J Therm Anal Calorim (2017) 128:1077–1091
DOI 10.1007/s10973-016-5972-y
A comparison study on non-isothermal decomposition kinetics
of chitosan with different analysis methods
Yu-Hua Hao1 • Zhen Huang1 • Qiao-Qiao Ye1 • Jing-Wen Wang1 • Xin-Yu Yang1
Xing-Yue Fan1 • Ya-Li Li1 • Yu-Wen Peng1
Received: 6 September 2016 / Accepted: 16 November 2016 / Published online: 30 November 2016
 Akadémiai Kiadó, Budapest, Hungary 2016
Abstract A thermal degradation study of chitosan in air
atmosphere has been carried out in detail through Fourier
transform infrared (FTIR) analysis, thermogravimetric
(TG) analysis and differential thermal analysis (DTA)
measurements. FTIR spectra reveal the variations of
chemical structures of chitosan in the course of thermal
degradation. The mass loss data were collected under the
heating rates of 5–30 K min-1. Kinetic analysis of chitosan
thermal degradation has been performed through isocon-
versional FWO, CR, MKN and Tang methods, and the
calculated results are basically comparable for these four
different methods. With the Arrhenius parameters
obtained, the four methods have been attempted to recon-
struct the temperature-dependent mass conversion curves
and have resulted in generally acceptable results. The TG
and DTA results suggest that two-stage thermal degrada-
tion processes may be better assumed. For more accurately
describing the thermal degradation process of chitosan, the
most probable reaction functions have thus been deter-
mined for these two stages, leading to greatly improved
calculation performance over the entire conversion range.
On the basis of the Arrhenius parameter values obtained,
the changes in entropy, enthalpy and Gibbs free energy,
and lifetime predictions have been estimated concerning
the thermal degradation processes of chitosan.
& Zhen Huang
huangzhen50@yahoo.com
1 natural polysaccharide and just next only to cellulose in the
Department of Packaging Engineering, Institute of Materials
Science and Chemical Engineering, Tianjin University of
Commerce, Tianjin 300134, People’s Republic of China
•
Keywords Chitosan  Thermogravimetric analysis 
Multiple heating rates  Thermal degradation simulation 
Non-isothermal kinetics
Introduction
Due to the significant impact of plastic waste on the
environment, many research efforts have been concentrated
now on searching for polymer materials, which would be
environment-friendly so as to manage the disposal of those
man-made plastics. A promising solution is the use of
biodegradable and compostable natural polymers such as
cellulose, chitin and chitosan, and these polymers can
readily degrade in various environmental conditions by
breaking of main macromolecular chains, splitting of
fragments of the main chains or side constituents and
release of volatile non-toxic species. Among these natural
polymers, chitosan has received ever-increasing attention
due to its excellent properties such as biocompatibility,
biodegradability and non-toxicity, and thus, it has been
extensively used in the food industry, cosmetics, agricul-
ture, biomedicine and waste water treatment [1–3]. Chi-
tosan is known to be a b-(1 ? 4)-linked linear copolymer
of 2-acetamido-2-deoxy-b-D-glucopyranose and 2-amino-
2-deoxy-b-D-glucopyranose units. It is obtained in alkaline
media by the incomplete deacetylation of chitin, mainly
coming from the by-product of the fishing industry [1–3].
Apart from its biological properties, it has also pos-
sessed appreciated mechanical strength and high water
affinity as a high molecular mass hydrophilic biopolymer.
In addition, chitosan along with chitin is the second richest
nature. Because of these important biological, chemical
and physical features, chitosan and its derivatives have
123
1078
been extensively investigated for their preparation, prop-
erty characterization and applications [1–3]. Indeed, as an
environment-friendly polymer, the recycling of chitosan is
often of primary interest to understand its thermal
decomposition features, and its degradation pathway has
ever been studied by various methods [4–10]. The knowl-
edge of laboratory-level thermal pyrolysis kinetics may
help better understand thermal decomposition processes
and be profitably applied for subsequent process design and
optimization and valid predictions. Thus, further studies
shall be developed to determine its thermal stability as well
as to allow a better understanding on the degradation
functions and kinetics aspects involved in the thermal
degradation.
Thermogravimetric (TG) analysis method has been
widely employed by many researchers to study the kinetics
of the thermal degradation of chitosan and its derivatives
[4–16]. To mathematically describe the decomposition
process, the kinetic triplet parameters, i.e., Ea, A and f(a),
must be obtained from experimental TG data by means of
theoretical reaction models. The three kinetic components
include two Arrhenius parameters, namely apparent acti-
vation energy (Ea) and pre-exponential factor (A), and one
analytical expression describing the kinetic reaction func-
tion f(a) in terms of mass conversion degree a. Practically,
the kinetic triplet values can be used to reproduce the
original thermal degradation data and predict the kinetic
features beyond the experimental temperature region as
well if they are correctly determined. In addition, the
parameter Ea may be used to discuss the thermal stability of
the substances investigated. Among these works, isother-
mal or non-isothermal conditions and many different
kinetic analysis methods have been employed by the sci-
entist community to determine the apparent activation
energy of the thermal decomposition of chitosan and its
derivatives, in the form of films or powders, under air or
inert nitrogen atmosphere [4–16].
However, a comparison between these studies reveals a
general lack of agreement between the different studies
concerning the Ea values determined due to the different
conditions employed and sometimes the incomplete
characterization of the polymers as well. For examples,
Peniche-Covas et al. [4] have carried out their study on
thermal degradation of chitosan in dynamic and isother-
mal conditions, and they found Ea = 181 kJ mol-1 and
Ea = 183–227 kJ mol-1, respectively. Tang et al. [5]
have reported that using the model-free Friedman’s
method the values of Ea range between 150 and
300 kJ mol-1 depending on the conversion degree,
whereas by means of the distributed activation energy
model the Ea value obtained is 189 ± 34 kJ mol-1. De
Britto et al. [6] have found that the Ea is between 137.9
and 157.0 kJ mol-1 for 0.05 \ a \ 0.19 in the case of
123
Y.-H. Hao et al.
isothermal conditions, but the Ea value is 82.1 kJ mol-1
under non-isothermal conditions in an inert atmosphere.
López et al. [7] have obtained the Ea value ranging
between 183.9 and 142.6 kJ mol-1 for a conversion
degree of 0.1 \ a \ 0.9, but they found that it is
127.9 kJ mol-1 if calculated by using ASTM E698.
Georgieva et al. [8] have obtained the Ea value of 126 and
99.1 kJ mol-1 for the first and second stages, respec-
tively. Muraleedharan et al. [9] have recently attempted
six different isoconversional methods for Ea estimation,
and the Ea values are found to span between 148.6 and
204.6 kJ mol-1 for 0.10 \ a \ 0.90, agreeing very well
with those calculated with the maximum peak methods.
Therefore, more efforts are required for carrying out in-
depth kinetic analysis and thus providing better under-
standing of chitosan thermal degradation.
The objective of this work is to study the thermal
features and degradation kinetics of the chitosan sample
under air atmosphere by means of thermogravimetric
analysis, along with infrared analysis and differential
thermal analysis. The kinetic parameters like Ea and ln
A were determined from the non-isothermal mass loss
data using four different temperature integral methods
along with the first-order reaction assumption. The per-
formances of the isoconversional Flynn–Wall–Ozawa
method [17, 18], Coats–Redfern method [19], Mad-
husudanan–Krishnan–Ninan approximation method [20]
and Tang simulation method [21] have been thoroughly
compared by reconstructing the temperature-dependent
mass conversion curves. Based on the FWO calculations,
the most suitable reaction functions have been scanned
for better describing the two thermal pyrolysis stages of
chitosan. With the kinetic parameters of the activation
energy Ea and ln A of chitosan, the changes in entropy,
enthalpy and Gibbs free energy, and lifetime predictions
have been made concerning the thermal degradation
processes of chitosan.
Experimental
Materials
Chitosan raw material was purchased from Zhengzhou Jinli
Bioscience and Technology Development Co. (Henan,
China), its viscosity average molecular weight was
2.1 9 105 and the degree of deacetylation of chitosan was
more than 92%. The sample was received in the form of
powder packaged in sealed aluminum/polyethylene bags.
To remove any moisture or volatile present in the sample,
the powder was dried at 423 K for 2 h and then immedi-
ately used for analysis measurements.
A comparison study on non-isothermal decomposition kinetics of chitosan with different…
Infrared analysis
Fourier transform infrared (FTIR) analysis measurement
was conducted on the dried and heated chitosan samples with
a Bruker Alpha-H infrared spectrophotometer. The original
chitosan sample after directly mixed with KBr powder was
pressed to obtain a transparent disk for FTIR analysis. Off-
line FTIR analysis was also performed on thermally heated
chitosan, and the heated sample was prepared by using a
thermal analyzer described below. The chitosan sample was
heated in air from ambient to a designed temperature at a
heating rate of 10 K min-1 and then held for 10 min, fol-
lowed by taking the sample out of the thermal analyzer and
mixing it with KBr powder for FTIR analysis. The FTIR
spectra were obtained in the wave number range of
400–4000 cm-1 with a resolution of 4 cm-1.
Thermal degradation analysis
Thermal decomposition measurements were taken on a
Shimadzu DTG-60 analyzer with a simultaneous thermo-
gravimetric (TG) analysis and differential thermal analysis
(DTA). For each measurement, approximately 6 mg of the
chitosan sample was fed into the sample holder and then
heated up to 750 K at a heating rate of 5, 10, 15, 20 and
30 K min-1. The carrier gas was air at a flow rate of
30 mL min-1. The TG and DTA data were automatically
recorded on the DTG-60 analyzer, and the first derivative
of thermogravimetry (first DTG) was achieved by using the
companied software kit.
Theoretical background and kinetic methods
The kinetics of solid reactions is described by various
explicitly analytical equations taking into account the
special features of their decomposition reactions. The
reaction rate for a solid reaction may be represented
through the degree of conversion, a, according to the for-
mula as follows:
w0  wt
a¼ ð1Þ
w0  wf
where wt, w0 and wf are, respectively, the mass at time t,
initial mass and final mass of the sample, and they are all
collected from experimental mass loss results. Then, the
kinetic equation of the reaction process can be generalized
as the following:
da
¼ kðTÞf ðaÞ
dt
where da/dt is the mass conversion rate, T is the absolute
temperature (K), k(T) is the degradation rate constant, and
1079
f(a) is the differential form of a kinetic model function. For
very common non-isothermal measurements, the sample
was heated at a constant rate of b. Then, b = dT/
dt = constant. The temperature dependence of the rate
constant k(T) is usually described by the Arrhenius
equation:
 
Ea
kðTÞ ¼ A exp  ð3Þ
RT
where A is the pre-exponential factor and R is the gas
constant. Substitution of Eq. (3) in Eq. (2) gives:
 
da A E
¼ exp  f ðaÞ ð4Þ
dT b RT
Equation (4) is the fundamental expression to calculate
kinetic parameters from the experimental TG data. The
conversion function f(a) for solid-state reactions can be
generalized as follows:
f ðaÞ ¼ am ð1  aÞn ½ lnð1  aÞp ð5Þ
where m, n and p are empirically obtained exponent fac-
tors, one of them always being zero [22, 23]. For a specific
solid-state reaction, the expression of f(a) depends on the
reaction mechanism behind. However, the combination of
different m, n and p values makes it possible for Eq. (5) to
describe all probable reaction functions.
After separating variables and integrating, Eq. (4) may
be transformed as:
Za ZT  
da A Ea
gðaÞ ¼ ¼ exp  dT ð6Þ
f ðaÞ b RT
0 T0
where g(a) is the integral form of the reaction model
function, and the right-hand side of Eq. (6) is a well-known
temperature integral function that has no analytical solution
but can be determined by using either numerical methods
or approximations. The latter has been considered in this
paper for kinetic analysis.
Isoconversional kinetic analysis methods
Model-free isoconversional methodology used for kineti-
cally analyzing non-isothermal experiments is recom-
mended from ICTAC kinetics committee because model-
free methods are believed to be the most reliable methods
for calculating the activation energy of thermally activated
reactions [24, 25]. Model-free methods can calculate the
activation energy, Ea, at progressive conversion values, a,
ð2Þ without any modelistic assumptions. By means of isocon-
versional methods, the activation energy at a given degree
of conversion a does not depend on the heating rate. At
present, isoconversional methods based on multiple heating
123
1080
programs are the most popular method that can unscramble
the kinetics of thermal decomposition reactions.
Flynn–Wall–Ozawa method
Flynn–Wall–Ozawa method [17, 18] derived from Doyle
approximation, called the FWO method here for simplicity
purpose, is a very successful isoconversional methodology
in analysis of non-isothermal experiments, and through this
model-free method, the activation energy can be more
reliably determined. The FWO method may be written as
follows:
 
AEa Ea
log b ¼ log  2:315  0:4567 ð7Þ
RgðaÞ RT
Obviously, the value of Ea can be computed by using the
FWO method for any particular degree of conversion.
Therefore, according to Eq. (7), plotting log b against 1/T
should give a series of straight lines for different conver-
sion levels, the slope of which are directly proportional to
the original activation energy Ea. Once the integral reaction
function g(a) is correctly known, the pre-exponential factor
ln A can be simply determined from the above expression.
Initially, the first-order reaction with g(a) = -ln(1 - a)
has been adopted for kinetic analysis of chitosan thermal
degradation. With the kinetic parameters calculated, the
thermal degradation curves could be reconstructed for
evaluating the calculation performance.
Coats–Redfern method
Coats and Redfern [19], after making some approxima-
tions, have derived the following model-free expression:
     
b AR 2RT Ea
ln 2 ¼ ln þ ln 1   obtained from the intercepts if the g(a) is not properly
T E
 a gðaÞ  E a RT
AR Ea
 ln  ð8Þ
Ea gðaÞ RT
According to Eq. (8), a plot of ln(b/T2) against 1/T
should produce a straight line for each conversion. Obvi-
ously, the values of the activation energy Ea can be simply
obtained from the slope of straight lines. However, the pre-
exponential factor ln A cannot be directly calculated from
the intercepts only if the most appropriate reaction function
g(a) is found. The method given above has been initially
proposed for analyzing kinetic data recorded at a single
heating rate and later extended to evaluate multi-heating-
rate data, sometimes called as the isoconversional Kis-
singer–Akahira–Sunose method [26]. Here, it is denoted as
the CR method and well known to have been successfully
used for extensively studying the decomposition kinetics of
different solid substances.
123
Y.-H. Hao et al.
Madhusudanan–Krishnan–Ninan method
Later, Madhusudanan et al. [20] have proposed three dif-
ferent new approximate formulae for temperature integral
calculation. Of these approximations, the one given below
performs the best and is denoted as the MKN method in the
present study.
  "   #
b A Ea 0:884318 Ea
ln 1:884318 ¼ ln  1:001928
T gðaÞ R RT
 0:389677 ð9Þ
Apparently, a straight line could be yielded for each
conversion a if plotting ln[b/T1.884318] against 1/T. Readily,
the values of Ea and ln A can be, respectively, calculated
from the slope and intercept terms, provided that a reaction
function g(a) is explicitly given.
Tang method
Similarly, Tang et al. [21] have attempted the numerical
analysis to boost the accuracy of the temperature integral
approximation and put forward to a newly modified form to
the MKN method with relatively improved accuracy and
reliability. This approximation, denoted as the Tang
method, can be expressed as below:
  "   #
b A Ea 0:894661 Ea
ln 1:894661 ¼ ln  1:00145033
T gðaÞ R RT
 0:37773896 ð10Þ
Accordingly, the plots of ln[b/T1.894661] against 1/T
should result in a straight line for each chosen conversion,
and the values of a series of Ea can be calculated from the
slopes of resultant lines. Similarly, the ln A cannot be
scanned.
Results and discussion
FTIR characterization
Figure 1 shows the FTIR spectra obtained for character-
izing chemical structures of pristine chitosan before and
after heated from ambient to 473, 623 and 773 K in air
atmosphere at a heating rate of 10 K min-1. Figure 1a
shows that the positions of absorption peaks for the dried
chitosan sample are consistent with those reported in the
literature [7]. In the region of 3000–3700 cm-1 of FTIR
spectra, chitosan exhibits a strong and broad absorbent
band centered at 3420 cm-1 due to the axial stretching
vibration of OH group overlapped with that of the N–H
A comparison study on non-isothermal decomposition kinetics of chitosan with different…
d arising from the thermal loss of CH2 groups from chitosan
Transmittance/%
c
b fused rings. As for the amide I and amide II bands, respec-
a
4000 3600 3200 2800 2400 2000 1600 1200
Wavenumber/cm–1
Fig. 1 FTIR spectra of the dried chitosan sample from ambient
(a) heated to 473 K (b), 623 K (c) and 773 K (d) in air atmosphere at
a heating rate of 10 K min-1
group. This spectral band is broad because of the presence
of strong hydrogen bonds in chitosan macromolecules. The
two peaks observed at 2922 and 2875 cm-1 may be
attributed to the asymmetric and symmetric stretching
vibrations of CH2 groups. The peak appearing at
1655 cm-1 corresponds to the axial stretching vibrations of
the acetamido C=O groups and is popularly named as
amide I band characteristic of chitosan with acetylated
units, while the peak at 1596 cm-1 can be assigned as the
amide II band, produced by the overlapping of in-plane
bending deformation of the amino N–H groups and the
stretching vibration of C–N groups. Meanwhile, the
absorption peaks at 1421 and 1379 cm-1 may be, respec-
tively, assigned to the coupling of C–N axial stretching
vibration and N–H angular deformation, and the multiple
peaks corresponding to the polysaccharide skeleton,
including the vibrations of the glycosidic linkage, C–O and
C–O–C stretching vibrations, are observed in the range of
1154–897 cm-1.
Figure 1b shows the same FTIR spectra with those of
Fig. 1a, indicating that there is no thermal degradation
happened to the chitosan after heated in air to 473 K from
room temperature. But heating chitosan in air to 623 K or
further 773 K has subsequently resulted in thermal degra-
dation, as evidenced by the obvious variations of FTIR
spectra shown in Fig. 1c, d. A careful examination of
Fig. 1c, d shows that the strong spectral band of hydrogen
bonding centered at 3420 cm-1 becomes too much weaker
as compared to Fig. 1a, b, possibly due to the removal of
large amounts of OH and NH groups arising from thermal
degradation [27, 28]. The removal of NH groups can also be
reflected the disappearance of the absorption peaks at
1081
1379 cm-1. Likewise, the spectral intensity of two peaks at
2922 and 2875 cm-1 is also seen to drop a lot [28], plausibly
macromolecules. However, the multiple peaks over
1154–897 cm-1 for polysaccharide skeleton are found to
disappear after heating chitosan in air to over 623 K. Instead,
the presence of a new peak at 778 cm-1 is observed, possibly
related to the formation of complex carbon intermediate like
tively, at 1655 and 1596 cm-1, it can be seen that the two
peaks are replaced by a strong peak of 1608 cm-1 and a
shoulder peak of 1718 cm-1 shown in Fig. 1c and a little
broad but short peak of 1604 cm-1 shown in Fig. 1d. Rather
similar observations on residual chitosan products have also
800 400 been reported in the studies of Pawlak and Mucha [27] and
Zawadzki and Kaczmarek [28], and they have assigned this
spectral variation to the deacetylation of chitosan and for-
mation of carbonyl groups created. On the other hand, one
may note that the absorption peak at 1421 cm-1 is still
presented in Fig. 1c, d, seemingly evidencing the presence of
C–N groups in the residual products.
Thermal features of chitosan
Figure 2 shows the measured TG curves and the first deriva-
tive of the thermogravimetric (first DTG) curves of chitosan
obtained under air atmosphere at b = 5, 10, 15, 20, and
30 K min-1. The obvious mass loss has appeared at
510–570 K and terminated at 790–870 K, depending on the
constant heating rate used. The main mass loss of chitosan is
seen in the range of 510–870 K and then used for later kinetics
data analysis. It can be seen that each TG curve has clearly
gone through an inflection in the middle part of thermal
degradation process, and each first DTG curve has exhibited
two peaks where a local maximum mass loss rate (da/dt) has
been resulted at Tp1 and Tp2. Accordingly, the DTA curves
given in Fig. 3 have also presented two exothermic decom-
position peaks for each heating rate. These results seem to
suggest that the chitosan sample investigated may have
experienced two reaction stages of thermal decomposition in
air, agreeing with that reported in the literature [4–9].
According to the study of Ou et al. [15], the first stage may be
contributed to the deacetylation of the main chain and the
cleavage of glycosidic linkages of chitosan and the second
stage might be caused by the thermal destruction of pyranose
ring and the decomposition of the residual carbon.
As shown in Fig. 2a, the TG curve moves toward lower
temperatures as the heating rate decreases. The reason for
the temperature shift has been discussed in our previous
work [29], as a combined result of heat transfer resistance
and mass transfer resistance. The former may have caused
thermal lagging between the heater and chitosan sample
and temperature gradient between the sample inside and
123
1082 Y.-H. Hao et al.

(a) 100 100

5 K min–1
10 K min–1
80 15 K min–1
0
20 K min–1
Mass variation/%

30 K min–1
60

Thermal response/μV
–100
5 K min–1
40 10 K min–1
15 K min–1 –200
20 K min–1
20
30 K min–1
–300

0
400 600 800 1000 1200
T/K –400

(b)
–500
400 600 800 1000 1200
558.57 K 754.66 K
T/K
783.04 K
570.04 K
Fig. 3 DTA curves of the chitosan sample obtained under different
1st DTG/min–1

805.01 K
heating rates
831.91 K
576.98 K Obviously, it can be seen that all the degradation temper-
atures increase linearly as the heating rate rises up, indi-
857.64 K
cating the considerable influence of the heat rate on the
585.53 K 5 K min–1 degradation temperatures. The relations between b and T
10 K min–1
15 K min–1 are quantitatively expressed as follows:
20 K min–1  
594.83 K 30 K min–1
Tp1 ¼ 1:428b þ 544:35 K R2 ¼ 0:969
 
Tp2 ¼ 4:135b þ 740:29 K R2 ¼ 0:973
400 600 800 1000 1200
T/K T5 ¼ 1:388b þ 511:87 K ðR2 ¼ 0:882Þ
T50 ¼ 1:705b þ 597:32 K ðR2 ¼ 0:918Þ
Fig. 2 TG curves (a) and first DTG curves (b) of the chitosan sample
obtained under different heating rates where R2 is the linear correlation coefficient. The linear
increase in thermal degradation temperature along with the
outside, especially at higher heating rates. The latter may increment of the heating rate is obviously a result of the
have rendered the decomposition and gasification not uni- thermal hysteresis discussed above.
versally happened to the whole sample, especially for the
sample inside where the reaction might have been some- 900
T5
what delayed. Likewise, Fig. 2b shows that the first DTG Tp1
peaks become stronger and wider as heating rate increases T50
from 5 to 30 K min-1, and in the meantime the peak 800 Tp2
temperature is promoted. Similar observation has also
applied to the DTA peaks as shown in Fig. 3. Actually,
T/K

700
such thermal lagging observation is very often met for
multiple heating-rate experiments [30, 31].
For better examining the effect of heating rates on the 600
thermal stability of chitosan, the temperatures of 5% mass
conversion (T5), maximum decomposition peak (Tp1),
second maximum decomposition peak (Tp2) and 50% mass 500
0 5 10 15 20 25 30 35
conversion (T50) of the chitosan sample under five different
β /K min–1
heating rates are abstracted from correspondent TG curves,
and then, the relationship between the heating rate (b) and Fig. 4 Relationship between b and thermal degradation temperatures
thermal degradation temperature (T) is plotted in Fig. 4. of the chitosan sample

123
A comparison study on non-isothermal decomposition kinetics of chitosan with different…
Kinetic analysis of chitosan thermal decomposition
FWO and CR methods
The isoconversional FWO and CR methods both are the
most frequently used temperature integral method for
analyzing kinetic thermal decomposition processes of
various substances [e.g., 32–36] and then are attempted in
this study to investigate the thermal degradation process of
the chitosan sample. To initialize the kinetic analysis, the
conversion rate a values and correspondent temperature
T values have been abstracted from TG curves obtained at
five different heating rates (5–30 K min-1).
These two methods are used to plot a series of linear
curves at all selected conversion levels according to
Eqs. (7) and (8), respectively. From the plots of ln b versus
1/T or ln(b/T2) versus 1/T, the Ea and ln A values at each
specific value of a can be conveniently obtained from the
slope and the intercept of the correspondent straight line. It
should be noted that the Ea values are independent on the
reaction function of g(a), but the ln A values cannot be
calculated if not using a g(a) function.
As discussed above, it may be possible that there are two
different stages during thermal degradation process of
chitosan. For the purpose of calculation simplicity, the two
stages may be taken to be independent, and the first-order
reaction function could be initially assumed for each stage.
The calculation results from the two FWO and CR methods
are given in Table 1, and Fig. 5 presents the Arrhenius
plots over the two-stage conversion range. Figure 5 shows
that very nice linear Arrhenius plots are resulted by using
the two methods, as also reflected by the correlation
coefficient R2 values that are very close to unity as listed in
Table 1. Table 1 shows that the Ea and ln A values
obtained from two methods for the two stages are generally
comparable to each other for each conversion value. For
the FWO method, the Ea value obtained varies from 106.18
to 138.96 kJ mol-1 for the second stage and
98.45–127.38 kJ mol-1 for the second stage as the con-
version level a varies from 0.10 to 0.90, and the ln A from
21.42 to 28.27 min-1, and 15.16 to 18.60 min-1 for the
first and second stages, respectively. While for the CR
method the Ea value estimated spans from 102.64 to
136.25 kJ mol-1 and from 92.24 to 120.33 kJ mol-1 for
the first and second stages, respectively. The ln A thus
obtained varies from 20.35 to 27.57 min-1 for the first
stage and from 13.47 to 17.05 min-1 for the second stage,
correspondent to the A value from 7.07 9 105 to
9.39 9 1011 min-1 over the whole thermal degradation
range.
Based on the calculations, the Ea and ln A values are
seen to be strongly dependent on the a value and vary
considerably during the whole conversion process. Such
1083
variation could be related to complicated reactions and
various species produced in the thermal decomposition
process. As the conversion continues, the degradation
reaction might become more difficult or less and result in
many different species, subsequently requiring higher or
lower activation energy to overcome. For this reason, the
Ea and ln A values cannot be kept constant over the whole
decomposition process. Table 1 shows that both parame-
ters are considerably higher at the same conversion levels
for the FWO method than the CR method. A further
examination of Table 1 shows that the FWO method has
resulted in 2.62–7.33 kJ mol-1 higher Ea values and
0.69–1.73 min-1 larger ln A values than the CR method.
However, if compared with those data reported in the lit-
erature [4–9], the discrimination among these works is
rather obvious, probably attributed to different isothermal
or non-isothermal experimental conditions employed and
kinetic analysis methods used.
With the kinetics parameters of ln A and Ea obtained,
the TG curves measured at different heating rates can be
reconstructed by using the FWO and CR methods. As
seen from Eqs. (7) and (8), the conversion a can be
easily represented as a function of temperature, and then,
the simulation can be carried out. Figure 6 presents the
calculated conversion results along with the experimental
data. As shown in Fig. 6, the two methods give generally
acceptable correlations to the experimental mass con-
version–temperature results, especially for the heating
rates of 5–15 K min-1. On the other hand, they seem-
ingly fail to perform well for two cases of 20 and
30 K min-1, and obvious calculation deviations against
experimental data are observed in the transition tem-
perature range of the two decomposition stages, indi-
cating that the first-order reaction function assumed may
be not appropriate for describing the decomposition
process of chitosan.
Tang and MKN methods
Using Eqs. (9) and (10, the Ea and ln A values can be
conveniently obtained using the MKN method or Tang
method. The calculation results from these two methods
are given in Table 2. Figure 7 presents the plots of
ln[b/T1.884318] versus 1/T or ln[b/T1.894661] versus 1/T for
the MKN method or Tang method, respectively. As can be
seen, the two methods have resulted in linear Arrhenius
plots over the two-stage conversion range, and such good
linearity has also been reflected by the correlation coeffi-
cient presented in Table 2. It can be seen that the Ea and ln
A values obtained from these two methods are almost
identical to each other for each conversion level over the
two thermal degradation stages. For the MKN method, the
Ea value varies from 102.96 to 136.57 kJ mol-1 and 92.71
123
1084 Y.-H. Hao et al.

Table 1 Kinetic parameters obtained by using FWO and CR methods along with the first-order reaction assumption
a FWO method CR method
-1 -1 2
Ea/kJ mol ln A/min R Ea/kJ mol-1 ln A/min-1 R2

First stage
0.10 106.57 21.49 0.9893 103.32 20.50 0.9876
0.20 106.18 21.42 0.9991 102.64 20.35 0.9989
0.30 110.05 22.30 0.9995 106.54 21.27 0.9994
0.40 113.96 23.18 0.9985 110.53 22.20 0.9982
0.50 118.58 24.21 0.9968 115.27 23.28 0.9962
0.60 123.45 25.27 0.9949 120.31 24.41 0.9939
0.70 129.41 26.55 0.9929 126.12 25.77 0.9918
0.80 136.98 28.10 0.991 134.35 27.41 0.9895
0.90 138.96 28.27 0.9935 136.25 27.57 0.9924
Average 120.46 24.53 117.30 23.64
Second stage
0.10 103.19 16.18 0.9949 97.76 14.70 0.9938
0.20 98.45 15.16 0.9952 92.24 13.47 0.9941
0.30 101.02 15.30 0.997 94.44 13.58 0.9963
0.40 105.19 15.74 0.9981 98.41 14.03 0.9976
0.50 109.03 16.17 0.9986 102.11 14.47 0.9982
0.60 111.73 16.45 0.9989 104.64 14.75 0.9986
0.70 113.24 16.58 0.999 105.97 14.87 0.9987
0.80 116.85 17.07 0.9989 109.52 15.38 0.9985
0.90 127.38 18.60 0.9994 120.33 17.05 0.9992
Average 109.56 16.36 102.82 14.70

to 120.89 kJ mol-1 for the first and second stages,
respectively. The ln A values are seen to fluctuate from
20.60 to 27.79 for the first stage and from 13.75 to 18.39
for the second stage, correspondent to the A value of
9.39 9 105–1.18 9 1012 min-1 over the whole thermal
degradation process. In the case of the Tang method, rather
similar calculations have been resulted, and the Ea and ln
A values range from 92.70 to 136.58 kJ mol-1 and from
13.66 to 27.71 min-1 over the whole conversion range,
respectively.
A comparison of Tables 1 and 2 shows that the FWO
method has resulted in the highest values, followed by the
comparable MKN and Tang methods, and finally the CR
method. It is observed that the MKN method has yielded
2.62–7.33 kJ mol-1 higher Ea values than the CR method
along with 0.69–1.73 min-1 larger ln A values. However, the
dependence of Ea and ln A on a exhibits generally the same
trend for the four methods.
Figure 8 shows the calculation results by using the
MKN and Tang methods, along with experimental data.
Unsurprisingly, relatively satisfactory correlations against
the experimental data have resulted by using the two
methods, similar to those of the FWO and CR methods.
Comparing Fig. 8 with Fig. 6, it is obvious that the four
methods exhibit generally comparable simulation perfor-
mance. These results further reflect that the first-order
reaction assumption with different temperature integral
methods has not achieved desirable results for the
description of the thermal degradation of the chitosan
sample, and therefore, deep investigation must be taken to
scan more suitable reaction function for getting better
results.
Determination of the most probably reaction function
In order to better search a more appropriate reaction
function, totally 27 well-known conversion functions [23]
have all been scanned, and Table 3 lists some reaction
functions selected for further determining the pyrolysis
process of chitosan. A few works [8, 37, 38] have con-
sidered a relatively simple procedure for determining the
most correct reaction function, i.e., g(a). For this purpose,
the following expression must be used:
 
AEa ex
ln½gðaÞ ¼ ln þ ln 2 þ ln hðxÞ  ln b ð11Þ
R x
where x = E/RT and h(x) is expressed by the fourth Senum
and Yang approximation formulae [39]:

123
A comparison study on non-isothermal decomposition kinetics of chitosan with different… 1085

(a) 1.6 (a)100

Stage
α One Two
1.4 80
0.10

Conversion α /%
0.20
0.30 60
1.2 0.40 FWO method
log β

0.50 5 K min–1
0.60
0.70
40 10 K min–1
1.0
0.80 15 K min–1
0.90 20 K min–1
20
0.8 30 K min–1

0
450 550 650 750 850 950
0.6
1.1 1.3 1.5 1.7 1.9 2.1 2.3 T/K
1000/T/K–1
(b) 100
(b) –9

Stage 80
α One Two

Conversion α /%
0.10 60
0.20 CR method
–10 0.30
0.40 5 K min–1
ln(β /T 2)

40 10 K min–1
0.50
0.60 15 K min–1
0.70 20 K min–1
0.80 20
–11 0.90 30 K min–1
0
450 550 650 750 850 950
T/K

–12 Fig. 6 Reconstructed temperature-dependent mass conversion curves

1.1 1.3 1.5 1.7 1.9 2.1 2.3
by using the FWO method (a) and CR method (b) over the whole
1000/T/K–1 conversion range

Fig. 5 Arrhenius plots of log b versus 1/T for the FWO method
(a) and ln(b/T2) versus 1/T for the CR method (b) at selected
conversion a values
x4 þ 18x3 þ 86x2 þ 96x
hð x Þ ¼
x4 þ 20x3 þ 120x2 þ 240x þ 120
Accordingly, plotting ln[g(a)] versus ln b is made over
the conversion range considered, resulting in a straight
line for each reaction function g(a). Then, the most
probably reaction function g(a) can be determined, pro-
vided that the slope of the resultant straight line should be
equal to -1.0000 and the linear correlation coefficient R2
should be equal to unity. To do this, a temperature must
be properly selected within each stage of thermal degra-
dation process, and then, the conversion a values corre-
sponding to multiple rates can be abstracted from TG
curves at the same temperature selected. Therefore, the
temperature range of each stage must be determined for
chitosan thermal degradation prior to properly selecting a
temperature [8, 37, 38]. It may be noted that the values of
Ea and ln A do not influence the shape of the most correct
reaction function determined.
Figure 9 shows the kinetic curves obtained for the case
of 10 K min-1 using some conversion functions with dif-
ferent values of n listed in Table 3. As can be seen, all the
kinetic curves start to bend at about 595 K, further sug-
gesting that the chitosan degradation probably may have
occurred in two stages. Similar observations have also
ð12Þ applied for the other four heating rates, but the curve-
bending temperature turns to be higher at higher heating
rate. Obviously, the obtainment of two-stage decomposi-
tion is consistent very well with previous discussion on first
DTG results. Based on these results, it can be approxi-
mately deduced that the first stage could happen from 510
to 620 K and the second stage from 620 to 870 K,
respectively. Consistently, Georgieva et al. [8] have
reported that chitosan might have undergone two decom-
position stages with similar temperature ranges.
In this work, 580 and 770 K are selected for the two
degradation stages of chitosan, and then, the correspondent
conversion values are abstracted from TG curves at these
two temperatures under multiple rates of 5–30 K min-1.
Subsequently, all the reaction functions presented in
Table 3 have been tested according to Eq. (11) for each
decomposition stage. Thus, the relationships between
ln[g(a)] and ln b are readily obtained along with the cor-
relation coefficient of linear regression. Table 4 presents
the calculation results for a few g(a) functions complying
with the above-mentioned requirement and one of which is

123
1086 Y.-H. Hao et al.

Table 2 Kinetic parameters obtained by using MKN and Tang methods along with the first-order reaction assumption
a MKN method Tang method
-1 -1 2
Ea/kJ mol ln A/min R Ea/kJ mol-1 ln A/min-1 R2

First stage
0.10 103.63 20.74 0.9877 103.63 20.66 0.9877
0.20 102.96 20.60 0.9989 102.96 20.51 0.9989
0.30 106.86 21.51 0.999 106.86 21.42 0.9994
0.40 110.85 22.44 0.9982 110.86 22.35 0.9982
0.50 115.60 23.52 0.9962 115.60 23.43 0.9962
0.60 120.64 24.65 0.994 120.64 24.56 0.9940
0.70 126.81 26.00 0.9918 126.82 25.91 0.9918
0.80 134.66 27.55 0.9896 134.67 27.55 0.9896
0.90 136.57 27.79 0.9925 136.58 27.71 0.9925
Average 117.62 23.87 117.63 23.79
Second stage
0.10 98.20 14.97 0.9939 98.19 14.88 0.9939
0.20 92.71 13.75 0.9939 92.70 13.66 0.9942
0.30 94.95 13.86 0.9964 94.92 13.77 0.9964
0.40 98.94 14.31 0.9976 98.92 14.22 0.9976
0.50 102.64 14.75 0.9982 102.63 14.66 0.9982
0.60 105.19 15.03 0.9986 105.34 14.94 0.9986
0.70 106.52 15.16 0.9987 106.51 15.06 0.9987
0.80 110.08 15.67 0.9986 110.07 15.58 0.9986
0.90 120.89 17.33 0.9992 120.88 17.24 0.9992
Average 103.35 14.98 103.35 14.89

supposed to be the most appropriate reaction function for
chitosan.
As listed in Table 4 for the first stage, the slope deter-
mined from Jander equation (D3 function) seems to be the
closest to -1.000 and the linear correlation coefficient R2
is rather near to unity as well. Then, it can be deduced that
the mechanism function with integral form gðaÞ ¼
h i2
ð3=2Þ 1ð1aÞ1=3 and differential form f ðaÞ ¼
h i1
ð1aÞ2=3 1ð1aÞ1=3 belongs to three-dimensional
diffusion-controlled reaction (spherical symmetry) and is
the most probable describing function for the first decom-
position stage. Concerning the second stage of chitosan
thermal degradation, the slope closest to -1.000 along with
more satisfactory correlation coefficient R2 can be obtained
with the Zhuravlev—Lesokhin—Tempelman equation (D5
function), which is also three-dimensional diffusion-con-
trolled reaction with integral form gðaÞ ¼ ð3=2Þ
h i2
ð1aÞ1=3 1 and differential form f ðaÞ ¼ ð1aÞ4=3 =
h i
1ð1aÞ1=3 .
After obtaining the most probable reaction functions for
the first and second stages of thermal degradation of chi-
tosan, the temperature-dependent conversion curves under
multiple heating rates have been newly reconstructed with
the FWO method, and the results are graphically presented
in Fig. 10. A comparison of Fig. 10 with Figs. 6 and 8
shows that greatly improved simulation performance has
been obtained under multiple heating rates for the whole
thermal degradation curves of chitosan, especially for the
transition temperature ranges. These results indicate that
the D3 and D5 functions tend to be the most probable
reaction functions for the first and second stages of chi-
tosan thermal decomposition process. However, in the
study of Georgieva et al. [8], the thermal degradation of
chitosan has been reported to comply with chemical reac-
tion type function with the reaction order of 3 or 1 for the
first and second stages, respectively.
Calculation of thermodynamic parameters
Based on the transition state theory, the rate constant expres-
sion can be given as the well-known Eyring equation [8]:

123
A comparison study on non-isothermal decomposition kinetics of chitosan with different… 1087

(a) 3.7 (a) 100

Stage
α One Two 80

Conversion α /%
3.1 0.10
0.20
0.30 60
0.40
0.50 MKN method
ln β

2.5 0.60 40
0.70 5 K min–1
0.80 10 K min–1
0.90 20 15 K min–1
20 K min–1
1.9
30 K min–1
0
450 550 650 750 850 950
T/K
1.3
1.1 1.3 1.5 1.7 1.9 2.1 2.3
1000/T/K–1 (b) 100

(b) –8.5
80

Conversion α /%
Stage
α One Two 60
0.10
0.20 Tang method
ln(β /T 1.894661)

–9.5 0.30 40 5 K min–1

0.40 10 K min–1
0.50
0.60
15 K min–1
20 20 K min–1
0.70
0.80 30 K min–1
–10.5 0.90 0
450 550 650 750 850 950
T/K

Fig. 8 Reconstructed temperature-dependent mass conversion curves

–11.5 by using the MKN method (a) and Tang method (b) over the whole
1.1 1.3 1.5 1.7 1.9 2.1 2.3
conversion range
1000/T/K–1

Fig. 7 Arrhenius plot of ln[b/T1.884318] versus 1/T for the MKN whole chitosan decomposition, DG#, DH# and DS# can be
method (a) or ln[b/T1.894661] versus 1/T (b) for Tang method at obtained for the formation of activated complex from the
selected conversion a values reagent, and the calculated results are presented in Table 5.
It is seen that the DG# value increases from 117.44 to
  121.73 kJ mol-1 for the first stage and 131.78–161.01
jkB T DG# kJ mol-1 for the second stage as the conversion level a varies
kðTÞ ¼ exp 
hP  RT#    from 0.10 to 0.90. The positive change in Gibbs free energy
jkB T DH DS# DG# reflects that the total energy of the system increases over
¼ exp   exp  ð13Þ
hP RT RT the whole thermal degradation, mainly by means of heat
absorbing. According to thermodynamic definitions, it can be
where j is the transmission coefficient and usually taken to be
deduced that the degradation reaction is non-spontaneous
unity for monomolecular reactions; kB and hP are Boltzmann
process [15]. Furthermore, it is well known that the magnitude
constant and Plank constant, respectively. DG#, DH# and DS#
of DG# measures how far a reaction is from equilibrium, and
are the Gibbs free energy, enthalpy and entropy of activation for
then, the larger the value of DG#, the further the reaction is
the formation of activated complex, respectively. Considering
from equilibrium and the further the reaction must shift to
that DG# ¼ DH #  TDS# and DH # ¼ Ea RT, a com- reach equilibrium. Table 5 also shows that the averaged DH#
parison between the Arrhenius equation and the Eyring equa- values are, respectively, 112.72 and 96.88 kJ mol-1 for the
tion, i.e., Eqs. (3) and (13), may readily lead to: first and second stages, indicating how large the energy dif-
 #
evkB T DS ference between the activated complex and the reagent is.
A¼ exp ð14Þ Obviously, the DH# values are all positive, and it means that
h R
the involved reaction is a thermodynamically unfavorable
Then, the values of DG#, DH# and DS# can be calculated endothermic process. As for the change in activation entropy
along with thermodynamic definitions. Based on the results DS#, Table 5 shows that the DS# values are mostly negative,
of Ea and ln A calculated with the CR method over the but they are 4.63, 17.16 and 16.64 J mol-1K-1 as a is 0.70,

123
1088 Y.-H. Hao et al.

Table 3 Selected reaction functions of g(a) and f(a) for describing thermal degradation process of chitosan
Symbol Name of the function f(a) g(a)

F1 First order 1-a  lnð1aÞ

h i
F3/2 One and half order (1 - a)3/2 2 ð1aÞ1=2 1
F2 Second order (1 - a)2 a=ð1aÞ
h i
F3 Third order (1 - a)3 ð1=2Þ ð1  aÞ2 1
h i
Fn nth order at n = 1 (1 - a)n 1ð1aÞ1n =ð1nÞ
D1 Parabola low 1/a a2/2
D2 Valensi 1 a þ ð1aÞ lnð1aÞ
½ lnð1aÞ
h i1 h i2
D3 Jander
ð1aÞ2=3 1ð1aÞ1=3 ð3=2Þ 1ð1aÞ1=3
h i
D4 Ginstling–Brounstein ð1aÞ1=3 =1ð1aÞ1=3 ð3=2Þ 1ð2=3Það1aÞ2=3
h i h i2
D5 Zhuravlev–Lesokhin–Tempelman ð1aÞ4=3 = 1ð1aÞ1=3 ð3=2Þ ð1aÞ1=3 1
h i h i2
D6 Anti-Jander ð1 þ aÞ2=3 = ð1 þ aÞ1=3 1 ð3=2Þ ð1 þ aÞ1=3 1
h i1 h i
D7 Anti-Ginstling–Brounstein ð3=2Þ 1 þ 2a=3ð1 þ aÞ2=3
1ð1 þ aÞ1=3
h i1 h i2
D8 Anti-Zhuravlev–Lesokhin–Tempelman
ð1 þ aÞ4=3 1ð1 þ aÞ1=3 ð3=2Þ ð1 þ aÞ1=3 1

–10 Table 4 The most probable reaction function g(a) and calculation
results for thermal degradation of chitosan
–11
Symbol Slope R2
–12
First stage
ln[g (α)/T 2]

–13
F1 ln½gðaÞ ¼ 0:5505 ln b þ 0:6166 0.9344
F3 ln½gðaÞ ¼ 0:8376 ln b þ 1:8723 0.9604
–14 n = 0.33 n = 0.5 D1 ln½gðaÞ ¼ 0:8730 ln b  0:5018 0.9154
n = 0.67 n = 0.75
n=1 n = 1.25 D2 ln½gðaÞ ¼ 0:9426 ln b  0:1777 0.9219
–15 n = 1.5 n = 1.75 D3 ln½gðaÞ ¼ 1:0206 ln b  0:9218 0.9285
n=2 n=3
–16 D4 ln½gðaÞ ¼ 0:9686 ln b  1:5638 0.9242
1.15 1.35 1.55 1.75 1.95
D5 ln½gðaÞ ¼ 1:1859 ln b  0:1794 0.9398
1000/T/K–1
D7 ln½gðaÞ ¼ 0:8185 ln b  1:8862 0.9118
Fig. 9 Coats–Redfern plots for thermal degradation of chitosan at Second stage
10 K min-1 using chemical reaction assumptions with different F1 ln½gðaÞ ¼ 0:3681 ln b þ 1:4342 0.9844
reaction order values of n F3/2 ln½gðaÞ ¼ 0:7824 ln b þ 3:4573 0.9669
F2 ln½gðaÞ ¼ 0:5533 ln b þ 2:3598 0.9748
0.80 or 0.90 in the first stage, respectively. Further, the
F3 ln½gðaÞ ¼ 1:3337 ln b þ 6:0384 0.9579
absolute DS# values are relatively smaller for the first stage
than for the second stage. Being a state function, DS is com- D3 ln½gðaÞ ¼ 0:5427 ln b þ 0:4850 0.9908
monly understood as a measure of disorder for a thermody- D5 ln½gðaÞ ¼ 0:9726 ln b þ 2:2703 0.9779
namic system. The negative values of DS# indicate that the
produced activated complex could be more structurally
ordered than the reactants, and thus, the reaction is unfavor- Estimation of lifetime
able and may be classified as ‘‘slow.’’ In the meantime, large
DS# values suggest that is far for the system from the initial Lifespan estimation is very helpful to properly select
equilibrium state to the final thermodynamic equilibrium polymers for different specific applications, and it may be
state. Similar observations have also been reported elsewhere determined by the accelerated air oven aging studies;
[8, 15]. however, this kind of methods usually takes very long time

123
A comparison study on non-isothermal decomposition kinetics of chitosan with different… 1089

100 certain amount. In this work, the life period of chitosan, tp,
has been estimated as the time when its mass loss reaches
5%, i.e., a = 0.05 and can be estimated by using the fol-
80
lowing equation:
 
Conversion α /%

 lnð1  aÞ Ep
60 tp ¼ exp  ð15Þ
Ap RTp
FWO method
40 5 K min–1 where Ep is the activation energy and usually evaluated
10 K min–1 from Kissinger’s plot of ln(b/T2p) against 1/Tp [40], g(a) is a
15 K min–1
20 20 K min–1
thermal conversion function and approximately assumed to
30 K min–1 be the first-order reaction, Ap is the pre-exponential factor
and evaluated as follows [8]:
0
450 550 650 750 850 950  
bEp Ep
T/K Ap ¼ exp  ð16Þ
RTp2 RTp
Fig. 10 Reconstructed temperature-dependent mass conversion
curves under different heating rates using the FWO method and with With these prerequisite assumptions, the time to undergo
D3 and D5 functions as the most probable reaction functions for the equivalent thermal damage at different temperatures or
respective first and second thermal degradation stages of chitosan the time to various damages under isothermal conditions
can be readily estimated. It should be noted that the
Table 5 Thermodynamic parameters of DS#, DH# and DG# calcu- method used here is very rough and may lead to high
lated for thermal degradation of chitosan
errors in lifetime predictions, but the estimation does
a DS#/J mol-1 K-1 DH#/kJ mol-1 DG#/kJ mol-1 provide certain information for subsequent thermal
applications.
First stage
Figure 11 presents the Kissinger’s plots of ln(b/T2p)
0.10 -35.83 99.05 117.44
versus 1/Tp for two stages, yielding two straight lines,
0.20 -37.59 98.24 118.11
from which the apparent activation energy Ep can be
0.30 -30.43 102.06 118.45
calculated from the slope, and it is 125.43 or
0.40 -23.17 105.99 118.64
77.47 kJ mol-1 for the first stage or the second stage,
0.50 -14.67 110.68 118.79
respectively. Obviously, the averaged Ea listed in
0.60 -5.87 115.67 118.95
Tables 1 and 2 is substantially lower than the Ep for the
0.70 4.63 121.81 119.19
first stage but greatly higher than the Ep for the second
0.80 17.16 129.60 119.80
stage. Then, the pre-exponential factor Ap can be obtained
0.90 16.64 131.41 121.73 in accordance with Eq. (16), and it is slightly affected by
Average -12.13 112.72 119.01 the heating rate. The ln Ap value averaged over multiple
Second stage heating rates is 25.66 min-1 for the first stage or
0.10 -62.90 92.57 131.78 9.19 min-1 for the second stage, respectively. Obviously,
0.20 -78.57 86.82 138.01
0.30 -80.80 88.79 143.71
0.40 -79.17 92.56 148.27
–9
0.50 -77.12 96.10 151.91
Stage 1:
0.60 -76.05 98.48 154.83
E = 125.43 kJ mol–1, R 2 = 0.988
0.70 -76.12 99.69 157.23
0.80 -72.83 103.11 159.26 –10
ln(β /T 2)

0.90 -59.92 113.78 161.01

Average -73.72 96.88 149.56
–11
Stage 2:
E = 77.47 kJ mol–1, R 2 = 0.978

periods for materials lifespan measurements. For practical –12

applications, the service life is a critical parameter to var- 1.1 1.3 1.5 1.7 1.9

ious polymer-based articles. Usually, the physical proper- 1000/T/K–1

ties of polymer materials will decrease considerably and Fig. 11 Kissinger’s plots of ln(b/T2) versus 1/T for the first and
fail to service properly when their mass loss approaches second stages of thermal degradation of chitosan

123
1090 Y.-H. Hao et al.

(a) 7 Conclusions
6
In this work, non-isothermal decomposition behavior of
5 chitosan has been investigated with temperature up to
800 K under air atmosphere. FTIR results evidence the
log tp /day

4 thermal deterioration of chitosan macromolecule structure,

corresponding to the decrease in absorbance peaks related
3
to OH, NH and CH2 groups, and the disappearance of the
2 amide I and amide II bands and absorbance peaks con-
nected to polysaccharide skeleton. Resultant TG and DTA
1 results demonstrate that the thermal features of chitosan are
strongly depend on the heating rates, and two-stage
0
280 310 340 370 400 430 degradation process may be assumed. Kinetic analysis over
T/K the entire conversion range has been made on mass loss
curves under multiple heating rates. Using the isoconver-
(b) 9
323 K sional FWO, CR, MKN and Tang methods, the Arrhenius
373 K parameter Ea and ln A values are estimated for each stage
7
423 K along with the first-order reaction assumption. The calcu-
lation performances for the four methods are generally
log tp /day

5 comparable to each other for reconstructing the tempera-

3 relations against experimental data are observed for the
1
–1
0.1 0.2 0.4 0.6 0.8
Conversion α
Fig. 12 Lifetime predictions of the thermal decomposition kinetics
of chitosan: a dependence of the lifetime on temperature at 5% mass
loss, b dependence of the lifetime on mass conversion
the values of Ep and ln Ap obtained for the first stage
should be substituted into Eq. (15) for lifetime predictions
as 5% mass conversion is occurred in the first stage of
thermal degradation of chitosan, and the predicted results
are shown in Fig. 12 along with the first-order reaction
assumption. Figure 12a shows that the lifetime is strongly
dependent on environmental temperature and decreases
exponentially with the increase in the temperature. The
predicted values are consistent with those reported by
Georgieva et al. [8]. On the other hand, the lifespan is
observed to exponentially increase with the chitosan mass
conversion under isothermal conditions, as shown in
Fig. 12b. According to such predictions, it may be inter-
estingly estimated that chitosan requires about 49,000, 94
or \1 day for 5% mass loss at 323, 373 and 423 K,
respectively. Therefore, the life period prediction is much
more meaningful since it provides very interesting infor-
mation about the thermal stability of polymer-based
materials.
ture-dependent mass loss curves, but relatively poor cor-
transition temperature range of two thermal degradation
stages. Further attempt has showed that the diffusion-con-
trolled reaction function with differential form f ðaÞ ¼
h i1
ð1  aÞ2=3 1  ð1aÞ1=3 or f ðaÞ ¼ ð1aÞ4=3 = ½1
1.0
ð1aÞ1=3  is the most probable describing function for the
first and second decomposition stages, subsequently lead-
ing to greatly improved correlation performance over the
entire conversion range. With the FWO method, the Ea
values span from 98.45 to 138.96 kJ mol-1 and the ln
A from 16.38 to 26.95 min-1 over the entire conversion
range. A comparison of calculation results shows that the
FWO method has led to the highest Ea and ln A values,
followed by the MKN and Tang methods, and the lowest
by the CR method.
Acknowledgements The authors would like to thank National Stu-
dents’ Innovation and Entrepreneurship Training Program (No.
201510069032) and Tianjin University of Commerce (TJUC-2015-
003) for funding this project.
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