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Vol. 15 No. 2
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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Vol. 15 No. 2
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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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.
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
PIChE Journal
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.
0.4567
1.92
1.0008
( 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
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
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
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PIChE Journal
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Calculated E (kJ/mol)
Ozawa-Flynn-Wall
95.4178
Kissinger-Akahira-Sunose
87.7722
Starink
88.2044
88.5013
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)
ln A = aE b
(8)
g()
[-ln(1- )]1/2
Nucleation of order
)]2/3
[-ln(12/2
Diffusion on a plate
1/2
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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PIChE Journal
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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
REFERENCES
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Resources, Conservation and Recycling 39: 325-340.
[2] S.V. Joshi, L.T. Drzal, A.K. Mohanty, S. Arora (2004). Are natural fiber composites
environmentally superior to glass fiber reinforced composites? Composites: Part A
35: 371376.
[3] T. Corbire-Nicollier, B.G. Laban, L. Lundquist, Y. Leterrier, J. Manson, O. Jolliet
(2001). Life cycle assessment of biofibres replacing glass fibres as reinforcement in
plastics. Resources, Conservation and Recycling 33: 267287.
[4] P. Budrugeac (2005). Some methodological problems concerning the kinetic analysis
of non-isothermal data for themal and thermo-oxidative degradation of polymers and
polymeric materials. Polymer Degradation and Stability 89: 265-273.
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