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62 Propellants, Explosives, Pyrotechnics 18,62-68 (1993)

Thermal Decomposition of BAMO/HMX Propellants


Yoshio Oyumi

Third Research Center, Technical Research and Development Institute, Japan Defense Agency, 1-2-10 Sakae, Tachikawa,
Tokyo 190 (Japan)

Kiyotaka Inokami, Kazuhiro Yamazaki, and Koki Matsumoto

Technical Research and Development Center, Harima Plant, Daicel Chemical Industries, LTD., 805 Umaba Ibogawa, Ibo,
Hyogo 67 1- 16 (Japan)

Thermische Zersetzung von BAMO/HMX-Treibstoffen DBcomposition thermique de propergols BAMO/HMX


Die thermische Zersetzung von BAMOIHMX-Komposit-Treibstof- La dCcomposition thermique de propergols composites BAMO/
fen wurde untersucht mittels isothermer Thermogravimetrie (TGA) HMX a CtC CtudiCe au moyen de la thermogravimktrie isotherme
und Differentialkalorimetrie (DSC) in Heliumatmosphiire und verlief (TGA) et de la calorimCtrie diffkrentielle (DSC) dans une atmosphkre
durchweg in zwei Stufen nach einer Reaktion 1. Ordnung. Die Wir- d’hClium et s’est dCroulCe B chaque fois en deux Ctapes selon une r6ac-
kung des Vemetzungsverhaltnisses auf die beschleunigte Alterung der tion de ler ordre. L’effet du taux de rkticulation sur le vieillissement
BAMO/HMX-Treibstoffe wurde ebenfalls gemessen und zwar mittels accCltrC des propergols BAMO/HMX a Cgalement CtC mesure au
IR-Spektroskopie und Gaschromatographie. Die beschleunigte Alte- moyen de la spectroscopie IR et de la chromatographie gazeuse. Le
rung wurde durchgefuhrt bei 347 K mehrere Wochen lang. Bei einem vieillissement accC1CrC a CtC realis6 a 347 K pendant plusieurs semai-
sehr niedrigen Vernetzungsverhaltnis der BAMO/HMX-Treibstoffe nes. Pour un taux de rkticulation trks faible des propergols BAMO/
bildete sich ein Hohlraum zwischen HMX und BAMO-Binder durch HMX, une cavitC se forme entre les liants HMX et BAMO par forma-
Entwicklung von N2, CO, und H20 wahrend der beschleunigten Alte- tion de N2, C02 et H20 pendant le vieillissement acctlCr6. Une exo-
rung. Eine Exotherme, verursacht durch die Zersetzung des Azidbin- therme, causCe par la dicomposition du liant azide, a initiC et accC1CrC
ders, initiierte und beschleunigte die thermische Zersetzung des HMX. la dCcomposition thermique du HMX. La vitesse de combustion du
Die Abbrandgeschwindigkeit des BAMO/HMX-Treibstoffs war propergol BAMO/HMX Ctait suptrieure B celle du liant BAMO et du
groRer als die des BAMO-Binders und des HMX allein. Allerdings HMX seul. Toutefois, il n’a pas Ct6 possible de maintenir la combusti-
konnte der Abbrand des Treibstoffs bei einem niedrigen Druck, bei on du propergol une pression faible, a laquelle sa vitesse de combus-
welchem seine Abbrandgeschwindigkeit gleichgroR wie beim BAMO- tion etait Cgale B celle du liant BAMO.
Binder war. nicht aufrechterhalten werden.

Summary r CH2N3 1r 1
Thermal decomposition of BAMO [bis(azidomethyl)oxetane/tetra-
hydrofuran copolymer]/HMX composite propellants was studied by
isothermal TGA (thermogravimetric analysis) and DSC (differential BAMO
scanning calorimetry) in helium atmosphere, which was showing
overall two steps first-order kinetics. The effects of cross-link ratio on
the accelerated aging of the BAMO/HMX propellants were also meas- mers have been reported(4.5).Faber et al.(4) determined the
ured with infrared spectroscopy and gas chromatography. The acceler-
ated aging was conducted at 347 K for several weeks. BAMO/HMX
kinetics of decomposition of the azide group by monitoring
propellants for a very low cross-link ratio made the cavity between the N2 evolution from 5-SO mg of the samples slowly heat-
HMX and BAMO binder by N2, CO,, and H 2 0 evolutions during ed in a vacuum effusion cell connected to a quadrupole
accelerated aging. An exotherm, generated by the decomposition of mass spectrometer. Rapid-scanning Fourier transform
azide binder, initiated and accelerated the thermal decomposition of infrared spectroscopy (10 scans/s) was used to characterize
HMX. The burning rate of BAMO/HMX propellant was larger than
those of BAMO binder and HMX, respectively. However, the propel- the slow (5 K/min) and rapid thennolysis (SO K-255 K/s) of
lant could not maintain the combustion at low pressure, at which its azide polymers at the applied pressure (1-1000 psi Ar)(s).
burning rate was equal to that of BAMO binder. However, it is noteworthy that, unlike C-nitro and N-nitro
compounds, pressure and heating rate are found to exert rel-
1. Introduction atively little influence on the product concentration of azide
decomposition. The azide group decomposes before the
In the search for new energetic binder materials, consid- polymer backbone does(5)so.
erable interest has developed in the synthesis and character- The decomposition kinetics of azide prepolymer, poly-
ization of polymers containing azide side chains(’-3).The mer binder and BAMO/HMX propellants at a range of 430 K
chemical structure of 60/40 mol% bis(azidomethy1)oxe- to 510 K are reported here. The isothermal thermolysis was
tane/tetrahydrofuran copolymer (BAMO) is shown below. also used to determine the effects of accelerated aging and
The thermal decomposition studies on the azide poly- the cross-link ratio on the decomposition mechanism.
Propellants, Explosives, Pyrotechnics 18,62-68 (1993) Thermal Decomposition of BAMO/HMX Propellants 63

2. Experimental gas cell was kept at 347 K for several days and then the
evolved gas measurements were carried out in some inter-
2.1 Samples vals.
Gas chromatography was carried out by Shimadzu GC-
BAMO/HMX propellant used in this study consisted of 14A gas chromatograph equiped with TCD (thermal con-
25% BAMO binder and 75% HMX and was cured by IPDI ductive detector) and Porapack Q glass column. Helium
(isophorone diisocyanate) with cross-linking agent of TMP was used as a carrier gas at a flow rate of 50 ml/min. The
(trimethylol propane) at 333 K for two weeks. The cross- temperatures of the column and the detector were 323 K
link ratios (p,) of 0.01 and 0.25 were used in this study. The and 353 K, respectively. One gram of sample was put into
low value of p, was emphasized in tensile elongation at the the sealed glass sample tube purged with helium and then
low temperature range. The accelerated aging was conduct- kept at 347 K for two weeks. The gas tight microsyringe
ed at 347 K for several weeks. was used to pick evolved gases through silicone rubber sep-
tum and to inject them into the gas chromatograph.
2.2 Thermal decomposition studies
2.4 Burning rate measurements
TGA (thermogravimetric analysis) data were obtained
using a Seiko SSC5200 TGPTA220 with a helium flow The burning rates of the propellants were measured with
rate of 150 ml/min. In isothermal runs samples were heated a chimney type strand burner which was pressurized with
to experimental temperatures with a heating rate of nitrogen. The size of the propellant samples was 7 mm x
180 K/min and then were kept at constant temperature for 7 mm in cross-section and 70 mm in length. Three fuse
over 30 min. Isothermal condition was obtained within wires were passed through the propellant sample in 15 mm
3 min after the heating was started. The samples, weighing intervals. The ignition of the propellant samples was con-
around I mg, were placed in a small unconfined aluminum ducted by an electrically heated nichrome wire attached on
cell 3 mm-high with an inside diameter of 5 mm. Since the top of the propellant sample.
these cells were not hermetically sealed, gaseous products
could escape. 3. Thermal Decomposition
Differential scanning calorimetry measurements (DSC)
were made on a Seiko SSC5200 DSC120 with a 10 K/min 3.1 Cross-link
heating rate in a helium flow (150 ml/min). 1.5 mg of the
samples were placed in a small confined aluminum cell Cross-link has been necessary for propellants to make
with an inside depth of 2 mm and an inside diameter of three-dimensional network structure. The azide polymers
4 mm. Isothermal DSC were made on the same apparatus which differ from conventional polymer are high energy
with a helium flow rate of 150 ml/min. In isothermal runs supply itself, and yet they act as fuel component. We have
the samples were heated to experimental temperatures with studied the influence of cross-link ratio to thermal decom-
a heating rate of 180 K/min and then were kept at constant position mechanism which is significant responsible for
temperature for 30 min to 240 min. Isothermal condition energy emission.
was obtained within 3 min after the heating was started. Typical relationship of (CA/CAo) versus time for BAMO
The calorimeter was calibrated using indium and tin stan- binder is shown in Figure 1. The straight lines were
dards. The decomposition kinetic parameters of the samples obtained until a C&A" of 70%. This result indicates that
were calculated by measuring the weight loss versus time to the decomposition reaction of BAMO binder occured in an
evaluate the first-order rate coefficients. The integrated overall first-order kinetics at these experimental tempera-
form of the differential equation, -dCA/dt = kCA, is given ture ranges. Rate coefficients and temperature for BAMO
below: binder and BAMO prepolymer are listed in Table 1. The
In CA = In CAo - k t or In (CA/CAo) = - k t, Arrhenius plots of these samples are shown in Figure 2. The
kinetic parameters calculated are:
where CAo=initial mass,
CA = mass at time, t,
k = first-order rate coefficient, and 100
t = time.
90
A plot of h(CA/CA") versus t will give a straight line
with slope, -k. =
-
r 7

80
V

2.3 Gus analyseS 1


70

Gas analyses were conducted by infrared spectroscopy


and gas chromatography. Infrared spectroscopy was carried I I I 1
0 50 100 150 200
out by a JEOL JIR-5500 FT-IR spectrometer. One gram of
Time Cminl
aged sample was put into the 15 cm long gas cell and
purged with argon gas until no absorption bands were Figure 1. Mass change versus time for the isothermal runs of BAMO
observed in the infrared spectroscopy measurement. The binder.
64 Y. Oyumi, K. Inokami, K. Yamazaki, and K. Matsumoto Propellants, Explosives, Pyrotechnics 18, 62-68 (1 993)

Table 1. Rate Coefficients for Isothermal Decomposition of BAMO 3.2 HMX


Binder and BAMO Prepolymer
It is known that the phase transition of HMX from
Compound Mass[mg] T[K] k[rnin-’]xl03 Weight loss[%]
polymorph to 6 polymorph occurs at 460 K, and exothermal
1.0 452 0.35 7.6 decomposition is starting at 540 K, then HMX decomposes
0.9 459 0.59 13.6 most rapidly at melting temperature(6) of 551 K. On the
BAMO 0.9 463 0.88 19.6
binder 1.o 47 3 2.11 25.8
other hand, BAMO binder decomposes at the temperature
1 .0 482 4.50 30.1 range of 450 K - 540 K, which is around 90 K lower than
1.0 492 9.46 21.6 that of HMX. The effect of the binder decomposition on the
1.2 501 18.0 27.6 HMX decomposition mechanism was studied using isother-
1.o 509 33.5 32.8 mal decomposition runs at the temperature range of
1.1 456 0.56 12.6 420 K - 507 K.
1.1 464 1.15 17.8 Typical relationship of (C,/C,O) versus time for
BAMO 0.9 474 3.28 29.9 BAMO/HMX propellant is shown in Figure 3. Two sets of
prepolyrner 0.9 484 6.02 27.8
30.8
straight lines were obtained as expected. At the point of
1.0 495 16.4
1.1 504 24.1 30.8 12% weight loss observed, the character of overall first-
1.o 511 49.4 33.6 order kinetics was changed. The first part of the straight
line is hereinafter referred to as “first-stage reaction” and
the second part is “second-stage reaction”. Rate coefficients
and temperature for propellant samples are listed in Table 2.
100
80 - I I i
- The Arrhenius plots are shown in Figure 4. The kinetic
o Binder -
parameters calculated are:
40 -
-
e0
l for first-stage reaction,
In kl = 41.2 - 160,20O/RT (420 K - 501 K) and
x 20-
-n for second-stage reaction,
In k2 = 46.8 - 174,30O/RT (420 K - 501 K).
.f 10-
8.0-
x
n 6.0-
W
+A

4.0-
.I

.c..
0

F 2.0-
0
U

:0.8-
Ds
1.0-

0.6-

0 507K
50
0 50 100 150 200
Tiwe Cninl
Figure 2. Arrhenius plots of BAMO binder and BAMO prepolymer. (5) With aging

100

for BAMO binder, 90


In k = 39.9 - 153,800KT (452 K - 509 K) and
for BAMO prepolymer, 80
In k = 40.7 - 156,20O/RT (456 K - 5 11 K), E
u

L I0
where the activation energy, Ea is in J/mol. 0
1
0
These results indicate that the three-dimensional network
structure formation plays little role on the rate determina- 60
tion step of polymer decomposition. Theoretical mass
change (CA/CAo)for BAMO is 22% for azidomethyl side-
chain decomposition producing nitrogen and 44% for side- 50
0 50 100 150 200
chain decomposition with nitrogen and hydrogen cyanide. (A) Without w i n g Time Cninl
The weight loss at an isothermal run of 509 K was 32.8%
and showed that the side-chain in decomposition did not Figure 3. Mass change versus time for the isothermal runs of BAMOI
complete on these condition. HMX propellants with and without aging.
Propellants, Explosives, Pyrotechnics 18,62-68 (1993) Thermal Decomposition of BAMO/HMX Propellants 65

Table 2. Rate Coefficients for Isothermal Decomposition of


BAMO/HMX Propellant with and without Aging AFirst stage for unaged
vSecond stage f o r unaged
Compound Mass T k,[rnin-l] k2[min-l] Weight OFirst stage for aged
oSecond stage for aged
[mgl [Kl xi03 xi03 [%I
IOSS

1.2 420 0.0082 0.038 10.4


0.8 43 1 0.021 0.17 25.7
1 .o 444 0.112 0.562 9.8
1.o 446 0.101 0.714 7.1
0.9 449 0.23 1 1.102 13.9
BAMO/HMX 1.2 457 0.510 3.26 39.4
propellant 1.o 46 1 0.673 4.09 37.7
without 1.1 465 0.729 6.22 40.8
aging 0.8 472 1.72 11.0 46.2
1.1 478 2.15 11.5 35.0
1.2 483 3.66 24.8 41.2
1.o 488 5.83 42.7 54.6
1.o 494 6.80 68.3 57.3
1.1 50 1 13.9 162.7 67.3
1.2 42 1 0.0084 0.05 9.8
1.o 43 1 0.028 0.163 13.7
1.o 436 0.036 0.173 5.5
1.1 44 1 0.067 0.441 16.7
1.o 446 0.076 0.661 28.2
1.1 449 0.174 1.38 16.5
1.1 455 0.231 1.99 26.0
1.o 459 0.425 3.38 33.1
BAMO/HMX 0.9 464 0.785 6.59 42.9
propellant 1.1 469 0.896 7.11 33.3
with aging 1.O 474 1.57 12.1 42.5
1.o 478 2.04 17.3 43.3
1.o 482 3.42 22.6 40.9
0.9 485 7.58 38.8 56.1
0.8 488 7.58 36.9 44.5
0.9 494 13.5 86.3 62.9
1.o 498 13.9 109.1 60.8
0.5 507 26.3 186.4 60.1

The first-stage reaction is considered to the decomposi- Figure 4. Arrhenius plots of BAMO/HMX propellants with and with-
tion of BAMO binder itself, because the rate of the first- out aging.
stage reaction is similar to that of BAMO binder. The rate
of decomposition of HMX in the solid phase is reported(7)
as In k = 29.9 - 159,00O/RT (449 K - 503 K). The decom- transformation at this temperature range. Therefore, its
position of HMX might be the predominant reaction in the endothermic reaction might affect the reaction between the
second-stage reaction, but the decomposition of BAMO binder and HMX. QDsc of isothermal runs at over 495 K
binder also occured in these temperature ranges. According shows that the secondary reaction between the binder and
to the weight loss of BAMO binder itself shown in Table 1, HMX does not complete at these temperature conditions.
the expected max weight loss from the binder in the propel-
lant is less than 8%. However, most isothermal runs of the Table 3. Heats of Decomposition obtained by Isothermal DSC Runs
propellant lost their weight more than the weight of the (QDSC)
binder. These results indicate that the HMX decomposition
occurs even at 431 K and is activated by the binder decom-
position.
DSC thermogram of the propellant heated at 10 K/min
showed the exotherm peak at 526 K, which was 25 K lower
502 24 3,300 85
than that of HMX and even 6 K lower than that of the bind- 27 3,300 85
498
er itself. However, the exotherm of the binder was observed 495 24 3,300 85
separately from that of HMX in the isothermal runs, shown 488 23 2,900 74
in Figure 5. 478 24 2,400 62
Heats of decomposition obtained by isothermal DSC 470 25 1,900 49
460 19 1,500 38
runs (QDSC) and the ratio with Q D s c at a heating rate of 10 450 - 400 10
K/min are listed in Table 3. The effectiveness of HMX on
Q D s c rapidly dropped at below 460 K. HMX has p -+ 6 (a) heated at 10 Wmin
66 Y. Oyumi, K. Inokami, K. Yamazaki, and K. Matsumoto Propellants, Explosives, Pyrotechnics 18,62-68 (1 993)

5001-

-
v
I

2 IWY-
P

I-

\
300Y.
0 I0 20 30 40
rime [mini ~ i . e Lninl
(C) At 488 K LO) A t 602 K

4001 490Y
4601

-
Y

Y
-
Y
z

Ia8ox
a
c

2801, 290K
0 60 I20 180 240 o 17.5 35 52.5 70
Time [ n i n l Time [ m i d
(A) At 460 X (8) At 478 X

Figure 5. Isothermal DSC thermograrns of BAMO/HMX propellants.

4. Accelerated Aging

4.1 Gas analyses

BAMO/HMX propellant cured at pt of 0.01 evolved


gases in the accelerated aging at 347 K for 7 days, although Untreated
the propellant cured at pt of 0.25 did not change on the
same condition. The photo-pictures of aged propellant sur- Figure 6 . Surface pictures of BAMO/HMX propellants with and with-
face were shown in Figure 6. According to these surface out aging.
pictures, evolved gases gathered around HMX particles and
made the cavity between HMX particle and BAMO binder. 7 days at 347 K. The absorption bands of C 0 2 were
As the aging proceeds, the size of the cavity became larger observed at around 2350 cm-1 and 668 cm-1. HzO and traces
and the color of the propellant also became darker. BAMO of CO were also detected. N o additional gases were
was suggested as a better candidate than HTPB (hydroxyl observed at additional 32 days aging.
terminated polybutadiene) for nitramines from the surface The gas chromatogram is shown in Figure 8. Nitrogen
energy point of view(@. was the predominant product from the accelerated aging
However, BAMO might not be effective in improving and was assumed to be produced by the partial decomposi-
nitramine-binder adhesion at the low pt. The evolved gases tion of the azidomethyl side-chain.
produced nitramine-binder dewetting and the HMX parti- The main evolved gases during the aging were Nz,COz,
cles act as stress concentrators producing high local stress and HzO. N2 and C02 were produced by the decomposition
values at the poles of the particles. When a critical stress is of azidomethyl side-chain and that of the by-products of the
reached a cohesive failure occures within the binder, form- isocyanate end group with a small amount of H20 in HMX
ing a small cavity. crystalline and/or BAMO binder. It was also considered
The evolved gases were analyzed by IR spectroscopy that residual H2O was released slowly from HMX crystal-
and gas chromatography. Figure 7 shows IR spectrum of line during the aging.
evolved gases from the aged propellant in the gas cell kept
Propellants, Explosives, Pyrotechnics 18, 62-68 (1993) Thermal Decomposition of BAMO/HMX Propellants 67

0.12

a?
c
4 0.08
M
<
a

0.04

4000 3200 2400 1800 1400 ioaa Figure 7. IR spectrum of evolved gases
Wavenumbers during the aging.

CH=NH 5. Burning Rates


7H2N3 I
-0CHzCCH2-
I
j -0CHZCCHz-
I
+ 2 Nz
CH2N3 CH=NH Figure 9 shows the burning rates of BAMO/HMX pro-
pellant and BAMO binder. The propellant could not main-
tain the combustion below 3 MPa, at which its burning rate
was equal to that of BAMO binder. The burning rate of
BAMO/HMX propellant was larger than those of BAMO
binder and HMX, respectively. The pressure exponent was
increased by the addition of HMX. The solid line is the
4.2 Rate of decomposition burning rate of HTPB/HMX(20%/80%) propellant. Based
on the burning rate data shown in Figure 9, BAMO binder
Typical relationship of (CA/CAo)versus time for the accelerates the burning of HMX.
aged BAMO/HMX propellant is shown in Figure 3, which
is showing overall two steps first-order kinetics. Rate coef- 6. Conclusions
ficients and temperature for the aged propellant samples are
listed in Table 2. The Arrhenius plots are shown in Fig. 4. Thermal decomposition of BAMO/HMX composite pro-
The kinetic parameters calculated are: pellants with and without accelerated aging was studied,
for first-stage reaction,
In kl = 43.8 - 170,50O/RT (421 K - 507 K) and
for second-stage reaction,
In k2 = 46.8 - 174,300/RT (421 K - 507 K).
There is no effect of the aging of the second-stage reac- -
0

n
Binder
Propellant I '
I
tion and also first-stage reaction is less affected by the
aging.

1
I I I L
2 4 6 8 10
0 1 2 3 4 Pressure CMPa3
Retension t i m e [mh]
Figure 9. Burning rate versus pressure for BAMO/HMX propellants
Figure 8. Gas chromatogram of evolved gases during the aging. and BAMO binder.
68 Y. Oyumi, K. Inokami, K. Yamazaki, and K. Matsumoto Propellants, Explosives, Pyrotechnics 18,62-68 (1993)

which was showing overall two steps first-order kinetics. (3) K. Bando, K. Sato, K. Inokami, T. Miyazaki, K. Yamazaki, and
BAMO/HMX propellants for a very low cross-link ratio K. Matsumoto, “3,3-Bis(azidomethyI)oxetane(BAMO)-Based
Propellants. ( I ) Syntheses and Characterization of BAMO-Based
made the cavity between HMX particle and BAMO binder Polymers”, Kogyo Kayeku 51,228 (1990).
by N2, CO,, and H 2 0 which were produced during the (4) M. Farber, S. P. Harris, and R. D. Srivastava, “Mass Spectromet-
aging condition. An exotherm, generated by the decomposi- ric Kinetic Studies on Several Azido Polymers”, Combust. Flame
tion of BAMO binder, initiated and accelerated the thermal 55,203 (1984).
decomposition of HMX. The burning rate of BAMO/HMX (5) Y. Oyumi and T. B. Brill, “Thermal Decomposition of Energetic
Materials. 12. Infrared Spectral and Rapid Thermolysis Studies of
propellant was larger than those of BAMO binder and Azide-Containing Monomers and Polymers”, ibid. 65, 127 (1986).
HMX, respectively. However, the propellant could not (6) P. G . Hall, “Thermal Decomposition and Phase Transition in
maintain the combustion at low pressure, at which its burn- Solid Nitramines”, J. Chem. SOC.,Faraday Trans., Part 2 , 67, 556
ing rate was equal to that of BAMO binder. ( 1971 ) .
(7) M. A. Schroeder, “Critical Analysis of Nitramine Decomposition
Data: Activation Energies and Frequency Factors for HMX end
7. References RDX Decomposition”, Technical Report BRL-TR-2673, NTIS
AD-A160543 (1985).
(1) M. B. Frankel, E. R. Wilson, D. 0. Wooley, and C. L. Hamer- (8) J. M. Bellerby and Ch. Kiriratnikom, “Explosive-Binder Adhesion
mesh, “Energetic Azidn Compounds”, Final Report of Office of and Dewetting in Nitramine-Filled Energetic Materials”, Propel-
Naval Research, Arlington, VA, NTIS AD-A1 10292 (1982). lants, Explos., Pyrntech. 14,82 (1989).
(2) G . E. Manser, R. W. Fletcher, and M. R. Knight, “High Energy
Binders”, Final Report to Office of Naval Research, Arlington,
-
VA, ONR Contract NOOO14-82-C-0800 (1985). (Received January 17, 1992; Ms 4/92)