J Therm Anal Calorim

DOI 10.1007/s10973-017-6666-9

Catalytic effect of lead oxide nano- and microparticles on thermal

decomposition kinetics of energetic compositions containing
TEGDN/NC/DAG
Vahid Mirzajani1 • Khalil Farhadi1 • Seied Mahdi Pourmortazavi2

Received: 3 February 2017 / Accepted: 28 August 2017

 Akadémiai Kiadó, Budapest, Hungary 2017

Abstract The catalytic effect of lead oxide nano- and Introduction

microparticles (PbO) on the thermal behavior and decom-
position kinetics of energetic formulations composed of Triethylene glycol dinitrate (TEGDN), which commonly
nitrocellulose (NC), triethyleneglycol dinitrate (TEGDN) utilized as an energetic plasticizer in propellant and
and diaminoglyoxime (DAG) was investigated by simul- explosive formulations, is a nitrated alcohol ester attained
taneous thermogravimetric analysis and differential scan- from the triethylene glycol. This energetic compound with
ning calorimetry. The results show that lead oxide nano- the chemical structure shown in Scheme 1 is prepared as a
and microparticles could significantly alter thermal pattern pale yellow oily liquid [1]. Triethylene glycol dinitrate is
of the studied energetic compositions. The effect of lead somewhat similar to the nitroglycerin and commonly is
oxide content on thermal behavior of energetic composi- being considered as a replacement for the nitroglycerin in
tions was also studied, and the results revealed that addi- the propellants due to its lower sensitivity. TEGDN/NC as
tion of different amounts of lead oxide caused to shift in the an energetic mixture is composed of triethyleneglycol
DSC peaks. Moreover, the catalyst decreases activation dinitrate and nitrocellulose, while this composition might
energy of the decomposition stage of energetic composi- be utilized in the double-base propellant formulations.
tion at about 20–40 kJ mol-1. However, the catalyst Diaminoglyoxime (DAG), as an explosophore, is utilized
enhances decomposition temperature of TEGDN/NC/DAG in the rocket propellant compositions as an additive for
energetic compositions. By the aid of DSC data resulted by providing both effects of ballistic modification and cooling
non-isothermal methods, the thermokinetic parameters [2–5]. Meanwhile, catalyst addition to the propellant for-
such as activation energy (Ea), frequency factor (A), the mulations may improve their combustion performance
critical ignition temperature of thermal explosion, the self- effectively [6]. Lead compounds are widely utilized to
accelerating decomposition temperature (TSADT) and also achieve this aim and applied as the ballistic modifiers in the
thermodynamic parameters of the studied energetic com- solid propellant compositions [7].
positions were calculated and compared. Transition metal oxides (TMOs) are imperative class of
chemicals with the wide range of applications in various
Keywords Lead oxide  Nanoparticles  Combustion areas of material science, chemistry and physics [8]. TMOs
catalyst  Kinetic parameters  TEGDN  Nitrocellulose  such as PbO, CuO, Fe2O3 and TiO2 are utilized in the
Energetic compositions  Thermal decomposition production of propellants as catalyst. The particle size of
TMOs is highly effective in their catalytic efficiency, while
nano-sized TMOs could provide interested catalytic effects
& Seied Mahdi Pourmortazavi in the decomposition of energetic compositions [9–11].
pourmortazavi@yahoo.com
Nano-sized TMOs unveil exclusive physicochemical
1
Department of Analytical Chemistry, Faculty of Science, properties than those of bulk and these nanoparticles have
Urmia University, Urmia, Iran received considerable attention recently due to their cat-
2
Faculty of Material and Manufacturing Technologies, Malek alytic, magnetic and electronic properties [8].
Ashtar University of Technology, Tehran, Iran

123
 V. Mirzajani et al.

Scheme 1 Chemical structure O

of triethylene glycol dinitrate
(TEGDN)
O O O N
N O O O

Nanomaterials have attained incredible attention due to to them and their NC content was reduced to 65 or 63%,
their specific characteristics, i.e., high surface area, small respectively. The energetic samples were prepared homo-
pore size, and their possible production in three dimen- geneously as proposed previously by Refs. [5, 7].
sional forms, which make enable their development as the
advanced materials with the sophisticated applications FT-IR, NMR, SEM and XRD characterizations
[12]. Thus, investigation on the effect of nanoparticles on
thermal behavior and decomposition kinetic of energetic Diaminoglyoxime was characterized after synthesis and
formulations and compositions is vital in order to acquire purification by NMR and FT-IR techniques. NMR spec-
valuable information about safe storage, handling and uti- trum of the compound in DMSO was recorded on a
lization of the compositions contained nanoparticles. This BRUKER 250 MHZ spectrometer. The IR spectrum of
valuable knowledge could be resulted by thermal analysis DAG was obtained on a FT-IR spectrometer (PerkinElmer
systems, i.e., TG, DSC and DTA [13–26]. Spectrum model 1605) utilizing the KBr coins. Scanning
In this paper, effect of lead oxide nano- and micropar- electron microscope (Hitachi S4160) was applied to
ticles as the combustion catalyst on decomposition reaction examine the morphology and particle size of synthesized
kinetic of the energetic formulation composed of tri- lead oxide nanoparticles and the prepared energetic com-
ethyleneglycol dinitrate (TEGDN), nitrocellulose (NC) and positions. The X-ray powder diffraction (XRD) analysis
diaminoglyoxime (DAG) was studied by TG–DSC systems was carried out on a Rigaku D/max 2500 V diffractometer
under non-isothermal conditions. Also, an attempt was equipped with a Cu target and a graphite monochromator.
made in this study to determine thermokinetic parameters
correspond to the thermal decomposition of the examined TG–DSC studies
energetic compositions. This is hoped that the present study
be helpful for future investigations on the characterization Thermal analyses of the energetic compositions were per-
of the propellants composing TEGDN/NC/DAG. formed by a Mettler TA4000 thermal analyzer and a DSC
(made by Mettler Toledo Co., Switzerland). The applied
operation conditions during TGA analyses were as: the
Experimental sample mass of about 4 mg; an alumina crucible; purging
of N2 gas with the flowing rate of 80 mL min-1; heating
Materials rate (u) of 10 C min-1 at a temperature range of
50–400 C. Meanwhile, the applied operating conditions
The fibrous NC polymer used in the present research was for the DSC analyses were including: the sample mass of
of commercial grade with about 12.0% nitrogen content about 1.5 mg; an alumina crucible; 50 mL min-1 as
[27]. TEGDN was prepared in the organic chemistry lab- flowing rate of N2 purging in a temperature range of
oratory (MUT, Tehran) as proposed by refs. [28, 29]. Also, 50–300 C.
synthesis and purification of DAG [30] preparation of lead
oxide nanoparticles [31, 32] were carried out, respectively,
in the organic chemistry laboratory and inorganic chem- Results and discussion
istry laboratory (MUT, Tehran) as proposed previously.
Lead oxide microparticles were purchased from Merck Chemical composition and structure of the synthesized and
(Germany). The studied energetic sample (control sample purified DAG were investigated by FT-IR and NMR
or ES-1) was containing of 66% (by mass fraction) NC, techniques. FT-IR spectrum of DAG is observed in Fig. 1,
25% TEGDN, 3% centralite II and 6% DAG. Other ener- while the typical functional groups of the compound are
getic samples (ES-2, ES-3) and (ES-4, ES-5) were com- obvious the spectrum. The N–H2 groups are responsible for
posed of similar components with previous sample, while the peaks at 3369.0, 3463.8 and 1665.3 cm-1, while OH
either 1 or 3% PbO nano- or microparticles was introduced group are answerable for the observed peaks at 2800–3300

123
Catalytic effect of lead oxide nano- and microparticles on thermal decomposition kinetics of…

52
50

45

40

35
Transmitance %

30

25

20

15

10
3369.0
951.6
5 3463.8
1665.3
1444.2
–1
4000 3500 3000 2500 2000 1500 1000 500450

Wavenumber/cm–1

Fig. 1 FT-IR spectrum of the prepared DAG

5.2
9.7
and 1444.2 cm-1. Furthermore, C = N and N–O groups (a)
are accountable for the appeared strong peaks at 1573.2
and 951.6 cm-1, respectively.
1
H NMR spectrum of the DAG presented in Fig. 2a
reveals two peaks at d = 5.2 ppm and d = 9.7 ppm
attributed to the 4H in NH2 and 2H in OH, respectively. On
the other hand, 13C NMR spectrum of the synthesized DAG
presented in Fig. 2b exhibited a peak at 145.9 ppm which
1.000

2.012
may be attribute to the bonding of NOH and NH2 groups to
the carbon atom.
12 10 8 6
ppm
Characterization of the prepared PbO nanoparticles
145.9
SEM image of the synthesized lead oxide nanoparticles is
(b)
given in Fig. 3. As seen, the PbO nanoparticles possess a
spherical geometry with an average diameter about 38 nm.
Also, the XRD pattern of the prepared lead oxide
nanoparticles is given in Fig. 4. As seen in this figure, all
the diffraction peaks appeared in the resulted pattern are in
agreement with the crystalline structure of the lead oxide
from the diffraction software (JCPDS No 038-1477). The
average crystallite size of product particles was calculated
by Debye–Scherrer equation where in this equation (Eq. 1)
D is accountable for the mean crystalline size, the X-ray
wavelength (k) for Cu Ka is equal to 1.5418 Å, b is cor-
responding to the full peak width at the half maximum 200 150 100
(FWHM) and h is attributed to the diffraction angle [33]. ppm
The results of calculation showed that the obtained PbO
Fig. 2 a H-NMR spectrum of the prepared DAG. b C-NMR
nanoparticles have an average crystalline size less than spectrum of the prepared DAG
40 nm.

123
 V. Mirzajani et al.

0:9k 25
D¼ ð1Þ ϕ = 10 °C min–1
b cos h
Exo
205.50 °C
20

Thermal behavior of the pure components

Heat flow/wg–1
15
Thermoanalytical curve of DAG presented in Fig. 5 shows
an endothermic peak at about 200 C corresponding to the
10
melting phenomenon. However, DAG is decomposed
exothermally at 205.5 C, exactly after it’s melting (at
200 C). These results are compatible with previous report 5
on DAG [34] which explained the occurrence of a main Endo
thermal degradation of DAG at the temperature ranges of 0
180–230 C, simultaneous with the melting of the 0 40 80 120 160 200 240 280 320 360
compound. Temperature/°C
Thermal analysis result of the nitrocellulose sample
Fig. 5 DSC curve of the pure DAG
(with 12.0% nitrate content) is given in Fig. 6. As seen, the
DSC curve exhibits a single sharp exothermic behavior

10
202.3 °C ϕ = 5 °C min–1
Exo 9
8

7
Heat flow/W g–1

0
0 50 100 150 200 250 300 350 400 450
Temperature/°C

Fig. 3 SEM images of the prepared PbO nanoparticles Fig. 6 DSC curve of the pure NC (with 12.0% nitrate content)

Fig. 4 XRD pattern of the

(111)

80
prepared lead oxide
nanoparticles
60
(020)
(200)

(311)
Counts

(131)

40
(222)

(040)
(220)

(202)
(201)

(022)

20

0
10 20 30 40 50 60 70
Position/°2θ
Peak list

00-038-1477

123
Catalytic effect of lead oxide nano- and microparticles on thermal decomposition kinetics of…

1.8
199 °C ϕ = 2 °C min–1
1.6
Exo
1.4

1.2
Heat flow/W g–1

0.8

0.6

0.4

0.2

0
0 50 100 150 200 250 300 350
Temperature/°C

Fig. 7 DSC curve of the pure TEGDN

with a maximum temperature of 202.3 C, which is in

agreement with the previous study [27]. Meanwhile, the
DSC curve of TEGDN, presented in Fig. 7, shows a single
sharp exothermic peak during its decomposition with a
maximum temperature of about 199 C.

Characterization of the energetic compositions

by SEM

Figure 8 shows the SEM images for the prepared energetic

samples. SEM image of the energetic sample in the
absence of PbO nanoparticles (Fig. 8a) shows that the
sample is homogeneous and no agglomeration of the
ingredients was observed. On the other hand, Fig. 8b, c
present the SEM images for the energetic samples con-
taining 1 and 3% PbO nanoparticles (ES-2 and ES-3),
respectively. As seen in the SEM images, the nanoparticles
are distributed through the samples uniformly and no
considerable agglomeration of the ingredients was
observed.

Catalytic effect of PbO nano- and microparticles

on thermal behavior of energetic compositions

The results of this report reveal the catalytic effect of lead

oxide particles as additive on the thermal behaviors of Fig. 8 SEM images of the investigated energetic samples a without
TEGDN/NC/DAG energetic compositions. It has been PbO nano- and microparticles, b with 1% PbO nanoparticles and
reported [35, 36] that metal compounds could yield two c with 3% PbO nanoparticles
types of catalytic effects: (a) positive catalytic effect,
which increases the burning rate and in contrast lowers the thermal decomposition of TEGDN/NC/DAG energetic
required activation energy for initiating thermal decom- composition was studied by thermal analysis. TG–DSC
position of the composition, and (b) negative catalysts, curves of the investigated energetic compositions at the
which exhibit a reverse trend. Previous researches per- heating rate of 10 C min-1 are shown in Fig. 9. In Fig. 9a
formed about catalytic effect of metal compounds shows thermal pattern of TEGDN/NC/DAG sample in the absence
diverse influences on burning rate and thermal decompo- of lead oxide (ES-1) is given, which exhibits a single mass
sition of the energetic compositions [36, 37]. In this work, loss stage starting from 194.7 C. The maximum DSC peak
the catalytic activity of the nano- and microparticles on temperature of 196.6 C with the mass loss about 80.3% is

123
 V. Mirzajani et al.

observed for this stage. DSC curve of the energetic sample for this stage (Fig. 9b). DSC curve of the sample con-
containing 1% PbO nanoparticles (ES-2) shows a sharp taining 3% PbO nanoparticles (ES-3) shows similarly a
exothermic event with the onset temperature of 196.6 C sharp exothermic behavior which starts from 195.4 C and
and maximum peak temperature of 199.8 C; while TG maximizes at the temperature of 200.5 C; also the mass
analysis of the sample reveals a mass loss of about 77.0% loss of the sample at this stage is about 73.5%. (Figure 9c).

12
(a) 120 (b) 120 9

TG TG 8
10 Exo Exo
100 100
7
8 6
80 80

Heat flow/W g–1

Heat flow/W g–1

5

Mass/%
Mass/%

6
60 60 4
4
3
40 40
2 2
DSC 1
20 0 20 DSC
0

0 –2 0 –1
0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400
Temperature/°C Temperature/°C

(c) 120 10 (d) 12

TG
100 8 Exo Exo 10

80 6 8
Heat flow/W g–1

Heat flow/W g–1

Mass/%

60 4 6

40 2 4
DSC

20 0 2

0 –2 0
0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400
Temperature/°C Temperature/°C

(e) 9

Exo 8
7

6
Heat flow/W g–1

0
0 50 100 150 200 250 300 350 400
–1
Temperature/°C

Fig. 9 TG/DSC curves for energetic samples at heating rate of or ES-3, d control sample ? 1% micro-PbO or ES-4, e control
10Cmin-1 in N2 atmosphere: a control sample or ES-1, b control sample ? 3% micro-PbO or ES-5
sample ? 1% nano-PbO or ES-2, c control sample ? 3% nano-PbO

123
Catalytic effect of lead oxide nano- and microparticles on thermal decomposition kinetics of…

DSC curve of the sample containing 1% PbO microparti-

2200 2066.2
cles (ES-4) shows similarly a sharp exothermic behavior

Heat of decomposition/Jg–1
which starts from 177.8 C and maximizes at the temper- 2000
1779.24
ature of 199.1 C. (Figure 9d); also DSC curve of the
sample containing 3% PbO microparticles (ES-5) shows 1800

similarly a sharp exothermic behavior which starts from

1600
176.5 C and maximizes at the temperature of 201.6 C. 1367.06
(Figure 9e). A summary of DSC results for TEGDN/NC/ 1400 1242.3
1212.3
DAG energetic compositions containing different amounts
of PbO nano- and microparticles are also presented in 1200

Table 1. According to the DSC data, it could be concluded

1000
that both nano- and micro-PbO particles enhance the 1 2 3 4 5
decomposition temperature of TEGDN/NC/DAG energetic Sample number
composition. By comparing the maximum peak tempera-
ture of the investigated energetic samples in presence of Fig. 10 The heats of decomposition for the energetic samples (the
values are resulted from the average DSC exothermic peak areas
nano- and micro-PbO; generally it is obvious that there is obtained at various heating rates)
no significant difference between thermal decomposition
temperatures of TEGDN/NC/DAG energetic composition
modified with nano- and microparticles.
Addition of PbO catalyst (either micro or nano) to the Kinetic parameters for thermal decomposition
samples efficiently decreases the heat of decomposition for of energetic samples
the energetic composition. Nevertheless, increasing of PbO
catalyst contents (either micro or nano) in the samples The involved processes during solid-state decomposition
slightly decreases the heat of decomposition released from reactions generally are complex and their thermokinetic
this energetic composition. The described trend in the parameters could be determined by some well-known
decrement of the heat of decomposition is shown in methods, i.e., Kissinger, Starink and Ozawa–Flynn–Wall
Fig. 10. As seen in this figure, the energetic sample in the (O.F.W.) [38–48]. These methods were jointly employed in
absence of PbO catalyst has the highest heat of decompo- the present study to calculate the Arrhenius parameters,
sition while the sample containing 3% of the nano-catalyst i.e., activation energy (Ea ) and pre-exponential factor
has the lowest. (A) based on the DSC data for the studied energetic sam-
ples. The first utilized method for determining the Arrhe-
Effect of DSC heating rate on decomposition nius parameters was Kissinger [38–43], in which the
of energetic samples activation energy is obtained as follow (Eq. 2):
u AR Ea
Figure 11 presents DSC curves for decomposition of the Ln ¼ Ln  ð2Þ
Tm2 Ea R T m
studied energetic samples at different heating rates (i.e., 2,
5, 7 and 10C min-1). As seen in this figure, decomposi- While, u is the DSC heating rate, Tm is the temperature
tion peaks of the samples were shifted to the higher tem- of the DSC peak at maximum heat flow, and R is the
peratures by increasing the heating rate. Table 1 shows universal gas constant. The activation energies for the
these shifts in the peak temperatures quantitatively. studied energetic samples were obtained by DSC data
resulted at different heating rates (Table 1). The results of
 
drawing Ln Tu2 against 1/Tm were linear plots for all
m
Table 1 Maximum peak temperature of the investigated energetic studied samples, which confirm thermal decomposition of
samples at different heating rates
the samples undergoes no distinction at different applied
Heating rate/C min-1 Decomposition temperature/C heating rates [44–46]. Meanwhile, the slope of these linear
ES-1 ES-2 ES-3 ES-4 ES-5 plots was equal to -Ea/R. In the next step, the Arrhenius
factor or log (A/S-1) was calculated via following equation
2 182.9 181.9 184.8 181.2 184.9 recommended by ASTM E698 (Eq. 3) [47] using the cal-
5 187.2 191.3 189.7 188.7 194.0 culated value of activation energy (Ea).
7 192.5 195.9 193.1 193.7 198.6
10 196.6 199.8 200.5 199.1 201.6
½u Ea exp ðRETam Þ
A¼ ð3Þ
R Tm2

123
 V. Mirzajani et al.

12 12
(a) (b)
2 °C min–1
2 °C min–1
10 10 5 °C min–1
Exo 5 °C min–1
Exo
7 °C min–1 7 °C min–1
8
10 °C min–1 8 10 °C min–1
Heat flow/W g–1

Heat flow/W g–1

6
6
4
4
2
2
0

0
–2 0 50 100 150 200 250 300 350 400
0 50 100 150 200 250 300 350 400
Temperature/°C –2 Temperature/°C

(c) 10 (d) 12
2 °C min–1 2 °C min–1
5 °C min–1 Exo 5 °C min–1
Exo 8 10
7 °C min–1 7 °C min–1
10 °C min–1 10 °C min–1
8
6
Heat flow/W g–1
Heat flow/W g–1

6
4

4
2

2
0
0 50 100 150 200 250 300 350 400
0
Temperature/°C 0 50 100 150 200 250 300 350 400
–2
Temperature/°C

9
(e)
2 °C min–1
8
Exo 5 °C min–1

7 7 °C min–1
10 °C min–1
6
Heat flow/W g–1

0
0 50 100 150 200 250 300 350 400
–1
Temperature/°C

Fig. 11 Effect of DSC heating rate on decomposition temperature of the presence of 3% nano-PbO (ES-3); d control sample in the
investigated energetic samples: a control sample (ES-1); b control presence of 1% micro-PbO (ES-4); e control sample in the presence
sample in the presence of 1% nano-PbO (ES-2); c control sample in of 3% micro-PbO (ES-5)

The resulted values of the activation energy and (Ea) values for these energetic samples were computed via
Arrhenius factor for the studied energetic samples are Starink method [48] by the aid of Eq. 4. In this method, the
presented in Table 2. On the other hand, activation energy plot of Ln ðu Tm1:92 Þ against the inverse of maximum peak

123
Catalytic effect of lead oxide nano- and microparticles on thermal decomposition kinetics of…

Table 2 Comparison of kinetic parameters for thermal decomposi- A Ea Ea

tion of energetic samples obtained by Kissinger, Starink and O.F.W. log u ¼ log  2:315  0:4567 ð5Þ
R g ðaÞ RTm
methods
Sample Method Ea/kJ mol-1 Log/A/s-1 r Q In this equation, g(a) represents integral function of the
conversion. O.F.W. is a multiple scanning method and
ES-1 Kissinger 190.4 19.4 0.9620 0.2223 belongs to the model-free isoconventional approaches;
Starink 190.6 19.4 0.9621 0.2223 thus, this method allows predicting of the activation energy
O.F.W. 188.3 19.2 0.9648 0.2222 independently [49]. Also, the values of Arrhenius factor
ES-2 Kissinger 151.7 14.9 0.9989 0.0364 (A) for the energetic samples were computed by Eq. (3)
Starink 151.9 14.9 0.9989 0.0364 [52–54]. Table 2 gives the resulted values of activation
O.F.W. 151.6 14.8 0.9991 0.0362 energy (Ea) and Arrhenius factor (log A) for decomposition
ES-3 Kissinger 171.0 17.1 0.9441 0.2787 of the investigated energetic samples calculated by Kis-
Starink 171.1 17.1 0.9477 0.2806 singer, Starink and O.F.W. methods for comparison. In
O.F.W. 169.9 16.9 0.9434 0.2804 fact, the presented data in this table are helpful for
ES-4 Kissinger 152.0 14.9 0.9860 0.1286 checking the validity and constancy of the values of acti-
Starink 152.2 15.0 0.9861 0.1288 vation energy obtained by different methods. As seen in
O.F.W. 151.8 14.9 0.9873 0.1339 this table, the activation energies and Arrhenius factors
ES-5 Kissinger 162.7 16.0 0.9980 0.0501 computed by Kissinger method for decomposition of the
Starink 162.9 16.0 0.9980 0.0501 energetic samples are comparable with those resulted by
O.F.W. 162.1 15.9 0.9981 0.0511 Starink and O.F.W. methods. However, the computed
values by O.F.W. method are faintly lower than those
r Linear regression
resulted by two other methods. Totally, these results con-
Q Standard mean square deviation
firm the reliability of the calculations. The resulted kinetic
data point out that TEGDN/NC/DAG energetic composi-
tions treated with (micro or nano) PbO catalyst have lower
activation energy values and thus require lower energy for
initiating of their decomposition reaction. In fact, positive
temperature at different heating rates permits the prediction
catalytic effect of PbO particles lowers the required energy
of the activation energy. Fortunately, this method is usable
for initiation of the reaction and later increases the burning
for computing the activation energy by the aid of following
rate [55]. Therefore, PbO catalyst is capable to reduce the
equation, neglected of a accurate knowledge about the
energetic barrier for commencing of the reactions and
reaction mechanism:
hence leads to acceleration of the decomposition process
u Ea [56]. Meantime, comparing catalytic effect of micro- and
Ln ð Þ þ 1:0008 ¼C ð4Þ
Tm1:92 R Tm nanoparticles of lead oxide on the thermal decomposition
The results of drawing of Ln (u Tm1:92 ) against reverse of TEGDN/NC/DAG energetic composition shows that
of peak temperature at maxima for the studied energetic PbO microparticles have lower positive catalytic effect on
samples were straight lines, while their slopes were utilized the thermal decomposition of energetic compositions in
to calculate the values of the activation energy. Meantime, comparison with PbO nanoparticles, while this behavior
the corresponded values of Arrhenius factor (A) for each of may arise from the specific characteristics of nanoparticles,
these energetic samples were obtained by Eq. (3) [49]. i.e., small particle size and high surface area.
Also, Ozawa–Flynn–Wall (O.F.W.) as the third method In addition, the thermodynamic parameter values cor-
was employed to predict the values of activation energy responding to the thermal activation of the studied ener-
(Ea) for the studied energetic samples. This method is getic samples are calculable utilizing the following
based on the kinetics equations utilized for the heteroge- equations [57–60]. Thus, Eqs. 6–8 were utilized to predict
neous chemical reactions and could be presented as Eq. 5 the values of activation entropy (DS#), activation enthalpy
[49–51]. As seen in this equation, plotting of the heating (DH#) and free energy of activation (DG#).
rate logarithm against the converse of the maximum peak Ea DG6¼
temperatures resulted by different DSC peaks at various A exp ¼ m exp ð6Þ
RT RT
heating rates permits the computation of the activation
DH 6¼ ¼ Ea  RT ð7Þ
energy. In this method, similar to the previous methods,
determination of the activation energy without an exact DG6¼ ¼ DH 6¼  TDS6¼ ð8Þ
knowledge about the reaction mechanism is possible via
utilizing Eq. 5.

123
 V. Mirzajani et al.

In Eq. 6, m ¼ KB T=h (while h and KB symbolized Plank factor which is known as the critical ignition temperature
and Boltzmann constants, respectively). Table 3 presents (Tb). This factor shows the maximum temperature at which
the resulted values for the thermodynamic parameters the composition undergoes a thermal runaway [46, 52].
corresponding to the studied energetic samples. As seen in This temperature for each composition is predictable based
on the burning theory, while some thermokinetic parame-
this table, the positive values of DH 6¼ and DG6¼ for the
ters, i.e., activation energy, Arrhenius factor and heat of
energetic samples confirm that their decomposition reac-
reaction are essential. In the present study, the critical
tions are non-spontaneous and initiation of their reactions
temperatures corresponding to the thermal explosion (Tb)
requires introducing of the heat.
of the energetic samples were obtained via Eqs. (10–11) as
follows [62, 63]:
Calculation of decomposition reaction rate constant
Te ¼ Te0 þ b ui þ c u2i ; i ¼ 1  4 ð10Þ
The rate constant for decomposition reaction (k) of the pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Ea  Ea2  4Ea RTp0
energetic samples was computed by Eq. (9). The order of Tb ¼ ð11Þ
decomposition reaction for the studied energetic samples 2R
was assumed as the first order [61]: In Eq. 10, b and c are the coefficients, while R is the
universal gas constant. Te0 is commonly called self-accel-
log k ¼ log A  Ea=2:3RT ð9Þ
erating decomposition temperature (TSADT), while this
The values of reaction rate constant (k) for the energetic symbol is attributed to the onset temperature (Te) while
samples were computed by the use of activation energy u ! 0 and computed by Eq. (10). However, the resulted
(Ea) and Arrhenius factor (A) values resulted by different values were utilized for computation of critical tempera-
methods (i.e., Kissinger, Starink and O.F.W.) at 25 C as tures. The resulted temperatures are given in Table 3.
the environment temperature. Table 3 gives the resulted
values of log k for the energetic samples. By comparing of Comparison thermal stability of investigated
the reaction rate constant values, it could be found that the energetic samples
modified energetic samples with PbO nano- and
microparticles (ES-2 to ES-5) have reaction rate constants TG/DSC curves for the investigated energetic samples in
considerably higher than that the energetic sample without the absence and/or presence of the nano- and micro-PbO
lead oxide treatment (control sample or ES-1). These val- are presented in Fig. 9. The blank sample (ES-1 which has
ues of log k for the energetic samples confirm that both no PbO content) and the modified samples with nano- and
PbO nano- and microparticles have catalytic effects on the micro-PbO (ES-2 and ES-3 containing 1 and 3%
decomposition of the energetic samples and increase their nanoparticles and ES-4 and ES-5 containing 1 and 3%
decomposition reaction rate. microparticles, respectively) present similar thermal pat-
terns, and all of them display a single exothermic event
Critical ignition temperature during their thermal decomposition. However, the resulted
curves showed that thermal decomposition of the energetic
The safe storage and process of the studied energetic samples modified with nano- and micro-PbO occurred at
compositions require knowledge about another significant the higher temperatures. On the other hand, by comparison
thermal stability of the blank sample (ES-1) with the
samples containing nano- and micro-PbO, it was appeared
Table 3 Thermodynamic data for decomposition of the studied that the modified samples with nano- and microparticles
energetic samples have lower activation energy about 20–40 kJ mol-1. It
means that introducing of nano- and micro-PbO makes the
Sample DG6¼ / DH 6¼ / DS6¼ / Log k Tb / TSADT /
kJ mol-1 kJ mol-1 J mol-1 C C decomposition of TEGDN/NC/DAG energetic composition
more easily. However, comparing of the maximum peak
ES-1 129.6 186.6 123.9 -13.9 196.2 172.9 temperature of the investigated energetic samples in the
ES-2 131.5 148.0 36.9 -11.7 185.5 140.8 presence of nano- and micro-PbO shows that there is not
ES-3 131.3 167.2 79.2 -12.8 190.9 144.3 significant difference between thermal decomposition
ES-4 134.6 148.3 30.3 -11.6 189.1 208.0 temperatures, activation energies and frequency factors of
ES-5 136.1 159.0 50.7 -12.4 189.4 175.9 TEGDN/NC/DAG energetic composition modified with
nano- and microparticles.

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Catalytic effect of lead oxide nano- and microparticles on thermal decomposition kinetics of…

Conclusions 8. Nayak H, Jena AK. Catalyst effect of transition metal

nano oxides on the decomposition of lanthanum oxalate hydrate:
a thermogravimetric study. Int J Sci Res (IJSR). 2014;3:
The effect of PbO nano- and microparticles on thermal 381–8.
decomposition of TEGDN/NC/DAG energetic composi- 9. Martins S, Fernandes JB, Mojumdar SC. Catalysed thermal
tions was investigated via simultaneous differential scan- decomposition of KClO3 and carbon gasification. J Therm Anal
Cal. 2015;119:831–5.
ning calorimetery (DSC) and thermogravimetery (TG)
10. Kapoor IPS, Srivastava P, Singh G. Nanocrystalline transition
techniques. Thermokinetic and thermodynamic parameters metal oxides as catalysts in the thermal decomposition of
corresponding to the decomposition of different energetic ammonium perchlorate. Propellants Explos Pyrotech.
compositions were computed based on their DSC curves. 2009;34:351–6.
11. Mahinroosta M. Catalytic effect of commercial nano-CuO and
The values of the activation energy and frequency factor
nano-Fe2O3 on thermal decomposition of ammonium perchlorate.
for the studied energetic compositions were computed by J Nanostruct Chem. 2013;3:1–6.
some well-known methods. The results of this study show 12. Shahidzadeh M, Shabihi P, Pourmortazavi SM. Sonochemical
that the decomposition temperature of the energetic com- preparation of copper(II) chromite nanocatalysts and particle size
optimization via Taguchi method. J Inorg Organomet Polym.
positions in the presence of nano- and micro-PbO is higher
2015;25:986–94.
than the similar composition without PbO particles. How- 13. Shamsipur M, Pourmortazavi SM, Roushani M, Miran Beigi AA.
ever, the energetic samples containing nano- and micro- Thermal behavior and non-isothermal kinetic studies on titanium
PbO possess lower frequency factors and activation ener- hydride-fueled binary pyrotechnic compositions. Combust Sci
Technol. 2013;185:122–33.
gies. There is no significant difference between thermal
14. Rogers RN, Smith LC. Estimation of preexponential factor from
decomposition temperatures and activation energy values thermal decomposition curve of a weighed sample. J Anal Chem.
of TEGDN/NC/DAG energetic composition modified with 1967;39:1024.
nano- and microparticles. Besides, lower values of the 15. Mohan Murali BK, Ganesan V, Rao KB, Mohan VK. Hazard
characteristics of isosorbide dinitrate-lactose mixtures. J Hazard
critical ignition temperature (Tb) and the self-accelerating
Mater. 1979;3(2):177–82.
decomposition temperature (TSADT) of the energetic sam- 16. Sunitha M, Reghunadhan Nair CP, Krishnan K, Ninan KN.
ples in the presence of nanoparticles show higher sensi- Kinetics of Alder-ene reaction of Tris (2-allylphenoxy) triphe-
tivity of the energetic samples containing PbO noxycyclotriphosphazene and bismaleimides-a DSC study.
Thermochim Acta. 2001;374:159–69.
nanoparticles in comparing samples modified with the
17. Turcotte R, Vachon M, Kwok QSM, Wang R, Jones DEG.
microparticles. Based on the results of this study it could be Thermal study of HNIW (CL-20). Thermochim Acta.
concluded that the addition of PbO (either nano- or 2005;433:105–15.
microparticles) has a considerable effects on thermal 18. Pourmortazavi SM, Sadri M, Rahimi-Nasrabadi M, Shamsipur M,
Jabbarzade Y, Shafaghi Khalaki M, Abdollahi M, Shariatinia Z,
behavior of TEGDN/NC/DAG energetic compositions,
Kohsari I, Atifeh SM. Thermal decomposition kinetics of elec-
while PbO particle size has no substantial diverse effects trospun azidodeoxy cellulose nitrate and polyurethane nanofibers.
on thermal decomposition of these energetic samples. J Therm Anal Cal. 2015;119:281–90.
19. Azimfar F, Kohsari I, Pourmortazavi SM. Investigation on
decomposition kinetic and thermal stability of metallocene cat-
alysts. J Inorg Organomet Polym. 2009;19:181–6.
References 20. Om Reddy G, Srinivasa Rao A. Stability studies on pentaerytritol
tetranitrate. Propellants Explos Pyrotech. 1992;17:307.
1. Kanno H, Yamamoto H. (1995) US Patent 5476967. 21. Miran Beigi AA, Abdouss M, Yousefi M, Pourmortazavi SM,
2. Takahashi PM, Netto AVG, Mauro AE, Frem RCG. Thermal Vahid A. Investigation on physical and electrochemical prop-
study of nickel(II) pyrazolyl complexes. J Therm Anal Calorim. erties of three imidazolium based ionic liquids (1-hexyl-3-
2005;79:335–8. methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimida-
3. Stoner CE Jr, Brill TB. Thermal decomposition of energetic zolium bis(trifluoromethylsulfonyl) imide and 1-butyl-3-
materials 46. The formation of melamine-like cyclic azines as a methylimidazolium methylsulfate). J Mol Liq. 2013;177:
mechanism for ballistic modification of composite propellants by 361–8.
DCD, DAG, and DAF. J Combust Flame. 1991;83:302–8. 22. Mirzaei M, Lippolis V, Carla Aragoni M, Ghanbari M, Sham-
4. Talawar MB, Makashir PS, Nair JK, Pundalik SM, Mukundan T, sipur M, Meyer F, Demeshko S, Pourmortazavi SM. Extended
Asthana SN, Singh SN. J Hazard Mater. 2005;A 125:17–22. structures in copper(II) complexes with 4-hydroxypyridine-2,6-
5. Williams GK, Palopoli SF, Brill TB. Thermal decomposition of dicarboxylate and pyrimidine derivative ligands: x-ray crystal
energetic materials 65. Conversion of insensitive explosives (NTO, structure, solution and magnetic studies. Inorg Chim Acta.
ANTA) and related compounds to polymeric melon-like cyclic 2014;418:126–35.
azine burn-rate suppressants. J Combust Flame. 1994;98:197–204. 23. Shamsipur M, Miran Beigi AA, Teymouri M, Pourmortazavi SM,
6. Ravanbod M, Pouretedal HR. Catalytic effect of Fe2O3, Mn2O3, Irandoust M. Physical and electrochemical properties of ionic
and TiO2 nanoparticles on thermal decomposition of potassium liquids 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-
nitrate. J Therm Anal Calorim. 2016;124:1091–8. methylimidazolium trifluoromethanesulfonate and 1-butyl-1-
7. Yi JH, Zhao FQ, Hong WL, Xu SY, Hu RZ, Chen ZQ, Zhang LY. methylpyrrolidinium bis(trifluoromethyl-sulfonyl) imide. J Mol
Effects of Bi-NTO complex on thermal behaviors, nonisothermal Liq. 2010;157:43–50.
reaction kinetics and burning rates of NG/TEGDN/NC propellant.
J Hazard Mater. 2010;176:257–61.

123
 V. Mirzajani et al.

24. Singh G, Kapoor IPS, Mannan SM, Kaur J. Studies on energetic 44. Tompa AS, Boswell RF. Thermal stability of a plastic bonded
compounds, Part 8: thermolysis of salts of HNO3 and HClO4. explosive. Thermochim Acta. 2000;357–358:169–75.
J Hazard Mater. 2000;A79:1–18. 45. Criado JM, Perez-Maqueda LA, Sanchez-Jimenez PE. Depen-
25. Zeman S. New aspects of initiation reactivities of energetic dence of the pre-exponential factor on temperature. J Therm Anal
materials demonstrated on nitramines. J Hazard Mater. Calorim. 2005;82:671–5.
2006;A132:155–64. 46. Fathollahi M, Behnejad H. A comparative study of thermal
26. Keshavarz MH. Simple method for prediction of activation behaviors and kinetics analysis of the pyrotechnic compositions
energies of the thermal decomposition of nitramines. J Hazard containing Mg and Al. J Therm Anal Calorim.
Mater. 2009;162:1557–62. 2015;120:1483–92.
27. Pourmortazavi SM, Rahimi-Nasrabadi M, Rai H, Besharati-Sei- 47. ASTM E698. Test methods for Arrhenius kinetic constants for
dani A, Javidan A. Role of metal oxide nanomaterials on thermal thermally unstable materials.
stability of 1,3,6-trinitrocarbazole. Propellants Explos Pyrotech. 48. Starink MJ. The determination of activation energy from linear
2016;41:912–8. heating rate experiments: a comparison of the accuracy of iso-
28. Nicholas A, Alexander J, Michael P. (2012) US Patent conversion methods. Thermochim Acta. 2003;404:163–76.
20120130115A1. 49. Shamsipur M, Pourmortazavi SM, Hajimirsadeghi SS, Atifeh
29. Gouranlou F, Kohsari I. Synthesis and characterization of 1,2,4- SM. Effect of functional group on thermal stability of cellulose
butanetrioltrinitrate. J Asian J Chem. 2010;22:4221–8. derivative energetic polymers. Fuel. 2012;95:394–9.
30. Park DJ, Stern AG, Willer RL. A convenient laboratory prepa- 50. Ma H, Yan B, Li Z, Guan Y, Song J, Xu K, et al. Preparation,
ration of cyanogen. Synth Commun. 1990;20:2901–6. non-isothermal decomposition kinetics, heat capacity and adia-
31. Karami H, Karimi MA, Haghdar S, Sadeghi A, Mir-Ghasemi R, batic time-to-explosion of NTO. DNAZ. J Hazard Mater.
Mahdi-Khani S. Synthesis of lead oxide nanoparticles by Sono- 2009;169:1068–73.
chemical method and its application as cathode and anode of 51. Roduit B, Xia L, Folly P, Berger B, Mathieu J, Sarbach A, et al.
lead-acid batteries. J Mater Chem Phys. 2008;108(2):337–44. The simulation of the thermal behavior of energetic materials
32. Karami H, Karimi MA, Haghdar S. Synthesis of uniform nano- based on DSC and HFC signals. J Therm Anal Calorim.
structured lead oxide by sonochemical method and its application 2008;93:143–52.
as cathode and anode of lead-acid batteries. Mater Res Bull. 52. Abusaidi H, Ghaieni HR, Pourmortazavi SM, Motamed-Shariati SH.
2008;43(11):3054–65. Effect of nitro content on thermal stability and decomposition
33. Fazli Y, Pourmortazavi SM, Kohsari I, Sadeghpur M. Electro- kinetics of nitro-HTPB. J Therm Anal Calorim. 2016;124:935–41.
chemical synthesis and structure characterization of nickel sulfide 53. Pisharath S, Ang HG. Synthesis and thermal decomposition of
nanoparticles. J Mater Sci Semicond Process. 2014;27:362–7. GAP–Poly (BAMO) copolymer. Polym Degrad Stab.
34. Pourmortazavi SM, Farhadi K, Mirzajani V, Mirzajani S, Kohsari 2007;92(7):1365–77.
I. Study on the catalytic effect of diaminoglyoxime on thermal 54. Rocco J, Lima J, Frutuoso A, Iha K, Ionashiro M, Matos J, et al.
behaviors, non-isothermal reaction kinetics and burning rate of Thermal degradation of a composite solid propellant examined by
homogeneous double-base propellant. J Therm Anal Calorim. DSC. J Therm Anal Calorim. 2004;75:551–7.
2016;125:121128. 55. Wan-Fen Pu, Liu Peng-Gang, Li Yi-Bo, Jin Fa-Yang, Liu Zhe-
35. Kubota N. Propellants and explosives, chapter 7. New York: Zhi. Thermal characteristics and combustion kinetics analysis of
Wiley; 2007. p. 195–8. heavy crude oil catalyzed by metallic additives. Ind Eng Chem
36. Preckel RF. Plateau ballistics in NC propellant. ARS J. Res. 2015;54:11525–33.
1961;31:1286–7. 56. Li Y, Chenxia K, Huang C, Cheng Y. Effect of MnC2O4
37. Joshi AD, Singh H. Effect of certain lead and copper compounds nanoparticles on the thermal decomposition of TEGDN/NC
as ballistic modifier for double base rocket propellants. J Energy propellant. J Therm Anal Calorim. 2012;109:171–6.
Mater. 1992;10(4–5):299–309. 57. Shamsipur M, Pourmortazavi SM, Fathollahi M. Kinetic param-
38. Kissinger HE. Reaction kinetics in differential thermal analysis. eters of binary iron/oxidant pyrolants. J Energy Mater.
J Anal Chem. 1957;29:1702–6. 2012;30:97–106.
39. Pourmortazavi SM, Hosseini SG, Rahimi-Nasrabadi M, 58. Pourmortazavi SM, Rahimi-Nasrabadi M, Rai H, Jabbarzadeh Y,
Hajimirsadeghi SS, Momenian H. Effect of nitrate content on Javidan A. Effect of nanomaterials on thermal stability of 1,3,6,8-
thermal decomposition of nitrocellulose. J Hazard Mater. tetranitro carbazole. Cent Eur J Energy Mater. 2017;14:201–16.
2009;162:1141–4. 59. Eslami A, Hosseini SG, Asadi V. The effect of microencapsu-
40. Ma H-X, Song J-R, Hu R-Z. Non-isothermal kinetics of the lation with nitrocellulose on thermal properties of sodium azide
thermal decomposition of 3-nitro-1,2,4-triazol-5-one magnesium particles. Prog Org Coat. 2009;65:269–74.
complex. Chin J Chem. 2003;21(12):1558–61. 60. Olszak-Humienik M, Mozejko J. Thermodynamic functions of
41. Hu R-Z, Chen S-P, Gao S-L, Zhao F-Q, Luo Y, Gao H-X, Shi activated complexes created in thermal decomposition processes
Q-Z, Zhao H-A, Yao P, Li J. Thermal decomposition kinetics of of sulphates. Thermochim Acta. 2000;344:73–9.
Pb0.25Ba0.75(TNR)H2O complex. J Hazard Mater. 61. Pourmortazavi SM, Rahimi-Nasrabadi M, Kohsari I, Hajimir-
2005;A117:103–10. sadeghi SS. Non-isothermal kinetic studies on thermal decom-
42. Shamsipur M, Pourmortazavi SM, Hajimirsadeghi SS. Investi- position of energetic materials. J Therm Anal Calorim.
gation on decomposition kinetics and thermal properties of cop- 2012;110:857–63.
per fueled pyrotechnic compositions. Combust Sci Technol. 62. Pickard JM. Critical ignition temperature. Thermochim Acta.
2011;183:575–87. 2002;392:37–40.
43. Ma H-X, Song J-R, Zhao F-Q, Hu RZ, Xiao H-M. Nonisothermal 63. Tonglai Z, Rongzu H, Yi X, Fuping L. The estimation of critical
reaction kinetics and computational studies on the properties of temperatures of thermal explosion for energetic materials using
2,4,6,8-tetranitro-2,4,6,8-tetraazabicyclo [1, 3] onan-3,7-dione non-isothermal DSC. Thermochim Acta. 1994;244:171–6.
(TNPDU). J Chem Phys. 2007;A111:8642–9.

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