IJRRAS 25 (1) ● October 2015 www.arpapress.com/Volumes/Vol25Issue1/IJRRAS_25_1_04.

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KINETIC STUDY OF THERMAL DECOMPOSITION OF BASE BLEED

PROPELLANTS FOLLOWING FRIEDMAN AND OZAWA-FLYNN-
WALL METHODS
Priscila Simões Teixeira Amaral Paula1*, Michelle Gonçalves Mothé 2 & Cheila Gonçalves Mothé 2
1
Brazilian Navy Research Institute, Rio de Janeiro, 21931-095, Brazil
2
Federal University of Rio de Janeiro, School of Chemistry, Rio de Janeiro, 21949-900, Brazil

ABSTRACT
Explosives, propellants and pyrotechnics are the common classifications given to energetic materials. They can react
rapidly with an ignition and releases large amounts of energy with products generated in high velocity. Explosives are
very susceptible to initiation and as well as the pyrotechnics. Propellants usually need an ignition system to burn and
they have all the oxygen necessary for the combustion. Thermal analysis had been used in energetic materials studies.
This work reports the thermoanalytical results for commercial and synthesized base bleed propellants from TG/DTG
and DTA curves as well as the kinetic parameters of the decomposition reaction by applying isoconversional methods
as Friedman and Ozawa–Flynn–Wall using the Thermokinetics software.

Keywords: Energetic materials, Base bleed propellant, Kinetic study, Thermal analysis

1. INTRODUCTION
Energetic materials are compounds that comprise fuel and oxidizer components materials. They can be bonded
chemically in the same molecule or can be physically mixed [1]. Through an initiation, they release large amounts of
energy with products generated rapidly by the reaction. Explosives, propellants and pyrotechnics are the common
classifications given to energetic materials, as can be seen in figure 1. However, in the literature are also found other
classifications. According to Rice [2], the differences between explosives, propellants and pyrotechnics are in terms
of generated products and burning reaction rate. Akhavan [3] names these materials as chemical explosives and
classifies them according to their performances and uses being divided into three classes: primary explosives,
secondary explosives and propellants. The pyrotechnic compositions are also classified as chemical explosives. On
the other hand, Lee [4] terms the energetic materials as explosives divided into high explosives, propellants and
pyrotechnics. Oxley [5] classifies the high explosives into primary and secondary explosives and the propellants and
pyrotechnics are called low explosives.

Energetic Materials

Explosives Pyrotechnics Propellants

Figure 1. Common classification for energetic materials.

When it comes to propellants, they can have military and non-military purposes. Their applications go from the
propulsion of a rocket or missile to the automotive industry including the airbags, in this case just acting like a gas
generator.

Propellants can be solid or liquid. The solid ones have good versatility due to security, storage and easy handling. The
liquid propellants have more restriction because of their reactivity and special precautions in handling [6].

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 IJRRAS 25 (1) ● October 2015 Paula et al. ● Thermal Decomposition of Base Bleed Propellants

Solid propellants can be manufactured as grain and then they are named granulated propellant [1]. Depending on the
bonds of the compounds they are divided into homogeneous or heterogeneous.

The homogeneous propellants include the simple-base, double-base and triple-base propellants all made from
nitrocellulose. Heterogeneous propellants have a polymeric base and crystalline compounds and are known as
composite propellants [7]. In this last case, the organic and inorganic compounds are in highest percentages, however,
most of formulations contain stabilizers, burning catalysts, additives and plasticizers. One common polymeric base
for composite propellants is polyurethane. Polyurethanes present a structure that comprises soft and hard segments.
In general, the soft segments are usually oligomers with long methylene, oxy-methylene or other aliphatic sequences,
while the hard segments are urethane sequences brought together by reaction of short alkanediol with diisocyanate.
The soft and hard domains regulate their physical and mechanical behavior. An example of a chemical structure of
polyurethane is displayed in figure 2 [8].

Figure 2. Probable reaction between the polyol group and the isocyanate.

The polymeric matrix usually is the fuel for the combustion reaction. Nevertheless, solid reducing agents like
aluminum can be part of the composition [9].

The application and use of propellants exerts enormous influence in defense and military strategy of a country. One
composite propellant that has an important application in the military field is a gas generator propellant called base
bleed. However, there are few studies about base bleed propellant thermal decomposition involving kinetic data.

When a gun ammunition is propelled, a total drag is caused by the fluid mechanical reasons and it is the most important
performance factor. In the case of a projectile, the total drag can be divided into pressure drag, viscous drag and base
drag which has the major contribution for the total drag especially at transonic speed [10]. The base drag reduces the
range of the projectile once is a mechanical force acting against the movement of the gun ammunition.

According to Bournot [11], there are two ways of reducing the drag. One is to modify the shape of the projectile using
a boat tailed after body in order to reduce the base surface area and the other one is to inject a low velocity fluid behind
of the projectile obtaining the base bleed effect. In case of low velocity fluid injection, base bleed propellants are used.
Different from rocket propellants, they are not used for propulsion. During the burning of the base bleed propellant,
the evolved gases increase the pressure behind the projectile dropping the base drag value. Thus this effect extends
the range of the ammunition. Aiming to avoid the extinguishment of the propellant due to the pressure drop in the
combustion chamber when the projectile leaves the muzzle, an igniter is also arranged. figure 3 shows a projectile
model with a simple base bleed unit.

Propellant grain

Combustion chamber Igniter

Figure 3. Projectile with a base bleed unit.

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 IJRRAS 25 (1) ● October 2015 Paula et al. ● Thermal Decomposition of Base Bleed Propellants

Since the base of using energetic materials is thermal reaction, thermal analysis study becomes extremely relevant and
significant to evaluate base bleed propellants. The kinetic investigation is one of the most important applications of
thermal analysis, since the knowledge of the kinetic parameters, and the manufacturing process variables could be
better evaluated. Besides this, kinetic data are especially important to understand the material’s decomposition
mechanism. So, the study of the kinetics of those materials is very important due to hazard issues as well as its quality
and shelf-life [12].

1.1. Kinetic Study

Isoconversional methods

The “Model Free” is a model based on a transformation of a signal like heat flow or mass loss, on conversion degree
(α) for each stage of decomposition in which is possible to calculate kinetic parameters including the activation energy
and pre exponential factor. It consists on the determination of the conversion degree (α) as a function of reaction time
in a constant temperature or when the temperature varies linearly with time. Using thermogravimetric analysis, the
decomposed fraction (α) is defined according to eq. (1) [13]:

m0  m t
α (1)
m0  m f

Where m0 is initial mass, mt the mass at time t and mf the mass at the end of the reaction and the method is based on
the eq. (2) below:


d E
T
G(  )  
A (2)
f (  ) B T0
 exp  dT
0  RT 

where α is the conversion degree, A the pre-exponential factor, β the heating rate, T the absolute temperature, E the
activation energy, R the gas universal constant and G(α) represents the reaction mechanism. In order to determine the
kinetic parameters, some approximations were proposed by applying different kinetic models. By using thermokinetic
software, the kinetic study was done based on the conversional methods including Friedman and Ozawa-Flynn-Wall.
In both methods, the activation energies could be determined by analyzing plots recorded at different heating rates
[14].

The Friedman method has the eq. (3) for the calculation of the activation energy (E) and pre-exponential factor (A) by
plotting the logarithmic of the conversion rate (ln dα/dt) vs. 1/T [13]:

 d   d 
  ln A  ln f (  ) 
E
ln    ln  (3)
 dt   dT  RT

As in the Friedman method, the Ozawa-Flynn-Wall method can give the activation energy with a specific heating rate
β and it can be calculated from the slope of the isoconversional lines as shown in the eq. (4) [15]:

E
log   0.4567  cons tan t (4)
RT

The kinetic information calculated using isoconversional methods can provide more reliable insight into the kinetics
and mechanism of complex reaction processes since the activation energy (E) is calculated without any prior
knowledge of the analytical form of the conversion f (α) [13].

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 IJRRAS 25 (1) ● October 2015 Paula et al. ● Thermal Decomposition of Base Bleed Propellants

The objective of this work is to evaluate the kinetic parameters of thermal decomposition through thermal analysis of
base bleed propellants, commercial and synthesized samples by applying two models Friedman and Ozawa–Flynn–
Wall using a Thermokinetics software.

2. METHODOLOGY
2.1. Materials
Base bleed propellants samples named as A, B (commercials), C and D (synthesized) were studied. All of them had
polymeric matrix of polyurethane and ammonium perchlorate as oxidant agent.

2.2. Thermal characterization of propellants

The evaluations by TG/DTG and DTA were carried out on a TA Instruments model SDT Q600 with heating rates of
5, 10, and 20 °C min-1 in a nitrogen atmosphere with a flow rate of 100 mL/min. The sample sizes were about 1.5 mg
and the temperature range was from room temperature to 600 °C. The determination of the kinetics parameters was
performed by using “Model Free” with Netzsch Thermokinetics software for kinetic modeling.

3. RESULTS AND DISCUSSION

Figure 4 shows the comparison of TG curves for all base bleed propellant samples: A, B, C and D. As for the propellant
A, it can be observed that the thermal decomposition had three stages which started at 200 °C. The second stage
between 330 to 395 °C referred to polyurethane matrix decomposition [16, 17]. The third and last stage between 430
to 495 °C with a mass loss of 12%, showed a residue of 5% (600 °C) which was the highest amount between all
samples. The propellant B presented three stages of decomposition with the first one at the range of 200-280 °C. The
second stage was between 280-375 °C with a mass loss of 73% and from 375 until 425 °C there was no mass loss.
Then the third stage started at 425 going until 490 °C with a residue of 2% (600 °C). The thermogravimetric curves
for propellant C exhibited one stage of decomposition between 100-350 °C with a mass loss of 96% with an inorganic
residue of 4% (600 °C). The sample D showed three stages of decomposition at 150-250 °C, 250-390 °C and 430-480
°C respectively with a residue near to zero and it was the least amount of residue of all propellants samples. The
sample C presented a less thermal stability in the range of 300-350 °C.

Figure 4. TG curves for base bleed samples A, B, C and D.

Comparison of DTG curves for all base bleed propellants is shown in figure 5. It can be clearly seen that A and B
presented three peaks at 305, 370 and 440 °C for A and 275, 370 and 440 °C for B. As for propellant C it could be
observed only one sharp peak at 350 °C which was attributed to the presence of a burning catalyst that accelerated the
thermal decomposition. The D sample presented three peaks. The first peak was a slight one at 220 °C and the second
one at 370 °C referring to the main decomposition of the polyurethane matrix. The third and the last stage had a peak
at 450 °C.

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 IJRRAS 25 (1) ● October 2015 Paula et al. ● Thermal Decomposition of Base Bleed Propellants

Figure 5. DTG curves for base bleed samples A, B, C and D.

Figure 6 exhibits DTA curves for the base bleed propellants A, B, C and D. There was an endothermic event around
240 °C for all samples which is referred to as a transition between crystalline phases from orthorhombic to cubic of
the ammonium perchlorate [18]. Both samples A and B presented two exothermic events referring to oxidation process
following decomposition [19] at 310 and 370 °C and at 275 and 360 °C respectively. Concerning to C sample, there
was an exothermic event related to the oxidation process and final decomposition at 350 °C. For the propellant D, the
DTA curve showed four exothermic events at 285, 330, 370 and 450 °C suggesting that there are more components
in its formulation that passed by an oxidation process. Table 1 shows a summary of the thermal analysis of all samples.

Table 1. Summary of thermoanalytical results for base bleed samples from TG/DTG and DTA curves.

Propellant Temperature range Mass DTG DTA DTA Residue at

Sample per stage of loss(%) Peak Endo Exo 600°C(%)
decomposition on (°C) Peak Peak
TG (°C) (°C) (°C)
A 200-330 24 305 240 310 5
330-395 59 370 370
425-495 12 440

B 200-280 10 275 240 275 2

280-375 73 370 360
425-490 15 440

C 100-350 96 350 240 350 4

D 150-250 5 220 240 285 Non identified

250-390 87 370 330
430-480 8 450 370
480

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 IJRRAS 25 (1) ● October 2015 Paula et al. ● Thermal Decomposition of Base Bleed Propellants

Figure 6. DTA curves for base bleed samples A, B, C and D.

3.1. Determination of kinetic parameters by Friedman and Ozawa-Flynn-Wall methods

The Friedman analysis can be seen in figures 7, 8, 9 and 10 for base bleed samples A, B, C and D. Figure 7 exhibits
three peaks for sample A at the ranges of 254-333 °C, 302-417 °C and 417-497 °C respectively, showing that the
decomposition of propellant A occurs in three different stages confirming what TG/DTG curves showed. As for the
sample B, figure 8, the graph exhibited the same number of peaks seen before in the TG/DTG graph as well. The main
decomposition had a peak between 292 and 372 °C and the last one at around 407-527 °C.

Figure 9 demonstrates the single decomposition presented by sample C. It had a peak between 215-372 °C and after
the fast decomposition reaction many peaks were observed. Concerning to sample D, which graph can be seen in
figure 10, three peaks indicates the stages of decomposition, the same number shown by TG/DTG curves.

Friedman Analysis Cinetica Propelente A

log dx/dt
Friedman analysis A

-2.5

-3.0

-3.5 0.98

-4.0

-4.5

0.02

1.2 1.4 1.6 1.8 2.0 2.2

1000 K/T

Figure 7. Friedman analysis for base bleed sample A.

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 IJRRAS 25 (1) ● October 2015 Paula et al. ● Thermal Decomposition of Base Bleed Propellants

Friedman Analysis Cinetica Propelente B

log dx/dt

Friedman analysis B
-2.5

-3.0

0.98

-3.5

-4.0

-4.5 0.02

-5.0

1.2 1.4 1.6 1.8 2.0

1000 K/T

Figure 8. Friedman analysis for base bleed sample B.

Friedman Analysis Cinetica Propelente C com cromito

log dx/dt
Friedman analysis C
-2.0

-3.0

-4.0

0.98

-5.0 0.02

-6.0

1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6

1000 K/T

Figure 9. Friedman analysis for base bleed sample C.

Friedman Analysis Cinetica Propelente C sem cromito

log dx/dt
-2.0 Friedman analysis D

-2.5

-3.0

-3.5

0.98

-4.0

-4.5 0.02

-5.0

1.2 1.4 1.6 1.8 2.0 2.2

1000 K/T

Figure 10. Friedman analysis for base bleed sample D.

The Ozawa-Flynn-Wall model for samples A, B, C and D are presented in Figures 11, 12, 13 and 14. Figure 11 and
13 show more inclination in the beginning of the decomposition. Some isoconversional lines indicated the
decomposition of more than one component. Figures 12 and 14 also show regular parallels isoconversional lines
suggesting a good adjustment of OFW model in all cases.

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IJRRAS 25 (1) ● October 2015 Paula et al. ● Thermal Decomposition of Base Bleed Propellants

OFW Analysis Cinetica Propelente A

log Heating rate/(K/min)

0.98 0.02
Ozawa-Flynn-Wall analysis A

1.2

1.0

0.8

0.6
1.3 1.5 1.7 1.9 2.1
1000 K/T

Figure 11. Isoconversional graphic of Ozawa-Flynn-Wall for base bleed sample A.

OFW Cinetica Propelente B

log Heating rate/(K/min)

Ozawa-Flynn-Wall analysis B
0.90 0.02

1.2

1.0

0.8

0.6
1.3 1.5 1.7 1.9 2.1
1000 K/T

Figure 12. Isoconversional graphic of Ozawa-Flynn-Wall for base bleed sample B.

OFW Cinetica Propelente C com cromito

log Heating rate/(K/min) Ozawa-Flynn-Wall analysis C

0.80 0.02

1.2

1.0

0.8

0.6
1.6 1.8 2.0 2.2 2.4 2.6
1000 K/T

Figure 13. Isoconversional graphic of Ozawa-Flynn-Wall for base bleed sample C.

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 IJRRAS 25 (1) ● October 2015 Paula et al. ● Thermal Decomposition of Base Bleed Propellants

OFW Cinetica Propelente C sem cromito

log Heating rate/(K/min)

Ozawa-Flynn-Wall analysis D
0.95 0.02

1.2

1.0

0.8

0.6
1.4 1.6 1.8 2.0 2.2
1000 K/T

Figure 14. Isoconversional graphic of Ozawa-Flynn-Wall for base bleed sample D.

Figures 15 and 16 shows the graphs of the activation energies and the pre-exponential factor and their summary is
shown in table 2.

The profiles presented in figures 15 and 16 exhibited the dependence between (E) and log (A) versus conversion
degree for each sample according to the kinetic model. It showed that sample A decrease both values after 50% of
conversion in Friedman analysis while samples B, C and D increase their values.

Friedman Analysis Cinetica Propelente A

OFW Analysis Cinetica Propelente A
E/(kJ/mol) log(A/s^-1)

220
Friedman analysis A E/(kJ/mol)
Ozawa-Flynn-Wall analysis A
log(A/s^-1)

14

180
200 11
12

180 160

10
9
160
140
8
140
7
120
6
120

4 100 5
100

80 2
80
3

0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8

Fract.Mass Loss Fract.Mass Loss
a Friedman Analysis Cinetica Propelente B a OFW Cinetica Propelente B

E/(kJ/mol) log(A/s^-1) E/(kJ/mol) log(A/s^-1)

Friedman analysis B Ozawa-Flynn-Wall analysis B

1000 60 1600
100

800
40 1200 80

600

20 800 60

400

0 40
200 400

0 20
-20 0

-200
0
-40 -400

0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8

Fract.Mass Loss Fract.Mass Loss
b b

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 IJRRAS 25 (1) ● October 2015 Paula et al. ● Thermal Decomposition of Base Bleed Propellants

Friedman Analysis Cinetica Propelente C com cromito OFW Cinetica Propelente C com cromito

E/(kJ/mol) log(A/s^-1) E/(kJ/mol) log(A/s^-1)

Friedman analysis C Ozawa-Flynn-Wall analysis C 16

220

240
16
12
180

200
12
8
140
160
8
4
100
120

4
0
60
80

20 -4
40

0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8

Fract.Mass Loss Fract.Mass Loss
c Friedman Analysis Cinetica Propelente C sem cromito c OFW Cinetica Propelente C sem cromito

E/(kJ/mol) log(A/s^-1) E/(kJ/mol) log(A/s^-1)

200 Friedman analysis D Ozawa-Flynn-Wall analysis D

11

12 160
10
180

9
140
160
10
8

140 120
7

6
120
100

5
6
100
80
4
0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8
Fract.Mass Loss Fract.Mass Loss
d d

Figure 15. Graphics of E and log A versus converted Figure 16. Graphics of E and log A versus converted
fraction (α) for base bleed samples A (a), B (b), C (c) fraction (α) for base bleed samples A (a), B (b), C (c)
and D (d) in Friedman analysis. and D (d) in Ozawa-Flynn-Wall analysis.

Table 2. Summary of activation energies and pre-exponential factors results for base bleed samples from Friedman
and Ozawa-Flynn-Wall (OFW) model.
α Sample A Sample B
Friedman OFW Friedman OFW
E(KJmol-1) log A(s-1) E(KJ.mol-1) log A(s-1) E(KJ mol-1) log A(s-1) E(KJ.mol-1) log A(s-1)
0.1 100.01 6.22 111.21 7.11 210.96 16.84 186.88 14.78
0.2 125.23 8.04 109.03 6.85 144.90 10.12 152.77 11.18
0.3 156.16 10.62 128.69 8.46 171.86 12.32 158.70 11.47
0.4 181.04 12.72 143.13 9.65 190.63 13.84 166.85 12.05
0.5 198.03 14.09 157.85 10.87 215.97 15.93 179.26 13.03
0.6 184.34 12.90 168.30 11.72 230.04 17.00 192.44 14.09
0.7 163.54 11.05 169.33 11.75 374.33 28.48 231.71 17.29
0.8 71.23 2.82 82.27 4.18 361.14 24.13 481.32 33.98
0.9 259.04 16.48 262.40 17.29 535.65 36.00 445.43 30.35
α Sample C Sample D
0.1 129.57 9.37 104.27 7.17 132.83 8.96 121.61 8.18
0.2 141.02 10.07 121.63 8.56 146.00 10.10 134.20 9.19
0.3 164.49 12.05 140.61 10.16 146.28 9.99 138.90 9.53
0.4 183.66 13.65 157.09 11.55 150.80 10.28 142.45 9.76
0.5 202.66 15.24 171.35 12.73 156.55 10.76 145.66 9.97
0.6 213.56 16.18 184.78 13.86 162.86 11.30 148.77 10.21
0.7 216.25 16.44 193.76 14.60 172.14 12.10 152.71 10.53
0.8 234.22 17.97 200.19 15.14 184.01 13.08 158.66 11.02
0.9 -213,92 -19.44 -53.22 2.16 353.78 26.38 225.64 16.51

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 IJRRAS 25 (1) ● October 2015 Paula et al. ● Thermal Decomposition of Base Bleed Propellants

4. CONCLUSION
Regarding to thermal properties and kinetic study, it was made a comparison between commercial and synthesized
polymeric base bleed propellant samples in order to verify safety during the use for military application. Since there
are few kinetic data about base bleed propellants, the kinetic parameters including activation energy (E) and pre-
exponential factor (log A) of all samples were determined by Friedman and Ozawa-Flynn-Wall isoconversional
models. Results by thermal analysis showed that sample C presented the less thermal stability while the sample A
presented a higher one. All samples exhibited polymorphic transition at 240ºC due to the presence of ammonium
perchlorate. The graphic profiles of Friedman and OFW for propellant A were different from B, C and D. The samples
A and D presented smaller values of activation energy at 50 and 60% of decomposition while the propellant B showed
more thermal stability and highest activation energy for both Friedman (215.97 KJ mol-1) and OFW
(179.26 KJ mol-1) analysis.

5. ACKNOWLEDGEMENT
The author C.G.M. thanks the Brazilian Council for Scientific and Technological Development (CNPq) for the
financial support.

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