Summary

Card gap test, which is standardized in Japan Explosives Society,

was modied in order to apply it to solid rocket propellants and carried
out to evaluate sensitivities against shock stimuli. Solid propellants
tested here were mainly azide polymer composite propellants, which
contained ammonium nitrate (AN) as a main oxidizer. Double base
propellant, composed nitroglycerin and nitrocellulose (NC), and
ammonium perchlorate (AP)-based composite propellants were also
evaluated in order to compare with the azide polymer propellants. It is
found that the sensitivity was dominated by the oxidizer character-
istics. AP-and AN-based propellant had less sensitivity and HMX-
based propellant showed higher sensitivity, and the adding of NC and
TMETN were contributed to worse sensitive for the card gap test.
Good relationship was obtained between the card gap sensitivity and
the oxygen balance of propellants tested here.
1. Introduction
1.1 Card Gap Test
Rocket propellants have been required to be insensitive to
shock such as an unexpected drop at handling, bullet or
fragment impacts. Card gap test has an advantage to estimate
quantitative sensitivities of propellant against shock wave.
The test was originally standardized and conducted usually
for an estimation of sensitivity of explosives
(14)
. In this time,
the card gap test of Japanese test standard
(5)
has been
modied to suit for evaluating sensitivity of rocket propel-
lants
(6)
. The main modications occurred on the materials of
the gap plate and of the sample holder, poly(methylmetha-
crylate) (PMMA) to aluminum and polyvinyl chloride to
steel, respectively. It was for the purpose of diminishing a
loss of the energy of shock wave, generated by the donor, into
the sample because of a relatively lower sensitivity of
propellants compared to that of explosives.
1.2 Oxygen Balance
Oxygen balance is dened as the number of oxygen
equivalents per unit of propellant when a sample detonates
and all of each atom in the sample nally converts into the
following molecules:
C CO
2
; H H
2
O; N N
2
Therefore, when a propellant represents C
x
H
y
O
z
N
u
, the
reaction for the explosion is expressed below.
C
x
H
y
O
z
N
u
= xCO
2

y
2
H
2
O
u
2
N
2

1
2
2x
y
2
z

O
2
The oxygen balance is calculated as follows in an ideal
reaction described above.

1
2
2x
y
2
z

32
12x y 16z 14u
=
16 2x
y
2
z

12x y 16z 14u
(+)
Since propellant consists of binder, oxidizer and some
additives, ``x'', ``y'', ``z'' and ``u'' in C
x
H
y
O
z
N
u
are calcu-
lated from the molecular formula of each ingredient and the
composition percentage. For example, C
x
H
y
O
z
N
u
of the
propellant composed of oxidizer=binder =80=20 is calcu-
lated by using the molecular formula of the oxidizer
(C
a
H
b
O
c
N
d
) and the binder (C
e
H
f
O
g
N
h
), as follows:
x = 0:8a 0:2e; y = 0:8b 0:2f ;
z = 0:8c 0:2g; u = 0:8d 0:2h
Sensitivity of Solid Rocket Propellants for Card Gap Test
Eishu Kimura and Yoshio Oyumi
Third Research Center, Technical Research and Development Institute, Japan Defense Agency, 1-2-10 Sakae, Tachikawa,
Tokyo 190-8533 (Japan)
Empndlichkeit von Raketenfesttreibstoffen beim Card-Gap-Test
Der Card-Gap-Test, standardisiert durch die Japan Explosives
Society, wurde modiziert zur Anwendung bei Raketenfesttreibstoffen
und ausgefuhrt zur Bewertung der Empndlichkeit gegen
Stoeinwirkung. Die hier getesteten Festtreibstoffe waren haupt-
sachlich azidhaltige polymere Komposit-Treibstoffe, welche vor-
zugsweise Ammoniumnitrat als Oxidator enthielten. Doublebase-
Treibstoffe, zusammengesetzt aus Nitroglycerin und Nitrocellulose,
und ammoniumperchlorathaltige Komposit-Treibstoffe wurden eben-
falls ausgewertet zum Vergleich mit den azidhaltigen Poly-
mertreibstoffen. Es wurde gefunden, da die Empndlichkeit durch die
Oxidatoreigenschaften beherrscht wurde. AP- und AN-haltige Treib-
stoffe haben eine geringere, HMX-haltige Treibstoffe eine hohere
Empndlichkeit, die Zugabe von NC und TMETN trug zur Ver-
schlechterung der Empndlichkeit im Card-Gap-Test bei. Gute
Beziehungen zwischen der Empndlichkeit im Card-Gap-Test und der
Sauerstoffbilanz der hier untersuchten Treibstoffe wurden erhalten.
Sensibilite de propergols solides de fusees lors du test Card-Gap
Le test Card-Gap, standardise par la Japan Explosives Society, a ete
modie en vue d'etre utilise dans des propergols solides de fusees et
concu pour evaluer la sensibilite a l'effet de choc. Les propergols
solides testes etaient principalement des propergols composites poly-
meres a base d'azide, qui contenaient essentiellement du nitrate
d'ammonium en tant qu'oxydant. On a egalement evalue des proper-
gols a double base composes de nitroglycerine et de nitrocellulose et
des propergols composites a base de perchlorate d'ammonium en vue
de les comparer aux propergols polymeres a base d'azide. On a montre
que la sensibilite etait ma trisee par les proprietes oxydantes. Les
propergols a base d'AP ou d'AN ont une sensibilite plus faible, les
propergols a base de HMX une sensibilite plus elevee; l'addition de
NC et de TMETN a contribue a la deterioration de la sensibilite lors du
test Card-Gap. On a obtenue de bonnes relations entre la sensibilite
lors du test Card-Gap et le bilan d'oxygene des propergols etudies.
# WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0721-3115/99/03060090 $17.50:50=0
90 Propellants, Explosives, Pyrotechnics 24, 9094 (1999)
An intensity of detonation become a maximum at around
the oxygen balance of 0. The ideal reaction, as mentioned
above, may not occur in the practical detonation and
another kind of gases, such as CO, NO, NO
2
, were pro-
duced. The gas composition produced in the detonation is
strongly effective on the value of the oxygen balance
(7)
.
Kamlet mentioned the oxygen balance showed good
relationship in the impact sensitivity of organic high explo-
sives
(8)
. Kamlet used OB
100
, a measure of oxidant balance.
OB
100
was dened as 100(2d b 2a 2N
coo
)=(molecular
weight) for a material composition C
a
H
b
N
c
O
d
with N
coo
as
the number of carboxyl group. Storm and co-worker also
demonstrated correlation of sensitivity with only structural
information of the compound, by using the Sensitivity Index
(SI) dened as 100(d a (by2) N
co
)y(5(a b c d))
for C
a
H
b
N
c
O
d
with N
co
as the number of carbonyl groups
(9)
.
OB
100
and SI are similar to the oxygen balance of the
compounds. Herein, the oxygen balance described in Eq.
(*) was selected to perform correlation of sensitivity for the
card gap test with the structural information about solid
rocket propellants.
2. Experimental
2.1 Samples
The compositions of propellant samples are shown in
Table 1. The binders are based on BAMO=NMMO copoly-
mer (BN), GAP and HTPB. AN is chosen as a main oxidizer
fromthe insensitive point of view. AP, HMXand NC=NGare
used to compare with AN based propellant.
2.2 Calibration of Shock Pressure
It is necessary to characterize the shock wave intensity
through the gap plate. The characteristics are derived from
the shock wave velocity travelling in the aluminum plate.
The method was described in detail elsewhere
(6)
. Figure 1
shows relationship between aluminum length and shock
passing time in the detonation of the donor explosive. The
time is obtained by the least square tting to equation
t = a bL cL
2
:
t = 0:148 0:145L 3:98 10
4
L
2
(1)
The shock velocity, symbolized Us, at L(mm) from the top
of the gap plate is derived by differentiation in Eq. (1):
Us =
dL
dt
=
1
0:145 7:96 10
4
L
(2)
Then, the particle velocity, Up, in aluminum plate is cal-
culated from the shock Hugoniot for the aluminum used
here
(10)
and the measured Us:
Us = 5:35 1:34Up (3)
The particle velocity in the aluminum at interface of the
sample propellant can be extrapolated at L = 0 by the least
square tting since the relation between Up and aluminum
thickness is linear. The shock pressure, P, is obtained in the
Table 1. Composition of Propellant Samples
Sample BN GAP HTPB TMETN NC NG AN HMX AP Al Others
BN-based composite propellant
1 25 75 PbSt;4.9, CB;0.5
2 25 60 15 FeB;2.0, CuCr;3.0
3 25 50 25 FeB;2.0, CuCr;3.0
4 25 45 30 FeB;2.0, CuCr;3.0
5 25 40 35 FeB;2.0, CuCr;3.0
6 25 30 45 FeB;2.0, CuCr;3.0
7 25 15 60 FeB;2.0, CuCr;3.0
8 23 77 FeO;3.0, ZrC;2.0
GAP-based composite propellant
9 30 55 15 B;1.0, CB;0.6
10 20 20 60
11 15 15 20 50 CuCr;1.0, PbCi;2.0
12 18 80 2 FeO;1.0
HTPB-based composite propellant=Double base propellant
13 25 60 15 FeB;2.0, CuCr;3.0
14 12 71 17 FeO;2.0
15 37 33 14 BDR1;16.0
16 48 42 BDR2;10.0
BN: 3,3-Bis(azidomethyl)oxetane=3-nitratomethyl-3-methyloxetane (BAMO=NMMO) =7=3 binder; GAP: glycidyl azide polymer binder;
HTPB: hydroxyl-terminated polybutadiene binder; TMETN: trimethylolethane trinitrate; NC: nitrocellulose; NG: nitroglycerin; AN: ammonium
nitrate; AP: ammonium perchlorate; FeB: Butacene; CuCr: copper chromite; FeO: Iron oxide; ZrC: zirconium carbide; CB: carbon black; PbCi:
lead citrate; BDR1: polyol-based binder; BDR2: urethane-based binder.
Propellants, Explosives, Pyrotechnics 24, 9094 (1999) Sensitivity of Solid Rocket Propellants for Card Gap Test 91
Eq. (4) with initial propellant density, r, and Us and Up in
Eqs. (2) and (3):
P = rUsUp (4)
Table 3 shows the shock pressure as a function of the alu-
minum plate thickness.
2.3 Card Gap Test
The experimental setup shown in Figure 2 is almost the
same as the standard of Japan Explosives Society
(5)
. Pentolite
(PETN : TNT = 50 : 50, density: 1.62 g=cm
3
) is used as a
donor and it is initiated by #6 detonator cap. The material of
the gap plate was changed PMMA(JIS K6718, rst grade) to
aluminum (JIS H 4000, 6061, density: 2.703 g=cm
3
), shaped
60 mm circle with 530 mm thickness. The shock pressure
transmitted to sample propellant through the aluminum plate
may become approximately twice as large as that of PMMA
because of large density for aluminum in Eq. (4). The
material of the sample holder was also converted polyvinyl
chloride (JIS K 6741, VP-30) into steel (JIS G 3452, A32
carbon steel pipe), sized 42.7 mmouter diameter with 3.5 mm
thick and 50 mm long. This change is contributed to be a
larger shock pressure traveling in the sample because of more
restraint of sample in comparison with polyvinyl chloride
tube. The witness plate under sample is steel (JIS G 3141,
SPCC), sized 100 mm square with 2 mm thickness.
Three trials are conducted at the same gap length, varying
by 5 mm intervals in the thickness of aluminum plate and
determined whether ``go'' or ``no go''. Detonation of sample
propellant can be judged if cracks or holes were observed on
the witness plate. The critical gap length is determined when
detonation of sample was observed in all three trials. The
critical shock pressure is dened as the pressure given b y the
critical gap length.
3. Results and Discussion
An oxidizer in sample propellant dominated sensitivity of
the card gap test, as shown in Figure 3. Samples, whose main
oxidizer was AN or AP, showed lower sensitive to the card
gap test. The properties were independent on their binder,
such as BN, GAP and HTPB. Samples contained AP,
Figure 1. Relationship between gap length and shock passing time.
Figure 2. Setup for card gap test.
Table 2. Molecular Formula and Oxygen Balance for Samples
Sample Molecular formula Oxygen balance
1 C5.700 H10.825 O6.675 N6.800 0.57676
2 C3.300 H8.425 O3.675 N3.200 0.75317
3 C3.700 H8.825 O4.175 N3.800 0.70544
4 C3.900 H9.025 O4.425 N4.100 0.68578
5 C4.100 H9.225 O4.675 N4.400 0.66829
6 C4.500 H9.625 O5.175 N5.000 0.63856
7 C5.100 H10.225 O5.925 N5.900 0.60364
8 C2.484 H7.519 O3.701 N1.506 0.68372
9 C2.586 H6.643 O3.351 N3.011 0.61658
10 C2.324 H6.362 O3.934 N2.274 0.48299
11 C2.943 H6.476 O5.095 N2.302 0.41452
12 C1.324 H5.362 O5.095 N1.274 0.30032
13 C2.378 H7.280 O3.435 N2.414 0.65935
14 C0.853 H4.156 O2.903 N0.726 0.19857
15 C3.734 H5.500 O7.695 N3.002 0.18735
16 C4.725 H6.397 O8.761 N2.453 0.26179
Table 3. Shock Velocity, Particle Velocity and Shock Pressure in
Aluminum Plate
L Us Up P
mm mm=ms mm=ms GPa
50 5.41 0.0457 0.668
40 5.65 0.227 3.47
35 5.79 0.325 5.09
30 5.92 0.426 6.82
25 6.06 0.533 8.73
20 6.21 0.645 10.8
15 6.37 0.763 13.1
10 6.54 0.886 15.7
5 6.71 1.02 18.5
0 6.90 1.15 21.4
L: gap length, Us: shock velocity, Up: particle velocity, P: shock
pressure in aluminum plate
92 Eishu Kimura and Yoshio Oyumi Propellants, Explosives, Pyrotechnics 24, 9094 (1999)
however, burned out after the test because of its high
combustibility. It is impossible in this card gap test to
distinguish deagration from detonation since the witness
plate located under the sample propellant is used in the
judgement. No damage on the witness plate existed even in
the case of deagration.
The sensitivity got worse by adding of HMX, NC and NG.
Especially, sample 11 showed the critical gap length of
25 mm even it contains 50% AN in the composition. Table
4 summarized the critical gap length and the critical shock
pressure in the card gap test.
Figure 4(a) shows relations between oxygen balance listed
in Table 2 and critical shock pressure. Good relations were
observed for each binder, except for double base propellants.
The sensitivities became worse as oxygen balance increased.
The linear line for GAP-binder samples was shifted to higher
oxygen balance, compared with that for BN-binder samples,
though both of the slopes were almost the same. It means that
GAP binder is slightly more insensitive to shock stimuli than
BN binder. The insensitiveness of GAP binder is supported
that the critical gap lengths of AP- and AN-based samples are
0 mm, as shown in Figure 3, though those of BN-binder
samples are 5 mm. HTPB-binder sample were also more
insensitive than BN-binders, since sample 13 was located
at higher oxygen balance compared to sample 2 in Figure
4(a). The positions of the plot for double base samples
propellant had further higher oxygen balance and a different
correlation might exist from that of composite propellants.
No relation could be obtained because of only two samples
tested here.
Figure 4(b) indicates the relation between oxygen balance
and sensitivity of AP-based sample with AN- and HMX-
based ones. The values of oxygen balance for AP-based
samples of the respective binder showed only poor correla-
tion to the critical shock pressures. The reason why this poor
correlation is obtained may be that the criterion of ``go'' or
``no go'' determination in the card gap test is detonation of the
sample propellant. As mentioned before, burned-out phe-
nomena were observed in AP-based sample after trials of the
gap test because of its high combustibility. AP-based sample
was sensitive to initiation and then deagration occurred in
the shock ignitability test
(11)
.
Figure 3. Critical gap length.
Table 4. Results of Card Gap Test
Sample Lc (mm) Pc (GPa)
1 25 8.73
2 5 18.5
3 10 15.7
4 15 13.1
5 15 13.1
6 15 13.1
7 20 10.8
8 5 18.5
9 0 21.4
10 5 18.5
11 25 8.73
12 0 21.4
13 5 18.4
14 0 21.4
15 20 10.8
16 25 8.73
Lc: critical gap length, Pc: critical shock pressure
Figure 4. Correlation of card gap test with oxygen balance.
(a) without AP-based samples,
(b) with AP-based samples.
Propellants, Explosives, Pyrotechnics 24, 9094 (1999) Sensitivity of Solid Rocket Propellants for Card Gap Test 93
4. Conclusions
AP- and AN-based propellants showed relatively large
critical shock pressure but HMX- and NC-based propellants
were very sensitive in the card gap test. Three different
propellant binders, such as BN, GAP and HTPB, were
evaluated and difference in sensitivity was hardly observed
among them. It was found that the sensitivity was dominated
by the oxidizer characteristics.
In each binder type of propellant groups, linear relation-
ships were observed between the critical shock pressure and
the oxygen balance of the propellant, except AP-based
propellant. AP-based propellants tended to deagrate
because of its ignitability. The deagration phenomena
might not affect the measured value of the critical gap
length in this card gap test. The sensitivity became worse
as the oxygen balance increased in each propellant group.
The slope in BN binder propellant was almost the same as
that of GAP-binder propellant. When the oxygen balance was
the same, GAP-binder propellant was more insensitive than
that of BN one.
5. References
(1) M. Iida, S. Fujiwara, and M. Kusakabe, ``Shock Sensitivity of
Explosive Materials. I. Fundamental Experiments on Gap Test'',
J. Indust. Explos. Soc., Japan 33, 291 (1972).
(2) K. Hashizume and N. Sasaki, ``Card Gap Test of Industrial High
Explosives'', J. Indust. Explos. Soc., Japan 63, 34 (1975).
(3) S. Matsumoto, M. Tanaka, and T. Yoshida, ``Study of Card Gap
Test for Industrial Explosives'', J. Indust. Explos. Soc., Japan 37,
173 (1976).
(4) Y. Hirosaki, T. Ishida, K. Hattori, and H. Sakai, ``Card Gap Test of
Emulsion Explosive'', J. Indust. Explos. Soc., Japan 43, 323
(1982).
(5) ``Test Standard of Explosive Sensitivity (IV)'', Japan Explosives
Society (edit), 1995, pp. 92.
(6) Y. Oyumi, E. Kimura, and K. Nagayama, ``Initiation and Deto-
nation Properties of Azide Polymer Propellants'', J. Explos. Soc.,
Japan 55, 194 (1994).
(7) S. Nakahara, in: Kayakugaku Gairon (``Study of Explosives''),
Sangyotosho, Tokyo, 1983, pp. 4.
(8) M. Kamlet, ``The Relationship of Impact Sensitivity with Struc-
ture of Organic High Explosives. I. Polynitroaliphatic Explo-
sives'', Proc. 6th Sym. (International) on Detonation, (1976), pp.
313.
(9) C. B. Storm, J. R. Stein, and J. F. Kramer, ``Sensitivity Relation-
ships in Energetic Materials'', in: ``Chemistry and Physics of
Energetic Materials'', Kluwer Academic Press, Boston, 1990, pp.
605.
(10) S. P. Marsh, ``LASL Shock Hugoniot Data'', University of
California Press, Berkeley (1980).
(11) E. Kimura and Y. Oyumi, ``Shock Ignitability Test for Azide
Polymer Propellants'', J. Energetic Materials, 16 (2=3), 173185
(1998).
(Received May 7, 1998; Ms 12=98)
94 Eishu Kimura and Yoshio Oyumi Propellants, Explosives, Pyrotechnics 24, 9094 (1999)