COMBUSTION A N D F L A M E 85:185-194 (1991)

185

Comparison Between Shock Initiations of Detonation Using Thermally-Sensitive and Chain-Branching Chemical Models
J. W. DOLD
School of Mathematics, University of Bristol, Bristol BS8 ITW, United Kingdom

and A. K. K A P I L A
Department of Mathematical Sciences, Rensselaer Polytechnic Institute, Troy, New York 12180-3590, USA
This article shows that, unlike the situation in many other combustion problems, the progress towards detonation behind an initiating shock wave when the chemistry is modeled using a radical chain-branching mechanism is fundamentally different from the progress found when a global one-step model is used. In the latter case, a uniformly supersonic (shockless) wave of chemical activity is found to emerge at the end of an induction process. Only after this "induction flame" slows down significantly is it possible for a genuine propagation mechanism to create a Zeldovich-von Neumann-DSring detonation structure. When dominated by chain branching, the reaction wave produced by the induction process is subsonic, and can therefore be influenced by propagating thermodynamic disturbances (as originally pointed out by Strehlow). The resulting chemical-hydrodynamic interaction causes an acceleration of the wave prior to the emergence of the detonation. It is suggested that the existence of these two distinct forms of initiation may provide a means of testing for the relative importance of possible chain-branching and state-sensitive mechanisms in the initiation of detonations, especially where little kinetic data are yet available (as, for example, in condensed explosives).

INTRODUCTION Recent asymptotic analyses of the initiation of detonation using a large-activation-energy, onestep model for the chemistry [1-4] have revealed an interesting sequence of events, but one that is not always in qualitative agreement with experimental observations [5, 6]. In seeking an explanation, one finds that quite different physical events can be predicted if a radical chain-branching model for the chemistry is invoked. This article seeks to investigate this difference and to point out its implication concerning both the use of global, one-step chemical models for detonation problems and the experimental investigation of the chemical kinetics of explosives. Some discussion of the underlying physical and chemical reasons for the difference is also presented. If a strong piston-driven (or reflected) shock wave raises the temperature of a medium that is reacting via a single exothermic temperature-sensitive chemical step to a point at which the reaction becomes significant, then during an initial induction stage, the reaction-rate increases relatively slowly as a thermal runaway begins to set
Copyright 1991 by The Combustion Institute Published by Elsevier Science Publishing Co., Inc.

in. After a while, this induction process leads to a rapid and substantial energy release that starts at the piston face and always moves as a supersonic wave of chemical activity into the compressed medium. This wave is not, however, a Zeldovich-von Neumann-DSring detonation. In the manner identified by Zeldovich and Kompaneets [7], Clarke [8], and others [4, 9], it represents a "fast flame" that is dominated throughout its structure by reactive and supersonically convective processes. As such, the flow through the wave involves no shock and the wave assumes the form of a weak detonation (at least to begin with). Although Zeldovich and Kompaneets imagined such a wave as being initiated by a rapidly moving source of ignition (such as a very fast sequence of sparks), no such "thought experiment" is required to explain the reaction wave that emerges in the present context. Diffusive effects being insignificant, the wave should also not be confused with any other, laminar or turbulent, flame that is sustained by thermal and mass transport. On the contrary, the reaction wave that initially appears for a one-step,

0010-2180/91/$3.50

186 temperature-sensitive model of the chemistry simply travels too fast for its motion to be attributable to any propagation mechanism--it is a wave of chemical activity that moves faster than any acoustic signal within the system. Instead, the movement of this fast flame appears by virtue of the fact that chemical and fluid interactions during an induction process cause different points within the reacting medium rapidly to release their chemical energy at different times. This is somewhat analogous to Zeldovich's less precise concept of a "spontaneous flame" [10], which is notionally defined only in terms of homogeneous induction times that are calculated separately for every point based only on initial data. Because it therefore emerges from a spatially varying induction process, and not through any mechanism for propagation, it may be appropriate to refer to this particular reaction wave as an induction flame. This term is introduced purely for convenience at this stage in order to facilitate discussions below concerning the detailed nature of reaction waves that emerge within the shocked medium. In particular, the term is used to emphasize the role of induction, rather than any propagation mechanism, in determining the nature and movement of a wave of chemical activity. The term has also been usefully applied elsewhere in studying the inductive initiation of combustion with diffusive rather than compressible interactions [11, 12]. For a single-step, temperature-sensitive chemistry, the speed of the induction flame is actually found to be infinite at its moment of birth near the piston face (so that neighboring points explode almost simultaneously). The flame also continues to move supersonically--after one point explodes, the signal that it produces does not have time to reach any other point before it too explodes. However, the flame does slow down as it moves forwards, until its speed reaches the Chapman-Jouguet detonation speed with respect to the compressed, unburned medium ahead of it. This would typically happen well before it catches up with the initiating shock-wave [13]. At this stage, acoustic information begins to travel faster than the induction flame in the hottest, burned part of the medium, causing a shock-wave to form somewhere near the end of the chemical reaction. As this shock wave overtakes (and de-

J . W . DOLD AND A. K. KAPILA stroys) the now slower induction flame, it further increases the sound speed in its wake and so maintains a mechanism for propagation. A short but quasi-steady transient leads to the establishment of an underdriven Zeldovich-von Neumann-DSring detonation. A brief outline of the model and the essentials of the theoretical description of this sequence of events are presented below, greater detail being available in references [1-4]. Recent numerical analyses of detonations initiated by piston-driven shock waves in media that react via a one-step exothermic reaction of moderately large activation energy are in excellent agreement with this description [14, 15]. The fact that some experimental observations, both in gases and condensed explosives [5, 6], reveal a qualitatively different sequence of events, suggests that a different mathematical model is required to explain the actual progress to detonation in some materials. In these experiments, the wave of strong chemical activity that emerges after an induction stage is not found to be supersonic. Disturbances associated with the observed flame are thus genuinely able to self-propagate and may be able to steepen sufficiently to form a secondary shock wave before catching up with the leading or initiating shock. By examining a fairly simple three-step model for the chemistry, a description that is qualitatively closer to these experimental findings can be obtained. A numerical study of a similar system was first carried out by Strehlow and co-workers in the context of reflected shock initiation, and a summary of their results appears in Strehlow's textbook [6]. Our more generalized model consists of two radical-producing temperature-sensitive reactions (that may be endothermic), representing an initiation step and a chain-branching step. The third reaction is an exothermic radicalconsuming step of negligible activation energy that completes the chemical change. This scheme admits some useful asymptotic analysis and qualitatively mimics some of the features of hydrogen-oxygen as well as hydrocarbon combustion. Asymptotic solutions are obtained for the early behavior of the reaction-wave that emerges. This is sufficient to demonstrate the manner in which propagation mechanisms can operate and lead to an acceleration of the flame. The distinguished roles of the temperature sensi-

SHOCK INITIATION OF DETONATION tivities of each reaction are also easily understood. It is worth noting that while this reaction model and analysis are open to further generalization, they are sufficient to establish the principal objectives of this article in a relatively simple way. Since the results broadly agree with some experimental observations for detonation initiation [5], they may provide some clues about the actual chemical processes that take place in some condensed explosives, for which little kinetic data are yet available, For instance, it is by no means clear, a priori, that any intermediate reactants in such explosives would be produced via a chainbranching (self-catalyzing) process rather than (say) thermal decomposition. Indeed, bearing in mind the enormous pressures involved in the detonation of condensed explosives, one might anticipate a mechanical element in the decomposition of larger molecules, more sensitive to the thermodynamic state (including pressure) than to the presence of active radicals. The model examples of mole-preserving, thermally sensitive, and chain-branching reactions, which are studied here, serve primarily to illustrate the behavior at opposite ends of a spectrum of possible chemical pathways. After briefly outlining the reasons for the appearance of a supersonic induction flame through a single temperature-sensitive chemical step, we discuss the nature of the corresponding flame arising as a result of the three-step scheme. Only in one special case, for which the chain-branching reaction is insensitive to temperature, does this flame represent an induction flame--its path and chemical structure being determined only by spatially varying chemical kinetic induction processes and not by any propagation mechanism, in spite of the fact that it travels subsonically. However, if the reaction is sensitive to temperature, then thermal changes brought about by the propagation of pressure waves increasingly influence the movement of this flame from the moment of its birth at the piston face. With neither the one-step nor the three-step model do we take the analysis as far as considering the behavior of the flames as they approach the initiating shock-wave. Rather, the main intention of this article is to make use of asymptotic arguments to highlight the two fundamentally different possible types of reaction waves that can

187 emerge at the end of an induction period for different kinetic models. Particularly for condensed explosives, this may offer an experimental means of examining the relative importance of radical self-catalyzing (chain-branching) reactions and global thermodynamic sensitivity.

MODEL Fluid-Dynamic Equations

In order to model the nonlinear pressure, velocity and thermal interactions that take place in a detonating medium it is convenient to focus attention on the Euler equations for ideal gas-dynamic interactions. For values of the adiabatic coefficient 3, as high as three or more, it is believed that these equations provide a qualitatively adequate model for dynamic interactions in condensed explosives [16]. At the high velocities and short time-scales found in detonations, it is highly realistic to ignore diffusive effects, except perhaps within the internal structure of strong shock waves [17]. For these it is adequate to use Rankine-Hugoniot shock jump conditions. Also assuming that the chemical process preserves the number of molecules, the set of dimensionless equations becomes
7-1
PTt - "7 " Y - ' P t + PPUv, = P q t , Pt + P q t ,

(1)

ut + "r-lp,~ = 0 P = aT,

in which p is the density, P the pressure, T the absolute temperature, u the velocity, and q the amount of energy released by the chemistry. Subscripts are used to denote partial differentiation. Time is represented by t while ~k represents a Lagrangean (mass) coordinate defined by ~b = f~Xtp dx. The second of these equations (representing the effects of compressibility) can be derived from the mass conservation equation Pt + p2 u~ = 0 by using the first (energy conservation) equation and the last (gas state) equation to eliminate Pt and Tr The remaining (third) equation describes momentum conservation. We suppose that a solid piston of constant

188 dimensionless velocity u i drives a shock-wave of initial Mach number m i > 1 into the cold stationary unreacted explosive medium. Choosing the initial state of the medium behind the shock-wave to be the reference state for nondimensionalization (so that T = P = p = 1 at the initial instant behind the shock wave), the dimensionless state of the medium ahead of the shock is then given by the Rankine-Hugoniot conditions 7+1
P=Pi = 23M2 + 1 _ 7 ' 2/M 2 + 3'P=Pi =

J.W. DOLD AND A. K. KAPILA

One-Step Chemistry
A simple one-step model for the chemistry can be postulated in the form R ~ P. (6)

If r represents a normalized mass-fraction of the reactant R, that is always taken to be unity immediately ahead of the shock, then with an Arrhenius model for the reaction rate the chemical evolution is governed by the equation
r

rt +

e B(l-1/r) = 0

(7)

O/3
(2) for an appropriate choice of the dimensionless time-scale t. (It may be recalled that T = 1, initially, immediately behind the shock wave.) Strong temperature sensitivity is represented by the dimensionless activation temperature /3 being large. The system of equations is then closed by noting that the released chemical energy q is given by q= Q(1r) (8)

'7+1

with M/2-1
Ui=2
('7 + 1 ) M i

As the system evolves, driven by changes in the released chemical energy q, the shock Mach number M generally changes from its initial value. As this happens, the state of the medium immediately behind the shock becomes
2",tM 2 + 1 - "y

P=P=

2"YMi2 + 1

-7,
1 1,

2/ME

+ 7-

P = Po = 2 / M 2 + 3' m 21

(3)

u = u o = 2 (7 + 1 ) M V/ffii/Pi" while at the piston, the relevant boundary condition remains

U -U i.

for a dimensionless constant Q, representing the total chemical energy available in the unreacted mixture. With this model, taking r and the other dynamic variables T, P , and so on to be fixed ahead of the shock wave relies on assuming that the reaction rate ahead of the shock, i.e., exp[/3(1 - 1/T/)], is negligibly small. Since 1 - 1/T,. is negative, this assumption relies in /3 being large and is thus consistent only with an asymptotic description for 13 ~, 1.

Three-Step Chemistry
A simple model for the chemistry, involving radical production, chain branching, and exothermic completion of the reaction can be represented by the following three steps: I: F + M ~ Y + M ,
B: F+ Y" 2Y,

(4)

It is useful also to identify the dimensionless mass-flux through the shock-wave, given by m = M ~ with m i = M i v / & P i , (5)

kt

= e A(1/rt-

l/T) (9)

having m i < 1 for any M i > 1. In this way, the shock boundary conditions (Eq. 3) and the piston boundary condition (Eq. 4), are all parameterized by the single quantity m i (or, equivalently, M i ) for a given value of 7.

k B = e/rB-1/r) kc= 1.

C: Y + M--* P + M,

Taking f and y to represent normalized mass fractions of F and Y, respectively, the chemical

SHOCK INITIATION OF DETONATION

log k

189 uniformly very slow. For the purposes of this investigation, we may also consider cases for which the activation energy of the branching reaction B is moderately large 0 ~, 1, although it is also generally relatively small when compared with A. Provided the temperature in the medium ahead of the shock T/ is below TB, chain-branching is not able to build up the concentration of active radicals and a quasi-steady approximation for y can be justified, showing that ahead of the shock one should find
kzf
Y = Yi

t
T
I

1/T

I/TI

I/TB

llTi

Fig. 1. Variation of k t, k n, and k c with T. Crossover temperatures Tt and TB are on opposite sides of the initial postshock temperature of unity. Preshock temperature is T / <

kc

_ kB f

kt(T/),

(12)

rB.

evolution can then be modeled by the equations

ft + f(kt + Y k s ) = 0, "Yt = k t f + Y ( f k s - kc),

(10)

again for an appropriate choice of the time-scale t. The released chemical energy can be written as q = Q(1 - f ) - ( Q + D ) y , (11) where Q has the same meaning as previously, and D represents an amount of endothermic energy absorbed by the initiation and chain-branching reactions 1 and B in breaking down the reactant F into the energetic radical Y. Representing a recombination of active radicals, the completion reaction C should meet no significant activation energy barrier although other possibilities could be considered. It should be emphasized that this is only a sample model scheme that has been selected to illustrate the role of chain branching using an asymptotic approach. Figure 1 illustrates the ways in which the Arrhenius reaction "constants" k z ( T ) , k s ( T ) , and k c ( T ) are taken to vary with temperature. The "crossover" temperatures, T, and T s, at which the initiation and branching reactions become as fast as the completion reaction are taken to be, respectively, greater than and less than the dimensionless initial postshock temperature of unity. The initiation reaction I generally has a large activation energy, A ~, 1, required to destroy the relatively strong chemical bonds of the explosive F. As a result, this reaction tends to be

which is typically very small indeed unless T,. is close to Tn--representing a preshocked temperature only slightly below the level at which chainbranching would begin. The second asymptotic approximation in Eq. 12 is only valid if T~ is not close to TB and 0 ~, 1 so that k B can be neglected in comparison to k c = 1. The rate of change of f is then equally as small, so that it is reasonable to take f to be fixed at unity in the medium immediately ahead of the shock, with no significant change occurring until the shock raises the temperature of the medium above Ts. Once this happens, chain branching can dramatically accelerate the chemical process. ONE-STEP INITIATION Since many of the details of the way in which a detonation would arise from a single one-step large activation energy reaction appear elsewhere, only a very brief description is offered here, Induction In order to analyze the thermally driven induction stage that is relevant to this model, it is worth noting that order /3-1 perturbations cause significant changes in reaction rate. It is therefore appropriate to use the asymptotic expansions T1 +/3-'~b(~b, t ) , (13)

u - u i + /3-1v(~b, t ) ,

Pr-

1 + ('g/3)-Ip(~b, t ) ,
1 -- ( Q f l ) - l w ( f f , t)

190 for large [3, with which one obtains the reduced model
4~t = wt + ( 7 Pt + v, = Wt ,

J.W. DOLD AND A. K. KAPILA through the system at supersonic speeds. This finding is a direct result of the way in which the induction proceeds under the influence of Eqs. 14-16. Moreover, with blowup happening first at the piston-face, one finds [19] that
-- t I

1)Pt,

v t + p~ = 0, w t = e '.

(14)

+ KII~ (23/-1)/7,

(19)

Boundary conditions for these equations need to be applied at the piston face tk = 0, at which we have simply that v(0, t) -- 0, (15)

so that the path of blowup initially has infinite speed, since 7 > 1, and the mass-flux r~ decreases as the singularity moves forwards (remaining supersonic). Induction Flame The correct interpretation of the singular growth in the perturbation quantities defined in Eqs. 13 is that changes in T, P , u, and r cease to be small (of order [3-1) close to the singularity path t =

and at the leading shock-wave, which lies at ~k - m i t + [3- ' f ~ m 1 dt. Equations 3 can be used to deduce that we must have the shock boundary conditions (at ~k = m i t to leading order):
k(mit, t) = A r m ,, P(mit, v(mit, w(mit, t) = A p m l,

7(4).
(16) Since reaction and heat-release rates become very fast indeed according to the model (Eq. 7) when T is not close to unity, a quasi-steady structure can be analyzed for the resulting induction flames, confirming the Rayleigh line and Rankine-Hugoniot relationships Pand (3' + 1 ) ( P V - 2 Q(1 - r ) ,

t) = A u m l , t) = O,

in which the shock mass-flux perturbation m~ appears parametrically. The constants AT(m/), A p ( m i ) , and A u ( m i ) are easily found by differentiating Eqs. 3 and 5. It is worth noting that Clarke's equation [18] is derived by eliminating p, v, and w between Eqs. 14,
(4a t - "ye6)tt = (dp t - e~')~~.

1-

- ' y t h 2 ( V - 1) 1) + ( 7 1)(V-tP t

(17)

Under the bounded initial and boundary conditions (Eqs. 15 and 16) (or many more general conditions), Eq. 17 leads to a blowup in finite time [13, 19, 20]. In particular, for this shock-initiation problem, one always finds that 4~ --' oo as the time t approaches a supersonic path in space and time, t = 7(~b), as follows: lim 4~(~b, t) = oo,

respectively, in which the specific volume is V = 1/0. Most significantly, the induction-flame conforms to "weak detonation" solution paths in the Rankine-Hugoniot diagram, as illustrated by the Rayleigh line A - B in Fig. 2. Shock Formation--Propagating Flame As the induction flame slows down, its structure is determined by Rayleigh lines of decreasing negative slope as th decreases. When the slope of this line decreases to the point of tangency with the burned Hugoniot curve (the line A - C in Fig. 2) a sonic point is produced in the burned medium. At this point, acoustic information travels forwards as quickly as the induction flame itself and any further slowing down in the induction flame causes a shock wave to form in the hottest parts

with r~(~k) =

> 1.

The fact that the mass-flux rh, which is swept through the singularity path, is necessarily greater than unity indicates that the singularity moves

SHOCK INITIATION OF DETONATION

P

191 line. Initially, most of the chemical change takes place within an induction flame between these two lines. The solid line indicates the path of a shock wave that propagates ahead of the slowing induction flame, transforming it into a Zeldovich-von Neumann-D/Sring detonation.
THREE-STEP INITIATION
A

"~~.""".."""-."".. . "~,.....

Induction
V

//

Fig. 2. Quasi-steady, weak-detonation structure of an induction flame on a Rankine-Hugoniot diagram. Point A represents compressed, almost unreacted state ahead of the induction flame. As reaction proceeds, the state of the medium is described asymptotically by changes along a Rayleigh line (such as A - B), that passes through a sequence of intermediate Hugoniot curves (shown dotted), each corresponding to a partially completed stage of the reaction, towards the final burnt Hugoniot curve (shown solid). As flame slows down, point B moves from right to left on burned Hugoniot curve. Rayleigh line A - B corresponds to an instant when the flame is supersonic, and A - C to an instant when the flame is sonic, in relation to the following flow.

of the medium, thus introducing a mechanism for propagation. For details about this transition, the reader is referred to Refs. 1, 3, 4, and 21. An illustration of the transition process is presented in Fig. 3, where the dotted line represents the singularity path t = 7(~b) in the (~b, t) plane. Close behind this line, the reaction rate reaches a locally maximum value, represented by the dashed
t

The induction process with the three-step model of the chemistry is fundamentally different from the one-step thermally driven induction. Once the initial temperature behind the shock is raised above TB (initially to unity according to the nondimensionalization), the difference f k B - k c in Eq. 10 becomes positive. Indeed if 0(1 - Ta) is large, then k B becomes large, so that this difference is positive for a wide range of values of f . This leads to a rapid exponential chainbranching growth in the values of y. On the other hand, the values of y begin to grow from the tiny initial value Yi and are forced to increase initially at the very small rate k/(1). Thus, the values of y remain small for a prolonged period during which changes in temperature would also be small. As a result, temperature variations can be neglected during most of the chain-branching induction process, leading to the following composite asymptotic solutions for y and f (in which the subscript 1 denotes evaluation at T = 1):
ye(km-kcO(t-trf~/rn,) - k i l / ( kB1 -- k c l ) , E BI e (kin -

kct)(t-

t 1- ~// mi)

f-1k m - kcl

kole-(kn,-kct)tt

(21)

k m - kc1 + ktl - kcl ks1 -- k c l (t~b/mi),

where
Fig. 3. Sketch of transition to a Zeldovich-von NeumannDSring detonation structure in (~b, t) plane. Dotted line represents the singularity path t = t', dashed line represents the path of maximum reaction rate, and solid line is the locus of a shock wave that is born when the induction flame has slowed down just below the Chapman-Jouguet speed. Precursor shock is not shown.

t z = In ktl "~-~-/(ffn~ --- k c l )

e O(1/Tn-l) -- 1

( k a l -- k c l )

A(1 - 1 / T I ) + O ( 1 . / T B - 1)
+ O(e-Z(~/rB-').

(22)

192 In this, the boundary conditions y = Yi and f = 1 have been applied at the leading-order shock path ~b = m d . It may be noted that these asymptotic results require only that k m > k c l and that T be nearly constant. They do not rely on 0 being large, except insofar as the final estimate for tz in Eq. 22 becomes more accurate in this limit. The buildup in the normalized radical massfraction y first reaches order unity values near the piston face, ~b = 0, during the time

J.W. DOLD AND A. K. KAPILA the one-step induction flame described in the previous section. However, since m i < 1, this path is subsonic. As a result, pressure-wave disturbances produced by temperature changes associated with order unity changes in the value of y can propagate ahead of the path (Eq. 25). Unless the reaction constants k I, k B, and k c are (somehow) independent of temperature, these waves will then modify the Eqs. 21 and render the induction flame-path (Eq. 25) physically meaningless. It is worth noting that a variant of the model (Eq. 9), in which one could assume (say) a constant value for k B > 1 for all T _ TB, would produce a flame that follows the path of Eq. 25 until significant pressure disturbances catch up with the leading shock wave--after a time of the order of m i t t ~ ( 1 - mi). This follows from the observation that the initiation reaction I is only significant in Eqs. 10 when y = O ( k i ) . Thus the solutions (Eqs. 21) only tend to be sensitive to' changes in k t ( T ) when y is still very small, as it is close to the initiating shock-wave, and would thus be changed significantly only when propagating disturbances reach the shock wave.
Effect o f Pressure-Waves

(1)

t-

tI = 0

kai - kcz

(23)

Particularly if 0 is large, this time is relatively short in comparison to the chain-branching induction time t z. Because A is large, Eq. 22 identifies a distinguished limit. By the definition of k c in Eq. 9 the dimensionless radical recombination time is of order unity. The relative time scale of this exothermic reaction to the initial overall chainbranching induction time depends intimately on the value of
~o = a e - " / r B - 1 ) .

(24)

For order unity values of 0 this quantity is large, indicating that the time for radical recombination would be short compared with the induction time Only for moderately large values of 0, of the order of In A, do these times become comparable, or even reversed, in their relative orders of magnitude. Thus, depending on the values of A and 0, it can be seen that a wide range of possible chemical and thermodynamic structures would be parameterized by the quantity w.
Induction Flame

To illustrate the way in which pressure waves cause the region of strong chemical activity to move ahead of the induction flame path (Eq. 25) we only consider the very early behavior of the chemical wave in the case D = 0. If 0 is large, we can also consider the radical concentration y to increase towards unity in a vanishingly thin region about some path t = i(~b), which is initially approximated by ~(~b) = t z + ~b/m o + O(~b2). Following the passage of this chemical wave, the recombination reaction C causes heat to be released at the initial rate qt =
Q + O ( t - t).

In the absence of any propagation mechanism, Eqs. 21 show that values of y would increase rapidly along the path 1 ) (25)

At sufficiently early times, pressure and velocity variations are small so that linearized characteristic solutions of Eqs. 1-4 give T7-1 1 P7
- (ttI -

t =

tI +

~b/m i + 0

kBi

kcz

3-2m l+mo

( u - u,)

followed by a region of radical recombination. Since this result follows entirely from the solutions describing the induction process, it identifies an "induction flame" in an analogous way to

3/2 - m o
~b)Qm o
1 m o

(26)

in the region where ~b <_ t - t I < ~ / m o. At least

SHOCK I N I T I A T I O N OF D E T O N A T I O N for a while, no significant disturbance propagates ahead of the characteristic ~b = t - t I. The reaction model (Eqs. 9 and 10) now gives
Yt ~ Y k m eO'- 1),

193

II.1"

(27)

after linearizing the Arrhenius exponent and neglecting all but leading order terms. Using the solutions (Eq. 26), this equation can be integrated to give y - exp ( e ~ t - t ' - ' ~ ) - 1) - k e l
mi j,

(28)
with

3/2 - m 0
K = 1)Qmo 2

Fig. 4. Sketch of effect of pressure waves on induction flame in 3-step model. Precursor shock is identified by S, and dashed line parallel to it represents induction-flame path when pressure waves are not taken into account. Pressure waves accelerate the path of the reaction wave t = ~(~b) in the manner illustrated by the solid curve. Dotted line represents the leading characteristic t = t I + ~b. structure of the recombination region following t -- t. Alternatively, a numerical study (comparable to Strehlow's work [6]) could be carried out. The simple analysis above, however, is sufficient to illustrate the mechanism by which propagating disturbances would immediately modify a subsonic induction flame structure that arises when the three-step reaction scheme (Eqs. 9) describes the chemical process. CONCLUSION These fairly simple analyses serve to show that a quite different form of detonation initiation can be found when an exothermic change in a chemical state progresses at a rate that depends not only on thermodynamic quantities but also (through chain branching) on a radical concentration. Because the latter is independent of any thermodynamic quantities, induction times that are determined primarily by chain-branching processes become more-or-less uncoupled from any pressure and velocity interactions during an inductive evolution. Because such a coupling is inherent in systems that involve thermodynamically sensitive, one-step chemistries, quite different behavior is predicted. A significant part of the chemical change that takes place in many gaseous combustible systems is known to involve the production and reproduction of chemical radicals by chain-branching processes. It is therefore perhaps surprising that the

1 - mo

after using Eqs. 21 to set the values of y at the leading characteristic ff = t - t z. This solution is, of course, only valid at early times, but it is sufficient to show that the path i(ff), near which values of y increase substantially, has the asymptotic structure 1 ~-t1+~+ ( In 1 - r 1-m/~ mi / ] (29)
- t,+C//m i~ mi ]

for small values of ~b. It can thus be seen that rn o = m r In other words, the path starts out being close to the induction flame path (Eq. 25), but it moves ahead by an amount that progressively increases as propagating disturbances increase the rate of chain branching ahead of the wave. For comparison with Fig. 3, Fig. 4 illustrates (schematically) the movement of the path t = t(~k) in the (~k, t) plane. Temperature disturbances produced by the exothermic chemistry in the region t > i increase the rate of chain branching in the region between i and the leading characteristic ~b = t - t t and so cause the path t = i(ff) to advance forwards. A proper analysis of the further evolution of the reaction wave would require a fully nonlinear modeling of the compressible flow, coupled with the general form of the path i(~b) and the full

194 modeling of such systems using a simple one-step, temperature-sensitive Arrhenius reaction has led to numerous qualitatively correct solutions [22] describing a variety of combustion processes, such as, for example, wrinkled laminar flames or ignition and extinction criteria. The arguments presented here, however, show that significant qualitative differences arise in the modeling of detonation initiation. The notion of an 'induction flame' (presented in the introduction) that can be analyzed quite well using a one-step large activation energy model does not persist in the same way when the three-step model (Eqs. 9) is used. In particular, the solutions of the relevant equations describing the induction process predict the emergence of reaction waves that move supersonically in the former case, but subsonically in the latter case. Quite different patterns of observable chemical and pressure-velocity waves are thus predicted. In the case of the model with chain-branching, the propagation of these waves is able significantly to modify the corresponding chemical wave after a very short time. The amount of modification depends both upon the sensitivity of the branching chemical reaction and the size of the thermodynamic disturbances at any stage. Only, initially, before the latter have grown sufficiently to modify significantly the radical branching rate, does the notion of a subsonic induction flame apply moderately well. In the case of a one-step model, the supersonic induction flame remains immune to modification by forwards propagating thermodynamic waves until it slows down below the speed of these waves in the hottest part of the medium. This major difference between the results obtained using the two models of the chemistry indicates that a one-step model is probably not adequate for describing detonation initiation in explosives which are known to burn via a radical chain-branching process. To some degree, it also provides a means of experimentally testing the nature of the dominant chemical kinetic mechanism that may be involved in the detonation of an explosive, particularly (as in the case of many condensed explosives) when little kinetic information is yet available.

J.W. DOLD AND A. K. KAPILA

Bdzii. Research cooperation between the authors was facilitated by a NA TO collaborative research grant. J.W.D. is supported by a fellowship from the British Science and Engineering Research Council and was a visitor at the Institute for Mathematics and its Applications, Minneapolis, during the preparation of this paper. A.K.K. received partial support from a research contract with the Los Alamos National Laboratory.
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1. Kapila, A. K., and Dold, J. W., Ninth Symposium (International) on Detonation, Portland, Oregon, August 1989, in Press. 2. Dold, J. W., and Kapila, A. K., submitted. 3. Dold, J. W., and Kapila, A. K., submitted. 4. Dold, J. W., in Fluid Dynamical Aspects of Combustion Theory (A. Tesei and M. Onofri, Eds.), Longman, London, in press. 5. Sheffield, S. A., Engelke, R., and Alcon, R. R., Ninth Symposium (International) on Detonation, Portland, Oregon, August 1989, in press. 6. Strehlow, R. A., Fundamentals of Combustion, McGraw-Hill, New York, 1985, pp.396-405. 7. Zelsovich, Ya. B., and Kompaneets, A. S., Theory of Detonation, Academic Press, New York, 1960, p. 98. 8. Clarke, J. F., Prog. Ener. Combust. Sci. 15:241-271 (1989). 9. Kassoy, D. R., Annu. Rev. FluidMech. 17:267-287 (1985). 10. Zeldovich, Ya. B., Combust. Flame 39:211-214 (1980). 11. Dold, J. W., SIAM J. Appl. Math. 49:459-480 (1989). 12. Henderson, K. L., and Dold, J. W., SIAM J. Appl. Math. (in press). 13. Short, M., and Dold, J. W., submitted. 14. Clarke, J. F., and Singh, G., Lect. Notes Phys. 351:22-35 (1989). 15. Kapila, A. K., and Roytburd, V., Lect. Notes Phys. 351:374-382 (1989). 16. Fickett, W., and Davis, W. C., Detonation, University of California Press, Berkeley, 1979. 17. von KAxman, T., I Modelli nella Technica, Atti del Conveguo di Venezia, 1:643-651 (1955). 18. Clarke, J. F., The Mathematics o f Combustion (J. D. Buckmaster, Ed.), SIAM Publications, Philadelphia, 1985, pp. 183-245. 19. Jackson, T. L., Kapila, A. K., and Stewart D. S., S I A M J. Appl. Math. 49:432-458 (1989). 20. Dold, J. W., Lect. Notes Phys. 351:245-256 (1989). 21. Bdzil, J. B., and Kapila, A. K., submitted. 22. Buckmaster, J. D., and Ludford, O. S. S., Theory of Laminar Flames, Cambridge University Press, Cambridge, 1982, Chaps. 11 and 12.

This work benefited from useful discussions with Paul Clavin, Forman Williams, and John

Received 3 May 1990; revised 8 September 1990