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Kinetic Thermal Degradation of Cellulose, Polybutylene Succinate and a Green

Composite: Comparative Study

Article · January 2015

DOI: 10.12691/wjee-3-4-1

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World Journal of Environmental Engineering, 2015, Vol. 3, No. 4, 95-110
Available online at http://pubs.sciepub.com/wjee/3/4/1
© Science and Education Publishing
DOI:10.12691/wjee-3-4-1

Kinetic Thermal Degradation of Cellulose, Polybutylene

Succinate and a Green Composite: Comparative Study
Benarbia Abderrahim1, *, Elidrissi Abderrahman1, Aqil Mohamed1, Tabaght Fatima1, Tahani Abdesselam2,
Ouassini Krim3
1
Laboratory of Applied Chemistry and Environment- Department of Chemistry, Faculty of Sciences, Mohammed Premier University,
Oujda, Morocco
2
Laboratory of Physical Chemistry of Natural Resources and Environment - Department of Chemistry, Faculty of Sciences,
Mohammed Premier University, Oujda, Morocco
3
The chemical measuring room - Department of Chemistry, Faculty of Sciences, Mohammed Premier University, Oujda, Morocco
*Corresponding author: [email protected]

Abstract Polybutylene succinate (PBS), classed as biopolymer, was synthesized by condensation of succinic acid
with a lower excess of (1, 4) butanediol. The synthesized polymer was analyzed by FTIR, RMN, DSC and
ATG/ATD. Thermal degradation kinetics was investigated for cellulose, polybutylene succinate, physical blend of
both polymers (cellulose (80%) + PBS (20%)) and compared with polycaprolactone by dynamic thermogravimetry,
under nitrogen atmosphere from room temperature to 480 °C, at constant nominal heating rates: 5, 10 and 15 °C/min,
respectively. The Kissinger, Friedman, Flynn-Ozawa-Wall and Coatse - Redfern (modified) methods were
developed and the corresponding activation energies, frequency factors and reaction orders were determined.
Keywords: polybutylene succinate, synthesis, characterization, cellulose, blend, polycaprolactone,
thermogravimetry
Cite This Article: Benarbia Abderrahim, Elidrissi Abderrahman, Aqil Mohamed, Tabaght Fatima, Tahani
Abdesselam, and Ouassini Krim, “Kinetic Thermal Degradation of Cellulose, Polybutylene Succinate and a
Green Composite: Comparative Study.” World Journal of Environmental Engineering, vol. 3, no. 4 (2015): 95-
110. doi: 10.12691/wjee-3-4-1.

scission of the chains [5] and the cellulose has to undergo

unhealthy chemical process with harsh alkali and acid
1. Introduction treatment to improve its properties for industry.
Polybutylene succinate (PBS) has received extensively
In morocco, plastic industry is one of the largest attention, as one of the most representative and generally
chemical industrial activities in terms of quantity and acknowledged biodegradable aliphatic polyester [6]. This
diversity of application sectors, primarily dependent on polymer has excellent melt processability and good
fossil resources [1], these non biodegradable very long life chemical resistance [7]. Due to its high crystallinity
plastics, represent a source of visual pollution, discharge degree, PBS exhibits a slow biodegradation rate [8], either
soil and marine environment pollution. The law 22.10 in polymer and co polymer [9,10,11,12,13]. Now it is well
proposes the use of biodegradable plastics as alternative known that PBS can be produced from renewable
solution to overcome fossil resource plastic exploitation resources, by reacting succinic acid [14-21] and 1.4
[2]. butandiol [22,23,24]. In order to improve the physical
Biodegradable polymers, such as cellulose, were properties of PBS and contributing to reduce the
investigated in order to reduce environmental pollution overdependence on petroleum products, some methods
caused by plastic wastes [3,4]. Cellulose is the most have been reported such as adding nano clay [25,26,27];
abundant biopolymer on earth; its primary structure is a via cross linking reaction [28,29,30], but also by blending
linear homopolymer of glucose residues having D with other polymers to reach these objectives. Researchers
configuration and connected by β-(1→4) glycosidic are now focusing their efforts more on green materials
linkages. The two chain ends are chemically different, one specially cellulosics. Green composites obtained via
end has a D-glucopyranosyl group in which the anomeric mixing synthetic or/and natural polymers are materials
carbon atom is involved in a glycosidic linkage, whereas having ecofriendly attributes that are technically and
the other end has a D-glucopyranose residue in which the economically feasible while minimizing the generation of
anomeric carbon atom is free. This latter cyclic hemiacetal pollution [31].
function is in α, β anomeric equilibrium via a small The aim of the present work is to elaborate a green
proportion of free aldehyde form; the degree of composite by blending cellulose (80 %) and synthesized
polymerization (DP) of native cellulose depends on it polybutylene succinate (20%). The thermal characteristics
source. Indeed, the combination of procedures required to of cellulose, PBS and the green composites will be studied.
isolate, purify, and solubilize cellulose generally causes To better understand green blend polymer thermal
96 World Journal of Environmental Engineering

stability, all results will be compared with PCL thermal 2.4.2. Rayon X analysis DRX
degradation data. Polycaprolactone (PCL) is a much The rayon X analysis was carried out with Shimadzu
known biodegradable polymer derived from petroleum RX (Oujda – Morocco)
resources. PCL is intensively studied in terms of its
synthesis and properties evaluation. Its importance owes 2.4.3. Calorimetric Anaslysis
to its potential applications in various medical and non-
Differential scanning calorimetric (DSC) analysis were
medical fields like agriculture, medicine, pharmacy, and
performed by a TA DSC Q20 (United State). About 10 mg
also as environmentally friendly materials in packaging
of sample was placed in sealed aluminum capsules.
industry.
Samples were subjected to two scan from - 40 to 200 ° C
with a rate of 10 °C /min. The crystallinity degree (Xc)
[32], is calculated using the equation 1:
2. Materials and Methods
∆H m
X c (%) = x100 (1)
2.1. Materials ( w poly x∆H100 )
Cellulose (Mn = 300 g/mol), polycaprolactone (Mn =
10000 g/mol), 1, 4 - butanediol, succinic acid, paratoluene ΔHm: Polymer melting enthalpy calculated from second
sulfonic acid (APTS), acetic anhydride, titanium butoxide, scan,
pyridine, phenolphthalein, Potassium hydroxide, toluene, Wpoly: Massic fraction of polymer in blend (20%)
dichloromethane and ether were purchased from Sigma– ΔH100: Melting enthalpy of polymer100% cristallin
Aldrich Chemical Co. All reagents were used as received.
2.4.4. Fourier Transform Infrared (FTIR) Spectroscopy
2.2. Polybutylene Succinate Synthesis FTIR spectra were recorded using FTIR B8400S
Shimadzu (Oujda- Morocco) between 4000 and 600 cm-1
The polybutylene succinate was synthesized in two at resolution of 4 cm-1, using potassium bromide pellet
steps, by melting condensation using 1, 4 - butanediol, method.
succinic acid and paratoluene sulfonic acid. In a three-
necked round bottom flask equipped by Dean Stark, we 2.4.5. Nuclear Magnetic Resonance (1H-NMR)
introduced 1, 4 - butanediol (0.06 mol), succinic acid
The NMR spectra were recorded in UATARS - CNRST
(0.05 mol), paratoluene sulfonic acid (APTS) (0.1%) and
– RABAT- MOROCCO using BRUKER 250 MHZ
20 ml of toluene. The mixture was maintained under
spectrometer. Deuterated chloroform (CDCL3) with
continuous stirring at 140 °C during 24 hours to obtain
trifluoroacétic acid are used as solvent and
oligomers compounds. The organic solvent was
tetramethylsilane (TMS) as internal reference.
eliminated, we used rotary evaporator connected pump to
create a vacuum. After removing the organic solvent 2.4.6. Hydroxyl Value and Molecular Weight Number
Titanium Butoxide (0.1%) catalyst was added to the Average
mixture by maintaining constant stirring, the temperature
was carried out at 240 °C under vacuum for another 6 The polymer must be exactly weighted between (1 and
hours. The reaction mixture was dissolved in 2 g) placed in a 250 ml flask, then 20 ml of the acetylating
dichloromethane and precipitate in ether excess. White mixture (1 × V acetic anhydride and pyridine 3 × V) added,
polymer was removed by filtration and kept at 60°C under and the mixture is stirred until complete dissolution of the
vacuum for 24 hours. material was reached. The content was refluxed for 30 min,
then the solution was cooled down at room temperature
and 50 ml cold water was added. The free acetic acid was
2.3. Blend (cellulose (80%) + polybutylene titrated with standard potassium hydroxide (1 N) using
succinate (20%)) Preparation phenolphthalein as indicator. The procedure was repeated
An amount of cellulose (80%) and Polybutylene for blank titration under similar condition [33].
succinate (20%) was added to dichloromethane under
56.1× N × ( B − A)
constant stirring for 3 hours at room temperature. The HydroxylValue = (2)
mixture was poured in Petri dish, and kept at room W
temperature for solvent evaporation over night then dried N: Potassium hydroxide normality.
in desiccator containing a desiccant powder (P2O5) for 24 A: Volume of Potassium hydroxide solution used for
hours under vacuum and a blend materiel was formed. titration.
B: Volume of Potassium hydroxide solution used for
2.4. Characterization blank titration.
W: Weight of Copolymer sample taken.
2.4.1. Thermogravimetric Analysis TGA/DTA The average number of molecular weight was
Thermogravimetric analysis (TGA) was carried out calculated using the following expression:
with Shimadzu TA 60 (Oujda- Morocco). Samples were 103 × W
placed in alumina crucibles and were heated from room Mn = (3)
temperature to 480 °C under 50 ml/min N2 flow. Alumina N × (V − V0 )
crucible was used as reference. Nominal heating rates of 5, Where:
10 and 15 °C/min were settled, and continuous records of W: Weight of copolymer.
sample temperature, sample weight, its first derivative and N: Titer of a solution of Potassium hydroxide in ethanol.
heat flow were recorded.
 World Journal of Environmental Engineering 97

V: Volume of titrated solution. heating rates can be used to study the thermal
V0: Blank volume of titrated solution. decomposition of polymeric materials. Mathematical
models of thermal decomposition reactions make possible
2.4.7. Thermal Degradation: Theoretical Approach the understanding of the whole process and the
The thermal degradation kinetics can provide useful quantitative conclusions are useful for practical
information for polymeric materials processing and use applications from apparent kinetic parameter. The
conditions optimization. TGA/DTA use in kinetic Kissinger [34], Friedman [35], Flynn-Ozawa-Wall [36]
parameters determination has broadly raised interest and Coatse-Redfern (modified) [37] methods were
during last years. Moreover, the possibility of using developed Table 1, the corresponding activation energies,
different thermal histories can provide further frequency factors and reaction orders were determined
informations on the kinetic nature of the degradation [38].
process. Isothermal or dynamic TGA tests at constant

Table 1. Kinetic methods

Methods Equations Plots
dα Ea dα
1
Friedman Ln = Ln[Af(α)] + (− ) Y = Ln( ), X = [35]
dt RT dt
T
β Ea AR β
1
Kissinger Ln( ) = (− ) + Ln( ) Y = Ln � 2 � , X = [34]
Tp2 RTp Ea Tp
T 2p
Ea 1
Flynn-Wall-Ozawa Ln(β) = − + const Y = Ln(β) , X = [36]
RT T
β −AR Ea
Coatse- Redfern Ln[ ] = Ln[ ]− 1
2RT Ea Ln(1 − α) RT
β
Y = Ln( 2 ), X = [37]
(modified) T 2 �1 − � T
T
Ea
3.1. Synthesized of Polybutylene Succinate
3. Results and Discussion Synthesis of Polybutylene succinate by classical
polycondensation reaction is presented in Scheme1:

APTS
HOOC (CH2)2 COOH + HO (CH2)4 OH Oligomres

Ti(OC4H9)4
H O (CH2)4 O C (CH2)2 C O (CH2)4 O H
O O n
Scheme1. Synthesis of Polybutylene succinate (PBS) by polycondensation reaction

the peak present at 1341 cm-1 is assigned to –COO- bond

3.1.1. FTIR Characterization stretching vibration. The signal at 1158 cm-1 is a
The FTIR spectrum of Polybutylene succinate presented in characteristic of C–O–C stretching vibration in the
Figure 1 shows an absorption band at 2947cm-1 assigned to repeated –OCH2CH2 unit. These vibration bands described
the C–H bond stretching. The band intense appeared at below that the polycondensation reaction was successful
1716cm-1 correspond to carbonyl C=O stretching vibration and the polycondensat was obtained with a high yield.
characterizing the formation of ester group. Furthermore,

Figure 1. FTIR spectrum of Polybutylene Succinate synthesized

98 World Journal of Environmental Engineering

3.1.2. 1H-NMR Characterization CH2-OCO- group (c). Furthermore, the centered methylene
1
The H-NMR spectrum of Polybutylene Succinate is protons of 1, 4 - butanediol (b) gives a multiply at 1.6 ppm.
shown in Figure 2. For the analysis by the NMR method, The little peak at 3.4 ppm is attributed to methylene
the different structural units in the NMR spectrum are proton of CH2-O- at the chain extremity. The triply
distinguished. The peak present at 2.65 ppm is attributed appearing at 4.3 ppm shows clearly that the reaction takes
to the methylene protons of the succinic acid unit (a). The place between the diol and the diacid.
peak at 4.3 ppm is attributed to methylene protons of -

Figure 2. 1H-NMR spectrum of the polybutylene succinate

relatively obtained at around Tc = 62.5 °C. We observed a

3.1.3. DSC Analysis little crystallization peak at Tc = 90.2°C followed by pre-
In the Figure 3, during DSC run the main melting peak melting inflexion at Tpm = 100°C.
is at Tm ≈ 111 °C, The same results were obtained by K.
Chrissafis and al [40]. The main crystallization peaks are

Figure 3. DSC thermograms of the polybutylene succinate

 World Journal of Environmental Engineering 99

Figure 4. (a) RX spectrum of polybutylene succinate, (b) Melting enthalpies of the polybutylene succinate

From the Figure 4.a, the polybutylene succinate present (*) Xc (%): crystallinity degree in blend
height crystallinity and from the Figure.4.b, the Where ΔHm = 57.28 J/g is the melting enthalpy
crystallinity degree (Xc) in blend was calculated calculated from second scan, wpoly is the polymer massic
according to the equation 1: fraction in the blend (20%) and it is well known that ΔH100
= 110.3J/g melting enthalpy of polybutylene succinate 100%
∆H m
=X c (%) = x100 25.85% (1) cristallin [41].
(
w poly x∆H100 )
Table 2. Structure and properties of the prepared polyester.
Tm (°C) ΔHf J/g Χc (%) Mn (g/mol) Hydroxyl Number
111 57.28 25.85 1040 1.34
groups stretching. Bands at 2906 cm-1and 1373 cm-1 are
3.2. FTIR Characterization of the Commercial assigned to stretching and deformation vibrations of C-H
Cellulose and Polycaprolactone group in glucose unit. The absorption band at 898 cm-1 is
characteristic of β-glycosidic linkage between glucose
3.2.1. FTIR Characterization of the Commercial units. The signal at 1061cm-1 is assigned to -C-O- group
Cellulose of secondary alcohols and ethers functions existing in the
From FTIR spectrum of the cellulose (Figure 5), the cellulose chain backbone.
absorption band at 3391cm-1 is assigned to hydroxyl
100 World Journal of Environmental Engineering

Figure 5. FTIR spectrum of the commercial cellulose

2860cm-1 is assigned to C-H hydroxyl groups symmetric

3.2.2. FTIR Characterization of the Commercial stretching. The absorption band at 1722 cm-1 is assigned to
Polycaprolactone -C=O stretching vibrations of the ester carbonyl group.
From FTIR spectrum of the chosen polycaprolactone The absorption at 1238 cm-1 is assigned to C-O-C
(Figure 6), we remarked the following bands. The asymmetric stretching, but, the signal at 1160 cm-1 is
absorption band at 2940 cm-1 is assigned to the C–H assigned to -C-O-C- symmetric stretching.
hydroxyl groups asymmetric stretching. The band at

Figure 6. FTIR spectrum of the commercial polycaprolactone

reported in the Figure 7, we remarked that all

3.2.3. FTIR Characterization of the characteristic bands of the polymer functional groups are
Cellulose(80%)/PBS (20%) Composite depicted, but the intensity of C=O stretching vibrations of
From the FTIR spectrum of the physical blend the ester carbonyl group is lower than the intensity in pure
(cellulose (80%) and Polybutylene succinate (20%)) Polybutylene succinate.
 World Journal of Environmental Engineering 101

Figure 7. FTIR spectrum of the cellulose (80%)/PBS (20%) blend

2.92% is observed at T° = 306.30 °C. The physical blend

3.3. Thermal Kinetic Studies between cellulose (80%) and polybutylene succinate (20%)
presents - 2.92 % weight loss at 65.10 °C. If we compare
3.3.1. Comparative Thermal Degradation Kinetic between cellulose and the blend, we can see that
Studies of Cellulose, Polybutylene Succinate and thermostability temperature increases about 15.85 °C for
physical Blend of both Polymers the same percentage (- 2.92%), and we can note that
Thermal degradation of polybutylene succinate, cellulose adding only 20% of polybutylene succinate to the
and physical blend of both polymers was studied by their cellulose (80%) increases the thermostability. It is also
mass loss during heating. From thermogravimetric curves interesting to promote the biodegradability properties of
(TGA) (Figure 8), it can be seen that cellulose presents a PBS by physical blending [40,41,42]. The variations of
relatively lower thermostability. The polybutylene succinate DTA results for polybutylene succinate and physical blend
presents relatively good thermostability, since no significant of cellulose ((80%) and poly (butylene succinate) (20%))
weight loss occurred until 300 °C, and the weight loss of - are reported in Table 3.

Table 3. Differential thermal analysis (DTA) variations of cellulose, polybutylene succinate and the physical blend of both polymers at
heating rate (β: 10 °C/min).
DTA peak DTG peak
Samples Char yield Nature of DTA peak range
Ti maxima maxima Mn(g/mol)
β = 10 °C/min at 480 °C DTA peak (°C)
temperature (°C) temperature (°C)
56.65 Endo 30.00 - 96.56
Cellulose 100 % 49.25 3.62 % 350.10 300
360.85 Endo 115.53 - 392.46
PBS 112.79 Endo 69.08 -154.60
306.30 1.27 % 395.52
100 % 393.79 Endo 343.92 - 437.27 1040
63.49 Endo 33.14 - 92.32
Cellulose 80% 110.08 Endo 97.04 -127.07
65.10 3.90 % 354.35 ----
+PBS20 % 358.02 Endo 310.53 -382.08
389.64 Endo 382.08- 418.60

TGA
%
100.00

Cellulose
50.00 PBS
Blend

-0.00
-0.00 100.00 200.00 300.00 400.00 500.00
Temp [C]

Figure 8. TGA dynamic thermograms of Cellulose, PBS, and physical blend of both polymers at heating rate (β: 10 °C/min)
102 World Journal of Environmental Engineering

Figure 9. Derivative thermogrammes DrTG curves of (1) cellulose, (2) Polybutylene succinate and (3) the physical blend of both polymers at different
heating rates β: 5 °C/min; 10 °C/min and 15 °C/min. ; Tp is the fastest decomposing temperature used by Kissinger equation

Since, every isoconversional method has different Polybutylene succinate and the physical blend of cellulose
errors, the use of more than one method can give a range ((80%) and polybutylene succinate (20%)) were estimated
of values for the activation energy at every particular using Ozawa, Flynn and Wall (OFW) (Figure 10), Friedman
value of α. In our studies we used four methods. (Figure 11), Coatse-Redfern (modified) (Figure 12) and
Degradation activation energy of the studied cellulose,
 World Journal of Environmental Engineering 103

Kissinger (Figure 13) methods. All results are presented in to improper integration [19]. Activation energies calculated
Table 4 –Table 7. by Friedman is the double with acceptable values of
From the data in Table 4-Table 7, activation energies correlation coefficient. The activation energy calculated
values calculated by Ozawa method and Coatse-Redfern by Kissinger method is the lowest in the case of cellulose
(modified) method are close for cellulose, polybutylene with coefficient of determination R2 = 0.763 and physical
succinate and the physical blend of cellulose ((80%) and blend of cellulose ((80%) and polybutylene succinate
polybutylene succinate (20%)) with acceptable correlation (20%)) with coefficient of determination R2 = 0.861. In
coefficient close and superior to 90% in major cases, the our studies, we used activation energies calculated by
little difference can be explained by a systematic error due OFW method.

Figure 10. Ozawa plots of (1) cellulose, (2) polybutylene succinate, (3) blend of cellulose (80%) and polybutylene succinate (20%), fractional extent of
reaction: α = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9
104 World Journal of Environmental Engineering

Table 4. Activation energies (Ea) of cellulose, polybutylene succinate and Blend (cellulose 80%, PBS 20%) using fit of plots Flynn-Wall-Ozawa
(FWO) method
Cellulose Polybutylene succinate Blend (cellulose 80%, PBS 20%)
Α Ea (FWO) (Kj/mol) R2 Ea (FWO) (Kj/mol) R2 Ea (FWO) (Kj/mol) R2
0.1 56.49 0.842 119.91 0.998 255.70 0.663
0.2 109.97 0.937 117.88 0.999 196.63 0.919
0.3 128.13 0.967 133.95 0.997 196.02 0.888
0.4 137.44 0.980 138.94 0.990 187.01 0.888
0.5 141.16 0.987 147.02 0.981 186.39 0.891
0.6 141.07 0.985 155.35 0.980 187.52 0.817
0.7 141.40 0.992 160.54 0.983 189.47 0.803
0.8 140.69 0.994 163.68 0.989 188.57 0.987
0.9 190.06 0.534 179.07 0.999 190.55 0.968
Mean 131.82 146.26 197.54

Figure 11. Friedman plots of (1) cellulose, (2) polybutylene succinate and (3) blend of cellulose (80%) and polybutylene succinate (20%), fractional
extent of reaction: α = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9
 World Journal of Environmental Engineering 105

Table 5. Activation energies (Ea) of cellulose, polybutylene succinate and their blend (cellulose 80%, PBS 20%) using fit of plots Friedman (F)
method
Cellulose Polybutylene succinate Blend (cellulose 80%, PBS 20%)
Α Ef (Kj/mol) R2 Ef (Kj/mol) R2 Ef (Kj/mol) R2
0.1 147.08 0.986 239.21 0.999 343.11 0.5
0.2 268.14 0.981 237.26 0.999 434.04 0.932
0.3 283.87 0.968 290.30 0.980 414.58 0.827
0.4 276.99 0.999 278.15 0.965 348.48 0.883
0.5 278.63 0.993 314.68 0.972 358.97 0.874
0.6 278.37 0.996 330.76 0.988 374.28 0.730
0.7 272.36 0.999 320.50 0.990 375.29 0.805
0.8 268.57 0.997 333.31 0.999 360.42 0.971
0.9 269.49 0.928 400.94 0.986 373.43 0.948
Mean 260.38 305.01 375.84

Figure 12. Coatse-Redfern (modified) plots of (1) cellulose, (2) polybutylene succinate and (3) blend of cellulose (80%) and polybutylene succinate
(20%), fractional extent of reaction: α = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9
106 World Journal of Environmental Engineering

Table 6. Activation energies (Ea) of cellulose, polybutylene succinate and their blend (cellulose 80%, PBS 20%) using fit of plots Coatse-
Redfern (CR) (modified) method:
Cellulose Polybutylene succinate Blend (cellulose 80%, PBS 20%)
Α Ea (CR) (Kj/mol) R2 Ea (CR) (Kj/mol) R2 Ea (CR) (Kj/mol) R2
0.1 46.87 0.784 110.64 0.998 245.91 0.643
0.2 100.19 0.923 107.11 0.999 187.60 0.916
0.3 118.24 0.965 122.85 0.996 185.55 0.876
0.4 126.68 0.974 127.23 0.988 176.89 0.876
0.5 131.64 0.985 136.41 0.980 176.26 0.879
0.6 131.49 0.982 143.45 0.975 176.84 0.801
0.7 131.66 0.993 150.32 0.978 179.64 0.780
0.8 129.37 0.993 151.57 0.989 177.71 0.987
0.9 181.00 0.511 168.02 0.999 179.23 0.967
Mean 121.90 135.28 187.29

Figure 13. Kissinger plots of (1) cellulose, (2) polybutylene succinate and (3) blend of cellulose (80%) and polybutylene succinate (20%)
 World Journal of Environmental Engineering 107

Table 7. Activation energies (Ea) of cellulose, polybutylene succinate and their blend (cellulose 80%, PBS 20%) using fit of plots Kissinger (K)
methods.
Cellulose Polybutylene succinate Blend (cellulose 80%, PBS 20%)
Α Ea(K) (Kj/mol) R2 Ea(K) (Kj/mol) R2 Ea(K) (Kj/mol) R2
117.00 0.763 175.89 0.929 174.32 0.861
The terms 1/Tp and Ln (β/Tp2) could be obtained from activation energy is reported in Table 7. In case of
DrTG results of heating rate (Figure 9). Therefore, 1/Tp cellulose, Ea =117.00 Kj/mol with a correlation coefficient
was represented in (x) axis and Ln (β/Tp2) denoted as (y) of 0.763, for polybutylene succinate, Ea= 175.89 Kj/mol
axis. After three heating rates, the three values of Tp were with a correlation coefficient of 0.929, and for the blend of
substituted into the equation (11), a graph and a linear cellulose (80%) and polybutylene succinate (20%)
regression equation could be acquired. Calculated Ea=174.32 Kj/mol with correlation coefficient of 0.861.

Figure 14. Dependence of activation energy (Ea) on mass conversion (α), as calculated by OFW methods for cellulose, polybutylene succinate and
blend of cellulose (80%) and polybutylene succinate (20%)

According to the graph in Figure 14, the activation * Ea(PBS) = activation energy (Ea) on the mass
energy of the blend [cellulose (80%) and polybutylene conversion (α), as calculated by OFW method for the
succinate (20%)] has the largest value: poly (butylene succinate).
● For 0.1 ≤ α ≤ 0.2 EaBlend decrease > Ea(PBS) stable, * EaBlend = activation energy (Ea) on the mass conversion
EaCellulose increase, (α), as calculated by OFW method for the blend
● For 0.2 ≤ α ≤ 0.5 EaBlend > Ea(PBS) ≈ EaCellulose [cellulose (80%) and poly (butylene succinate) (20%)].
● For 0.6 ≤ α ≤ 0.8 EaBlend > Ea(PBS) increase > EaCellulose Reaction order (n) and pre-exponential factor (A) were
decrease determined in our approach by the use of equation 10.
● For α = 0.9 Ea Blend ≈ Ea(PBS) ≈ Ea Cellulose
β dα
* EaCellulose = activation energy (Ea) on the mass ( )
conversion (α), as calculated by OFW method for the Ln dT = nLn(1 − α ) + Ln( A) (10)
Ea
cellulose exp(− )
RT

𝛽𝛽𝛽𝛽𝛽𝛽
( )
Figure 15. Relationship between 𝐿𝐿𝐿𝐿 𝑑𝑑𝑑𝑑
𝐸𝐸 and Ln (1 - α) at β=10 °C/min for pyrolysis of the Cellulose(1), the PBS(2) and the physical blend
exp ⁡(− 𝑎𝑎 )
𝑅𝑅𝑅𝑅
[Cellulose (80%) + PBS (20%)](3): experimental and correlated results [43]
108 World Journal of Environmental Engineering

By using Microcal Origin as informatics software and pre- exponential factor A = 2.6.1011 min-1, for the blend
linear fit as application of these software (Figure 15), we [cellulose (80%) and polybutylene succinate (20%)] n =
found that for cellulose n = 1.68 and Ln(A) = 24.89, and 1.88 and Ln(A) = 35.89 and pre exponential factor A =
pre exponential factor A = 6.45.1010 min-1, for 3.89.1015. All results are summarized in Table 8.
polybutylene succinate n = 1.8 and Ln(A) = 26.30 and

Table 8. calculated values of activation energy, exponent n and pre-exponential factor for the thermal reaction mechanism of cellulose, PBS
and the physical blend (Cellulose (80%) + PBS (20%))
Sample Ea(Kj) n Pre-exponential factor A (min-1)
Cellulose 131.82 1.68 6.45.1010
Polybutylene succinate 146.26 1.80 2.6.1011
Blend of Cellulose (80%) + PBS (20%) 197.54 1.88 3.89.1015
The results show that the blend increases the activation Table 9. Activation energies of polycaprolactone using fit plots by
energy of thermal degradation and the reaction rate is Kissinger methods.
close to second order. It also promotes the rate of thermal Activation energy (Kj/mol)
degradation with high value of pre-exponential factor of Sample Kissinger method *αmax R2
(second reaction)
3.89.1015 min-1 including most of two states of general
Polycaprolactone 195.91 0.63 0.931
degradation mechanism: thermal disorganization of the
* Where αmax is the conversion corresponding to the maximum of a
structural blend polymer, which allows rapid thermal differential kinetic curve.
degradation of carbonic chains.
Table 10. Activation energies (Ea) of the polycaprolactone using fit
3.3.2. Comparative Thermal Degradation Kinetic of plots Flynn-Wall-Ozawa (FWO) method
Studies between the Blend [cellulose (80%) + PBS Activation energy
(20%)] and Polycaprolactone (PCL) Conversion α (Kj /mol) R2
Ozawa method
Thermal degradation of PCL was recently studied [44, 0.1 91.78 0.992
45, 46]. Persenaire et al. proposed a degradation 0.2 143.75 0.946
mechanism based on the results obtained from high- 0.3 168.78 0.958
resolution thermogravimetric analysis coupled to mass 0.4 179.39 0.980
spectrometry (MS) and Fourier transform infrared 0.5 183.29 0.989
spectrometry [44]. They concluded that PCL degradation 0.6 187.44 0.993
proceeds via elimination reaction which produces CO2, 0.7 191.05 0.997
0.8 190.54 0.998
CO and 5-hexenoic acid, and via unzipping depolymerization
0.9 190.60 0.999
to form ε-caprolactone. Mean 169.63 ---

DrTGA
%/min
DrTGA CAPROLACTONE
0.00

-10.00
667.81x
K

-20.00
675.80K

-30.00

687.53x
K

-40.00

300.00 400.00 500.00 600.00 700.00 800.00 900.00

Temp [K]

Figure 16. DrTGA DTG curves of polycaprolactone at different heating

rates β: 5 °C/min; 10 °C/min and 15 °C/min. ; Tp is the most rapidly Figure 18. Ozawa plots of polycaprolactone fractional extent of reaction:
decomposing temperature used by Kissinger equation α =0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9

TGA ATG POLYCAPROLACTONE REACTION RATE 10

%
100.00
305.00癈
-2.98%

50.00

-0.00
-0.00 100.00 200.00 300.00 400.00 500.00
Temp [C]

Figure 19. TGA dynamic thermograms polycaprolactone at heating rates

β: 10 °C/min
Figure 17. Kissinger plots of polycaprolactone
 World Journal of Environmental Engineering 109

In the case of PCL, the terms 1/Tp and Ln (β/Tp2) could Kissinger activation energy (Ea= 195.91 Kj/mol) was
be obtained from DrTG results (Figure 16). Thus, 1/Tp determined for the reaction (Table 9) with a correlation
was represented in (x) axis and Ln (β/Tp2) denoted as (y) coefficient value of 0.931 and αmax = 0.63. The values
axis (Figure 17). Using three heating rate values and by calculated by Kissinger method were nearest to values of
substituting three Tp values into the equation (13), a graph the activations energy (169.63 Kj/mol) calculated by
and a linear regression equation could be acquired. The Ozawa method (Figure 18) and Table 10.

Figure 20. Activation energy (Ea) dependence on mass conversion (α), as calculated by OFW method for the blend [cellulose 80%, polybutylene
succinate 20%] and polycaprolactone

From Figure 20, the physical blend has the highest composite blend [cellulose (80%) and synthesized
activation energy and takes place between fractional polybutylene succinate (20%)] and polycaprolactone are
extent of reaction α = 0.1 to 0.4. An inverse thermal inverse between α = (0.1- 0.4) and have the same values
character of the activation energies between blend between α = (0.5- 0.9).
polymer and commercial polycaprolactone was remarked.
The energies of the blend [cellulose (80%) + polybutylene
succinate (20%)] decreases while activation energies of Acknowledgments
commercial polycaprolactone increases. Between
fractional extent of reaction α = 0.5 to 0.9 activation This work was supported by CNRST under grant no:
energies of the blend [cellulose (80%), polybutylene PPR/2015/17. We thank greatly the CNRST for its support,
succinate (20%)] and commercial polycaprolactone take and the anonymous reviewers for their careful review and
the same allure. valuable suggestions on the manuscript.

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