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)

Introduction peroxides and other detonable substances has

When a condensed explosive suffers rapid been developed. This method has been used to
decomposition, the process can conveniently be predict how the critical amount of heat (or
divided into four stages of development. These temperature) varies with the physical and kinetic
For personal use only.

are initiation, deflagration, transition from properties of an explosive.

deflagration to detonation, and detonation. This
paper is concerned only with the initiation phase,
that is, the processes occurring during the period
of time until deflagration starts.
Macek (1) terms initiation as the stage in
which the chemical decomposition has not yet
released sufficient energy for self-propagation
and hence is dependent on an external source of
energy. If this external energy source is insufficient
or is removed before sufficient energy for self-
propagation (deflagration) is generated, the rate
of decomposition will slow down and cease.
The sensitivity of an explosive may then be
related to the minimum necessary amount of
external energy that must be imparted to the
explosive, within limited time and space in order
to accomplish initiation. It is usually assumed
that this energy is ultimately delivered to the
explosive in the form of heat.
Sensitivity poses a twofold problem. The first
is concerned with the mechanism of degradation
of the energy of the stimulus (shock, friction,
impact, etc.) into heat. This aspect of the problem
has not been investigated in this work. The second
aspect of sensitivity is fundamentally a heat
balance problem involving the kinetics of the
explosive reaction.
A method of calculating the critical amount of
heat energy necessary to initiate deflagration in
Hot-Spot Initiation
Belajev (2) in 1938 first demonstrated that
deflagrations in liquid explosives could be
initiated by very small hot spots in the explosive.
The theoretical treatment of the factors involved
in such a "thermal explosion" was first given by
van't Hoff (3), expanded by Frank-Kamenetski
(4), and applied by Robertson (5) to condensed
phase explosions. Rideal and Robertson (6)
applied this theory to obtain estimates of hot-spot
sizes and temperatures necessary to accomplish
initiation. Bowden and Yoffe (7) have collected a
considerable amount of experimental evidence in
support of this "hot-spot theory". Further
verification of these results has been reported by
Collins and Cook (8).
More recently Boddington (9) and Friedman
(10) have extended the original theoretical
treatment of Rideal and Robertson (6). Both
attempted an analytical solution of the heat bal-
ance equations, using a number of assumptions,
including non-depletion of the reagent. Bodding-
ton obtains an expression in terms of a parameter
4, whose value determines whether or not the
explosive will reach a critical stage. He also
reports an exact solution to the equations
(including reagent depletion) by a numerical
method, and uses this to calculate critical hot-spot
temperatures for several explosives as a function
 3222 CANADIAN JOURNAL OF
of time and size. The ranking of sensitivity
obtained agrees quite well with that of Rideal and
Robertson. Friedman's analytical solution was
used to calculate theoretical drop-heights for an
impact test through a correlation equation for 16
explosives. The theory predicts the experimental
sensitivities to within 40%. These results seem to
confirm the validity of this treatment in predicting
the sensitivity of solid explosives. In the present
work, a numerical solution to the heat balance
equations has been developed and solved using
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a high-speed digital computer. The method is
similar to, but not identical with, that of
Boddington (9).
Theory of Hot-Spot Initiation
In the development of the theory it is assumed
that a hot spot is formed in a liquid explosive by
an external energy stimulus. If this hot spot is to
have the possibility of surviving, its temperature
must exceed a certain critical value at which the
rate of heat production by decomposition in the
For personal use only.
hot spot is greater than the rate of heat dissipation
to the surroundings. This is the critical tempera- Heat Production
ture calculated by Rideal and Robertson (6).
This heat condition is referred to as criterion I. taking place at T OK can be expressed as:
-
-
-
HOT SPOT RlODUClNG
HEAT lap]
4---- HEAT LOST-
FIG. 1. Hot-spot model illustrating heat flow.
A situation meeting the conditions of criterion
I insures that the hot spot will survive for a time.
However, the possibility exists that the hot spot
will cool and die out at some later time, due to
consumption of the reactant which would reduce
the heat production and temperature, thus
quenching the reaction. In order t o consider this
possibility a new calculation procedure was
developed to monitor the temperature of a thin
spherical shell in the body of the explosive that
CHEMISTRY. VOL. 46, 1968
encloses the original hot spot. The situation is
shown schematically in Fig. 1. I t is assumed that
initiation is complete and propagation begins
when the temperature of this layer is equal to or
greater than the original hot-spot temperature.
This original hot-spot temperature is defined as
the critical temperature. This condition is referred
to as criterion 11.
Calculation of Heat Loss and Production
The heat calculation procedure employed was
basically that used by Rideal and Robertson (6).
In order to keep the treatment in terms of
experimentally determined quantities, the follow-
ing assumptions are made: (i) The explosive is
homogeneous and isotropic. (ii)The hot spots are
sharply defined spheres in an infinite amount of
explosive. (iii) The hot spots are formed in zero
time by an external energy source. (iv) The
decomposition reactions are first order. (v) Heat
loss proceeds only through the mechanism of
conduction. (vi) The heat of reaction is the same
as in the ordinary thermal decomposition.
The rate of a first order chemical decomposition
where k = Ae-EIRT,c = concentration in moles
per liter at time t, A = frequency factor, E =
energy of activation, and R = gas constant.
If Q is the heat of reaction per mole, the rate of
heat production per liter is:
Oi
i
The quantity of heat generated in a chosen
time interval "At" in a given volume, V, of
reactant is:
where V = volume of reactant in liters,
p = density (g/l),
M = gram molecular weight of reactant.
Rideal and Robertson (6) used eq. [2] and
assumed constant concentration for the short
time intervals considered. In this work eq. [2] is
extended to account for variation of reactant
concentration a s the reaction proceeds. By
integration of eq. [I ] we can obtain an expression
 BRUCKMAN AND GUILLET: HOT-SPOT INITIATION 1N EXPLOSIVES 3223

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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(ii) The hot-spot temperature is constant through-

If Q' is the heat of decomposition of the pure out its volume and during the time interval
reagent in cal/g, the total heat generated in a time considered (this would be valid near the critical
interval t - to in a hot spot of volume V will be temperature), i.e.
given by
+(t) = constant = 0,
Co -C
[51 q = VpQ'-
c0 where 8, = temperature of the hot spot in OK
- ambient temperature in OK.
where co and c are the concentrations at times to Using these relations, eq. [7] reduces t o
and t calculated by substitution in eq. [3].
Heat Loss
Consider a hot spot of temperature T OK
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formed in zero time in an explosive at To OK. The

variation of temperature outside the hot spot This integral can be evaluated in terms of the
caused by heat conduction is given by the Fourier error function to give:
equation in spherical polar coordinates as :
[91 0, = -
r
erfc
[1"~(,",;]
-

where K = thermal conductivity, p = density, If radiation and convection contribute negligible

s = specific heat, and 0 = T - To. heat loss, the heat lost by the spot is then:
If the radius of the hot spot is "a", the bound-
ary conditions are: [lo] q s = JlIm 4nr2psBrd r
0 = f(r) when t = 0 for r > a,
and where 0, is given by eq. [9].
0 = +(t) when t = 0 for 0 < r < a Equations [9] and [lo] wereused in an iterative
computer program which conducts a systematic
The solution of this problem is given by
search of initial hot-spot temperatures until the
Carslaw and Jaeger (1 1)
critical temperature for a specified time interval
1 rm and hot-spot size was found. The program used
both criteria I and I1 in calculating critical
temperatures.
Explosive Parameters
The physical and chemical parameters used in
x exp (I + rkB; 2a2)] dr' critical hot-spot temperature calculations are
given in Table I. The values of density, heat
capacity, and thermal conductivity were taken
+
rJn r-a
+[t - ]
( r - a)2
e p 2d p as 1.0 g/cm3, 0.3 cal/g, and 3.0 x cal/cm2
s/cm OC respectively. Variation of these param-
-2 eters was found (this work) to change the critical
where B = K/ps, p = a constant. hot-spot temperature only slightly.
 CANADIAN JOURNAL O F CHEMISTRY. VOL. 46, 1968

TABLE I
Explosive parameters

Molecular Heat of Activation Frequency

weight decomposition energy factor
Explosive (glmole) (kcal/mole) (kcal/mole) (s-I) Reference
--

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.
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I) and no correction was made for reagent 367

400
350
385
depletion. The results are shown in Table 11. It is C:T.M:T.N.A. 423 405
apparent that our calculations give slightly E.D.N.A. 432 400
higher critical temperatures, but the order of Y~Y' 456
63 8
425
590
sensitivity is the same. For these calculations the E.D.A.D.N. 639 600
hot-spot size was cm radius and the time *ProgramI,criterion I.Timc = lo-" s. Hot-spotradius = 10-3 cm.
interval s.
Table I11 compares the results of different temperature, and makes some changes in the
methods of calculation. It is apparent that if one ranking of sensitivity.
only considers the hot spot itself (criterion I), A comparison of the critical hot-spot tempera-
reactant depletion has only a slight effect on the tures (as calculated by program 2) with a variety
critical hot-spot temperature, except for the less of sensitivity tests is given in Table IV. It can be
sensitive explosives like ammonium nitrate. The seen that the ranking of explosives in terms of
shell model (criterion 11), however, causes a critical hot-spot temperatures is completely
considerable increase in the calculated hot-spot consistent with the rankings obtained by a wide

TABLE I11
Comparison of T, values calculated by various programs

Critical temperature ("C)

Criterion I, Criterion I, Criterion 11,
no reactant depletion reactant depletion reactant depletion
Explosive (computer program 1) (computer program 2) (computer program 3)
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.
A.N.
T.N.T.
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TABLE IV
For personal use only.

Critical hot-spot temperatures (T,) compared with experimental sensitivity tests*

-

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

range of experimental tests. This correlation is

very striking, especially in view of the experi-
mental difficulty and known variability in tests of
this kind. This leads one to the conclusion that
the calculations may indeed have some real
significance in terms of the mechanism of shock
initiation in explosives.
Presumably one may also estimate the sensi-
tivity of an unknown explosive by calculations of
this type. In view of this it became of considerable
interest to determine which of the chemical and
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physical properties of an explosive contribute

most to its sensitivity. With the computer cmrl,y
'O g / cm'

program this can be determined by selecting a d 02 06 '+O

~~~~~l~~ Haaf i c o l q - ' 1

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"
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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
For molecular weights greater than about 340 or
molar heats of decomposition less than 50 kcall
mole-' the amount of heat generated is no
longer sufficient to maintain the temperature of
the hot spot and decomposition will cease. The
occurrence of such a critical point allows one to
calculate the dilution necessary to render an
I explosive insensitive to hot-spot initiation.
I
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FIG. 4. Variation of T, with gram molecular weight
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(G.M.W.).
The value of T , is surprisingly insensitive to
relatively large variations in AH outside this
critical region, indicating that the probability of
initiation is nearly independent of the energy
released during explosion.
( e ) Arrtlenit~sParanzeters
Inspection of Fig. 5 indicates that by far the
greatest variation in Tcis caused by changes in the
Arrhenius parameters, and is therefore related to
the rate of decomposition of the explosive at a
particular temperature. The critical temperature
FIG. 5. Variation of T, with Arrhenius parameters:
(o) frequency factor, log A , (b) activation energy, E..
3227
300
10.' lo-6 10- 10.'
T ~ m eInterval (5-I)
FIG. 6. Variation of T, with hot-spot duration.
is lower than room temperature for activation
energies lower than 18 kcal/mole (Fig. 5 , line a),
and increases almost linearly with activation
energy until a critical value of the activation
energy is reached, above which the hot spot
cannot produce more heat than is conducted
away over the time interval considered, i.e. the
explosive becomes insensitive.
The value of Tc decreases rapidly as log A
increases (Fig. 5, line b), and there exists a lower
critical value below which the explosive becomes
insensitive.
(f) Tinze Interval
Figure 6 shows that the critical temperature is
a decreasing function of time until the time
interval considered exceeds s. Then, the
heat produced can no longer balance the heat
lost from the spot over the interval. This would
suggest that the shorter the duration of a thermal
shock, the less sensitive the explosive will be.
( g ) Hot-Spot Radius
Figure 7 shows that the value of Tc decreases
as the size of the hot spot increases although the
Hot-Spot R O ~ I U (cm)
S
FIG. 7. Variation of T, with hot-spot radius.
 3228 CANADIAN JOURNAL O F CHEMISTRY. VOL. 46,
effect is not as large as might have been expected.
Changing the radius from 1 mm to 10 m causes
only a 100 "C decrease in T,. The change is more
rapid at smaller radii and reaches a lower limit
between 10-3-10-4 cm beyond which the heat
flow cannot be balanced, and the explosive
becomes insensitive. This suggests that hot spots
must exceed a radius of cm to be effective
in initiating explosion.
Conclusions
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Several important conclusions may be drawn
from the results of these studies. First it is obvious
that the inclusion of the depletion of material in
the hot spot has an important bearing on the
calculation, and represents a considerable im-
provement over the theory of Rideal and
Robertson. Although the effect on the calculation
of critical hot-spot temperatures, T,, is not large,
the inclusion of depletion allows the prediction
of a number of critical points above or below
which explosion cannot be initiated regardless of
For personal use only.
the strength of the stimulus. In principle this
should permit the calculation of the amount of
diluent, for example, necessary to make an
explosive insensitive under all conditions of
initiation.
The other important conclusion is that the
sensitivity of an explosive to hot-spot initiation
is almost entirely dependent on its rate of
decomposition as a function of temperature, as
expressed by the Arrhenius parameters. This
effect far outweighs all others. Explosives with a
low activation energy and a high frequency factor
will tend to be highly sensitive to hot-spot
initiation. This effect is much more important
than the energy produced per gram (AHIM), the
1968
thermal conductivity or density, as long as certain
critical limits are exceeded. The application of
this to other types of explosives will be considered
in a further communication.
Acknowledgment
This work was made possible by a grant from
the Defence Research Board of Canada (Grant
No: DRB 9530-50) whose support is gratefully
acknowledged.
1. A. M A ~ E K .Chem. Rev. 62, 41 (1962).
2. A. F. BELAJEV. Compt. rend. acad. sci. U.R.S.S.
18, 267 (1938).
3. J. H. VAN'THOFF. Etudes de dynamique chimique.
F. Muller, Amsterdam. 1884.
4. D. A. FRANK-KAMENETSKI. Acta Physicochim.
U.R.S.S. 10, 365 (1939).
5. A. J. B. ROBERTSON.Ph.D. Thesis, Cambridge
University, Cambridge. 1947.
6. E. K. RIDEALand A. J. B. ROBERTSON.Proc. Roy.
Soc. London, Ser. A, 195 (1948).
7. F. P. BOWDENand A. D. YOFFE. Initiation and
growth of explosion. Cambridge University Press,
London. 1952.
8. T. K . COLLINS and M. A. COOK. The measurement
of sensitivity time lag and burning velocity of
explosives by drop test. T.R. No. 48, Contract
N7-ONR-45107, Proj. No. 357239, E. R. G., Univ.
of Utah. December 15, 1955.
9. T. BODDINGTON.Proc. 9th Int. Symp. Combustion.
Academic Press Inc., New York. 1963. p. 287.
10. M. H. FRIEDMAN. Proc. 9thInt. Symp. Combustion.
Academic Press Inc., New York. 1963. p. 294.
11. H. S. CARSLAW and J. C. JAEGER. Conduction of
heat in solids. 2nd ed. Oxford University Press,
London. 1959.
12. S. ROGINSKY.Physik. 2. Sowjetunion, 1,640 (1932).
13. A. J. B. ROBERTSON.Trans. Faraday Soc. 44, 977
(1948).
14. J. WENOGRAD.Trans. Faraday SOC.57,1612 (1961).
15. J. L. COPP, S. E. NAPIER,T. NASH, W. J. POWELL,
H. SKELLY, A. R . UBBELOHDE, a n d P. WOODWARD.
Trans. Roy. Soc. London, Ser. A, 241, 197 (1949).
16. H. HENKIN a n d R. MCGILL. Ind. Eng. Chem. 44,
6 (1952).