, if the system can be described by a single set of kinetic
lower during the initial reaction times when the polymer chains are parameters A, E and f(a)), or is composed by separable individual
still long and the fragments resulting from such a scission are not processes. The suitability of investigated processes could be
short enough to evaporate. Therefore, as the predetermined reac- checked by means of a model-free method, such as the one
tion rate is not yet achieved, the temperature keeps rising. At described by Friedman [45], which allows to determine whether
a certain point, when the polymer chains are sufficiently frag- the activation energy is actually independent of a. When
mented, the amount of material volatilized raises and the approaching complex reactions with overlapping events a more
temperature must drop in order to maintain the reaction rate detailed and individualized analysis would be required. In any case,
constant. A scheme illustrating this sequence of events is shown in the improved resolution provided by CRTA conditions allows for

Fig. 5. Experimental conversion (solid line), temperature (squares) and reaction rate (dotted line) against time curves obtained for the thermal decomposition of PBT under (a)
a linear heating rate of 1 K min1 and (b) constant rate conditions at 8.3  104 min1.
 P.E. Sánchez-Jiménez et al. / Polymer Degradation and Stability 96 (2011) 974e981 979

a better separation of overlapping events as it has been demon- the temperature follows an irregular profile that will depend upon
strated in literature [46]. the kinetic model followed by the process.
Fig. 6 shows the T-a plots obtained from a set of TG experiments
5. Validation of the shape analysis by real systems corresponding to the thermal decomposition of PE, PTFE, PBT and
PVC under a linear heating rate of 1 K min1. As it was expected all
The relationship found between the shape of the CRTA curves curves are sigmoidal in shape and no information can be immedi-
and the reaction mechanisms have so far been proved theoretically. ately extracted from them.
Next it will be tested by its application to the thermal degradation A single CRTA decomposition curve was also recorded for each
of four commercial polymers, i.e. polytetrafluoroethylene (PTFE), polymer at a reaction rate of 8.3  104 min1. Fig. 7 shows the
polyethylene (PE), poly(vinyl chloride) (PVC) and poly(1,4-butylene temperature versus a plots obtained from the thermal degradation
terephthalate) (PBT), and to evaluate the potential of this method in of each of them. The degradation curve of PE (Fig. 7a) shows an
thermal stability studies of polymers. The thermal decomposition inflection point, which is characteristic of a diffusion mechanism.
of PTFE, PE and PBT were studied in recent works [33,39,47], where The curve obtained from the decomposition of PTFE (Fig. 7b) shows
Friedman isoconversional method showed that the activation neither maximum, minimum nor inflection point, thus indicating
energy was independent of a and, hence, being single step an “n-order” law. On the other hand, the degradation of PBT clearly
processes suitable for the kind of analysis here proposed. The case presents a minimum that appears at a ¼ 0.26. This value is in-
of PVC was approached in another work, where it was shown that between the values obtained by the shape analysis (tabulated in
the degradation consists of two independent events, each due to Table 2) for random scission L2 and L3 models, indicating that
the decomposition of polymer sequences of different tacticities a random scission mechanism drives the decomposition of PBT. The
[48,49]. small deviation of the minimum values for the real CRTA curves as
Fig. 5a shows the conversion and temperature plots versus time, compared with those expected for the analysis of ideal models
as obtained for the thermal degradation of PBT under a linear could be understood if we consider that the ideal kinetic models
heating rate of 1 K min1. In these experiments, the weight loss is were proposed assuming some restricted conditions regarding
a direct measure of the reacted fraction while the derivative curve geometrical consideration that shall rarely be fulfilled in real
reflects the reaction rate. The conversion-time curve presents the systems [44,50e52]. It is also interesting to relate the decomposi-
sigmoidal shape that is typically obtained from conventional linear tion profile obtained for PBT (Fig. 7c) with the degradation scheme
heating runs while the evolution of temperature with time follows shown in Fig. 4. The positions that would correspond to the steps
a straight line according to the program set. On the other hand, (1), (2) and (3) for the initial part of a polymer decomposition by
Fig. 5b shows the conversion, temperature and reaction rate a random scission mechanism have been marked in Fig. 7c. Step (1)
as a function of time for the decomposition of the same PBT represents the initial undegraded state. Step (2) the start of the
under constant rate (CRTA) experimental conditions at chain breakage, when the amount of evolved material per time
8.3  104 min1. It can be noticed how the reaction rate is main- stands below the predetermined reaction rate and therefore the
tained approximately constant at the selected value. Alternatively, temperature keeps rising. At step (3) the chains have been

Fig. 6. Experimental temperature versus a plots corresponding to the thermal decomposition obtained under constant linear heating at 1 K min1 of (a) polyethylene, (b) poly-
tetrafluoroethylene, (c) poly(1,4-butylen)terephthalate; and (d) polyvinyl chloride.
980 P.E. Sánchez-Jiménez et al. / Polymer Degradation and Stability 96 (2011) 974e981

Fig. 7. Experimental temperature versus a plots corresponding to the thermal decomposition under CRTA conditions of (a) polyethylene, (b) polytetrafluoroethylene, (c) poly(1,4-
butylen)terephthalate; and (d) polyvinyl chloride. The kinetic model for each reaction as deduced from the shape of the curves is also marked under each plot.

shortened enough so that the fragments that evaporate signifi- degradation studies due to the complexity of the reactions and
cantly increase and the system are forced to cool down in order to would help to identify the kinetic model without the need to resort
maintain the reaction rate constant. to generic empirical models such as first or n order. Since the results
For the case of PVC dehydrochlorination, further clarification obtained from a kinetic analysis are heavily dependent on the
can be provided since it consists of two independent reactions kinetic model assumed, the capacity of a single CRTA experiment to
[48,49]. It is clear from Figs. 6 and 7 that both events are better hint the model that governs a reaction just by a mere glance at the
resolved in the CRTA curve (Fig. 7d) than in the TG one (Fig. 6d), shape of the temperatureetime curve, something that cannot be
illustrating the better resolution power of the CRTA experiment done in linear heating and isothermal runs, is extremely useful for
than the conventional one. The dominant event during most of any subsequent analysis and for preventing errors. The shape
conversion range is the first one that accounts up to approximately analysis here performed has been validated by its application to the
a ¼ 0.8 and has the typical shape of a nucleation process. In addi- thermal degradation of four commonly used commercial polymers:
tion, if it is taken into consideration that this first event accounts polytetrafluoroethylene (PTFE), poly(1,4-butylene terephthalate)
only up to a ¼ 0.8, the equivalent value of am appears at about 0.40 (PBT), polyethylene (PE) and poly(vinyl chloride) (PVC). All four
that corresponds to the value expected for an A2 nucleation have been found to decompose through different mechanisms,
mechanism. For the second step, the CRTA curve has sigmoidal namely “n-order”, random scission, diffusion and Avrami-Erofeev
shape, suggesting a diffusion controlled kinetic model. These mechanisms, respectively.
resulting models are in agreement with recent publications on the
thermal dehydrochlorination of PVC [48,49].
Acknowledgments
6. Conclusions
Financial support from projects TEP-03002 from Junta de
Here, it has been proven that a strong relationship exists Andalucía and MAT 2008-06619/MAT from the Spanish Ministerio
between the shape of the a-T CRTA curves and the kinetic model de Ciencia e Innovación is acknowledged. The work was also sup-
obeyed by the polymer thermal degradation process. Diffusion ported by a JAE-Doc contract (CSIC)
driven processes present an inflection point while random scission
and Avrami-Erofeev models show a minimum in the temperature.
Phase boundary controlled mechanisms have neither minimum nor References
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