PIChE Journal

J. M. O. Aberilla, T. P. Tumolva and M. Kubouchi (2014)

Vol. 15 No. 2

Comparative study of lifetime prediction methods

from thermal analysis of furan resin
J. M. O. Aberilla1, T. P. Tumolva1* and M. Kubouchi2
1

Department of Chemical Engineering, University of the Philippines, Diliman, Quezon

City 1101 Philippines
2
Department of Chemical Engineering, Tokyo Institute of Technology, Ookayama,
Meguro-ku, Tokyo 152-8551 Japan
*E-mail: terence.tumolva@coe.upd.edu.ph

Abstract
Modern societys search for sustainable materials has increased the investigation into
bio-based polymers that can potentially replace traditional polymers and their
composites. Most of the previous and current researches are focused on their
biodegradability as a potential solution to the increasing rate of plastic solid wastes
generation. Proper estimation of the serviceable lifetimes of such materials is therefore
needed to fully assess the viability of biothermosets and biothermoset-based plastic
composites as sustainable solution. Due to the long natural lifetimes of bio-based
polymers, degradation studies on these materials are facilitated by thermogravimetric
analysis (TGA) and differential scanning calorimetry (DSC). The International
Confederation for Thermal Analysis and Calorimetry (ICTAC) has published
recommendations for performing kinetic computations from thermal analysis data. A
sample of these recommendations were applied to the thermal degradation of
synthesized furan resin or polyfurfuryl alcohol from vegetable wastes. Results from
different methods show comparable values of kinetic parameters for the degradation of
the resin. These calculated parameters are employed to predict the useful lifetime of the
furan resin.
Keywords
lifetime prediction, thermal degradation, kinetics, furan resin

INTRODUCTION
Furan resin for fiber-reinforced polymeric composites
Over the last few years, awareness and understanding of the significant impact of
anthropogenically driven processes- primarily run by fossil fuel combustion- to climate
change has grown, which, in turn, has fueled various research works investigating options
to mitigate likely impacts. Ecological concern and global warming has initiated a
considerable interest in using natural or renewable materials to produce green products
and reduce anthropogenic carbon dioxide emissions by all possible means. One of the
identified mitigating schemes is the use of plant-based materials to produce highly
durable materials for long service life applications, such as natural fibers in fiber
reinforced bio-based thermosetting resins. Furan resin (polyfurfuryl alcohol) is a
biosynthetic thermoset derived from vegetable byproducts such as corn cobs. Compared
to other common resins, this highly stable polymer offers a very significant improvement
in the carbon storage potential of green composites when used as a matrix.
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PIChE Journal

J. M. O. Aberilla, T. P. Tumolva and M. Kubouchi (2014)

Vol. 15 No. 2

At present, there is already a great abundance of research on natural fiber reinforced

polymeric (NFRP) composites- mostly on the evaluation and improvement of mechanical
performance when using non-biodegradable composite matrices such as thermosetting
resins. However, limited data is available to gauge the environmental advantages of these
materials- in particular, the carbon storage potential with the use of renewable bio-based
materials. Several reports on life cycle analysis (LCA) applied to natural fiber-reinforced
composites have been published- mostly aimed to compare the environmental impact of
natural fibers with that of glass fibers in the form of carbon dioxide emission and total
energy consumption [1-3]. Since CO2 fixation capacity is the key environmental
parameter evaluated in this study, certain LCA principles are applied on the material to
serve as a guide and tool for the evaluation of carbon storage potential. For long-term
CO2 fixation, the bio-based carbon content of a material is just one of the parameters that
must be determined in order to evaluate overall carbon storage potential- another
parameter that must be considered is the lifetime of the material. In order to assess
environmental impact in comparison with other thermoset systems, lifetime/degradation
behavior of the furan resin matrix must be estimated since it can provide information on
the total energy consumption and CO2, including within the waste disposal stage.
Due to the long lifetime of highly stable furan (>102 years), it is definitely not feasible to
simply wait and directly measure the longevity of carbon fixation of the resin and its
composites; therefore, a different approach is necessary. One popularly known method of
predicting lifetime of polymeric materials is by thermogravimetric analysis (TGA). In this
study, TGA is performed to evaluate the thermal decomposition of furan by measuring
the weight loss at a fixed heating rate, and the parameters of the degradation kinetics are
obtained to establish lifetime.
Determination of kinetic parameters from thermal analysis
The rate of degradation of polymeric materials, commonly expressed as loss of mass, can
be parameterized as a function of temperature and extent of conversion in the form:

d
= k (T ) f ( )
dt

(1)

The temperature dependence of the rate is typically expressed by the Arrhenius equation:
E
k (T ) = A exp

RT

(2)

The pre-exponential factor, activation energy, and reaction model are collectively called
the kinetic triplet, and these parameters are determined to estimate lifetimes of materials.
Methodological problems associated with kinetic analysis of polymer degradation and
stability are well discussed in literature [4]. Both theoretical assumptions and
experimental conditions are known to affect the reliability of obtained values for
activation energy. To obtain high quality data, ICTAC recommends the use of 3-5
temperature programs (heating rates) and sample masses that do not create significant
internal thermal gradients.
Two methods used in this study are isoconversional methods and method of invariant
kinetic parameters. The general idea of isoconversional methods can be shown by taking
the logarithmic derivative of Equation (1) at a constant conversion.
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PIChE Journal

J. M. O. Aberilla, T. P. Tumolva and M. Kubouchi (2014)

Vol. 15 No. 2

ln ( d / dt )
E

=
1
dT
R

(3)

Equation (3) shows that the activation energy (at each conversion) can be determined
without prior assumption of a reaction model. In this type of method, the variation of the
activation energy with conversion should be investigated before determining the other
parameters of the kinetic triplet. Isoconversional methods can be further categorized as
differential or integral methods, depending on the thermal analysis data used. Differential
methods are more useful for experiments using DSC and DTA, while integral methods
are based on the integrated form of Equation (1). Alternatively, the method of invariant
kinetic parameters utilizes the strong correlation between the activation energy and the
pre-exponential factor, known as the compensation effect. This method is not as
commonly used as it requires more heating rates and calculations than isoconversional
methods.

METHODOLOGY
In this study, the furan resin is subjected to TGA at different constant heating rates using
the thermal analyzer Shimadzu DTG-60H. It must be clearly pointed out that for NFRP
laminates, the bio-based fibers are completely embedded within the stable thermosetting
resin, which prevents them from degrading; therefore the lifetime of the NFRP will be
completely dependent on the lifetime of the polymer matrix.

RESULTS AND DISCUSSION

Results from the thermogravimetric analysis are shown in Figure 1. Using these data,
various linearized forms of the kinetic equation can be fit using linear regression. For the
model-free method, two approximations [5,6] are used for the temperature integral.

0.9
0.8
0.7
0.6

0.5
0.4
0.3
0.2
0.1
0.0
400

500

600

700
T (K)

800

900

1000

Figure 1. Non-isothermal degradation profile at different heating rates ( 5oC/min, 10oC/min,

25oC/min).
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PIChE Journal

J. M. O. Aberilla, T. P. Tumolva and M. Kubouchi (2014)

Vol. 15 No. 2

The forms of integral isoconversional methods are derived from the integrated form of the
rate equation. Since this equation does not have an analytical solution, approximations are
used on the generalized linear form:

ln Bi
T
,i

E
= Const C

RT

(4)

The values of parameters B and C for integral methods used are shown in Table 1. This
form is convenient to use in this study as the pre-exponential factor and kinetic model are
lumped separate from the activation energy.

Table 1. Parameter values for Equation (4).

Method

Ozawa-Flynn-Wall (1966) [7]

0.4567

Kissinger-Akahira-Sunose (1971) [8]

1.92

1.0008

Starink (2003) [9]

The method of Vyazovkin involves the minimization of the function:

n

( E ) =
i =1 j i

I ( E , T ,i ) j

(5)

I ( E , T , j ) i

where the temperature integral term is defined and approximated by Agrawal and Cai as:
RT 2 1 2( RT / E ) E / RT
e

2
T
E 1 5( RT / E )
E
I ( E , T ) = exp
dT
2
0
RT
RT E + 0.66691RT e E / RT

E E + 2.64943RT

( Agrawal )

(6)
(Cai )

The built-in function fminsearch() of MATLAB (version R2010b) is used to locate the
minimum function value.
The activation energies calculated at each conversion value are plotted in Figure 2. Initial
inspection of the graph indicates that there is a consistent trend showing the variation of
activation energy with conversion. The initial mass loss ( < 0.20) with higher activation
energy is attributed to evaporation of volatile material. In the range of 20-80%
degradation, the E values may be considered to vary with minor significance with
respect to , as the difference between the maximum and minimum within the range is
less than 30% of the mean value [10]. This indicates that a single mechanism is followed
through the most part of the resin decomposition.
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PIChE Journal

J. M. O. Aberilla, T. P. Tumolva and M. Kubouchi (2014)

Vol. 15 No. 2

120

110

E (kJ/mol)

100

90

80

70

60
0.00

0.20

0.40

0.60

0.80

1.00

Figure 2. Variation of E with respect to conversion ( Flynn-Wall-Ozawa, Kissinger-Akahira-Sunose,

Starink, Vyazovkin [Agrawal approx.], * Vyazovkin [Cai approx.]).

The narrow range of values calculated (Table 2) shows the reliability of both integral and
model-free methods. Except for the Ozawa-Flynn-Wall method, the choice of temperature
integral approximation affects the resulting calculations minimally; based on the results,
there is a strong agreement between all the other methods, which suggests that the
activation energy for the degradation of furan resin is approximately 88 kJ/mol.

100000
10000

Lifetime (years)

1000
100
10
1
0.1
0.01
0.001
0

50

100

T (oC)
Figure 3. Predicted useful lifetime of synthesized furan resin.

50

150

200

PIChE Journal

J. M. O. Aberilla, T. P. Tumolva and M. Kubouchi (2014)

Vol. 15 No. 2

Table 2. Determination of activation energy.

Method

Calculated E (kJ/mol)

Ozawa-Flynn-Wall

95.4178

Kissinger-Akahira-Sunose

87.7722

Starink

88.2044

Vyazovkin (Agrawal approx.)

88.5013

Vyazovkin (Cai approx.)

88.4998

The method of invariant parameters [11] is used to obtain a model-free prediction for the
pre-exponential factor. A form based on the Cotes-Redfern method [4]:
AR E
g ( )
ln

= ln
2
E RT
T

(7)

This equation is applied with selected kinetic models of decomposition (Table 3) to

obtain coefficients a and b of the compensation effect:

ln A = aE b

(8)

Table 3. Kinetic models of decomposition.

Description

g()

Phase boundary reaction on a plate

[-ln(1- )]1/2

Nucleation of order

)]2/3

Nucleation of order 2/3

[-ln(12/2

Diffusion on a plate

1/2

Power law of order

3/2

Power law of order 3/2

For lifetime prediction, a phase boundary reaction model is expected for the system as the
geometry and mechanism of experimentation provides such conditions. Since a singlestep process can be assumed for the degradation, the kinetic equation can be expressed as:
t =

g ( )
A exp( E / RT0 )

(8)

This equation is to determine the time expected to reach a given conversion at a constant
temperature T0. Mass loss is taken to be the criteria of degradation, with 5% mass
decrease ( = 0.05) as the limit for usefulness. The predicted useful life of the resin at
different temperature conditions is shown in Figure 3.
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J. M. O. Aberilla, T. P. Tumolva and M. Kubouchi (2014)

Vol. 15 No. 2

CONCLUSION
Different methods of kinetic analysis were done on the thermal degradation of fiberreinforced furan resin to estimate its useful lifetime. A comparison of Vyazovkins
isoconversional method with integral methods yielded similar values of the activation
energy for the decomposition reaction. The choice between the two temperature integral
approximations used is also shown to insignificantly affect the results. While the reaction
mechanism was assumed based on geometry of the experimental setup, the preexponential factor was determined without neglecting the compensation effect. It is
recommended for future work that complete confirmation of the kinetic triplet be
concluded by verifying the reaction mechanism. Other optimization methods can also be
used on the TGA data to affirm the accuracy of the kinetic triplet.
The resin synthesized is estimated to have acceptable stability for carbon fixation based
on the kinetic analysis done. Aside from mass loss as criteria for useful lifetime, further
study can investigate the relevant physical and chemical properties as functions of the
resin degradation to create the full criteria for useful lifetime.

ACKNOWLEDGEMENTS
The authors would like to acknowledge the significant contributions of Hitachi Chemicals
Co., Ltd., to this research on furan resin.

NOMENCLATURE
A
E
g
R
T

pre-exponential factor (min-1)

activation energy (kJ/mol)
integrated conversion function/kinetic model
gas constant (8.314 J/mol-K)
temperature (K)
extent of conversion
heating rate (oC/min)

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PIChE Journal

J. M. O. Aberilla, T. P. Tumolva and M. Kubouchi (2014)

Vol. 15 No. 2

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