J Therm Anal Calorim (2015) 121:13831391
DOI 10.1007/s10973-015-4639-4
Non-isothermal dehydration kinetic study of a new swollen
biopolymer silver nanocomposite hydrogel
Mohammad Reza Sovizi1 Ghasem Fakhrpour1 Saleh Bagheri2,4
Ghasem Rezanejade Bardajee3
Received: 23 August 2014 / Accepted: 9 March 2015 / Published online: 2 April 2015
 Akademiai Kiado, Budapest, Hungary 2015
Abstract Thermal dehydration kinetic of a novel swollen
silver nanocomposite hydrogel (SNH), prepared based on
poly(acrylic acid) grafted onto salep as a water soluble
polysaccharide backbone, was studied by thermogravime-
try under non-isothermal conditions. The values of appar-
ent activation energies (Ea) and pre-exponential factors
(A) for a set of reaction models at 5, 10, 15, and
20 K min-1 heating rates were determined. The depen-
dence of the activation energy on the extent of conversion
was obtained by the model-free methods. Apparent acti-
vation energy (Ea) of the process was calculated from
KissingerAkahiraSunose and Tang isoconversional
methods. From the strong dependence of the Ea value on
the extent of conversion (a) for the investigated process, it
was found that the dehydration process of SNH is complex
and we cannot explain the whole process by a single
mechanism. In the low extent of conversion (a), Ea rapidly
decreases and the dehydration process is complex and
probably involving a combination of several processes. In
the range of a = 0.400.90, Ea is nearly constant and the
dehydration process can be assumed to follow a single-step
reaction. The results obtained from Criado and Invariant
& Mohammad Reza Sovizi
mrsovizi@yahoo.com
1
Department of Chemistry, Malek Ashtar University of
Technology, P.O. Box 16765-3454, Tehran, Iran
2
Department of Physical and Theoretical Chemistry, Faculty
of Chemistry, Tehran-North, Islamic Azad University,
1913674711, Tehran, Iran
3
Department of Chemistry, Payame Noor University,
P.O. Box 19395-3697, Tehran, Iran
4
Department of Chemistry, Kerman Branch, Islamic Azad
University, Kerman, Iran
kinetic methods, in the constant-Ea region, confirmed that
probable model for the dehydration process agreed with R3
model.
Keywords Non-isothermal dehydration  Silver
nanocomposite hydrogel  Thermogravimetric analysis 
Kinetic  Swollen biopolymer
Introduction
Hydrogel is a macromolecule network which can absorb
pure water up to hundred or thousand times of its dried
mass. The use of hydrogels as biomaterials has recently
gained great importance in view of the low toxicity and
high biocompatibility presented by many of them. The
main hydrogel application areas today include: (1) topical
applications as wound dressings, (2) drug delivery systems,
(3) transdermal systems, (4) dental applications, (5) in-
jectable polymers, (6) implants, (7) ophthalmic applica-
tions, and (8) stimuli-responsive systems [1].
To prepare successfully hydrogels with the desired
biological and physical properties, several factors such as a
biocompatibility, biodegradability, sterilizability, me-
chanical strength, drug loading capacity, water content
(degree of swelling), and the components of the hydrogels,
must be carefully considered [2].
The swelling kinetics behavior of many types of hy-
drogels is extensively studied [35], but there are much
lesser information concerning hydrogel mechanical prop-
erties and there are a few investigations concerning the
kinetics of hydrogel dehydration.
Vyazovkin points out that an alternative approach to
kinetic analysis is to use model-free methods that allow for
evaluating Arrhenius parameters without choosing the
123
1384
reaction model. The best-known representatives of the
model-free approach are the isoconversional methods.
These methods yield the effective activation energy as a
function of the extent of conversion. Knowledge of the
dependence Ea on a assists in both detecting multi-step
processes and drawing certain mechanistic conclusions. It
is sufficient to predict the reaction kinetics over a wide
temperature region [6].
As we know, thermogravimetric analysis (TG) is one of
the most convenient thermal analysis techniques used to
measure the mass change, thermal decomposition, and
thermal stability of composite materials [7]. Overall kinetics
can be obtained by measuring the change in mass of a sample
with time based on isothermal or non-isothermal thermo-
gravimetric data. Some valuable parameters, such as ap-
parent activation energy E, and pre-exponential factor A can
be calculated from a thermogravimetric curve [8, 9].
Knowledge of the kinetic parameters associated with thermal
degradation constitutes an important tool in estimating the
thermal behavior of composites under dynamic conditions.
The main aim of this study is to explore the thermal
dehydration, kinetics, and reaction model of a novel
swollen silver nanocomposite hydrogel (SNH) using solid-
state kinetic approaches.
Experimental
Materials
Salep was bought from a supplier in Kordestan, Iran
(Mn = 1.17 9 106 g mol-1, Mw = 1.64 9 106 g mol-1
(high Mw), PDI = 1.39, eluent = water, flow rate =
1 mL min-1, acquisition interval = 0.43 s, from GPC re-
sults). Silver nitrate (AgNO3, from Fluka, St. Louis, MO),
methylenebisacrylamide (MBA, from Merck, Darmstadt,
Germany) as across linker, ammonium persulfate (APS,
from Fluka, St. Louis, MO) as a water soluble initiator, and
acrylic acid (AA, from Merck) as a monomer were ana-
lytical grades and used without further purification.
Synthesis of SNH
The silver nanocomposite hydrogel was synthesized ac-
cording to general procedure reported by Rezanejad-Bar-
dajee et al. [10]. In general, salep (1.0 g) was added to
DDW (80 mL) at a three-neck reactor equipped with a
mechanical stirrer while stirring (200 rpm).After ho-
mogenization, 5 mL of AgNO3 solution (0.01 M) was
added to the reaction mixture and it was stirred for further
30 min. The reactor was placed in a thermostated water
bath preset at desired temperature (80 C), and 5 mL of the
AA monomer (0.12 M), 5 mL of the MBA crosslinker
123
M. R. Sovizi et al.
(6.5 9 10-3) and 5 mL of APS initiator (1.65 9 10-2 M)
were added and the reaction mixture was stirred until a gel-
like product was observed after around 20 min. Finally, the
reaction mixture was cooled to room temperature. The
product was poured into 100 mL of ethanol, remained for
2 h and then chopped to small pieces for further drying. To
remove the sol fraction of the mixture (uncrosslinked and
not grafted PAA, uncrosslinked salep and possibly also
some unreacted monomer), the dewatered hydrogel was
allowed to completely swell for overnight in plenty of
DDW (400 mL) and then dewatered in ethanol (200 mL,
2 h). The non-solvent ethanol was decanted, and then,
100 mL fresh ethanol was added. The chopped particles
were further remained for 24 h in ethanol to completely
dewater. The dewatered gel particles were filtered and
dried in oven (at 50 C) for 24 h. After grinding, the
powdered superabsorbent hydrogels were stored in the
absence of moisture, heat, and light.
SEM, TEM, FTIR and EDX experiments
Fourier transform infrared (FT-IR) spectroscopy measure-
ments were carried out at room temperature on a Jasco
4200 FT-IR spectrophotometer. Scanning electron mi-
croscopy (SEM) with energy dispersive X-ray analysis
(EDX) (Hitachi S-5200 SEM) and transmission electron
microscopy (TEM) (Hitachi H-700 CTEM) were used to
examine the morphology and dimensions of hydrogel
nanocomposites.
TG/DSC study
Thermogravimetric analysis and differential scanning
calorimetry (DSC) were carried out by a Rheometric Scien-
tific thermogravimetric analyzer TGA model 1000 M? and
DSC model SP. These analyses were performed with
20 0.1 mg samples of equilibrium swollen hydrogel in
platinum pans. Hydrogel dehydration was studied in dynamic
atmospheres of dry nitrogen, flowing at 10 mL min-1. Ex-
periments were performed at heating rates of 5, 10, 15, and
20 K min-1 from ambient temperature to 500 K.
Theoretical approach for kinetic study
The rate of kinetic process in solid state is usually based on
the following rate equation [11, 12]:
da
kTf a 1
dt
where a is a degree of conversion, f(a) is a dependent
kinetic model function, and k(T) is a temperature-depen-
dent reaction rate constant.
Non-isothermal dehydration kinetic study
The degree of conversion, a, can be determined in terms
of mass loss from the TG curves as follows:
m0  m
a 2
m0  mf
where m0, m, and mf are the initial, actual (at any tem-
perature T) and the final mass of the dehydration process,
respectively.
k(T) is often modeled successfully by the Arrhenius
equation:
 
Ea
kT A exp  3
RT
where Ea is the apparent activation energy, A the pre-ex-
ponential factor, T the absolute temperature, and R are the
gas constant. The following relationship can be defined for
non-isothermal experiments,
da da dt
 4 been seen, SEM and TEM images show porous structure
dT dt dT
where da/dT is the non-isothermal reaction rate, da/dt is the
isothermal reaction rate, and dT/dt is the heating rate (b).
Substituting Eq. (1) into Eq. (4) gives,
 
da A Ea
exp  f a 5 spectra (Fig. 1c) of polymer gel in absence (Fig. 1c-1) and
dT b RT
The conversion dependence of the process rate can be
expressed by using a common reaction models [6]. There
are many model fitting methods that extract the three ki-
netic parameters known as the kinetic triplet (A, Ea, and
model) from non-isothermal data. Two of these models
proposed by Kennedy and Clark (KC) [13], and Coats and
Redfern (CR) [14, 15]. These methods were used exten-
sively earlier in the solid-state kinetic analysis and they
continue to appear. Model-free methods calculate the re-
action activation energy (Ea) without modelistic assump-
tions which is usually done by grouping terms such as the
pre-exponential factor (A) and model into the intercept of a
linear equation and using the slope of that equation to
calculate the activation energy (Ea).
The KissingerAkahiraSunose (KAS) method deter-
mines the activation energies without a precise knowledge
of the reaction mechanism [16, 17]:
 
b AR Ea
ln 2 ln  : 6 95 % mass loss (Fig. 1d-3). The presence of nano-Ag in the
T Ea ga RT
A plot of the left-hand sides of Eq. (6) versus 1/T give a
group of straight lines at each a, which give apparent ac-
tivation energy from the slope for a particular a without
considering a selected model.
Another method proposed by Tang et al. as following
equation [18, 19]:
1385
   
b AEa
ln ln 3:635041  1:894661 ln Ea
T 1:894661 Rga
Ea
 1:001450
RT
7
The plots of ln(b/T1.894661) versus 1/T give a group of
straight lines. The apparent activation energy Ea can be
obtained from the slope -1.001450 Ea/R of the regression
line.
Results and discussion
Characterization of SNH
Figure 1 shows SEM and TEM images, FT-IR spectra, TG
curve and EDX of biopolymer swollen hydrogel. As can
and a highly uniform distribution of spherical nano-Ag
(510 nm) in SNH.
To provide some information about the existence of Ag
in SNH structure and the presence of desired functional
groups from salep and PAA in final hydrogels, the FT-IR
percent (Fig. 1c-2) of nano-Ag, salep (Fig. 1c-3) and PAA
(Fig. 1c-4) were recorded. Figure 1c-1 has shown absorp-
tion peaks at 1630 cm-1 and 1575 cm-1 relating to C=O
stretching vibrations of PAA (Fig. 1c-4) and glucomannan
repeating units (Fig. 1c-3) from salep. The peak observed at
3300 cm-1 is due to the stretching vibrations of OH and
COOH functional groups in the polymer networks. Fig-
ure 1c-2 has shown all the above characteristic peaks with a
slight shift to higher wavelengths (1645 and 1594 cm-1
relating to C=O stretching vibrations of PAA and gluco-
mannan repeating units, respectively). This shifting can be
attributed to the formation of coordination bond between
the nano-Ag and the electron-rich groups (such as C=O and
OH) present in the hydrogel network. Figure 1d shows
thermal decomposition of salep (Fig. 1d-1), polymer gel in
the absence (Fig. 1d-2) and presence (Fig. 1d-3) of nano-
Ag. In absence of nano-Ag, the hydrogel has followed two
main decomposition steps (near 80 %) at 500 C. However,
nano-Ag shifted thermal degradation steps to 560 C with
hydrogel networks can catalyze CO2 elimination from
polymer chains and accelerate the degradation process.
Thermogravimetric analysis of SNH
Figure 2a shows the TG and DTG curves, recorded in
N2 atmosphere, for the investigated sample of silver
123
1386 M. R. Sovizi et al.

(a) (b)

200 nm
20 nm

(c) c-1
(d)110
100
90
c-2 80
Transmitance %

70

TG %
60 d-3
50
c-3 d-1
40
30 d-2

20
c-4
10
0
4000 3000 2000 1000 600 100 200 300 400 500 600 700
Temperature/C
Wavelength (cm1)

(e) 100 C NO

80
Ag
60
Cps

Ag

40

20

0
0 1 2 3 4 5
Energy/K eV

Fig. 1 Characteristics of SNH biopolymer swollen a SEM image, b TEM image, c FT-IR spectra, d TG curve and e EDX

nanocomposite hydrogel at different heating rates (5, 10,
15, and 20 K min-1). The observed thermogravimetric
curves were moved to higher temperatures with to increase
in heating rate.
The values of initial dehydration temperature (Ti), final
dehydration temperature (Tf), peak temperature (Tp), peak
width (DT), and the degree of conversion at the maximum
rate amax of the TG/DTG, at different heating rates are
listed in Table 1. According to the obtained results, with
increasing heating rate, the values of characteristic tem-
peratures (Tp, Tf, and DT) of the TG/DTG curves also in-
crease. The values of amax decrease with increasing heating
rate. Increasing of heating rate leads to increase of the
maximums on DTG curves and peaks become more widen.
Figure 2b shows the DSC curve, recorded in N2 atmo-
sphere, for the investigated sample at 5 K min-1 heating
rate. It shows an endothermic peak with 1996 J g-1 peak
area in the dehydration process of the hydrogel.
The dependence of the apparent activation energy (Ea)
values to the extent of conversion (a) for the non-isother-
mal dehydration kinetics of the silver nanocomposite hy-
drogel was evaluated from the straight line slope of the
correspondent KAS and Tang isoconversional methods.
Figure 3 shows the variation of the apparent activation

123
Non-isothermal dehydration kinetic study 1387

(a) 1 90

0.3 80
Tang
0.8
70
0.8
KAS
0.6 60

Derivatve

Ea/kJ mol1
1.3

50
0.4 20 K min 1

1.8 40
15 K min1
30
0.2 10 K min1 2.3
5 K min1 20

0 2.8 10
300 330 360 390 420 450
Temperature/K 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
(b) 0.0

5.0
Fig. 3 The activation energy, Ea, plotted as a function of the extent
of conversion, a, for the dehydration of the SNH under non-
isothermal conditions
10.0
W/g

15.0
have shown that the decreasing dependence on Ea on a
corresponds to the kinetic scheme of an endothermic re-
20.0
versible reaction followed by an irreversible one [21]. For
such a process, Ea is limited by the sum of the activation
25.0
300 325 350 375 400 425 450 energy of the irreversible reaction and the enthalpy of the
Temperature/K reversible reaction at low conversions. At high values of
conversions, Ea is limited only by the activation energy of
Fig. 2 a TG and DTG curves, recorded in N2 atmosphere, for the
the irreversible reaction at high a. The dehydration process
investigated sample SNH at different heating rates, b DSC curve
recorded in N2 atmosphere, for the investigated sample of SNH at of SNH likely contains the endothermic stage at low extent
5 K min-1 heating rate of conversions (for w \ 0.40), which is specified by a high
value of the apparent activation energy (from 75.9 to
35.9 kJ mol-1). The decrease in the apparent activation
Table 1 The values of characteristic temperature (Ti, Tp, Tf, DT) and
amax for dehydration of SNH determined by thermogravimetric ana- energy in this range shows an increase in the rate of the
lysis at different heating rates dehydration which may be due to the influence of the water
vapor atmosphere self-generated around the SNH during
b/K min-1 Ti/K Tf/K DT/K amax Tp/K
the thermal dehydration process. In the conversion range of
5 324.6 401.1 76.5 0.781 368.4 a = 0.400.90, the apparent activation energy is nearly
10 317.0 404.0 87.0 0.709 385.9 constant, which is indicative of the single-stage character
15 323.8 416.0 92.3 0.643 394.4 of the irreversible process. In this region in which the ap-
20 323.9 438.1 114.2 0.627 409.9 parent activation energy is approximately independent of
the extent of conversion, the dehydration process can be
assumed to follow a single-step reaction, and the data can
be model fitted to reveal the dehydration mechanism [6].
energy, Ea, as a function of the extent of conversion a. It is The estimated activation energy is lower than a system
seen from Fig. 3, Ea decreases with extent of conversion like poly(acrylic acid) hydrogel. The average value of Ea is
(a). The values of Ea determined by the KAS and Tang 44.7 and 30.4 K mol-1 for poly(acrylic acid) hydrogel [6]
isoconversional methods are in good agreement. and SNH, respectively. It is well-known that carboxylic
The curves obtained in this work (Fig. 3) show a typical acid groups are very susceptible for a strong hydrogen
dependence for reversible reactions according to Vya- bonding both intermolecularly and intramolecularly. We
zovkin et al. [2022]. A decrease in Ea in the range of assume that the hydrogen bonding in SNH is lower than
a \ 0.4 may be an indication of the mass transfer con- poly(acrylic acid) hydrogel because SNH has lower car-
trolled diffusion mechanism [20]. Vyazovkin and Linert boxylic acid groups. The other reason can be attributed to

123
1388 M. R. Sovizi et al.

Table 2 Arrhenius parameters determined by CoatsRedfern and KennedyClark methods (model-fitting), for three kinetic models which best describe the investigated dehydration process

0.9968
0.9968
0.9932

0.9995
0.9982
0.9980
the presence of silver nanoparticles which can catalyze the
dehydration of the SNH.

R2
The apparent activation energy is approximately inde-
pendent of the extent of conversion (a = 0.400.90),

16.76

21.25
4.23

5.10

7.96

8.92
Ln A
which is indicative of the single-stage character of the ir-
reversible process. Therefore, in the region of Fig. 3 in

Ea/kJ mol-1
which Ea is nearly constant, the dehydration reaction can
be assumed to follow a single-step reaction under the re-

23.59
71.67
27.66

33.12
81.20
37.19
spective heating condition, and the data can be model fitted

20 K min-1
to reveal the dehydration mechanism.
In order to find the kinetic model of the hydrogel de-

Model
hydration process by model-fitting, KennedyClark and

D3

D3
R2

R3

R2

R3
CoatsRedfern methods were chosen. Therefore, to find
out the most probable model(s), the non-isothermal kinetic

0.9965
0.9963
0.9924

0.9994
0.9981
0.9978
data of hydrogel dehydration in the conversion region

R2
where the apparent activation energy is approximately
constant (a = 0.400.90) were fitted to each of the com-

19.94

25.30
10.88
5.13
6.20

9.72
Ln A
mon reaction models. As shown in Table 2 R2, R3, and D3
models give a higher coefficients of linear correlations at
10, 15, and 20 K min-1.

Ea/kJ mol-1
In order to determine the reaction kinetic model of de-
hydration process, the Criado method was chosen [23].

79.50
25.91
30.45

37.96
91.55
42.51
Figure 4 shows the theoretical masterplots of f(a).g(a)/

15 K min-1
f(0.5).g(0.5) versus a constructed from experimental data

Model
under different heating rates. The theoretical masterplots

D3

D3
R2
R3

R2

R3
corresponding to the f(a)g(a) functions for D2, D3, R2, and
R3 models are also shown in this figure. It is shown that the

0.9958
0.9949
0.9906

0.9992
0.9977
0.9975
all experimental masterplots of the dehydration process at 5,
10, 15, and 20 K min-1 are conformable with theoretical
R2

masterplots for the corresponding reaction models. The

20.48

26.10
11.10
5.03
6.16

9.89
comparison of the experimental masterplots with theoretical
Ln A

ones revealed that the kinetics of the dehydration of the

hydrogel was most probably describable by these models.
Ea/kJ mol-1

Determination of invariant kinetic parameters

79.89
25.92
30.49

38.48
92.45
43.05
10 K min-1

The method of invariant kinetic parameters allows one to

evaluate both ln A and Ea simultaneously without deter-
Model

mining the reaction model [24].

D3

D3
R2
R3

R2

R3

By the compensation relationship, a linear correlation

[25, 26]
0.9989
0.9988
0.9751

0.9980
0.9979
0.9978

ln Aj a bEa;j 8
R2

was observed in the investigated system, where j is an

35.74
36.43

63.97
64.65
30.18
2.64
Ln A

index that specifies each reaction model fj(a) assumed to

describe the process. The correlation parameters of a and
b in Eq. (8) are the parameters of the linear regression for
Ea/kJ mol-1

the set of ln A and Ea values can be obtained by any

(0.40 B a B 0.80)

120.46
118.33

194.15
192.02
20.69

94.38

method of kinetic parameter calculation based on the

variation of the applied model (a = ln kiso, an artificial
5 K min-1

isokinetic rate constant, and b = 1/RTiso where R and Tiso

Model

are the gas constant and an artificial isokinetic temperature,

D3
D2

D3
D2
R3

R3
KC

CR

respectively).

123
Non-isothermal dehydration kinetic study 1389

1.6 35

1.4 30

25
1.2
f( )g()/f(0.5)g(0.5)

20
1
5 K min 1
15

Ln A
0.8 10 K min1
10 5 k min1
15 K min1
0.6
20 K min1 10 k min1
5
0.4 R3
R2 0 15 k min1
0.2 D2 5
D3 20 k min1
0 10
0.40 0.50 0.60 0.70 0.80 0.90 1.00 10 20 50 80 110

Ea /kJ mol1
Fig. 4 Masterplots of theoretical f(a)g(a)/f(0.5)g(0.5) versus a for
D2, D3, R2 and R3 theoretical reaction models and experimental Fig. 6 The isokinetic relationships (ln A vs. Ea) obtained for the
masterplots for the dehydration of SNH at heating rates of 5, 10, 15 dehydration of SNH using KennedyClark method at different
and 20 K min-1 heating rates

Table 3 The values of a, b, kiso, and Tiso of Eq. (8) obtained by

40 different model-fitting methods for dehydration of SNH (for
0.40 B a B 0.90)
35
b/K min-1 a/min-1 b/mol kJ-1 kiso/min-1 Tiso/K R2
30 CR method
25 5 -2.2506 0.3392 0.1053 354.58 0.9965
10 -1.7695 0.3333 0.1704 360.86 0.9935
Ln A

20 15 -1.2051 0.3098 0.2997 388.23 0.9925

5 k min1
20 -1.3803 0.3035 0.2515 396.29 0.9803
15
10 k min1 KC method
10 5 -2.7750 0.3251 0.0623 369.96 0.9963
15 k min1
10 -2.3198 0.3196 0.0983 376.33 0.9923
5
20 k min 1 15 -1.9054 0.2968 0.1488 405.24 0.9926
0 20 -1.6200 0.2877 0.1600 418.06 0.9836
0 40 80 120
Ea/kJ mol1
different model-fitting methods for dehydration of SNH (in
Fig. 5 The isokinetic relationships (ln A vs. Ea) obtained for the
conversion range of a = 0.400.90 are given in Table 3.
dehydration of SNH using CoatsRedfern method at different heating
rates From Table 3, it can be seen that the isokinetic tem-
peratures (Tiso) lying in the region of the experimental
temperatures and this indicated that the reaction model f(a)
The invariant kinetic parameters, ln Ainv and Einv, are for conversions a C 0.40 was a properly chosen [27].
evaluated from several sets of bi and ai got at different Table 4 shows the calculated values of invariant kinetic
heating rates bi as follows: parameters according to Eq. (9) for both CR and KC
methods. Finally, to determine the unique probable reac-
bi ln Ainv ai Einv 9
tion model, we reconstructed f(a) numerically from ob-
A plot bi vs. ai should be a straight line whose slope and tained invariant kinetic parameters in the range of
intercept allows the evaluation of Einv and Ainv, a C 0.40. The f(a) reconstructed from the experimental
respectively. data at the 20 K min-1 is plotted in Fig. 7. This figure
The artificial isokinetic relationships for dehydration clearly shows the reconstructed f(a) from the experimental
process in the hydrogel, obtained by different model-fitting data, corresponding to the f(a) function for reaction model
methods (CR and KC methods), are shown in Figs. 5 and 6. R3. Jankovic et al. [6] have also shown the reconstructed
The values of a, b, kiso, and Tiso of Eq. (8) obtained by f() function from the experimental data of poly(acrylic

123
1390 M. R. Sovizi et al.

Table 4 Calculated values of invariant kinetic parameters according like poly(acrylic acid) hydrogel but both systems obey from
to Eq. (9) for both CR and KC methods the same reaction model.
Invariant parameter CR method KC method The calculated values of Arrhenius parameters for the R
reaction models (R2 and R3) by model-fitting methods in
Einv/kJ mol-1 26.90 31.07
conversion range of a = 0.400.90 are in good agreement
ln Ainv 6.69 6.96 with values of Ea and ln A obtained by different isoconver-
sional methods and invariant kinetic parameters. The mas-
terplot method and numerical reconstruction revealed that
the most probable model for the dehydration of the hydrogel
2.1 agrees with three-dimensional phase boundary (R3).
1.8

1.5
References
f ( )

1.2
0.9 R3
R2
0.6
20 K min1
0.3
0 4. Jankovic B, Adnadevic B, Jovanovic J. Isothermal kinetics of
0.4 0.5 0.6 0.7 0.8 0.9 1
Fig. 7 The experimental kinetic function, f(a), reconstructed from
model-free analysis of the dehydration of SNH under non-isothermal
conditions for a C 0.40, at 20 K min-1 (b). The solid and dash lines
represent kinetic functions calculated from R2 and R3 theoretical
models
acid) hydrogel, corresponding to the f() function for re-
action model R3.
Conclusions
The kinetics of the non-isothermal dehydration process of
silver nanocomposite hydrogel (SNH) hydrogel was de-
termined from a series of thermoanalytical experiments at
different constant heating rates. The apparent activation
energy decreases with extent of conversion (a). The values
of Ea determined by the KAS and Tang isoconversional
methods are in good agreement. For a B 0.40, dehydration
under considered conditions is complex, which probably
involving a combination of several processes. Diffusion
processes probably participate in the investigated process
which is corresponding to the three-dimensional diffusion
mechanisms.
The approximately constant-Ea region of non-isothermal
dehydration follows a three-dimensional phase boundary (R3)
and a two-dimensional phase boundary (R2) kinetics at high
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