Combustion and Flame 221 (2020) 212–218
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Combustion and Flame
journal homepage: www.elsevier.com/locate/combustflame
Effect of ageing on the combustion of single base propellants
Bianca Figueirôa de Souza Defanti a,b, Letivan Gonçalves de Mendonça-Filho a,
Jakler Nichele a,c,∗
a
Chemical Engineering Department, Military Institute of Engineering, Rio de Janeiro, RJ, Brazil
Brazilian Navy Weapon System Directorate, Rio de Janeiro, RJ, Brazil
c
Defense Engineering Department, Military Institute of Engineering, Rio de Janeiro, RJ, Brazil
b
a r t i c l e
i n f o
Article history:
Received 10 February 2020
Revised 20 July 2020
Accepted 21 July 2020
Keywords:
Propellant ageing
Combustion properties
Burning rate
Closed vessel
a b s t r a c t
This paper shows how the combustion properties of single base nitrocellulose propellants are affected by
degradation by ageing. A single base gunpowder sample containing methyl centralite and ethyl centralite
as stabilizers was artificially aged by 10, 20 and 25 years. Closed vessel experiments were performed to
evaluate the burning rate, the dynamic vivacity, the maximum pressure, the force, and the covolume of
the gases produced. The propellant degradation was characterized by the Bergmann-Junk test, heat flow
calorimetry test (HFC), high performance liquid chromatography (HPLC) and gel permeation chromatography (GPC). Gel permeation chromatography was especially useful to describe the degradation process.
The results found for the burning rate suggest the existence of two phases during ageing: intensification
and passivation. The intensification phase occurs while the propellant samples maintain the chemical
stability and the passivation phase was observed for the unstable samples.
© 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
1. Introduction
Single base propellants constitute an important class of energetic materials which are used in ammunitions of small guns to
large caliber weapons. These propellants are basically made from
nitrocellulose. Other substances can be added in small portions to
improve its mechanical properties, to reduce the combustion temperature, to modify the burning rate, to facilitate the loading of
ammunition, and to slow down its chemical degradation [1,2].
It is common for ammunition to be stored for large periods before being used. Therefore, the ammunitions which use single base
propellants require special attention. Nitrocellulose, their main ingredient, undergoes spontaneous and autocatalytic decomposition
which results in a pronounced chemical degradation [3–8]. The
self-ignition is favored in degraded NC based propellants and it
was the reason of large accidents in different countries, such as
Zimbabwe (1981), North Korea (1991), USA (1996, 1997, 1998),
Brazil (1996), Finland (1999), Japan (20 0 0), El Salvador (20 0 0),
India (2001, 2016), Russia (2002), Syria (2007), Tanzania (2009),
Cyprus (2011) [9,10].
Besides the chemical integrity, the combustion properties of
propellants must also be maintained during the propellant service
life. However, the effect of ageing on the combustion properties
of propellants is not clear. Literature reports that ageing can increase or decrease the maximum pressure developed in the combustion chamber depending on the propellant formulation [11].
Recent works concluded that the effect of ageing on combustion
properties depends on the ageing method applied [12,13].
The present work investigated the effect of ageing on the combustion of single base propellants and presents new results which
clarify the question. Samples of single base propellants were submitted to artificial ageing and typical combustion properties used
in ballistic studies were measured: calorific value, maximum pressure, mean dynamic vivacity, maximum burning rate, covolume,
and force. The degradation level of the propellants was evaluated by measuring the NO volume evolved, the stabilizer content, the mean molecular weight distribution of nitrocellulose, and
the maximum heat flux during ageing, using the Bergmann-Junk
method, the high-performance liquid chromatography (HPLC), the
gel permeation chromatography (GPC), and the heat flow calorimetry (HFC) techniques, respectively.
2. Theoretical background
2.1. Evaluation of chemical degradation of single base propellants
∗
Corresponding author at: Military Institute of Engineering, Rio de Janeiro, RJ,
Brazil.
E-mail address: jakler@ime.eb.br (J. Nichele).
Nitrocellulose is a polymer derived from cellulose nitration. Due
to the low bond energy of the H2 C–O–NO2 group, these bonds
https://doi.org/10.1016/j.combustflame.2020.07.029
0010-2180/© 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
B.F.S. Defanti, L.G. Mendonça-Filho and J. Nichele / Combustion and Flame 221 (2020) 212–218
breakdown easily, leading to a natural and autocatalytic degradation process [14,15].
The decomposition of a propellant can be estimated by monitoring the change in some chemical and physical properties. During this process some changes occur in weight, volume of gases
released, heat of combustion and concentration of stabilizer, for
example. The tests which evaluate the level of degradation of the
propellant are usually called chemical stability tests. Traditional
stability tests, such as the Abel heat test, methyl violet test, and
Bergmann–Junk test are limited. That is why new evaluation techniques based on analytical methods were developed, including
chromatographic and thermal analysis techniques [16].
Regarding to chromatographic techniques, some examples are
the high-performance liquid chromatography (HPLC), gas chromatography (GC), size-exclusion chromatography (SEC), and gel
permeation chromatography (GPC). The thermal analysis techniques include differential scanning calorimetry (DSC), heat flow
calorimetry (HFC), among others [14,15]. These techniques based
on heating can simulate the ageing process by submitting the propellant sample to high temperatures which accelerate the ageing.
Naturally, the higher temperatures may induce the occurrence of
other chemical reactions from a thermodynamic point of view. Because of that, international standards [17,18] are especially useful
to establish special conditions for each of these technique in order
to mitigate the effect of the extra reactions.
213
can be computed as the average of over P/Pmax in the range
0.3 ≤ P/Pmax ≤ 0.7 taken in steps of P/Pmax of 0.1. Finally, the burning rate is computed with Eq. (1) rewritten in the form
r=
de
de dz dP
=
·
·
dt
dz dP dt
(5)
where
V0 p
de
=
·
dz
S0 p
1
(6)
φ (z )
and
dz
1 1 + (η − 1/ρ )Pmax / f
=
dP
Pmax [1 + (η − 1/ρ )P/ f ]2
(7)
being z the mass fraction of the remaining propellant, which can
be aproximated by the ratio P/Pmax , V0 p (m³) the initial volume of
the propellant grain, S0 p (m²) the initial surface area of the propellant grain, φ (z) the dimensionless form function, and ρ (g/m³) the
propellant density. In Eq. (6), φ (z) is the ratio between the burning
surface area S and S0 p [22],
S
φ (z ) =
=
S0 p
1−
4θ z
( 1 + θ )2
(8)
where θ is the dimensionless form function constant and can be
calculated as the ratio of propellant grain thickness to length [27].
2.2. Solid propellants combustion
3. Methodology
The combustion in solid propellants is known as a very complex
surface phenomenon [19,20]. However, for simplicity, the burning
of these materials can be investigated from few quantities. The
burning rate of a propellant depends on the available surface of
the propellant grains, its geometry, the combustion chamber pressure, the initial temperature of the propellant and its formulation
[21].
The burning rate, r (m/s), can be defined as the rate of decrease
of the smallest thickness of the propellant grain e (m) [21,22], i.e.
r=
de
.
dt
(1)
Alternatively, as the gas produced during the combustion is related to the burning rate, r can also be expressed in terms of the
chamber pressure P (Pa) for a fixed volume [23,24]. The most usual
is the Vieille’s law [25,26], given by
r = β Pα ,
(2)
where the constants α and β depend on the chemical compositon
of the propellant [27].
The burning rate of propellants can be computed from pressure experimental data obtained with the closed vessel technique
[12,13,28–30]. With these data, other ballistic properties, such as
force f (J/g), specific covolume η (m³/g), and dynamic vivacity (1/Pa.s) can be calculated [22]. The recorded values of the maximum pressure in the combustion cell Pmax (Pa) and the corresponding loading density d (g/m³) – the mass of propellant divided
by the vessel volume –, allows one to obtain f and η from a linear
regression in the form
Pmax
= ηPmax + f.
d
(3)
The dynamic vivacity, given by
=
1 dP
1
· ·
,
Pmax P dt
(4)
provides information about the evolution of the surface area of
the propellant grains during the combustion [22]. From the values of computed with Eq. (4), the mean dynamic vivacity m
3.1. Samples ageing
Single base monoperforated gunpowder samples were used in
this study. The samples were made with nitrocellulose, methyl
centralite (MC) and ethyl centralite (EC) as stabilizers, and
dibutylphtalate (DBP) as plasticizer. They were aged artificially in
heating blocks using glass tubes with 1.4 cm in diameter and
18 cm in length, with stoppers, filled to the top. Each tube contained 17 g of propellant. The samples were maintained at 90 °C
and during 83.7, 167.5 and 209.3 h, which correspond to 10, 20 and
25 years of natural ageing, respectively, according to NATO/AOP48 Ed. 2 [17]. This standard establishes an activation energy Ea of
120 kJ/mol for ageing temperatures above 60 °C and Ea of 80 kJ/mol
for temperatures below 60 °C.
3.2. Chemical characterization of degradation
The aged samples were characterized in terms of its chemical
stability, decrease of its calorific value, the stabilizer consumption,
and molecular weight distribution of nitrocellulose.
The Bergmann-Junk test was applied to evaluate the chemical
degradation of the samples from the NO volume evolved [31–33].
5.0 g of propellant were heated at 132 °C by 5 h in a glass tube
coupled to a special glass tube with a KI solution (4.5% w/w). During the heating, the NO gases evolved were absorbed by the solution. The resulting solution was titrated with Na2 S2 O3 0.01 N
and an aqueous starch solution as indicator and the volume of NO
evolved VNO (mL/g) was computed.
Once nitrocellulose degradation is an exothermic process
[34,35], the heat production during artificial ageing process
provides information about the degree of degradation. Hence,
heat flow calorimetry (HFC) is specially useful. According to
NATO/STANAG 4582 [17], we used 10.5 g of propellant to fill the15
mL HFC vessel, corresponding to a loading density of 0.7 g/mL. Using a TNO HFC equipment, the sample was maintained at 85 °C for
5.98 days – time equivalent to an isothermal storage at 25 °C for 10
years –, while heat flux data were recorded as a function of time
214
B.F.S. Defanti, L.G. Mendonça-Filho and J. Nichele / Combustion and Flame 221 (2020) 212–218
(q × t). The decrease in the calorific value of the samples,
computed by
Q=
1
Q
Q, was
ttotal
qdt
(9)
0
where Q is the calorific value obtained with a traditional bomb
calorimetry test.
The changes in the propellant composition and structure resulted from ageing were evaluated with HPLC and GPC methods.
HPLC was used to determine the remaining stabilizer content in
the aged samples. The stabilizers were extracted from the samples
by diluting 1 g of propellant in aqueous solution of acetonitrile of
60% (v/v). The final solution was stirred during 4 h and rested for
1 h. After this time, the solutions were filtered and analysed on
a chromatograph coupled to an UV detector at 250 nm, using a
C-18 column with 2.7 μm, 4.6 × 50 mm. The mobile phase consisted of 50% (v/v) of acetonitrile-water solution at a flow rate of
0.7 mL/min, with column temperature of 35 °C. GPC technique was
used to evaluate the mean molecular mass distribution of nitrocellulose. 9 mg of each sample was diluted in 3 mL of tetrahydrofuran and the solution was stirred during 24 h. Then, 100 μL of this
solution was injected in the GPC system, using tetrahydrofuran as
the mobile phase. The test was performed at 40 °C. The GPC system has a refraction index detector and three columns with size
8.0 × 300 mm, being one for weight average molecular weight Mw
(daltons) in the range 30 0–20 0 0,0 0 0 Daltons and two for the range
100 – 300,000 Daltons, where
Ni Mi2
Mw = ,
Ni Mi
Fig. 1. VNO evolved during artificial ageing.
(10)
being Mi (daltons) the molecular weight of the polymer chain and
Ni the number of chains of that molecular weight. With the results,
the number average molecular weight Mn (daltons), given by
Ni Mi
Mn = ,
Ni
(11)
Fig. 2. Normalized decrease in the stabilizers content during artificial ageing.
and the polydispersity degree D (≡ Mw /Mn ) were determined.
3.3. Ballistic tests
The ballistic tests were performed using a TNO closed vessel
system with a 200 cm³ combustion cell. In order to produce a uniform combustion of propellant grains in the chamber [36], a small
bag containing 0.4 g of class 5 black powder also was used as igniter in addition to the electric match device.
The test allowed us to obtain the pressure evolution of the
gases generated during the propellant burning in the vessel. The
force and the covolume were computed using Eq. (3) and three
values of d: 10%, 12.5% and 15% (w/v). The dynamic vivacity and
the burn rate were calculated by a self-made computer code based
on Eqs. (4)–8.
4. Results and discussion
Fig. 3. Differential molecular weight distribution (dW/dlog M).
4.1. Chemical characterization of degradation
The results obtained with the Bergmann-Junk test showed how
the ageing process increased the VNO per unity of mass (Fig. 1). As
expected, the more aged the propellant, the greater the volume of
NO evolved in the test indicating the degree of degradation. In addition, HPLC tests demonstrated the reduction in stabilizer concentration typical of single base gunpowder ageing processes (Fig. 2).
For safety reasons, it is required that VNO < 1.8 mL/g and the decrease in stabilizer content was not bigger than 80% [17,33]. Once
the results showed that the gunpowder samples were safe for handling, other properties were evaluated.
The results of the differential molecular weight distribution obtained from GPC analysis is shown in Fig. 3 and the results obtained for Mn and D are shown in Fig. 4.
The Mn data are strongly correlated with the ageing time and
the results indicated that the molecular weight of nitrocellulose
chains decreased with ageing. In parallel, the increase in the polydispersity degree, except for the sample aged for 20 years, is related to the decrease in the uniformity of the molecular sizes,
which is in accordance to published data [37]. The results of Mn
also indicated that nitrocellulose degradation becomes more intense with ageing time.
B.F.S. Defanti, L.G. Mendonça-Filho and J. Nichele / Combustion and Flame 221 (2020) 212–218
Fig. 4. Mn and D data described in terms of ageing time. We found the correlation
Mn (t) = –0.1912t2 – 0.2757t + 155.27 (R2 = 0.99999), being t in years and Mn in
kDa.
Fig. 6. Results for the maximum pressure Pmax in terms of the ageing time measured for three loading densities: 10%, 12.5%, and 15%.
Fig. 7. Results obtained for the covolume η along ageing.
Fig. 5. Heat flow measurements for each sample of aged propellant.
Table 1
Results of qmax , Q and
215
4.2. Ballistic tests
Q obtained in the tests by HFC.
Sample
qmax (mW/kg)
Q (cal/g)
Unaged
Aged for 10 years
Aged for 20 years
Aged for 25 years
85.04
112.91
174.26
220.14
790
754
743
759
Q (%)
0.62
0.85
1.25
1.37
As the previous results, the increase of nitrocellulose degradation was observed in heat flow calorimeter test, by increase of heat
flow as a function of the ageing time (Fig. 5).
The results obtained for qmax (mW/kg) from heat flow calorimetry and Q (%) computed with Eq. (9) are presented in Table 1. The
sample aged for 25 years showed a qmax > 201 mW/kg, which is
considered unsafe for handling and storage, while the other samples are classified as safe, if isothermically storaged at 25 °C [18].
Table 1 also shows the calorific value, Q (cal/g), obtained from traditional calorimetry and the results did not show a clear trend of
increase or decrease for this property. Despite this, the decrease in
calorific value Q showed to be larger with the ageing time.
In summary, the samples aged for periods corresponding to 10
and 20 years of natural ageing were classified as safe according to
all quality parameters evaluated. On the other hand, the sample
aged for 25 years, was considered unsafe for handling and storage by HFC test, according to the criterion of STANAG 4582 [18].
This criterion is related to the calculation the critical heat generation based on the Kamenetskki-Semënov theory for a cylinder with
fixed diameter of 230 mm [9,38].
The results obtained from the ballistic tests allowed the computation of the combustion properties of the propellant samples Pmax ,
m , and rmax . Using the Pmax values found for each loading density
d, 10%, 12.5% and 15% (w/v) (Fig. 6), and the Eq. (3), the covolume,
η, and the force, f, were computed (Figs. 7 and 8). Preliminary tests
using the closed vessel indicated a very good repeatability of the
method.
The values of Pmax (Fig. 6) recorded during the closed vessel
tests for each loading density were practically equal. Although the
values of the maximum pressure obtained from gun firing tests are
different from the Pmax values obtained in closed vessel tests [39],
this is an important parameter to evaluate the performance of ammunition by comparison with a reference sample. The results indicated that Pmax was not affected by ageing.
The covolume of the gases (Fig. 7) produced in the combustion,
was determined from a linear regression procedure based on
Eq. (3). Except for 20 years of ageing, which presented a decrease in 15%, the values found are the same. It suggests that the
chemical composition of gases produced during the combustion is
practically the same. The discrepancy found for 20 years suggest
a transitional behavior in the chemical composition of the propellant. This transitional behavior is confirmed with the values found
for f (Fig. 8). By comparing the results plotted in Figs. 8 and 9, we
found a similar behavior between f and m at 20 years of ageing.
The dependence of m on d is shown in Fig. 9. For the highest
value of d investigated, d = 15%, m has increased 31% approximately at 20 years. In parallel, for d = 10%, m has increased only
2.5% at 20 years. The results indicated that variations in m are
216
B.F.S. Defanti, L.G. Mendonça-Filho and J. Nichele / Combustion and Flame 221 (2020) 212–218
Fig. 8. Results obtained for the force f along ageing.
Fig. 9. Results for the mean dynamic vivacity m in terms of the ageing time measured for three loading densities: 10%, 12.5%, and 15%.
Fig. 11. Burning rate versus fraction of the burnt propellant of the tests with (a)
d = 10%; (b) d = 12.5%; and (c) d = 15% (w/v). The highest values of rmax are found
for the samples aged for 20 years.
Fig. 10. Results for the maximum burning rate rmax in terms of the ageing time
measured for three loading densities: 10%, 12.5%, and 15%.
more intense for higher loading densities. However, as the ammunitions have particular loading densities, the ageing will led to different behaviors depending on the ammunition design.
In contrast, when rmax is computed from the closed vessel data
using Eqs. (5) to (8), an increase was observed from 0 to 20 years,
and a decreasing behavior after this. For the three values of d, the
profile of rmax × t was similar, as shown in Fig. 10. This behavior
is in accordance with the results found for double base propellants
[12]. However, as we used here longer ageing periods than in Ref.
[12], we observed the decrease in rmax for 25 years, in comparison
to 20 years.
Once the stabilizers MC and EC also act as combustion moderators [40], the increase in rmax was probably related to the decrease
in the stabilizers content for the samples classified as safe, even
though Mn of nitrocellulose decreased with the ageing time. It suggests that, in the initial phase, the nitrocellulose degradation does
not interfere in the burning rate, but the reduction of MC and EC
has a predominant effect. As a consequence, for the samples aged
for 10 and 20 years, it was observed the intensification of rmax . On
the other hand, the sample aged for 25 years, showed passivation
of rmax . As the stabilizer content is small (0.26%), the decrease of
Mn is crucial in this step.
The similar studies found on literature about double base propellants did not carry out a complete evaluation of the degradation
of the propellant samples [12,13]. Because of this, it was impossible to establish a direct comparison with the present work. However, it was observed in this study the phenomenon described in
Ref. [13,41]: the consumption of deterrents implies an increase of
the burning rate and the degradation of nitrocellulose implies a
decrease of the burning rate.
In addition, the evolution of the burning rate r as a function of
the burnt propellant fraction z is shown in Fig. 11. In the r × z
curves, the intensification and passivation phases were very clear
for z values between 50% and 90%. The 20 years ageing led to an
irregular burning, which indicates a transition phase. While the
degradation of nitrocellulose was less intense and the propellant
was safe for handling, a tendency to increase the burning rate was
B.F.S. Defanti, L.G. Mendonça-Filho and J. Nichele / Combustion and Flame 221 (2020) 212–218
observed. After nitrocellulose degradation increased significantly
leaving the propellant unsafe for handling, we found a decrease
in the burning rate.
Lastly, the results indicated that for the single base propellant
samples used in this investigation the chemical stability and ballistic properties are not correlated along ageing.
5. Conclusion
This research investigated how five combustion properties of
ballistic interest of single base propellants were affected by the
artificial ageing. The results of Mn found for the characterization
of the chemical degradation showed that his parameter is especially useful for this purpose because it clearly shows the length
reduction of the nitrocellulose chains. Concerning to the combustion properties rmax , η and f, the results indicated a transitional
behavior at 20 years of ageing. Among these three properties, rmax
is the most representative because it is directly related to the ageing time by the chemical degradation. The values obtained suggest
that rmax is affected in two phases: the first as an intensification
and the second as a passivation. A possible explanation for this behavior is that the burning rate is affected in different ways during
the propellant degradation process. In the beginning of the degradation process the changes in rmax are related to the consumption
of the stabilizers EC and MC, once they also act as combustion
moderators. In the second phase, the results demonstrate a bigger
degradation of nitrocellulose and suggest this degradation is the
reason for the decrease of rmax . It was also clear that the intensification phase occured while the propellant was chemically safe and
the passivation was observed when the propellant became unsafe
for handling and storage.
From this work some questions still remain to be answered and
they are the focus of next works of our group. Once the higher
temperatures of ageing may favor different reactions [42], new investigations must be performed using lower temperatures for the
artificial ageing in order to verify if the same trends observed here
will occur. Additionally, further research might explore in detail,
the results obtained with thermal analysis technique, as DSC, to
check the thermal decomposition kinetics for each ageing temperature.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgments
The authors acknowledge the Brazilian Navy and Brazilian Army
for supporting this research; R. Rosato, S. M. Souza and D. A. R.
Vallim from CBC (Companhia Brasileira de Cartuchos), M. F. Lemos
from Brazilian Navy Research Institute, L. P. F. de Araújo from
Brazilian Army Central Ammunition Depot for chemical stability
tests; J. C. C. S. Pinto from EngePol/COPPE/UFRJ for gel permeation chromatography analysis; A. R. Alcantara from EMGEPRON
for closed vessel tests; and R. L. B. Rodrigues from Military Institute of Engineering for supporting the samples preparation.
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