Int J Plast Technol (December 2014) 18(2):294–320

DOI 10.1007/s12588-014-9076-x
R E S E A R C H A RT I C L E

Thermogravimetric kinetics of degradation of HDPE

based MWCNTs reinforced composites

P. Rajeshwari & T. K. Dey

Received: 28 May 2014 / Accepted: 6 July 2014 / Published online: 14 July 2014
# Central Institute of Plastics Engineering & Technology 2014

Abstract High Density Polyethylene (HDPE) reinforced multiwalled carbon nano-

tubes (MWCNTs) composites with MWCNTs loading between 0.0011 and 0.0044
volume fractions are fabricated by melt mixing. The prepared nano-composites are
investigated by thermo-gravimetric analyzer (TGA) under nitrogen atmosphere at
various heating rates. TGA thermograms indicate only a marginal enhanced thermal
stability and no significant mass loss occurs up to ~400 °C. Thermal degradation
kinetics of HDPE/MWCNTs nano-composites has been examined in light of five
different analytical methods, viz., Coats-Redfern (CR) integral model fitting approach,
‘iterative’ based CR(modified) approach, integral form of the rate equation (i.e. FWO
and KAS), the differential iso-conversional based method of Friedman. The CR integral
model fitting based on 14 different kinetic models are analyzed for TGA data for
multiple heating rates. Our analysis indicates that the degradation mechanism of the
present nano-composites follows diffusion control (D2, D3 and D4) and first order
reaction (F1) mechanisms. The apparent activation energy (Ea) as a function of
conversion rate (α) estimated by CR (modified), FWO, KAS and FR methods are all
in fair agreement with each other and confirms decrease in Ea with increased loading of
MWCNTs. The pre-exponential factor (A) calculated also decreases with MWCNTs
concentration in HDPE. Activation energy (Ea) for different conversion rate (α)
calculated by iso-conversional methods (CR(modified), FWO, KAS and FR) indicates
contributions from at least two different degradation mechanisms, namely, diffusion
controlled (D2, D3, D4) and first order reaction (F1), which are consistent with the
findings of Coats-Redfern (CR) integral model.

Keywords HDPE/MWCNTs nano-composites . Thermal stability . Thermal degradation

mechanism . Activation energy . Kinetic models

P. Rajeshwari : T. K. Dey (*)

Cryogenic Engineering Centre, Indian Institute of Technology, Kharagpur 721302 West Bengal, India
e-mail: tapasdey@hijli.iitkgp.ernet.in
P. Rajeshwari
e-mail: rajeshwari.iitkgp@gmail.com
Int J Plast Technol (December 2014) 18(2):294–320 295

Introduction

Over the recent years, discovery of carbon nanotubes (CNTs) motivated significant
research in the development of nanotube reinforced polymer composites and investi-
gations of their various properties [1–3]. CNTs are the third allotropic form of carbon
and were synthesized for the first by Iijima in 1991 [4]. Ajayan et al.[5] reported the
first polymer nanocomposites using carbon nanotubes as a filler and since then it has
been considered as a unique reinforcements for different polymers, because of their
superior thermal, electrical, mechanical and chemical properties [6]. Thermal transport
properties of polymer composites can be tailored with the incorporation of CNTs due to
the excellent thermal conductivity of CNTs. Thermal conductivity of MWCNTs at
room temperature is reported to be >3,000 W/mK [7], which indicates that the thermal
properties of polymers can be tailored with the incorporation of CNTs. Consequently,
polymer/CNT nano-composites offer opportunity for numerous potential applications
in several domains, such as printed circuit boards, connectors, thermal interface
materials, heat sinks, and high-performance thermal management systems for satellite
structures down to electronic device packaging. [2].
Among the versatile polymer, HDPE is an widely used thermoplastics in electronic
packaging, automobile and other industrial sectors because of its well-balanced phys-
ical and mechanical properties and easy processability at a relatively low cost [8,9].
Several investigations on the thermal degradation kinetics of polymer nano-composites
based on HDPE have been reported by various authors [10–13]. Chrissafis et al. [14]
reported thermal degradation of HDPE/SiO2 nano-composites, and confirmed their
enhanced thermal stability. Cadek et al. [15] investigated mechanical and thermal
properties of amorphous and crystalline polymers with MWCNTs and reported appre-
ciable improvement in their properties. Shariati et al. [16] studied the thermal degra-
dation of ultra high molecular weight polyethylene (UHMWPE) based MWCNTs
nanocomposites prepared by in situ polymerization process. Commonly used process-
ing methods for the fabrication of CNTs filled polymer composites include solution
mixing, in-situ polymerization, and melt mixing [17]. Melt mixing is a commonly used
technique for thermoplastic polymers due to several advantages viz., fast production,
cost effectiveness, eco-friendly nature. In melt processing, CNTs are mechanically
dispersed into a polymer matrix in a high temperature and high shear force mixer or
compounder [6,18]. The shear forces help to break nano-tube aggregates and prevent
their agglomeration. Several researchers have used melt mixing for preparation of PE/
CNT composites [19–23], nylon-6/MWCNTs composites [24], as well as, carbon
nanotube/polyethylene (CNTs/PE) composites [25]. Kinetic analysis of polystyrene
under dynamic heating conditions using Coats–Redfern integral model-fitting method
[26] was reported by Brems et al. [27]. Recently Sanchez-Jimenez et al. [28] reported
thermal degradation of PS and discussed various limitations of model-fitting procedures
and concluded that random chain scission model is most appropriate to describe
polymer degradation reactions. To the best of our knowledge, detailed investigations
on the kinetics of thermal degradation of MWCNTs/HDPE composites are far from
being complete [14,16,29]. In view of the above, a detailed analysis of the kinetics of
thermal degradation of HDPE/MWCNTs has been attempted. The measured data are
discussed in terms of Coats-Redfern integral model-fitting method based on fourteen
different kinetic models, so as to identify the degradation reaction mechanism. Kinetic
296 Int J Plast Technol (December 2014) 18(2):294–320

parameters (viz., activation energy Ea and the frequency factor A) have been estimated
in light of various important iso-conversional models, (viz., Coats-Redfern (modified)
methods, Flynn Wall Ozawa (FWO), Kissinger-Akhaira-Sunose (KAS) and Friedman
(FR) methods and the variation of the activation energy (Ea) with conversion rate (α)
for these composites are discussed.

Experimental

Preparation of HDPE/MWCNTs nanocomposites

High-density polyethylene (HDPE) used in this study is of commercial grade (mol. Wt.
127,000 g/mol and density of 0.94 g/cm3) supplied by Loba Chemicals (India). The
multi-wall carbon nanotube (MWCNTs) (purity≥97 %, density 2.16 g/cm3) is obtained
from M/S Sky Spring Nano, USA. The diameter and length of the MWCNTs are
between 60 and 100 nm, and between 5 and 15 μm respectively. Composites with
various volume fractions of multi-wall carbon nanotubes in HDPE are prepared by melt
mixing in a temperature controlled ‘Sigmamixer’ (M/S. S. C. Dey & Co., Kolkata,
India) fitted with roller blades and a mixing head of volumetric capacity of 50 cm3. In
order to achieve a homogenous dispersion of MWCNTs nano-tubes in HDPE, the two
components are physically premixed before being fed in the sigma mixer. Melt
blending is performed at 240 °C with 50 rpm for 30 min. The resultant homogeneous
mixture of HDPE and MWCNTs is then slowly cooled to room temperature. Pieces cut
from the solidified HDPE/MWCNTs mixture are transferred to a stainless steel die and
is subjected to hot compression molding at 220 °C. On complete solidification under
pressure, HDPE/MWCNTs composite pellets are carefully taken out of the die. For the
present investigation, four different compositions ranging from 0.0011 to 0.0044
volume fraction MWCNTs in HDPE matrix have been prepared.

Thermogravimetric analyzer (TGA)

The thermal decomposition process of the HDPE/MWCNTs composites has been

studied using a Perkin Elmer Pyris Diamond DTA/TGA thermo-gravimetric analyzer.
Samples (12±0.5 mg) are placed in alumina crucibles. An empty alumina crucible is
used as reference. Samples are heated from ambient temperature to 800 °C in a 100 ml/
min flow of nitrogen gas. Data are continuously recorded for all the composites at a
heating rate of 5, 10, 15 and 20 °C/min.

Results and discussions

Thermal stability

The effect of incorporation of MWCNTs on the thermal stability of the composites are
studied using thermogravimetric data measured at four different heating rates (5, 10, 15
and 20 °C/min) under nitrogen atmosphere. Figure 1a, b show typical TG and DTG
thermograms of HDPE/MWCNTs composite with 0.0033 volume fraction loading of
Int J Plast Technol (December 2014) 18(2):294–320 297

Fig. 1 a. Weight (%) vs. temperature and b. derivative weight loss (DTG) vs. temperature curves for
HDPE/0.0033 vol. fraction of MWCNTs nano-composites at four different heating rates viz., β=5 °C/min,
10 °C/min, 15 °C/min and 20 °C/min

MWCNTs. It may be seen that with increasing heating rates, a shift in the degradation
temperature to higher temperatures is observed. This is expected because under high
heating rate shorter time is required by the composite to reach a given temperature.
Figure 2a, b shows typical TGA curves corresponding to the thermal degradation of
HDPE containing 0.0011, 0.0022, 0.0033 and 0.0044 volume fraction of MWCNTs at
a heating rate of 20 °C/min . Inset of Fig. 2a shows magnified plot of TG thermograms
between 400 and 500 °C for the present HDPE/MWCNTs composites with different
filler concentration and it shows that thermal degradation starts typically after ~5 %
weight loss. It may be noted that TGA data for HDPE/MWCNTs composites present
only marginal thermal stability and under nitrogen gas atmosphere all the samples
undergo rapid decomposition. From Fig. 2b it is seen that HDPE degrades with a sharp
single peak starting around 500 °C under N2 atmosphere. This peak originates from the
298 Int J Plast Technol (December 2014) 18(2):294–320

Fig. 2 a. Weight (%) and inset images shows magnified view of (TG%) vs. temperature thermograms b.
derivative mass loss (DTG) vs. temperature thermograms at a heating rate of β=20 °C/min as a function of
MWCNTs concentration in the samples

thermal scissions of C-C chain bonds accompanied by hydrogen transfer at the site of
scission [21]. The influence of MWCNTs on the thermal stability of HDPE are
determined using the temperatures associated with Tonset (20 % weight loss), T40 %
(40 % weight loss) and Tmax (DTG peak value) measured at different heating rates and
their values are summarized in Table 1. It may be noted that the average values of
decomposition onset temperature (Tonset) and the temperature at 40 % weight loss
(T40 %) of the present composites varies between 465.59 and 470.96 °C and between
477.01 and 480.36 °C respectively. Furthermore, it is seen that the DTG peak temper-
ature (Tmax) corresponding to the maximum degradation rate for HDPE/MWCNTs
composites lies between 487.52 and 489.52 °C. Thus, with increasing loading of
MWCNTs in HDPE, a small variation is noticed in Tonset, T40 % and Tmax, which
Int J Plast Technol (December 2014) 18(2):294–320 299

Table 1 Thermal data obtained from TG-DTG curves studied at multiple heating rates for all compositions of
HDPE/MWCNTs polymer nano-composites

Composition Heating rate Tonset T40 % Tmax.% Carboneous Oxidation

(β) (°C/min) (°C) (°C) (°C) char (at Index (OI)
600 °C) (%)

HDPE+MWCNT 5 457.602 466.203 473.883 0.325 0.022

(0.0011 vol. fract) 10 468.546 473.983 484.871 0.303 0.021
15 469.107 484.756 491.888 0.094 0.006
20 475.278 485.396 499.446 0.156 0.010
Avg. 467.633 477.584 487.522 0.219 0.014
HDPE+MWCNT 5 455.863 465.098 473.511 0.208 0.014
(0.0022 vol. fract) 10 467.310 476.998 487.088 0.815 0.056
15 467.494 479.258 494.747 0.059 0.004
20 482.389 491.795 500.451 0.375 0.026
Avg. 468.264 478.287 488.949 0.364 0.025
HDPE+MWCNT 5 455.151 464.680 474.447 0.980 0.068
(0.0033vol.fract.) 10 468.960 478.363 486.669 0.114 0.007
15 475.562 485.264 495.136 0.368 0.025
20 484.184 493.141 501.847 0.110 0.007
Avg. 470.964 480.362 489.525 0.393 0.026
HDPE+MWCNT 5 454.062 464.303 472.783 0.821 0.036
(0.0044 vol. fract.) 10 459.361 471.732 485.812 0.133 0.008
15 468.992 481.611 493.178 0.556 0.048
20 479.946 490.430 500.774 0.340 0.026
Avg. 465.590 477.019 488.136 0.462 0.029

confirms a marginal enhancement in thermal stability. Similar small improvement of

the thermal stability of PA6-CNT composites have also been reported by Kumar et al.
[30]. The carbonaceous char (CR) of HDPE/MWCNTs composites at 600 °C increases
with increasing MWCNTs loading and the average value of the oxidation index (OI) for
the present composites lies between 0.014 and 0.029 (Table 1). It may be noted that the
thermal stability of HDPE/MWCNTs composites is increased slightly for samples with
0.0011 to 0.0033 volume fractions loading of MWCNTs. However, beyond 0.0033
volume fraction loading of MWCNTs, the thermal stability decreases. Similar behavior
has been reported for UHMWPE nanocomposites containing MWCNTs [16].

Theoretical approach

In the thermogravimetric analysis of polymeric materials, the degree of conversion or

reaction extent (α) is determined using:


m0  mT ;t
α¼
 ð1Þ
m0  m f
300 Int J Plast Technol (December 2014) 18(2):294–320

where m0 is the initial sample mass, mf is the final sample mass after the non-isothermal
runs and mT,t represents the mass of the sample at arbitrary temperature T (or time t).
The rate of degradation or conversion, dα/dt, is a function of temperature dependent
rate constant, k(T), and differential form of a kinetic model function, f(α), is given by,
dα
¼ k ðT Þ f ðαÞ ð2Þ
dt
According to Arrhenius equation, the temperature dependent rate constant, k(T) can
be described as:
 
E a
k ðT Þ ¼ Aexp ð3Þ
RT
where, A is the pre-exponential factor (s−1), Ea is the activation energy of the
degradation reaction (kJ/mol), R is the universal gas constant and T is the reaction
temperature. The term f(α) is assumed to follow a simple nth order relationship which
depends on the particular decomposition mechanism given by,
f ðαÞ ¼ ð1  αÞn ð4Þ
Thus, the fundamental equation for the kinetics of thermal degradation is derived in
terms of combination of Eqs. 2–4, which leads to the following universal expression:
 
dα n E a
¼ Að1  αÞ exp ð5Þ
dt RT
For non-isothermal experiments, the thermal decomposition rate is related to dα/
dt=(dα/dT)(dT/dt)=βdα/dT, and the integrated form of Eq. 5 is given as:

Zα ZT  
dα A E a
F ðαÞ ¼ ¼ exp dT ð6Þ
ð1  αÞn β RT
0 T0
where, β is the heating rate. The temperature dependent part of Eq. 6 cannot be solved
analytically, and therefore, several approximation methods are proposed for using TG
and DTG data. Integration of Eq. 6 from an initial temperature (T0) to the peak
temperature (Tp) corresponding to a degree of conversion (α0), where α0 =αp, is given
as:
Zαp ZT p  
dα A E a
g ðαÞ ¼ ¼ exp dT ð7Þ
f ðαÞ β RT
α0 T0

where, g(α) is the integral function of conversion [31].

Thermal degradation kinetic analysis

There are several methods for non-isothermal degradation kinetic analysis of TG

thermograms [32–35]. A number of integral and differential methods have been
proposed over the years for deriving the kinetic parameters, viz., activation energy
(Ea), pre-exponential/frequency factor (A) and reaction order (n) based on TGA data
Int J Plast Technol (December 2014) 18(2):294–320 301

with single or multiple heating rates. In the present investigation five different analyt-
ical methods (viz., Coats-Redfern (CR) [26], Coats-Redfern (modified) [36,37], Flynn-
Wall-Ozawa (FWO) [38,39], Kissinger-Akahira-Sunose (KAS) [40,41] and Friedman
[42] methods) are employed for evaluating the kinetic parameters and identifying the
possible degradation mechanisms. All these five methods are known to be the most
commonly used representatives for studying the degradation kinetics of polymer
composites,

Coats-Redfern method

Coats-Redfern method [26] also known as “Coats Redfern model fitting method” is
generally regarded as a versatile method for identifying the mechanisms of thermal
degradation from the TGA data. Coats-Redfern provides the following correlation:
   
g ðαÞ AR E
log ¼ log − ð8Þ
T 2 βE 2:3RT
 
If for a fixed heating rate (β), the correct g(α) is used, the plot of log gTðα2 Þ versus
1/T should yield a straight line with high correlation coefficient and from which the
activation energy (Ea) and the frequency factor (A) can be estimated.

Coats-Redfern (modified) method

Coats-Redfern (modified) method [36,37] is an iso-conversional “iterative” approach

which provides multiple heating rate application on CR integral based fitting method.
CR (modified) approach facilitates accurate estimation of kinetic parameters (viz., Ea
and A) with respect to degree of conversion (α). Modified Coats-Redfern equation is as
follows:
 
β AR Ea
ln ¼ ln − − ð9Þ
T ð1  2RT=E a Þ
2 E a lnð1  αÞ RT
The left-hand side of Eq. 9 is a weak function of Ea, the process must occur
iteratively by first assuming a value of Ea, then recalculating the left-hand side until
convergence occurs [45]. By this method, (Ea/R) is calculated by an iterative approach,
followed by two steps: in the 1st step ln(β/T2) is plotted against 1/T, which gives slope
(Ea/R) of straight line: in the 2nd step the obtained result is substituted in the left hand
term of Eq. 9 and the slope is recalculated by plotting the left term versus 1/T. This
recalculating process is carried out until convergence of Ea value. The pre-exponential/
frequency factor (A) is obtained from the intercept. CR (modified) approach is known
to be more accurate than Coats-Redfern model fitting method for the determination of
kinetic parameters (viz., Ea, A etc.) [36].

Flynn-Wall-Ozawa (FWO) method

The iso-conversional method of Flynn, Wall and Ozawa (FWO) [38,39] uses Doyle’s
approximation [43] of the temperature integral. For an nth order reaction, FWO gives an
accurate estimation of kinetic parameters. This method involves the measurement of the
302 Int J Plast Technol (December 2014) 18(2):294–320

temperature (T), corresponding to the fixed degree of conversion (α), from the
experiments performed at multiple heating rate (β). Flynn–Wall–Ozawa (FWO) pro-
posed the following expression:

0:457E a AE a
log β ¼ þ log  2:315 ð10Þ
RT F ðαÞR
The plot of log β versus T−1 plot should yield a straight line and the activation


energy (Ea) is then determined from the slope −0:457ERa of log β vs. T−1 plot.

Kissinger-Akahira-Sunose (KAS) method

Kissinger-Akahira-Sunose (KAS) method [40,41] also is an iso-conversion method.

Vyazovkin et al. [44] recommended the KAS method for its accuracy in estimation of
activation energy values (Ea). At a given conversion (α), the relation between the
heating rate (β) and temperature (T) is given as:
    
β AR Ea
ln 2 ¼ ln − ð11Þ
T E a g ðαÞ RT

For each conversion (viz., α = constant), the activation energy (Ea) is obtained from
the slope (−Ea/R) of the fitted straight lines between ln(β/T2) and T−1 obtained from the
TGA data recorded at multiple heating rates.

Friedman (FR) method

The differential iso-conversional method proposed by Friedman [42] relates the loga-
rithm of conversion rate (dα/dT) as a function of reciprocal temperature (T−1) in the
following form:
   
dα Ea
lnβ ¼ lnA þ nlnf ðαÞ  ð12Þ
dT RT
where, T represent the temperatures for a constant conversion (α) determined from
TGA thermograms at multiple heating rates (β). Thus, if the kinetics does not change
with conversion, the plots between lnβ(dα/dT) vs. T−1 should give a set of parallel lines
having (−Ea/R) as slope. Using Eq. 12, it is possible to evaluate Ea over a wide range of
degree of conversions.

Thermal degradation kinetics

Coats-Redfern integral model fitting method

Coats Redfern integral model fitting method, using 14 different integral kinetic func-
tions (Table 2), have been examined with the present TGA data within the conversion
range of 10%≤α≤90%. Figure 3a–h shows the plots between (lng(α)/T2) versus (1/T)
obtained after fitting the experimental curves to the different kinetic integral function
Int J Plast Technol (December 2014) 18(2):294–320 303

Table 2 Kinetic Models, differential functions f(α) and kinetic integration functions g(α) of the most
common reaction mechanisms operating in solid state reactions

Kinetic Models Symbol f(α) = (dα/dt)/k g(α)= ∫(f(α))−1dα

Diffusion mechanisms
1D-diffusion D1 1/2(α) α2
2D-diffusion D2 [−ln(1−α)]−1 (1−α)ln(1−α)+α
2/3 1/3 −1
3D-diffusion (Jander equation) D3 1.5(1−α) [1−(1−α) ] [1−(1−α)1/3]2

2α 
3D-diffusion (Ginstling- D4 1.5[(1−α) −1]
1/3 −1
1− 3 −ð1−αÞ2=3
Brounshtein equation)
n-th order reactions
First-order F1 1−α −ln(1−α)
Second order F2 (1−α)2 −1+(1−α)−1
Third order F3 (1−α)3 0.5[−1+(1−α)−2]
Phase boundary reactions
Plane symmetry R1 1 α
Cylindrical symmetry R2 2(1−α)1/2 1−(1−α)1/2
Spherical symmetry R3 3(1−α)2/3 1−(1−α)1/3
Prout-Tompkins B1 α(1−α) lnα−ln(1−α)
Nucleation and nuclei growth
Avrami-Erofeev A2 2(1−α)[−ln(1−α)]1/2 [−ln(1−α)]1/2
Avrami-Erofeev A3 3(1−α)[−ln(1−α)]2/3 [−ln(1−α)]1/3
3/4
Avrami-Erofeev A4 4(1−α)[−ln(1−α)] [−ln(1−α)]1/4

(g(α)) based models. The activation energy (Ea) calculated from the slope of the best
fitted straight lines for two different heating rates 5 and 20 0Cmin−1 are given in
Table 3. It may be seen that for different kinetic models, the activation energy (Ea)
for the degradation process at a heating rate of 5 °C/min for HDPE composites
containing 0.0011, 0.0022, 0.0033 and 0.0044 volume fraction of MWCNTs vary
between 35.914 and 319.99, 36.43 and 321.058, 38.788 and 325.167, 31.013 and
317.56 (kJ mol−1) respectively. Similarly, for a heating rate of 20 °C min−1 the
activation energy (Ea) lies between 24.824 and 261.845, 27.69 and 263.147, 33.71
and 265.249, 23.019 and 257.23 respectively. It is interesting to note that the same
model (CR) gives different values for Ea and A for different heating rates. Chrissafis
[33] argued that the use of only one heating rate (as in CR method) for the determi-
nation of the kinetic parameters fails to serve any practical purpose. He further
suggested that the only reason for which single heating rate model fitting method can
be used is to derive information about the involvement of the possible degradation
reaction mechanisms. It may be noted that, amongst the 14 different kinetic models
applied for the present composites only four models (viz., 2D-diffusion equation
g(α)=(1−α)ln(1−α)+α; 3D-diffusion (Jander equation) g(α)=[1−(1−α)1/3]2, 3D-
diffusion (Ginstling - Brounshtein equation) gðαÞ ¼ ð1−2α=3Þ−ð1−αÞ =3 and first
2

order reaction mechanism (F1) g(α)=−ln(1−α) respectively) best fit the present data
and the corresponding average values of the kinetic parameters, viz., the activation
304 Int J Plast Technol (December 2014) 18(2):294–320

Fig. 3 Typical plots between (lng(α)/T2) versus (1/T) obtained for four different heating rates using Coats-
Redfern integral model fitting method for HDPE/0.0033 vol. fraction MWCNTs. The line shows the fitted
kinetic integral function (g(α)) corresponding to a. D2-model, b. D3-model, c. D4-model, d. F1-model, e. A3-
model, f. F2-model, g. A4-model and h. R1-model

energy (Ea), the pre-exponential factor (A) and the correlation coefficient (R2) as a
function of MWCNTs loading are summarized in Table 4 respectively. Interestingly, it
may be noted that the activation energies of HDPE/MWCNTs composite initially
increases for 0.0011 to 0.0033 volume fraction loading of MWCNTs. However, further
increase of MWCNTs to 0.0044 volume fraction, the activation energy decreases for all
the applied kinetic models at different heating rates. This is in consistent with the results
of Shih et al. [46]. Furthermore, it is seen that at higher temperature, the diffusion based
kinetic models, viz., D2, D3 and D4 are more dominant than the D1 model. Similarly,
of the nth order reaction models (F1-F3), at lower temperature lower activation energies
are obtained for first order reaction model (F1), which refers to ‘random nucleation
with one nucleus on the individual particle’ [31].
The initial lower values of activation energy indicate the kinetics of the early
degradation stages to be limited by initiation at the weak links, and the higher values
of the activation energy observed during the later stages indicate that decomposition of
polymers becomes fairly constrained by degradation which was further initiated by
random scission. Similar observations have been reported earlier [46,47] and is thought
to be due to the fact that random chain scission proceeds slower at lower temperatures
as lower activation energy is favored at lower temperatures, and in case of specific
chain end scission process higher activation energy is favored at higher temperatures.
The deviations of activation energies based on fourteen different kinetic models were
calculated from the following expression [47]:
ðE 1  E 2 Þ
Deviationð%Þ ¼ X 100% ð13Þ
E1
where E1 is the activation energy calculated at the heating rate of 5 °C/min−1 and E2 is
the activation energy calculated at the heating rate of 10, 15 or 20 °C/min−1. The
deviations of activation energies have been calculated for all the 14 different kinetic
models. The Ea (deviation %) for the four best fitted kinetic models (D2, D3, D4 and
Table 3 Apparent activation energy Ea (KJ/mol) of the prepared HDPE/MWCNTs nano-composites calculated from Coats and Redfern based integral model fitting method at different
heating rates viz., β=5 °C/min and β=20 °C/min

Kinetic HDPE+MWCNT (0.0011v.f) HDPE+MWCNT (0.0022v.f) HDPE+MWCNT (0.0033v.f) HDPE+MWCNT (0.0044v.f)

models
β=5 °C/min β=20 °C/min β=5 °C/min β=20 °C/min β=5 °C/min β=20 °C/min β=5 °C/min β=20 °C/min

Ea KJ/ R2 Ea KJ/ R2 Ea KJ/ R2 Ea KJ/ R2 Ea KJ/ R2 Ea KJ/ R2 Ea KJ/ R2 Ea KJ/ R2

mol mol mol mol mol mol mol mol

D1 245.127 0.9881 215.145 0.9801 247.293 0.9877 219.542 0.9825 249.431 0.9839 221.376 0.9832 234.186 0.9895 192.432 0.9833
D2 244.432 0.9987 219.345 0.9971 245.571 0.9983 221.475 0.9978 247.974 0.9991 223.275 0.9934 236.541 0.9986 198.661 0.9943
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D3 249.574 0.9973 221.256 0.9967 250.643 0.9970 227.397 0.9982 252.119 0.9986 222.322 0.9967 244.724 0.9984 213.739 0.9984
D4 252.245 0.9988 223.671 0.9984 253.148 0.9984 229.762 0.9974 255.413 0.9982 217.336 0.9993 243.134 0.9970 226.249 0.9968
F1 245.821 0.9984 210.456 0.9977 247.932 0.9981 213.892 0.9981 249.154 0.9988 213.072 0.9976 240.385 0.9989 205.426 0.9959
F2 272.429 0.9585 223.436 0.9497 275.406 0.9584 237.291 0.9407 279.149 0.9858 236.491 0.9889 257.474 0.9485 207.447 0.9395
F3 314.232 0.9062 246.407 0.8944 317.444 0.9063 251.631 0.8822 327.457 0.9148 263.982 0.8876 280.618 0.8922 218.361 0.8803
R1 115.273 0.9772 87.561 0.9692 118.669 0.9817 96.432 0.9867 116.235 0.9828 109.331 0.9984 115.993 0.9886 92.324 0.9825
R2 140.761 0.9885 114.109 0.9877 142.126 0.9822 119.297 0.9881 145.416 0.9965 127.559 0.9989 135.154 0.9963 98.301 0.9975
R3 148.919 0.9983 102.769 0.9976 151.274 0.9930 109.314 0.9980 153.911 0.9982 134.894 0.9980 132.427 0.9973 102.978 0.9962
B1 319.996 0.9943 261.845 0.9939 321.058 0.9972 263.147 0.9912 325.167 0.9914 265.249 0.9970 317.559 0.9945 257.234 0.9915
A2 79.127 0.9964 65.734 0.9977 81.236 0.9979 67.145 0.9943 83.154 0.9967 69.752 0.9976 77.523 0.9943 62.159 0.9947
A3 47.459 0.9918 35.775 0.9930 49.955 0.9925 39.559 0.9902 50.084 0.9951 44.259 0.9985 48.055 0.9914 33.286 0.9944
A4 35.914 0.9865 24.824 0.9879 36.431 0.9850 27.691 0.9842 38.788 0.9985 33.710 0.9872 31.013 0.9804 23.019 0.9822
305
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Table 4 Average values of estimated kinetic parameters (Ea, A), Correlation Coefficient (R2) and Activation
energy Deviation percentage values of the prepared HDPE/MWCNTs nano-composites calculated by Coats
Redfern integral model fitted method

Sample Coats redfern integral model fitted values Activation energy deviation % values

Kinetic Average Average R2 Deviation % Deviation % Deviation %

models Ea (KJ/ (A) (β= (β= (β=
mol) (min−1) 10 °C/min) 15 °C/min) 20 °C/min)

HDPE+MWCNT D2 232.926 1.45×1015 0.9981 2.721 5.843 10.263

(0.0011 vol. D3 236.267 4.32×1015 0.9983 3.077 6.743 11.346
fract) 16
D4 238.684 5.37×10 0.9976 2.603 7.572 11.327
F1 228.981 2.75×1013 0.9983 5.844 7.170 14.386
HDPE+MWCNT D2 234.859 1.87×1015 0.9976 2.411 5.223 9.812
(0.0022 vol. D3 239.826 2.89×1016 0.9945 2.334 5.653 9.274
fract)
D4 241.214 4.78×1016 0.9976 2.491 7.126 9.238
F1 230.833 3.58×1014 0.9989 6.358 7.498 13.729
HDPE+MWCNT D2 237.610 3.86×1015 0.9980 1.866 4.891 9.960
(0.0033 D3 240.373 2.01×1015 0.9987 1.766 5.049 11.818
vol.fract.)
D4 241.003 2.76×1015 0.9993 2.446 6.780 14.907
F1 232.101 1.88×1016 0.9989 5.499 7.397 14.481
HDPE+MWCNT D2 219.206 4.43×1013 0.9982 5.415 7.884 16.014
(0.0044 vol. D3 231.492 6.73×1015 0.9987 2.109 6.855 12.661
fract.)
D4 234.779 7.68×1015 0.9972 2.155 4.643 6.944
F1 225.367 3.43×1013 0.9992 3.532 6.914 14.542

F1) at three different heating rate (10, 15 and 20 °C/min−1 are also noticeable in
Table 4. It have been found that the calculated deviation % of Ea for D2, D3, D4 and
F1 model are smaller than those of all other applied kinetic models. This suggests that
amongst the 14 different kinetic models D2, D3, D4 and F1 model are appropriate to
account for the thermal degradation mechanism of HDPE/MWCNT nano-composites.

Coats-Redfern (modified) method

For conversion (α) between 10 and 90 % and for each of the heating rates (5, 10, 15
and 20 °C/min), the left-hand side of Eq. 9 is plotted with respect to T−1, for the
HDPE/MWCNTs composites and are shown in Fig. 4a–d. The CR (modified) plots
obtained from the TGA thermo-grams recorded at four different heating rates (using the
‘iterative’ process as discussed earlier) yields parallel straight lines. Finally, the esti-
mated slope of each line gives Ea/R, which when substituted into the intercept gives the
pre-exponential factor (A). The estimated values of Ea, A and the corresponding
correlation coefficients (R2) for the thermal degradation of HDPE/MWCNTs compos-
ites by CR (modified) method are summarized in Table 5. The best fitted lines shown in
Fig. 4a–d acquire correlation coefficient (R2) between 0.9907 and 0.9975. For all the
composites, Ea varies with degree of conversion (α). Average activation energy
estimated using modified CR method corresponding to four different heating rates of
Int J Plast Technol (December 2014) 18(2):294–320 307

Fig. 4 CR (modified) method plots for a. 0.0011 vol. fraction b. 0.0022 vol. fraction c. 0.0033 vol. fraction
and d. 0.0044 vol. fraction of HDPE/MWCNTs nano-composites

5, 10, 15 and 20 °C/min are~245.431, 229.166, 227.334 and 215.173 KJ mol−1

respectively. The dependence of the activation energy (Ea) on the conversion rate
(α), occurs into two discrete stages (Fig. 5). In the first stage, for values of (α)
between 10 and 20 % small weight loss occurs, whereas in the second stage (the
plateau region) between 20 and 90 % substantial increase in weight loss is apparent.
Usually, the two step feature for Ea vs. α plot is rather a typical feature for several
polymers [14,29]. The frequency factor (A) estimated using modified CR approach for
conversion (α) between 10 and 90 % for the present composites are summarized in
Table 5.

Flynn-Wall-Ozawa (FWO) method

The second method employed is a “model free” iso-conversional model by Flynn-Wall-

Ozawa (FWO), which allow estimation of the activation energy (Ea) assuming that the
conversion function f(α) does not change with heating rate for all the values of α.
Typical linear plots between log(β) and 1000/T obtained for the present composites at
various conversion rates (α) are shown in Fig. 6a–d. For all the samples, the iso-
conversional plots for different conversions are found to be nearly parallel straight lines
 308

Table 5 Activation energy (Ea), Pre-exponential Factor (A) and Correlation Coefficient (R2) for the prepared HDPE/MWCNTs nano-composites estimated by Coats-Redfern (CR-
modified) method in between the conversion range α=10–90 %

Conversion (α) HDPE+MWCNT (0.0011v.f) HDPE+MWCNT (0.0022v.f) HDPE+MWCNT (0.0033v.f) HDPE+MWCNT (0.0044v.f)

Ea KJ/mol A min−1 R2 Ea KJ/mol A min−1 R2 Ea KJ/mol A min−1 R2 Ea KJ/mol A min−1 R2

10 211.596 5.24×1010 0.9981 186.037 7.52×1008 0.9951 194.562 3.47×1009 0.9971 199.443 8.65×1009 0.9992
20 233.065 2.72×1012 0.9986 220.865 3.83×1011 0.9963 217.454 2.26×1011 0.9879 209.282 5.83×1010 0.9991
12 12 11 11
30 239.417 9.65×10 0.9986 229.808 2.07×10 0.9985 224.452 8.72×10 0.9968 213.899 1.51×10 0.9991
40 245.341 3.02×1013 0.9985 232.091 3.56×1012 0.9960 227.729 1.78×1012 0.9915 216.172 2.60×1011 0.9921
50 250.035 7.56×1013 0.9985 233.587 5.28×1012 0.9909 233.528 5.38×1012 0.9881 218.628 4.40×1011 0.9964
60 253.468 1.54×1014 0.9956 238.934 1.43×1013 0.9958 235.772 8.84×1012 0.9908 219.893 6.10×1011 0.9963
70 258.375 3.83×1014 0.9959 239.272 1.71×1013 0.9957 235.402 9.38×1012 0.9914 219.049 6.04×1011 0.9919
80 258.092 4.14×1014 0.9984 240.695 2.48×1013 0.9957 236.074 1.21×1013 0.9853 222.534 1.20×1011 0.9951
90 259.487 6.07×1014 0.9958 241.201 3.14×1013 0.9989 241.029 3.22×1013 0.9874 217.659 6.34×1011 0.9964
Mean 245.431 1.86×1014 0.9975 229.166 1.10×1013 0.9958 227.334 7.87×1012 0.9907 215.173 4.41×1011 0.9961
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Fig. 5 Dependence of activation energy (Ea) versus conversion rate (α) for various compositions of
HDPE/MWCNTs nano-composites calculated by CR (modified) method

indicating a complex weight loss process involving several mechanisms. The best fitted
lines shown in Fig. 6a–d have correlation coefficient (R2) between 0.9914 and 0.9977,
which implies that FWO approach is suitable over the applied conversion range
(10 % ≤ α ≤ 90 %). The activation energy (Ea) estimated using FWO approach
corresponding to different conversions (α) for various compositions of
HDPE/MWCNTs composites are shown in Table 6. Usually, with increasing α, if Ea
changes it usually indicates involvement of a complex reaction mechanism, whereas, if
Ea remains independent of α then the existence of a single-step reaction is concluded
[14]. As seen in Table 6, the values of the activation energies vary with the conversion
for all the composites and the average activation energy for HDPE/MWCNTs compos-
ites obtained are ~245.13, 229.67, 227.927 and 216.372 KJ mol−1. Figure 7 shows the
dependence of the activation energy (Ea) as a function of the conversion rate (α) for
various compositions of HDPE/MWCNTs composites. The observed dependence of Ea
on α indicates complex reaction formation, with contributions from at least two different
mechanisms which contributes to weight loss [14]. The increase in activation energy
(Ea) with the extent of degradation suggests a change in the rate limiting step [48]. In the
present composites, the dependence of the activation energy on the conversion rate (α)
occurs into two discrete stages (i.e., 10%≤α≤20% and 20%≤α≤90%). The calculated
A corresponding to each conversion (α) for all compositions of HDPE/MWCNTs
composites estimated using FWO approach are summarized in Table 6.

Kissinger-Akahira-Sunose (KAS) method

The third “model free” method (KAS) employed is also based on iso-conversional
approach. Typical linear plots between ln(β/T2) versus 1000/T for the HDPE/MWCNTs
composites are shown in Fig. 8a–d. The KAS plots calculated for four different heating
rates also yields parallel straight lines, whose slopes allow estimation of the activation
310 Int J Plast Technol (December 2014) 18(2):294–320

Fig. 6 Flynn Wall Ozawa (FWO) method plots for a. 0.0011 vol. fraction b. 0.0022 vol. fraction c. 0.0033
volume fraction and d. 0.0044 vol. fraction of HDPE/MWCNTs nano-composites

energy (Ea). The values of Ea, A and the correlation coefficient (R2) estimated by KAS
are given in Table 7. Figure 9 shows the conversion (%) versus activation energy (Ea)
plot, which clearly display two stages. In the first stage, for values of (α) between 10
and ~30 % small weight loss occurs, whereas in the second stage (the plateau region)
between 30 and 90 % substantial increase in weight loss is apparent (viz., 10%≤α≤
30% and 30%≤α≤90%). Mean activation energy for HDPE/MWCNTs composites
obtained by KAS approach are 244.168, 228.386, 226.52 and 213.598 KJ mol−1
respectively, which are very close to those estimated by FWO method. The pre-
exponential factors (A) corresponding to each conversion for all the composites by
KAS approach lies between 8.86×1016 and 5.96×1014 (Table 7).

Friedman (FR) method

The fourth method employed is a differential iso-conversional based method by

Friedman. The characteristic plots (Eq. 12) of ln(βdα/dT) versus 1/T for all
compositions of HDPE/MWCNTs composites are shown in Fig.10a–d. A linear
Table 6 Activation energy (Ea), Pre-exponential Factor (A) and Correlation Coefficient (R2) for the prepared HDPE/MWCNTs nano-composites estimated by Flynn-Wall-Ozawa
(FWO) method in between the conversion range α=10–90 %

Conversion (α) HDPE+MWCNT (0.0011v.f) HDPE+MWCNT (0.0022v.f) HDPE+MWCNT (0.0033v.f) HDPE+MWCNT (0.0044v.f)

Ea KJ/mol A min−1 R2 Ea KJ/mol A min−1 R2 Ea KJ/mol A min−1 R2 Ea KJ/mol A min−1 R2

10 212.678 5.87×1014 0.9974 188.397 1.04×1013 0.9940 196.478 4.46×1013 0.9948 201.062 1.06×1014 0.9993
20 233.227 1.23×1016 0.9988 221.613 1.90×1015 0.9967 218.372 1.15×1015 0.9893 210.583 3.18×1014 0.9992
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16 15 15 14
30 239.338 2.61×10 0.9987 230.189 6.04×10 0.9987 225.107 2.66×10 0.9971 215.068 5.02×10 0.9992
40 245.024 5.49×1016 0.9987 232.426 7.18×1015 0.9964 228.273 3.73×1015 0.9924 217.289 6.00×1014 0.9929
50 249.529 9.78×1016 0.9986 233.895 7.82×1015 0.9918 233.835 7.98×1015 0.9893 219.687 7.38×1014 0.9968
60 252.835 1.46×1017 0.9961 239.021 1.55×1016 0.9962 236.037 9.79×1015 0.9918 220.937 7.71×1014 0.9967
70 257.538 2.70×1017 0.9963 239.389 1.42×1016 0.9962 235.713 7.99×1015 0.9923 220.188 5.91×1014 0.9928
80 257.315 2.21×1017 0.9985 240.784 1.53×1016 0.9961 236.380 7.74×1015 0.9868 223.548 8.66×014 0.9957
90 258.699 2.27×1017 0.9962 241.325 1.36×1016 0.9991 241.150 1.39×1016 0.9887 218.983 3.34×1014 0.9968
Mean 245.132 1.17×1017 0.9977 229.671 9.05×1015 0.9961 227.927 6.12×1015 0.9914 216.372 5.36×1014 0.9966
311
312 Int J Plast Technol (December 2014) 18(2):294–320

Fig. 7 Dependence of activation energy (Ea) versus conversion rate (α) for various compositions of
HDPE/MWCNTs nano-composites calculated by Flynn-Wall-Ozawa (FWO) method

relationship between ln(βdα/dT) and 1/T is seen for all the composites and for
conversion (α) between 10 and 90 %. Activation energy for each α is calcu-
lated from the slopes of the best linear fits (R2 ~0.9986) of the measured data
and are given in Table 8. Mean activation energies for HDPE/MWCNTs
composites with 0.0011, 0.0022, 0.0033 and 0.0044 volume fractions of
MWCNTs estimated using Friedman approach are 248.738, 235.736, 227.028
and 219.021 KJ mol−1 respectively. As observed in the case of CR (modified),
FWO and KAS methods, Friedman (FR) approach also display typical ‘two
steps’ features in the variation of the activation energy (Ea) with conversion
(α). Further, the calculated average values of A for HDPE/MWCNTs are found
to be between ~1.59×1017 and 1.57×1015.
Finally, the results obtained on the kinetic parameters using the above four
iso-conversional methods (viz., CR (modified), FWO, KAS and FR) are sum-
marized in Table 9. It may be noted that the pre-exponential factor (A) of
HDPE/MWCNTs composites, estimated by all the four iso-conversional models,
decreases with increase in filler (MWCNTs) concentration in HDPE. This
decrease in A indicates reduction in the mobility of the polymer chains [49].
Generally, thermal degradation in polymer starts with the formation of free
radicals, which is passed on to the adjacent chains via both inter and intra-
molecular chain reactions, followed by a termination step [49,50]. Therefore,
the decreasing trend in frequency factor (A) in the present composites suggests
that addition of MWCNTs in HDPE contributes towards suppression of such
chain transfer reactions. The variation of activation energy (Ea) with conversion
(α), for all compositions of HDPE/MWCNTs composites estimated by the
above discussed four iso-conversional approaches, clearly demonstrate that the
results based on the integral form of the rate equation (i.e. FWO and KAS), the
differential iso-conversional based method of Friedman, as well as, the ‘itera-
tive’ based CR (modified) approach are all found to very close to each other
(Table 9). However, the average Ea estimated by Friedman approach deviates
Int J Plast Technol (December 2014) 18(2):294–320 313

Fig. 8 Kissinger-Akhaira-Sunose (KAS) method plots for a. 0.0011 vol. fraction b. 0.0022 vol. fraction c.
0.0033 vol fraction and d. 0.0044 vol. fraction of HDPE/MWCNTs nano-composites

by ~3–4 % from those calculated using other three models. The observed
differences in activation energies are believed to originate because of a system-
atic error in FR approach due to improper integration [8,33]. The reason behind
it might be the employment of instantaneous rate values in the Friedman
method which are highly sensitive to experimental noise. Nevertheless, the
basic features of Ea vs. conversion (α %) plots calculated using the iso-
conversional approaches are nearly identical (Figs. 5, 7, 9 and 11). For lower
loading (<0.0033 volume fraction) of MWCNTs, Ea vs. conversion rate (α)
shows two stage degradation. This is usually attributed to the diffusion effect
which becomes more important for thermal degradation of polymers at higher
temperatures. However, it is important to note that the activation energy
obtained for composite with higher volume fraction loading of MWCNTs
(viz., ~0.0044) is nearly constant, as calculated using all the iso-conversional
approaches discussed above. This constancy of Ea with conversion rate (α)
between 0.2 and 0.8 suggests a single-step degradation based reaction [51] that
appears to be commenced by random scission mechanism. Therefore,
HDPE/MWCNTs composites with volume fraction loading of MWCNTs (be-
tween 0.0011 and 0.0033) follow diffusion based mechanism (viz., D2, D3 and
 314

Table 7 Activation energy (Ea), Pre-exponential Factor (A) and Correlation Coefficient (R2) for the prepared HDPE/MWCNTs nano-composites estimated by Kissinger-Akahira-
Sunose (KAS) method in between the conversion range α=10–90 %

Conversion (α) HDPE+MWCNT (0.0011v.f) HDPE+MWCNT (0.0022v.f) HDPE+MWCNT (0.0033v.f) HDPE+MWCNT (0.0044v.f)

Ea KJ/mol A min−1 R2 Ea KJ/mol A min−1 R2 Ea KJ/mol A min−1 R2 Ea KJ/mol A min−1 R2

10 211.951 5.28×1014 0.9979 197.501 4.57×1013 0.9815 197.478 4.48×1013 0.9989 199.718 7.82×1013 0.9969
20 231.236 8.89×1015 0.9968 211.938 3.76×1014 0.9924 212.653 4.26×1014 0.9991 207.006 2.94×1014 0.9726
16 15 15 14
30 242.835 4.76×10 0.9979 225.907 3.01×10 0.9975 220.995 1.37×10 0.9962 210.996 4.73×10 0.9822
40 244.654 5.24×1016 0.9996 230.364 5.22×1015 0.9961 227.046 2.97×1015 0.9999 212.817 7.95×1014 0.9766
50 250.080 1.08×1017 0.9995 231.956 5.69×1015 0.9971 231.992 5.64×1015 0.9982 220.271 9.09×1014 0.9991
60 251.366 1.15×1017 0.9993 235.020 8.10×1015 0.9975 235.270 8.34×1015 0.9991 221.214 8.83×1014 0.9994
70 253.870 1.49×1017 0.9992 237.062 9.78×1015 0.9978 236.625 8.93×1015 0.9986 220.825 8.86×1014 0.9955
80 255.762 1.73×1017 0.9987 238.838 1.13×1016 0.9970 238.819 1.09×1016 0.9983 218.093 6.21×1014 0.9995
90 255.754 1.42×1017 0.9987 246.891 3.44×1016 0.9984 237.804 7.60×1015 0.9994 211.444 4.26×1014 0.9995
Mean 244.168 8.86×1016 0.9986 228.386 8.65×1015 0.9986 226.520 5.14×1015 0.9986 213.598 5.96×1014 0.9913
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Int J Plast Technol (December 2014) 18(2):294–320 315

Fig. 9 Dependence of activation energy (Ea) versus conversion rate (α) for various compositions of
HDPE/MWCNTs nano-composites calculated by Kissinger-Akhaira-Sunose (KAS) method

Fig. 10 Friedman (FR) method plots for HDPE/MWCNTs nano-composites for a. 0.0011 b. 0.0022 c. 0.0033
and d. 0.0044 vol. fraction of MWCNTs fillers
 316

Table 8 Activation energy (Ea), Pre-exponential Factor (A) and Reaction Order (n) of the prepared HDPE/MWCNTs nano-composites estimated by Friedman (FR) method in between
the conversion range α=10–90 %

Conversion (α) HDPE+MWCNT (0.0011v.f) HDPE+MWCNT (0.0022v.f) HDPE+MWCNT (0.0033v.f) HDPE+MWCNT (0.0044v.f)

Ea KJ/mol A min−1 R2 Ea KJ/mol A min−1 R2 Ea KJ/mol A min−1 R2 Ea KJ/mol A min−1 R2

10 241.019 3.29×1016 0.9984 229.132 3.14×1015 0.9986 223.356 3.90×1014 0.9981 220.018 7.51×1013 0.9973
20 266.359 1.29×1017 0.9971 251.875 4.18×1015 0.9931 240.961 4.19×1015 0.9992 222.698 3.87×1015 0.9996
17 15 15 15
30 253.445 5.99×10 0.9928 241.727 9.08×10 0.0048 233.545 2.39×10 0.9926 223.168 2.07×10 0.9924
40 253.976 2.79×1017 0.9804 238.534 5.68×1015 0.9997 231.362 1.99×1015 0.9995 223.533 1.67×1015 0.9971
50 254.857 1.29×1017 0.9987 241.793 4.18×1015 0.9991 229.297 1.69×1015 0.9973 221.521 1.37×1015 0.9918
60 249.294 7.39×1016 0.9974 242.279 3.62×1015 0.9995 228.441 2.11×1015 0.9992 218.866 1.79×1015 0.9996
70 242.641 7.09×1016 0.9986 231.917 3.55×1015 0.9964 218.398 1.39×1015 0.9701 214.744 1.07×1015 0.9760
80 238.584 6.39×1016 0.9988 227.016 3.41×1015 0.9989 218.279 1.49×1015 0.9988 216.312 1.17×1015 0.9993
90 238.475 6.19×1016 0.9986 217.358 3.50×1015 0.9993 219.622 1.39×1015 0.9990 210.337 1.07×1015 0.9993
Mean 248.738 1.59×1017 0.9956 235.736 4.48×1015 0.9986 227.028 1.89×1015 0.9948 219.021 1.57×1015 0.9947
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Int J Plast Technol (December 2014) 18(2):294–320 317

Table 9 Summary of kinetic parameters for HDPE/MWCNTs composites as estimated by various iso-
conversional models

Sample Iso-conversional models Average (Ea) KJ/mol Average (A) min−1 R2

HDPE+MWCNT (0.0011v.f) CR(modified) 245.431 1.86×1014 0.9975

FWO 245.132 1.17×1017 0.9977
KAS 244.168 8.86×1016 0.9986
17
FR 248.738 1.59×10 0.9956
HDPE+MWCNT (0.0022v.f) CR(modified) 229.166 1.10×1013 0.9958
FWO 229.671 1.78×1016 0.9961
KAS 228.386 8.65×1015 0.9986
FR 235.736 4.48×1015 0.9986
HDPE+MWCNT (0.0033v.f) CR(modified) 227.334 7.87×1012 0.9907
FWO 227.927 6.12×1015 0.9914
KAS 226.521 5.14×1015 0.9986
FR 227.028 1.89×1015 0.9948
11
HDPE+MWCNT (0.0044v.f) CR(modified) 215.173 4.41×10 0.9961
FWO 216.372 5.36×1014 0.9966
KAS 213.598 5.96×1014 0.9913
FR 219.021 1.57×1015 0.9947

D4) and for composites with MWCNTs volume fraction (≥0.0044) follows a
first order reaction mechanism (F1-model), which is consistent with CR integral
model fitting analysis.
It is important to note that average activation energy (Ea) estimated by the
above integral and differential based iso-conversional approaches, viz., CR
(modified), FWO, KAS and FR decreases with increasing loading of
MWCNTs in HDPE (Table 9). Similar behavior has also been reported for
thermal degradation of PBS/MWCNTs composites [46] and is attributed to the
presence of the active groups, such as the hydroxyl group on the surface of the
MWCNTs which enhances their catalytic effects on thermal degradation [16].
However, this is in contrary to that estimated by CR integral based model
fitting approach, which display increased activation energy for MWCNTs load-
ing up to 0.0033 volume fraction in HDPE and beyond which it decreases. The
observed difference in the kinetic parameters between iso-conversional and CR
integral fitting approaches may be attributed to the temperature measurement
errors in CR approach [45,52–54]. Further, differences between the fitted data
and the logarithm of the data and the differences between analyzing rate and
fraction-reacted data [45] involved in CR integral fitting approach contributes to
the uncertainty in the estimated kinetic parameters. Vyazovkin et al. [55–57]
also demonstrated that the model-fitting method is not a reliable process to
determine the kinetic parameters and ‘iterative’ based CR (modified) method is
regarded as a more accurate approach. Finally, the magnitude of both Ea and A,
as well as, the variation (Fig. 5,7,9,11) of the activation energy (Ea) with
318 Int J Plast Technol (December 2014) 18(2):294–320

Fig. 11 Dependence of activation energy (Ea) versus conversion rate (α) for various compositions of
HDPE/MWCNTs nano-composites calculated by Friedman (FR) method

conversion (α) obtained by iterative based CR (modified) method are in good

agreement with other three iso-conversional approaches (FWO, KAS and FR).

Conclusions

HDPE/MWCNTs nano-composites with varied compositions are prepared using

melt blending technique in a temperature controlled twin roller sigma mixture and
a detailed analysis of their TGA data measured at various heating rates are performed
to investigate their thermal stability and thermal degradation kinetics and mecha-
nisms. Incorporation of nano-tubes (MWCNTs) in HDPE shows only a marginal
improvement in Tonset, T40 % and Tmax. Analysis of the thermal degradation of the
HDPE/MWCNTs composites are performed using four iso-conversional methods
(i.e., modified CR, FWO, KAS and FR) to estimate the kinetic parameters, viz.,
activation energy as function of conversion (α) between 10 and 90 %. Both activa-
tion energy (E a ) and the frequency factor (A) calculated by the above iso-
conversional methods are fairly close to each other. Decrease in frequency factor
(A) with increasing loading of MWCNTs, indicates reduction of the mobility of the
polymer chains in the composites. The TGA data of the composites taken at four
different heating rates have been tested using CR integral fitting approach with 14
different degradation mechanisms and we confirm that only four kinetic models
(viz., D2, D3, D4 and F1) fits the present data. Moreover, activation energy (Ea) for
different conversion rate (α) calculated for composites with lower loading of
MWCNTs in HDPE by iso-conversional methods (viz., modified CR, FWO, KAS
and FR) indicates contributions from at least two different degradation mechanisms
contributing to the weight loss and follow diffusion based mechanisms (viz., D2, D3
and D4), while composites with higher volume fraction of MWCNTs follow a first
order reaction mechanism (F1) over the entire conversion range (10%≤α≤90%).
Int J Plast Technol (December 2014) 18(2):294–320 319

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