Thermal decomposition and safety assessment of 3,3'-dinitrimino-5,5'-bis(1H-1,2,4-triazole) by DTA and ARC

Article abstract of DOI:10.1007/s10973-018-6973-9

Thermal decomposition and safety assessment of 3,3'-dinitrimino-5,5'-bis(1H-1,2,4-triazole) (DNABT) were investigated by thermogravimetry–derivative thermogravimetry–differential scanning calorimetry (TG-DTG-DSC), differential thermal analysis (DTA), and accelerating rate calorimetry (ARC). The result of TG-DTG-DSC at a heating rate of 10 °C min^-1 indicated that an endothermic decomposition and an exothermic decomposition occurred at 133.98 and 210.86 °C, respectively. The apparent activation energy (E_a) and pre-exponential factor (A) of the exothermic decomposition, and the free energy of activation, activation enthalpy, and activation entropy at initial decomposition temperature (T_p0) were calculated from the DTA curves recorded at the heating rates of 1, 2, 4, 8 °C min^-1. The critical temperature of thermal explosion (T_bp0) obtained by Ozawa’s and Kissinger’s methods were calculated as 205.01 and 205.14 °C, respectively. The result of ARC indicated that the self-heating decomposition started at 200.22 °C and ended at 232.66 °C. The self-heating decomposition parameters, including the onset temperature, final temperature, temperature at maximum rate, maximum temperature rate, adiabatic temperature rise, and time to maximum rate were obtained, and these parameters were corrected by thermal inertia factor. The E_a and A under adiabatic condition were also calculated. In addition, the self-accelerating decomposition temperature (T_{SADT, 50kg}) was calculated as 175.37 °C. These results could contribute to improve the safety in the reaction, transportation, and storage processes of DNABT.

Full text of DOI:10.1007/s10973-018-6973-9

Journal of Thermal Analysis and Calorimetry
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Thermal decomposition and safety assessment of 3,30-dinitrimino-5,50-
bis(1H-1,2,4-triazole) by DTA and ARC
Fang Bao1 Gongzheng Zhang1 Shaohua Jin2 Chunyuan Zhang2 Hu Niu2
•
•
•
•
Received: 2 September 2017 / Accepted: 5 January 2018
´
´
Ó Akademiai Kiado, Budapest, Hungary 2018
Abstract
Thermal decomposition and safety assessment of 3,30-dinitrimino-5,50-bis(1H-1,2,4-triazole) (DNABT) were investigated
by thermogravimetry–derivative thermogravimetry–differential scanning calorimetry (TG-DTG-DSC), differential thermal
analysis (DTA), and accelerating rate calorimetry (ARC). The result of TG-DTG-DSC at a heating rate of 10 °C min-1
indicated that an endothermic decomposition and an exothermic decomposition occurred at 133.98 and 210.86 °C,
respectively. The apparent activation energy (Ea) and pre-exponential factor (A) of the exothermic decomposition, and the
free energy of activation, activation enthalpy, and activation entropy at initial decomposition temperature (Tp0) were
calculated from the DTA curves recorded at the heating rates of 1, 2, 4, 8 °C min-1. The critical temperature of thermal
explosion (Tbp0) obtained by Ozawa’s and Kissinger’s methods were calculated as 205.01 and 205.14 °C, respectively. The
result of ARC indicated that the self-heating decomposition started at 200.22 °C and ended at 232.66 °C. The self-heating
decomposition parameters, including the onset temperature, final temperature, temperature at maximum rate, maximum
temperature rate, adiabatic temperature rise, and time to maximum rate were obtained, and these parameters were corrected
by thermal inertia factor. The Ea and A under adiabatic condition were also calculated. In addition, the self-accelerating
decomposition temperature (TSADT, 50kg) was calculated as 175.37 °C. These results could contribute to improve the safety
in the reaction, transportation, and storage processes of DNABT.
Keywords 3,30-Dinitrimino-5,50-bis(1H-1,2,4-triazole) Á Thermal decomposition Á Non-isothermal kinetics Á
Safety assessment Á DNABT Á ARC
Introduction
calculated detonation velocity (8355 m s-1) is higher than
that of 2,4,6-triamino-1,3,5-trinitrobenzene (TATB)
(8114 m s-1), and its impact sensitivity (3 J) is higher than
that of 2,4,6-trinitrotolune (TNT) (15 J) [6, 7]. Its high-
nitrogen energetic salts were first synthesized by
Wang et al. [7], and some of them can be considered as the
potential substituted candidates of 1,3,5-trinitro-1,3,5-tri-
azacyclohexane (RDX), such as diammonium bis[3-(5-ni-
troimino-1,2,4-triazolate)] and carbonic dihydrazidinium
bis[3-(5-nitroimino-1,2,4-triazolate)] (CBNT).
During the last decade, considerable efforts have been
focused on the development of nitrogen-rich heterocyclic
compounds [1–5]. Nitrogen-rich heterocyclic compounds
have played and will continue to play an important role in
the field of energetic materials owing to their good thermal
stability, low impact sensitivity, and high detonation
properties.
3,30-Dinitrimino-5,50-bis(1H-1,2,4-triazole) (DNABT) is
an important nitrogen-rich heterocyclic compound. Its
However, before DNABT obtains practical application,
much work should be done in order to get a more com-
prehensive understanding of it. The thermogravimetry–
& Shaohua Jin
derivative
thermogravimetry–differential
scanning
jinshaohua@bit.edu.cn
calorimetry (TG-DTG-DSC), differential thermal analysis
(DTA) and accelerating rate calorimetry (ARC) were car-
ried out. The thermokinetic parameters of the exothermic
decomposition and thermodynamic parameters at initial
1
School of Chemistry and Chemical Engineering, Beijing
Institute of Technology, Beijing, China
2
School of Materials Science and Engineering, Beijing
Institute of Technology, Beijing, China
123

F. Bao et al.
decomposition temperature (Tp0) were obtained from DTA.
The self-heating decomposition parameters, adiabatic
decomposition kinetic parameters, time to maximum rate
(TMR), and self-accelerating decomposition temperature
(TSADT) were obtained from ARC. To the best of our
knowledge, up to now, there are no report regarding the
thermal decomposition and safety assessment of DNABT
under non-isothermal and adiabatic conditions.
Experimental equipments and conditions
The TG-DTG-DSC measurement was performed with a
PerkinElmer STA6000 simultaneous thermal analyzer at a
heating rate of 10 °C min-1 under a nitrogen flow of
50 mL min-1. The non-isothermal DTA measurements
were performed with a Shimadzu DTG-60H simultaneous
thermal analyzer at the heating rates of 1, 2, 4, 8 °C min-1
under a nitrogen flow of 50 mL min-1. All samples were
2.0 mg and placed in open alumina crucibles, and they
were heated from 50 to 400 °C.
Experimental
The ARC measurement was performed with a Thermal
Hazard Technology accelerating rate calorimeter in the
Heat–Wait–Search mode. The experiment conditions of
DNABT by accelerating rate calorimeter are compiled in
Table 2.
Materials
DNABT was prepared [6] (as shown in Scheme 1): Oxalic
acid (20.0 g, 159 mmol) was added to a stirred mixture of
hydrochloric acid (37.5%, 60 mL) and aminoguanidinium
bicarbonate (45.4 g, 332 mmol). The reaction was stirred
at 70 °C for 1 h, and the precipitate was collected by fil-
tration. The white solid was dissolved in water (240 mL)
and alkalized with sodium hydroxide to pH 14. The reac-
tion mixture was heated to reflux for 1 h and subsequently
acidified with acetic acid to pH 4. The white precipitate
was collected by filtration and dried to yield 3,30-diamino-
5,50-bis(1H-1,2,4-triazole) (DABT). Nitric acid (65%,
9 mL) was added slowly to a mixture of DABT (3.0 g,
18 mmol) and concentrated sulfuric acid (98.0%, 27 mL)
at 0 °C. The reaction mixture was warm to room temper-
ature and stirred for 1 h. The yellow transparent solution
was poured on ice, and the white precipitate was collected
by filtration and recrystallized from boiling water to yield
DNABT (3.7 g, 13 mmol, 70.0%) as colorless crystalline
solid. IR (KBr pellet): 3183, 1697, 1575, 1508, 1448, 1383,
Results and discussion
Thermal decomposition processes
The TG-DTG-DSC curve at a heating rate of 10 °C min-1
is given in Fig. 1. From the TG and DTG curves, two mass
loss processes were observed. The first process was a slow
decomposition in the range between 133.98 and 157.98 °C,
and the mass loss was 12.40%. This was a dehydration
process, and the theoretically calculated value of the
dehydration process was in exact accordance with the
experimental value. The second process was an exothermic
decomposition in the range between 210.86 and 263.22 °C,
and the mass loss was 50.40%. From the DSC curve, the
peak temperatures of the two mass loss processes were
determined as 142.01 and 237.11 °C, respectively.
1332, 1306, 1237, 1173, 1057, 994, 948, 782, 714 cm-1
;
1H NMR (400 MHz, d6-DMSO): 8.46, 6.58 ppm; 13C
NMR (100 MHz, d6-DMSO): 153.35, 142.23 ppm.
The compound of DNABT was additionally character-
ized by single-crystal X-ray spectroscopy. The result of
single-crystal X-ray spectroscopy indicated that one
molecule of DNABT was associated with two molecules of
H2O. Crystallographic data and parameters as well as the
morphology are compiled in Table 1.
Non-isothermal decomposition kinetic
parameters
The DTA curves of DNABT are shown in Fig. 2, indicated
that there were two exothermic decomposition during the
decomposition of DNABT. The onset temperatures
(159.03, 164.90, 172.70, 183.21 °C), peak temperatures
(193.20, 203.36, 212.60, 221.80 °C), and final
Scheme 1 The synthesis route
of DNABT
HO
O
NH
1) HC1
H2N
HN
N
N
N
N
NH
+
NH H2CO3
2) NaOH
N
H
H2N
3) CH3COOH
O
N
OH
NH2
H
N
N
O2N
NH
H2SO4/HNO3
0 °C
HN
NO2
N
N
H
N
123

Thermal decomposition and safety assessment of 3,30-dinitrimino-5,50-bis(1H-1,2,4-triazole) by…
Table 1 X-ray data and
Parameters
Values
Parameters
Values
parameters of DNABTÁ2H2O
Formula
C4H4N10O4Á2H2O
292.20
F(000)
˚
300.0
Formula mass/g mol-1
Crystal system
Space group
k
Mo–Ka/A
0.71073
Monoclinic
P21/n
T/K
296
Theta max/°
Dataset h max
Dataset k max
Dataset l max
Reflections
No. of parameters
R1, wR2
25.090
Color, habit
Colorless, needle
5.2417
6
˚
a/A
21
˚
b/A
17.8787
6.3099
7
˚
c/A
847
a/°
b/°
c/°
90
97
112.431
90
0.0370, 0.1059
1.067
S
3
˚
Volume/A
546.59
Device type
Solution
Oxford Xcalibur3 CCD
SHELXS-97
SHELXL-97
Multi-scan
Z
2
Calculated density/g cm-3
l/mm-1
1.775
Refinement
Absorption correction
0.162
Table 2 Experimental conditions of DNABT by ARC
Parameters
Values
Parameters
Values
Sample mass/g
Sample heat capacity default/kJ kg-1 K-1
0.1017
Start temperature/°C
End temperature/°C
Temperature step/°C
Temperature rate sensitivity/°C min-1
Wait time/min
50
2.00
350
15
Test cell type
Hastelloy
14.1784
0.42
Test cell mass/g
Test cell heat capacity/kJ kg-1 K-1
0.02
15
Test mode
Heat-wait-search
Calculation temperature step/°C
0.20
120
5
60
5
1 °C/min
2 °C/min
4 °C/min
8 °C/min
221.80 °C
212.60 °C
237.11 °C
4
TG
100
DTG
0
40
20
3
80
2
203.36 °C
193.20 °C
–5
60
1
40
DSC
0
–10
–15
0
Δ
210.86 °C 263.22 °C
20
–1
–2
142.01 °C
0
–20
350 400
150 200 250 300
Temperature/°C
0
50 100
0
100
200
300
400
Temperature/°C
Fig. 1 TG-DTG-DSC curve of DNABT at a heating rate of 10 °C min-1
Fig. 2 DTA curves of DNABT at the heating rates of 1, 2, 4, 8 °C min-1
temperatures (211.08, 218.66, 229.01, 239.34 °C) of the
first exothermic decomposition were observed at the heat-
ing rates of 1, 2, 4, 8 °C min-1, respectively. The onset
temperatures (211.08, 218.66, 229.01, 239.34 °C) and final
temperatures (248.78, 256.65, 262.66 272.45 °C) of the
second exothermic decomposition were observed at the
heating rates of 1, 2, 4, 8 °C min-1, respectively. However,
it was difficult to identify the peak temperatures of the
second exothermic decomposition at the heating rates of 1,
2, 4, 8 °C min-1. There was only a single discernible
exothermic peak during the two exothermic decomposition
123

F. Bao et al.
ꢀ
ꢁ
due to the well overlap of the two processes. When the
heating rate was high, the final temperature of the first
exothermic decomposition and the overlapping of two
exothermic decomposition were increased. A complete
overlap of the two exothermic decomposition is observed
Ah
¼
DG ¼ Ea À RTP0 ln
;
ð5Þ
ð6Þ
ð7Þ
kBTP0
¼
DH ¼ Ea À RTp0;
¼
¼
DH À DG
¼
in Fig. 1 at a heating rate of 10 °C min-1
.
DS ¼
;
Tp0
To determine the non-isothermal decomposition kinetic
parameters of energetic materials, Ozawa’s method [8] and
Kissinger’s method [9] were employed. The Ozawa’s
equation (1) and Kissinger’s equation (2) are given below:
where Tpi is the peak temperature of a heating rate of bi,
a and b are the coefficients, h is the Planck constant, kB is
the Boltzmann constant. The Tp0, DG=, DH= and DS= are
listed in Table 3.
ꢀ
ꢁ
0:4567Ea
1
log b ¼ À
þ C;
ð1Þ
ð2Þ
R
Tp
Critical temperature of thermal explosion (Tbp0
)
"
#
ꢀ
ꢁ
ꢀ
ꢁ
b
Tp2
Ea
1
RA
Ea
ln
¼ À
þ ln
;
The critical temperature of thermal explosion (Tbp0) is
R Tp
calculated by Eq. (8) [12, 13]:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
where Ea is the apparent activation energy which was
where b is the heating rate, Ea is the apparent activation
energy, R is the gas constant, Tp is the peak temperature, C
is an arbitrary constant and A is the pre-exponential factor.
The logb against 1/Tp and ln(b/T2p) against 1/Tp were two
straight lines. According to Eqs. (1) and (2), the slops of
two lines were used to calculate the activation energies.
According to Eq. (3), the obtained activation energies were
used to calculate the logarithm of pre-exponential factor
(log A/s-1).
Ea À Ea2 À 4EaRTP0
Tbp0
¼
ð8Þ
2R
obtained by Ozawa’s or Kissinger’s method.
Self-heating decomposition parameters
Under experiment conditions of ARC, heat from the
exothermic reaction of the sample induced the temperature
rise of both the sample and the reaction cell. The rela-
tionship between the real adiabatic and near-adiabatic
conditions was described as follows [14, 15].The corrected
and measured self-heating decomposition parameters of
DNABT are given in Table 4.
ꢂ
ꢃ
Ea
RTp2
Ea
A ¼ b
exp
;
ð3Þ
RTp
where Ea is the apparent activation energy which was
obtained by Ozawa’s or Kissinger’s method. The Ea, log A/
s-1 and corresponding regression coefficient (r) are listed
in Table 3.
MbCv;b
/ ¼ 1 þ
ð9Þ
MsCv;s
ꢀ
ꢁÀ1
Thermodynamic parameters at initial
decomposition temperature (Tp0)
1
R
To;corr
¼
þ
ln /
ð10Þ
To Ea
The initial decomposition temperature (Tp0) in the
exothermic decomposition process corresponding to b ? 0
is calculated by Eq. (4) [10, 11]. The free energy of acti-
vation (DG=), activation enthalpy (DH=), and activation
entropy (DS=) are calculated by Eqs. (5), (6), and (7) [11]:
Tf;corr ¼ /DTad þ To;corr
DTad;corr ¼ /DTad
mo;corr ¼ /mo
mm;corr ¼ /mm
Tm;corr ¼ To;corr þ /ðTm À ToÞ
ð11Þ
ð12Þ
ð13Þ
ð14Þ
ð15Þ
Tpi ¼ Tp0 þ abi þ bb2i i ¼ 1; 2; 3; 4;
ð4Þ
Table 3 Non-isothermal kinetic and thermodynamic parameters of DNABT
Method
Ea/kJ mol-1
log A/s-1
r
Tp0/°C
DG=/kJ mol-1
DH=/kJ mol-1
DS=/J mol-1 K-1
Tbp0/°C
Ozawa
132.90
131.77
13.73
13.61
0.9974
0.9971
190.71
190.71
126.24
126.23
129.04
127.91
6.04
3.64
205.01
205.14
Kissinger
123

Thermal decomposition and safety assessment of 3,30-dinitrimino-5,50-bis(1H-1,2,4-triazole) by…
Table 4 Self-heating decomposition parameters of DNABT by ARC
Parameters
Values
Corr.
Parameters
Values
Corr.
Onset temperature/°C
200.22
0.09
199.77
Adiabatic temperature rise/°C
Time to maximum rate/min
Maximum pressure/bar
32.45
31.15
14.53
30.28
982.34
Onset temperature rate/°C min-1
Temperature at maximum rate/°C
Maximum self-heating rate/°C min-1
Final temperature/°C
3.05
909.46
1.03
–
223.66
407.84
232.66
12,348.08
1182.11
Thermal inertia factor
–
Rearranging Eq. (17), we had [15]:
TMR
TMRcorr
¼
ð16Þ
mT
i
/
kà ¼ kC0nÀ1
¼
;
ð18Þ
h
nDTad
TfÀT
DTad
where / is the thermal inertia factor, Mb is the test cell
mass, Cv,b is the test cell heat capacity, Ms is the sample
mass, Cv,s is the sample heat capacity. To,corr and To are the
corrected and measured onset decomposition temperature,
respectively; Tf,corr and Tf are the corrected and measured
final decomposition temperature, respectively; DTad,corr and
DTad are the corrected and measured adiabatic temperature
rise, respectively; mo,corr and mo are the corrected and
measured onset temperature rate, respectively; mm,corr and
mm are the corrected and measured maximum self-heating
rate, respectively; Tm,corr and Tm are the corrected and
measured temperature at maximum rate, respectively;
TMRcorr and TMR are the corrected and measured time to
maximum rate, respectively.
where k* is a pseudo-zero-order rate constant at the tem-
perature T. According to the Arrhenius equation, one could
obtain [15].
ꢀ ꢁ
Ea
R
1
ln kà ¼ ln C0nÀ1A À
:
ð19Þ
T
The curves of lnk* versus T-1 for the self-heating
decomposition of DNABT are illustrated in Fig. 4. The Ea
and A could be calculated from the plot, and they are listed
in Table 5.
Time to maximum rate (TMR)
The ARC curves of DNABT are given in Fig. 3. As
shown in Fig. 3a, both a dehydration process and a self-
heating decomposition were observed. The dehydration
process started at 109.66 °C and ended at 123.05 °C, and
the pressure was increased by 1.30 bar during this period.
The self-heating decomposition started at 200.22 °C and
ended at 232.66 °C, within the time span of 50.65 min
(Fig. 3b). The maximum self-heating rate and maximum
According to the literature, the TMR and T have the fol-
lowing relationship [15].
ꢀ ꢁ
Ea
1
RT2
h
i
ln TMR ¼
À ln A þ ln
:
ð20Þ
C0nÀ1
nDTadEa
Tf ÀT
R T
DTad
From Table 5, n = 4, Ea was 659.59 kJ mol-1, log A/
s-1 was 66.01. Then, the plot of TMR versus T is given in
Fig. 5.
temperature
rate
were
407.84 °C min-1
and
20.54 bar min-1, respectively (Fig. 3c, d). It should be
noted that the released energy is in excess and therefore
would cause damage to the instrument if the decomposition
of DNABT was allowed to occur in a closed vessel.
Self-accelerating decomposition temperature
(TSADT
)
The TSADT is defined as the lowest ambient temperature in
air at which self-accelerating decomposition may occur
within a substance in the packaging as used in transport and
storage. The adiabatic decomposition kinetic parameters
were used for the estimation of the TSADT for DNABT in a
50 kg package. Firstly, Eq. (21) is used to get the time
Adiabatic decomposition kinetic parameters
For an nth-order single-step reaction with a single reaction,
the self-heating rate could be expressed as following [15]:
ꢀ
ꢁ
n
dT
dt
Tf À T
DTad
mT ¼
¼ k
DTadC0nÀ1
;
ð17Þ
constant (s), and then, the temperature of no return (TNR
)
would be obtained from the curve of TMR versus T. Lastly,
the TSADT was calculated based on Eq. (22) [16, 17].
where mT is the temperature rate at the temperature T, k is
the rate constant of the reaction at temperature T, T is the
temperature at time t, C0 is the initial concentration of the
reactant.
123

F. Bao et al.
240
230
220
210
20
15
10
5
400
300
200
100
0
20
15
10
5
a
b
Temperature
Pressure
Temperature
Pressure
200
190
0
0
0
100 200 300 400 500 600 700
Time/min
350 360 370 380 390 400 410 420
Time/min
25
240
230
220
210
20
15
10
5
c
d
Temperature
400
Pressure
Pressure rate
20
15
10
Temperature rate
300
200
100
0
5
0
200
190
0
–5
350 360 370 380 390 400 410 420
Time/min
350 360 370 380 390 400 410 420
Time/min
Fig. 3 ARC curves of DNABT. a Temperature and pressure versus time, b decomposition temperature and pressure versus time, c decomposition
temperature and temperature rate versus time, d decomposition pressure and pressure rate versus time
0
Table 5 Thermal decomposition kinetic parameters of DNABT by
ARC
n = 0
n = 1
n
Ea/
kJ mol-1
log A/s-1
r
–2
n = 2
n = 3
n = 4
0
1
2
3
4
368.11
441.59
515.06
588.54
659.59
37.08
44.40
51.72
59.04
66.11
0.9801
0.9846
0.9873
0.9890
0.9910
–4
–6
–8
0.00204
0.00206
0.00208
0.00210
0.00212
T–1/K–1
heat transfer coefficient U = 5 J m-2 K-1 s-1 had been
chosen for prediction of the TSADT. The TSADT of DNABT
was calculated as 175.37 °C.
Fig. 4 Curves of lnk* versus T-1 for the self-heating decomposition
of DNABT
MsCv;s
s ¼
;
ð21Þ
ð22Þ
Comparison of onset temperatures of DNABT
with other energetic materials
Ua
RTN2R
Ea
TSADT ¼ TNR
À
;
Muravyev et al. [5] obtained the onset temperatures of
some widely used energetic materials by ARC, such as
1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), dihydroxy-
lammonium 5,50-bistetrazole-1,10-diolate (TKX-50), and
octogen (HMX). Their onset temperatures are listed in
Table 6.
where U is the heat transfer coefficient and a is the contact
area of the system and environment. Assuming 50 kg
DNABT is loaded in the cylinder with the height of 60 cm
and the diameter of 30 cm, so the contact area of the
system and environment was 0.5652 m2. In this study, the
123

Thermal decomposition and safety assessment of 3,30-dinitrimino-5,50-bis(1H-1,2,4-triazole) by…
40
30
(n = 4). The self-accelerating decomposition temper-
ature (TSADT, 50kg) was calculated as 175.37 °C.
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Fig. 5 TMR versus temperature
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monium 5,50-bistetrazole-1,10-diolate (TKX-50). Phys Chem
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Compounds
RDX
177
TKX-50
192
DNABT
200.22
HMX
217
To/°C
From Table 6, it could be concluded that the onset
temperature of DNABT was determined in the ARC
experiments was found to be lower than that of HMX, but
higher than that of TKX-50.
Conclusions
In conclusion, the thermal decomposition and safety
assessment of DNABT by TG-DTG-DSC, DTA, and ARC
were reported in detail.
9. Kissinger HE. Reaction kinetics in differential thermal analysis.
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Thermal decomposition behaviour, kinetics, and thermal hazard
evaluation of CMDB propellant containing CL-20 by
1. The TG-DTG-DSC measurement showed that the
endothermic dehydration process started at 133.98 °C
and ended at 157.98 °C, and the exothermic decom-
position started at 210.86 °C and ended at 263.22 °C.
2. The non-isothermal decomposition kinetic and ther-
modynamic parameters that were obtained by the
Ozawa’s and Kissinger’s methods for DNABT showed
good correlation, but the values obtained by Ozawa’s
method were slightly higher than those obtained by
Kissinger’s method.
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ˇ
ˇ
´
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3. The critical temperature of thermal explosion (Tbp0
)
obtained by Ozawa’s and Kissinger’s methods were
calculated as 205.01 and 205.14 °C, respectively.
4. The adiabatic experiment by ARC revealed that the
self-heating decomposition started at 200.22 °C and
ended at 232.66 °C, within the time span of 50.65 min.
The maximum self-heating rate was calculated as
407.84 °C min-1. The apparent activated energy under
adiabatic condition was calculated as 659.59 kJ mol-1
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