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Theoretical Calculations of Hot-Spot Initiation in Explosives
Theoretical Calculations of Hot-Spot Initiation in Explosives
H. J. BRUCKMAN,
JR. AND J. E. GUILLET
Department of Chemistry, University of Toronto, Toronro 5 , Ontario
Received March 15, 1968
The heat balance equations for the thermal decomposition of hot spots in explosives have been solved
using an iterative computer method. This yields a value of T,, the critical temperature for hot-spot
initiation, which is a function of the size and duration of the hot spot and of the physical and chemical
properties of the explosive. It is demonstrated that there is a strong correlation between the ranking
of explosives in terms of shock sensitivity and their ranking in terms of T,. In general explosives having
low values of T, are more sensitive to shock and other forms of accidental initiation than those having-
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high values.
Using the computer program, it was shown that the major factor affecting T, was not the energy
released in the explosion, but the rate of decomposition, as expressed in terms of the parameters A a n d
E, in the Arrhenius equation. Consideration of reagent depletion also indicated certain limits beyond
which the heat production cannot be maintained for the time necessary to initiate explosion a n d
insensitivity should result. Considerations of this type could be used to predict safe handling procedures
for explosives.
Canadian Journal o f Chemistry, 46, 3221 (1968)
of time and size. The ranking of sensitivity encloses the original hot spot. The situation is
obtained agrees quite well with that of Rideal and shown schematically in Fig. 1. I t is assumed that
Robertson. Friedman's analytical solution was initiation is complete and propagation begins
used to calculate theoretical drop-heights for an when the temperature of this layer is equal to or
impact test through a correlation equation for 16 greater than the original hot-spot temperature.
explosives. The theory predicts the experimental This original hot-spot temperature is defined as
sensitivities to within 40%. These results seem to the critical temperature. This condition is referred
confirm the validity of this treatment in predicting to as criterion 11.
the sensitivity of solid explosives. In the present
work, a numerical solution to the heat balance Calculation of Heat Loss and Production
equations has been developed and solved using The heat calculation procedure employed was
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a high-speed digital computer. The method is basically that used by Rideal and Robertson (6).
similar to, but not identical with, that of In order to keep the treatment in terms of
Boddington (9). experimentally determined quantities, the follow-
ing assumptions are made: (i) The explosive is
Theory of Hot-Spot Initiation homogeneous and isotropic. (ii)The hot spots are
sharply defined spheres in an infinite amount of
In the development of the theory it is assumed explosive. (iii) The hot spots are formed in zero
that a hot spot is formed in a liquid explosive by time by an external energy source. (iv) The
an external energy stimulus. If this hot spot is to decomposition reactions are first order. (v) Heat
have the possibility of surviving, its temperature loss proceeds only through the mechanism of
must exceed a certain critical value at which the conduction. (vi) The heat of reaction is the same
rate of heat production by decomposition in the as in the ordinary thermal decomposition.
For personal use only.
for the concentration of reagent c as a function of The equation can be simplified if two further
time t in the form conditions are imposed on the system: (i) The
ambient temperature is initially constant through
the material, i.e.
and the rate of heat production per liter can now
be expressed as ,f(r) = constant at t = 0.
Since only the difference between ambient and
hot-spot temperature is required, the constant
can be set equal to 0 if the hot-spot temperature
x exp
E
[-RT - (t - to)Ae-EiRT
I is also adjusted.
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TABLE I
Explosive parameters
Pentaerythritol
tetranitrate (P.E.T.N.) 316 74 47.0 6.3 x 10'" 6
Cyclonite (R.D.X.) 207 191 47.5 3.2x1Ols 6
Cyclotetramethylenetetra-
nitramine (C.T.M.T.N.A.) 276 253 52.7 5.Ox1OLq 6
Ethylenedinitramine
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(E.D.N.A.)
Tetrvl
~thylenediamine
dinitrate (E.D.A.D.N.) 176 129 40.5 1 .3 x loi3 6
Ammonium nitrate (A.N.) 80 13.5 40.5 6.3 x l o x 3 6
Nitroglycerine (N.G.) 227 114* 48.0 3 .Ox 1020 12
Trinitrotoluene (T.N.T.) 227 114* 34.4 2.5 x l o L 1 13
'Estimated value.
Calculations . TABLE I1
Comparison of T, values ("C)*
The first calculations performed were those
done by Rideal and Robertson (6). In this case Explosives This work Rideal and Robertson
only the hot spot itself was considered (criterion
:EgN.
For personal use only.
TABLE I11
Comparison of T, values calculated by various programs
TABLE IV
For personal use only.
Imnact
sensitivity U.S. Naval U.S. Naval
T,("c) (cm) T,("C) Figure of Impact time Ordinance Ordinance Figure of Tc PC)
(Program 2, [250 s] insensitivity lag impact test gap test insensitivity [3nigsample]
Explosive this work) (ref. 14) (ref. 10) (ref. 14) (ref. 6) (ret. 6) (ref. 1) (ref. 1) (ref. 15) (ref. 16)
N.G.
P.E.T.N.
R.D.X.
- - - -
C.T.M.T.N.A.
E.D.N.A.
Tetryl
E.D.A.D.N.
T.N.T.
A.N.
'Time = s, hot-spot radius = cm.
3226 CANADIAN JOURNAL OF CHEMISTRY. VOL. 46, 1968
particular set of properties and determining the FIG. 2. Variation of T, with (a) density, a n d (b)
variation in T , as one of these is varied over the specific heat of a hypothetical explosive.
range of interest. A hypothetical explosive is
considered with the properties given in Table V. ( c ) Thermal Co~zd~illctil;ity
The results of the calculations are shown in Figure 3, line a, shows that the critical tempera-
Figs. 2-7. ture rises rapidly at low values of thermal con-
TABLE V ductivity and becomes almost linear variation for
the higher values. Near a "critical conductivity"
For personal use only.
Properties of hypothetical explosive the temperature rises sharply and past this critical
value the explosive becomes insensitive. In this
Explosive parameter Symbol Value condition heat is always conducted away from
Density P 1.0 g/cm3 the hot spot faster than it can be produced. This
Specific heat s 0.5 cal/g could explain the desensitizing effects of alumin-
Thermal conductivity K 4.0 x cal/cm2 ium powder, for example, with certain explosives.
deg cm
Molecular weight M 200 g/mole
Heat of decomposition AH 80.0 kcal/mole ( d ) Molecular Weight a1zdHeat of Decon~positio~z
Activation energy E 31.52 kcal/mole Figure 3, line b, and Fig. 4 show that changes
Frequency factor A 2.7 x l 0 l 5 s - I in molecular weight and heat of decomposition
are equivalent t o changes in the heat of decompo-
sition per gram of explosive. This quantity has a
( a ) Density critical value which is reflected in critical molec-
Figure 2, line a, shows that the critical tempera- ular weight and molar heat of decomposition.
ture increases slowly as density decreases, then
more rapidly until a "critical density" is reached,
e.g. between 0.4 and 0.5 g/cm3 for the hypotheti-
cal explosive. At or below this density the heat
produced in the hot spot can never be greater than
the heat lost due to conduction. Below this
density the explosive becomes insensitive to hot-
spot initiation.
(b) Specijic Heat
Figure 2, line b, shows that the critical tempera-
ture increases very slightly with specific heat. At
very low values of specific heat, the critical zsoo I
09 04 06
I I
08
I 80
K icol /cmZ d e g crn I x 10'
temperatures begin to drop rapidly indicating a : , 20 100 130
I ZOO
rapid increase in sensitivity. However, over the A H ( k c 0 1 mole-')
usual ranges, T , is nearly independent of specific FIG.3. Variation of T, with (a) thermal conductivity
heat. a n d (b) molar heat of decomposition.
BRUCKMAN AND GUILLET: HOT-SPOT INITIATION 1~ EXPLOS~VES 3227
300
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T ~ m eInterval (5-I)
Hot-Spot R O ~ I U (cm)
S
FIG. 5. Variation of T, with Arrhenius parameters:
(o) frequency factor, log A , (b) activation energy, E.. FIG. 7. Variation of T, with hot-spot radius.
3228 CANADIAN JOURNAL O F CHEMISTRY. VOL. 46, 1968
effect is not as large as might have been expected. thermal conductivity or density, as long as certain
Changing the radius from 1 mm to 10 m causes critical limits are exceeded. The application of
only a 100 "C decrease in T,. The change is more this to other types of explosives will be considered
rapid at smaller radii and reaches a lower limit in a further communication.
between 10-3-10-4 cm beyond which the heat
flow cannot be balanced, and the explosive Acknowledgment
becomes insensitive. This suggests that hot spots
must exceed a radius of cm to be effective This work was made possible by a grant from
in initiating explosion. the Defence Research Board of Canada (Grant
No: DRB 9530-50) whose support is gratefully
Conclusions acknowledged.
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