Sie sind auf Seite 1von 4

CHEM. RES.

CHINESE UNIVERSITIES 2012, 28(3), 516519

Thermal Behavior and Thermal Safety of Nitrate


Glycerol Ether Cellulose
XU Si-yu1, ZHAO Feng-qi1*, YI Jian-hua1, GAO Hong-xu1, SHAO Zi-qiang2,
HAO Hai-xia1, HU Rong-zu1 and PEI Qing1
1. Science and Technology on Combustion and Explosion Laboratory,
Xian Modern Chemistry Research Institute, Xian 710065, P. R. China;
2. School of Materials Science and Engineering, Beijing Institute of Technology,
Beijing 100081, P. R. China
Abstract The thermal behavior, nonisothermal decomposition reaction kinetics and specific heat capacity of nitrate
glycerol ether cellulose(NGEC) were determined by thermogravimetric analysis(TGA), differential scanning calorimetry(DSC) and microcalorimetry. The apparent activity energy(Ea), reaction mechanism function, quadratic equation of specific heat capacity(Cp) with temperature were obtained. The kinetic parameters of the decomposition reaction are Ea=170.2 kJ/mol and lg(A/s1)=16.3. The kinetic equation is f ()(4/3)(1)[ln(1)]1/4. The specific heat
capacity equation is Cp=1.2856.276103T+1.581105T2(283 K<T<353 K). With these parameters, the thermal
safety properties of NGEC were studied, such as the self-accelerating decomposition temperature(TSADT), critical
temperature of thermal explosion(Tb) and adiabatic time-to-explosion(tTlad). The results of the thermal safety evaluation of NGEC are: TSADT=459.6 K, Tb=492.8 K, tTlad=0.8 s.
Keywords Nitrate glycerol ether cellulose; Thermal decomposition reaction kinetics; Thermal safety property
Article ID 1005-9040(2012)-03-516-04

Introduction

Nitrocellulose(NC) is a major binder of solid rocket or gun


propellant and is a basic material of maintaining mechanical
properties and energy properties for a long time. However,
there is a contradiction between mechanical properties on the
one hand and energy properties on the other hand for NC. For
NC, the energy property decreases with nitrogen content
decrease, while the mechanical property decreases, especially
at a low temperature, with nitrogen content increase because of
bad consistency between NC and nitroglycerin(NG). So the
development of high energy solid propellant has been
restricted[1,2]. In order to find an excellent substitute of NC, a
lot of work has been done. Recently, nitrate glycerol ether
cellulose(NGEC), a ramification of NC, has been synthesized.
It is a new kind of thermal plastic cellulose binder and its appearance is similar to that of nitrocellulose. There are small
molecule branch chains in the big molecule main chain of
NGEC[35]. The physical and chemical properties of the two
materials are different obviously. In order to study the thermal
safety of NGEC, the thermal behavior, thermal decomposition
mechanism, specific heat capacity(Cp) and thermal safety
property parameters were investigated by thermogravimetric
analysis(TGA), differential scanning calorimetry(DSC) and
microcalorimetry. The results obtained are very useful for
understanding the thermal properties and application of NGEC.

2
2.1

Experimental
Sample

The sample used in the experiments was NGEC made in


Beijing Institute of Technology(China). It is a white powder,
and nitrogen percentage is 13.1%. Its formula is [C9H12O15N4]n
and the chemical structural formula is shown in Fig.1.

Fig.1

2.2

Structural formula of NGEC

Experimental Equipments and Conditions

The DSC experiments were carried out on a differential


scanning calorimeter(DSC, Model 204HP Netzsch Co., Germany). Samples about 1.00 mg were heated at rates of 2.5, 5,
7.5, 10, 12.5 and 15 K/min under the protection of flowing
nitrogen gas(purity 99.999%, flowing rate 40 mL/min).
Thermogravimetric analysis of sample was carried out on
a thermogravimetric analyzer(Model TGA2950, TA Co., USA)
at a heating rate of 10 C/min and a N2 flow of 40 mL/min.
The specific heat capacity of NGEC was determined on a

*Corresponding author. E-mail: npecc@163.com


Received July 13, 2011; accepted August 30, 2011.
Supported by the Foundation of National Key Laboratory of Science and Technology on Combustion and Explosion of China
(No.9140C3503011004).

No.3

XU Si-yu et al.

Micro-DSCIII apparatus(Setaram Co., France) and the amount


of sample was 76.8 mg. The heating rate was 0.10 K/min from
283.1 K to 353.2 K, in which the precisions of temperature and
heat flow were 1.0104 K and 0.2 W, respectively. The principle for measuring the continuous specific heat capacity is
shown as follows:

Cp =

( As Ab )
ms

(1)

where As and Ab are the heat flows of the sample and blank,
respectively, ms is the amount of the sample, and is the
heating rate.

Results and Discussion

3.1 Thermal Behavior and Nonisothermal Reaction Kinetics


The DSC curves at different heating rates at 0.1 MPa and
TG-DTG curves at a heat rate of 10 K/min for NGEC sample
are shown in Figs.2 and 3, respectively. There is only an exothermic peak on each DSC curve at 0.1 MPa. From the typical
DSC and TG-DTG curves(Figs.2 and 3), it can be seen that
NGEC has an intense exothermic decomposition process with a
mass loss of about 87.8% during thermal decomposition. From
Fig.2, some important parameters at different heating rates are
obtained, such as the beginning temperature(T0), the extrapolated onset temperature(Te), peak temperature(Tp) and exothermic decomposition enthalpy(Hd). These parameters are listed
in Table 1.

517

obtained with the conversion degree of main exothermical peak


changing from 0.08 to 0.84. Five integral methods(General
integral, MacCallum-Tanner, atava-estk, Agrawal, and
Flynn-Wall-Ozawa) and one differential method(Kissinger)
were employed[69]. The calculated values of Ea, lgA, linear
correlation coefficient(r) and standard mean square deviation(Q)
are listed in Table 2. The decomposition reaction mechanism
functions of NGEC sample are listed in Table 2, too.
Table 1

Values of T0, Te, Tp and Hd of the thermal


decomposition process determined by DSC
curves at different heating rates()
Initial value

/(Kmin1)

T0/K
422.6
427.5

2.5
5.0

Hd/(Jg1)
1709
1834

Tp/K
492.0
498.6

7.5

432.4

487.4

502.6

1939

10.0

435.6

490.9

505.3

1920

12.5

439.4

493.3

507.6

1942

15.0

442.3

494.6

510.4

1782

Table 2

Kinetic parameters for the decomposition


process of NGEC sample at 0.1 MPa*

Method

/(Kmin1)

Generalintegral

2.5
5
7.5

Ea/(kJmol1 lg(A/s1)
)
161.5
15.4
166.5
16.0

0.9864
0.9854

0.3613
0.3887
0.3940

165.4

15.9

0.9852

10

171.4

16.6

0.9845

0.426

12.5

176.2

17.1

0.9847

0.4079

15

0.3406

175.5

17.1

0.9872

MacCallum-

2.5

161.8

15.4

0.9876

0.0679

Tanner

167.0

16.0

0.9867

0.0730

7.5

0.0740

atava-estk

Agrawal

Fig.2

Te/K
474.8
483.0

DSC curves of NGEC sample at different


heating rates under 0.1 MPa

Heating rate/(Kmin1): a. 2.5; b. 5; c. 7.5; d. 10; e. 12.5; f. 15.

165.9

15.9

0.9865

10

172.1

16.6

0.9859

0.0775

12.5

176.9

17.2

0.9860

0.0766

15

0.0640

176.2

17.1

0.9884

2.5

161.0

15.4

0.9876

0.0679

165.8

16.0

0.9867

0.0730

7.5

0.0740

164.9

15.8

0.9865

10

170.6

16.5

0.9859

0.0775

12.5

175.2

17.0

0.9860

0.0766

15

0.0640

194.5

17.0

0.9884

2.5

161.5

15.4

0.9864

0.3613

166.5

16.0

0.9854

0.3887

7.5

0.3940

165.4

15.9

0.9852

10

171.4

16.6

0.9845

0.4126

12.5

176.2

17.1

0.9847

0.4079

15

175.5

17.1

0.9872

0.3406

Mean

170.2

16.3

0.9862

0.2287

Flynn-Wall-Ozawa

178.2(EpO)
148.6(EeO)

Kissinger

179.5

Mechamism function

0.9987(EpO) 0.0010
0.9986(EeO)
17.7

0.9986

0.0056

f()(4/3)(1)[ln(1)]1/4

* E with the subscript of eO, and pO is the apparent activation energy


obtained from the extrapolated onset temperature(Te) and the peak temperature(Tp) by Ozawas method.

Fig.3

TG-DTG curves of NGEC sample at a heating


rate of 10 K/min
The data of DSC curves of NGEC at six different heating
rates were dealt with mathematic means. The values of Ea were

3.2 Self-accelerating Decomposition Temperature


(TSADT)
The values(T00, Te0 and Tp0) of the initial temperature point
at which DSC curve deviates from the base line(T0), onset

518

CHEM. RES. CHINESE UNIVERSITIES

temperature(Te) and peak temperature(Tp) corresponding to


0 were obtained by Eq.(2), and the self-accelerating decomposition temperature(TSADT) was obtained by Eq.(3)[1015].
The values of T00, Te0(or TSADT) and Tp0 are 416.9, 459.6 and
481.5 K, respectively.
(2)
T0(or e or p)=T00(or e0 or p0)+a+b2+c3+d4
TSADT=Te0
(3)
where a, b, c and d are coefficients.

Vol.28

wide temperature application.

3.3
Thermal Ignition Temperature(TTIT) and
Critical Temperature of Thermal Explosion(Tb)
The thermal ignition temperature(Tbe0 or TTIT) was obtained by substituting EeO and Te0 into Eq.(4)[9,10], and the critical temperatures of thermal explosion(Tbp0 or Tb) was obtained
by substituting EpO and Tp0 into the equation. The values of TTIT
and Tb are 472.1 and 492.8 K, respectively. The values of Tb for
NGEC show that the threshold for ignition and thermal explosion is larger.

EO EO 2 4 EO RT0
(4)
2R
where EO is the value of E obtained by Ozawas method and R
is the gas constant.
Tb =

3.4 Thermodynamic Parameters of Activation


Reaction
The entropy of activation(S), the enthalpy of activation
(H ), and the free energy of activation(G) of the main exothermic decomposition process corresponding to T=Tp0, A=AK,
and E=EK were obtained by Eqs.(5)(7)[1113]. The values of
S, H and G are 114.5 J/(molK), 167.7 kJ/mol and 133.6
kJ/mol respectively. The positive vales of G indicate that the
exothermic decomposition of NGEC must proceed under the
heating condition.

Fig.4

3.6

Determination results of the continuous Cp(a) and


heat flow with(b) and without(c) NGEC

Adiabatic Time-to-explosion(tTlad)

Energetic materials need time from the beginning thermal


decomposition to thermal explosion under adiabatic conditions.
It is called the time as the adiabatic time-to-explosion[10,1315].
Ordinarily, we use heating rate(dT/dt) and critical heating
rate(dT/dt)Tb in thermal decomposition process to evaluate the
thermostability of energetic materials. However, we can calculate the tTlad by means of following Eqs.(9)(11)[10,1315] when
we have obtained a series of experimental data. As an important
parameter, it is very easy and intuitionistic to evaluate the
thermostability of energetic materials according to the magnitude of tTlad.

S
k T
A = B exp

h
R

E
A exp
RT

S
H
kBT
exp
exp

=
h

R
RT

(5)
(6)

G = H TS
(7)
where kB is the Boltzman constant and h is the Plank constant.

3.5

Specific Heat Capacity

Fig.4 shows the determination results of the specific heat


capacity of NGEC by a continuous specific heat capacity mode
of Micro-DSCIII apparatus. It can be seen that the Cp of NGEC
presents a good linear relationship with temperature in the determined temperature range. And the specific heat capacity
equation is obtained by the result. It is shown as Eq.(8).
Cp=1.2856.276103T+1.581105T2
(8)
(283 K<T<353 K), R2=0.9989
So the calculated standard molar specific heat capacity of
NGEC by Eq.(8) is 230.20 J/(molK) at 298.15 K. Although
only 70 K range is taken in the determination process, the
specific heat capacity equation obtained is a stable and continuous, which can provide a reference and some help for the

dT
E
= QA exp
f ( )
dt
RT
t
Tbp0 C p exp ( E RT )
dT
= dt =
0
Te 0
QAf ( )
Cp

tTlad

Tbp0

Cp

Te 0

dT

(9)
(10)
(11)

where t is the adiabatic time-to-explosion, Q is the exothermic


value, A is the pre-exponential factor, E is the apparent activation energy of the main exothermic stage, R is the gas constant,
f () is the most probable kinetic model function, and is the
fraction of conversion.
The scope of the temperature integration is from Te0 to
Tbp0. The reaction mechanism function is f ()=(4/3)(1)
[ln(1)]1/4. The value of tTlad for NGEC is 0.8 s via
Eqs.(9)(11), acco(8)rding to the above experimental results.
The adiabatic time-to-explosion of NGEC is a very short time,
and it can be proved credible according to the change of DSC
curve in the exothermic decomposition stage.

Conclusions

There is one main exothermic decomposition process in


DSC and TG-DTG curves according to NGEC. The kinetic
function in differential form, apparent activation energy and
pre-exponential constant of this reaction are (4/3)(1)
[ln(1)]1/4, 170.2 kJ/mol and 1016.3 s1, respectively.
The values of S, H and G of the main exothermic
decomposition of NGEC are 114.5 J/(molK), 167.7 kJ/mol and
133.6 kJ/mol, respectively.

No.3

XU Si-yu et al.

The specific heat capacity equation of NGEC is


Cp=1.285 6.276103T+1.581105T2(283K<T<353K) and the
standard molar specific heat capacity is 230.2 J/(molK) at
298.15 K.
The thermal safety properties of NGEC, such as TTIT, Tb
and tTlad are 472.1 K, 492.8 K and 0.8 s, respectively. These
data show that the threshold for ignition and thermal explosion
is larger, while the transition from thermal decomposition to
thermal explosion is easier.

[6]

[1]

Shao Z. Q., Zhang Y. D., Yang F. F., L S. Y., Wang J. X., Chinese
Journal of Energetic Materials, 2008, 16(5), 609

[2]

Xu W., Wang X. J., Liu X. X., Li Z. L., Journal of Rocket Propulsion, 2007, 32(2), 44

[3]

Wang F. J., Yang F. F., Wang J. N., Shao Z. Q., Chin. J. Explos. &
Propell., 2006, 29(6), 51

[4]

Shao Z. Q., Wang F. J., Yang F. F., Zhao F. Q., Tan H. M., Chin. J.
Energ. Mater., 2004, 12(3), 138

[5]

Shao Z. Q., Wang W. J., Wang F. J., Sun J. G., Tan H. M., Liao B.,
Cellul. Sci. & Tech., 2004, 12(2), 1

Hu R. Z., Gao S. L., Zhao F. Q., Shi Q. Z., Zhang T. L., Zhang J. J.,
Thermal Analysis Kinetics, 2nd Ed., Science Press, Beijing, 2008

[7]

Gao H. X., Zhao F. Q., Hu R. Z., Xu K. Z., Zhang H. H., Wang P.,
Du Z. M., Xu S. Y., Yi J. H., Ma H. X., Chang C. R., Song J. R.,
Chem. J. Chinese Universities, 2008, 29(5), 981

[8]

Xu K. Z., Song J. R., Zhao F. Q., Ma H. X., Gao H. X., Chang C. R.,

[9]

Zhang H., Hu R. Z., Zhao F. Q., Gao H. X., Ma H. X., Chem. Res.

Hu R. Z., J. Hazard. Mater., 2008, 158, 333


Chinese Universities, 2010, 26(3), 436
[10]

References

519

Zhang T. L., Hu R. Z., Xie Y., Li F. P., Thermochim. Acta, 1994,


244, 171

[11]

Yi J. H., Zhao F. Q., Xu S. Y., Gao H. X., Hu R. Z., Chem. Res.


Chinese Universities, 2008, 24(5), 608

[12]

Yi J. H., Zhao F. Q., Xu S. Y., Zhang L. Y., Gao H. X., Hu R. Z., J.


Hazard. Mater., 2009, 165, 853

[13]

Xue L., Zhao F. Q., Xing X. L., Xu S. Y., Pei Q., Gao Y., Hu R. Z.,
Chem. Res. Chinese Universities, 2010, 26(4), 626

[14]

Hu R. Z., Zhao F. Q., Gao H. X., Zhang J. Q., Zhang H., Ma H. X.,
Chin. J. Chem. 2009, 27(11), 2145

[15]

Zhao F. Q., Hu R. Z., Zhang H., Gao H. X., Zhao H. A., Ma H. X.,
Chem. Res. Chinese Universities, 2010, 26(5), 829

Das könnte Ihnen auch gefallen