ON THE BACKWARD SUPERDETONATION IN HOMOGENEOUS EXPLOSIVES Olivier Heuz and Francis Chaiss CEA-DIF, B.P.

12 , 91680 Bruyres-le-Chtel Cedex, France We discuss the existence and main features of the backward superdetonation as the result of a theoretical, numerical and experimental study about initiation from a reflected shock. This leads us to explain the general setup process of the superdetonation. A new field is then opened to access the properties of the equations of state and chemical kinetics of explosives. INTRODUCTION Recent studies have shown nonexplained phenomena in the mechanisms involved in the shock to detonation transition. Several questions remain unanswered about the build up process and properties of the superdetonation in homogenous explosives. In 2000, LEAL et al.1 obtained results in nitromethane that show clearly the existence of the superdetonation and excluded its birth at the barrier/explosive interface. They also concluded that a single Arrhenius did not fit the chemical behavior of shocked nitromethane. In 2001, HIGGINS et al. 2,3 have seen light emission after reflected shocks, in sensitized nitromethane, that may be associated to reactive processes. The present study, based on initiation of nitromethane after reflected shocks, allows us to give a new light on these phenomena. In 1980, PRESLES et al. 4 saw no chemical reaction in nitromethane after shock reflection on aluminum. HIGGINS et al. obtained initiation of sensitized nitromethane after reflection on steel. After studying the effect of the reflection material on the explosive temperature, we explain these former results and show how we can improve them to obtain initiation of pure nitromethane on reflected shock. Moreover, a numerical study linked to the study of characteristic curves gives accurate informations about the build up process and the nature of the superdetonation. These results, applied to reflected shock initiation, lead obviously to the possible existence of the backward superdetonation. INFLUENCE OF TEMPERATURE For several decades, most modelings about shock initiation phenomena have been based on pressure, although it is acknowledged that they mainly depend on temperature. In most cases, the monotonic dependency of temperature versus pressure in a shock wave allows this analogy. But in some cases, it may lead to wrong explanations of the initiation phenomena. For instance, after double shocks, the quantitative trends of pressure and temperature are very different: a small pressure jump followed by a strong one corresponds to a strong temperature jump and then a small one. Some consequences of this fact have been pointed out by PARTOM 5. Figure I shows the qualitative behavior of temperature versus first and second shocks pressure. It shows that the derivative of temperature versus pressure for the second shock is much lower than for the first shock. Then, with two shocks, we need a higher pressure to reach the same temperature obtained with a single shock. This behavior is obvious if we compare the pressures required to obtain the dashed line temperature of the figure by one or two shocks. This may explain why the modeling of PARTOM was very successful compared to sophisticated hot spot theories for heterogeneous explosives.

We do not mean that there is no hot spot influence, but that their influence is in most cases lower than the effect of this simple thermodynamic property.

FIGURE I: SHOCK TEMPERATURE VERSUS FIRST AND SECOND SHOCKS PRESSURE. BUILD UP OF THE SUPERDETONATION Numerous experimental studies about homogeneous explosives have stated the existence of a superdetonation which is a reactive wave running behind a shock wave until they merge in an overdriven detonation and further in a steady detonation. It may be expected that the superdetonation appears at the interface between the impact material and the explosive. But, in [1], it was clearly shown that it is not the case. The first principles of our explanation have been proposed by HARDESTY 6. The chemical reactions mainly depend on the explosive temperature. The existence of an induction delay suggests that no exothermic reactions occur in a first step. The first exothermic reactions appear after a finite delay following the shock wave (Fig II). Then, we have a continuous process i.e. a finite reaction rate and a slowly growing behavior of main properties (pressure temperature, sound speed ) versus time.

FIG II: BUILD UP OF THE SUPERDETONATION Since the sound speed increases versus burn fraction , the pressure gradient becomes steeper and finishes in a discontinuous reactive wave which is the superdetonation. In other words, from the initial large thickness exothermic reaction zone, the faster perturbations corresponding to =1 catch up the slower ones for which =0. They behave as a reactive piston, the reaction zone thickness decreases and they gather in a reactive discontinuity: the superdetonation. SHEFFIELD et al. 7 assumed an accumulation of sonic compression waves. Here, we mean that these are reactive waves. This explains why the superdetonation does not appear at the interface: the initial exothermic reaction rate is finite and corresponds to a finite reaction zone thickness, and the superdetonation appears only when all these reactive perturbations gather to form a discontinuity. EXPLANATION BY CHARACTERISTIC CURVES We can illustrate our description with the result of numerical simulations. For that purpose, we have built a 1D hydrocode based on a second order numerical scheme. We used the CW2 equation of state 8,9, which is suited for

both the explosive and the detonation products with two different sets of parameters. The unreacted nitromethane equation of state was fitted on the Hugoniot : D = 1647 + 1.637 u with Grneisen coefficient =1.19, and Cv=1211 J/kg.K (data given by MADER 10 and PRESLES 4). The detonation products equation of state was fitted on data calculated by HEUZ 11. For the chemical kinetics scheme we used a two steps first order Arrhenius law: explosive [E] free radicals [R] products [P] . We consider that the first step is not exothermic i.e. the equation of state of the free radical is the same as the explosive E.o.S.. The first step is quicker than the second one at low temperatures and slower at high temperatures.

Appendix I). That means to solve the differential equation:

dx = u + c dt

(=1, 0, -1)

The whole C+ network obtained for a shock to detonation transition is given in Fig III.

d [E ] dt = k1 .[E ] d [R ] = k1 .[E ] k 2 .[R ] dt d [P ] = k 2 .[R ] dt This scheme is slightly different from NUNZIATO et al. 12 who assumed two parallel Arrhenius reactions. Such a modeling allows us to reproduce the main features of the shock to detonation transition of nitromethane: time-distance diagram, induction delay versus initial projectile velocity From an hydrodynamic point of view, the signature of a shock wave in a time space diagram is the fishbone structure of the characteristic curves merging on the up side and the down side of the shock trajectory when the time increases. For the purpose of the present study we have developped a post-processing of hydro-calculations to draw the characteristics curves C+, Co and C- (see

FIGURE III. CHARACTERISTICS C+ FOR A SHOCK TO DETONATION TRANSITION.

Fig IV shows a zoom of the neighborhood of the superdetonation. Most of the features were expected: upstream supersonic and downstream subsonic incident shock wave, upstream supersonic and downstream sonic detonation wave, and upstream supersonic superdetonation. Almost all the reactions happen on the discontinuity lines of the superdetonation and detonation. But the present study provides also new information : there is a

quasi-sonic behavior downstream to the superdetonation and an expansion fan from it down to a straight rear sonic line.

BACKWARD SUPERDETONATION We now introduce a numerical experiment which is intended to provide a superdetonation (see Figure V) from a reflected shock wave.

FIGURE V: INITIATION OF AN EXPLOSIVE FROM 1D REFLECTED SHOCK EXPERIMENT.

FIGURE IV. CHARACTERISTICS C+ FOR A SHOCK TO DETONATION TRANSITION (ZOOM).

There are several consequences : the quasi-sonic behavior downstream to the superdetonation insures that no downstream perturbation can reach the superdetonation and extinguish it. Then, the Jouguet's downstream criterion about the detonation can be extended to the superdetonation. The flow can be divided in the three independent zones: - upstream zone (non reacted), - downstream expansion fan (reacted), - rear zone (reacted), separated by two sonic lines: the superdetonation /detonation and the rear sonic line.

A projectile impacts an explosive can in a 1D plane configuration. The projectile's material and velocity, and the explosive thickness are chosen to give no initiation from the incident shock wave. In our calculations, we took an aluminum projectile, an aluminum entrance wall, pure nitromethane for the explosive and tungsten for the reflection wall. The same material for projectile and entrance wall provides a constant pressure. A high impedance material is recommended to obtain initiation on the reflected shock. Let us assume an initial velocity of 1800 m/s. Predictions from a pressure based chemical kinetics yields initiation of the explosive with an aluminum reflection wall, although experiments indicate no reaction. The impacts provide a pressure of about 16 GPa in aluminum, 6.3 GPa in NM, and 12.5 GPa after reflection on aluminum. Results from [1] give an induction delay less than 0.12 s for this pressure, that means nearly immediate initiation. Our calculations are quite different. We obtain a temperature of about 1065 K in NM after the incident shock, that is expected to correspond to an induction delay higher than 10 s, from our

calculations and WALKER et al. experiments 13. After reflection on an aluminum wall, we obtain about 1350 K and then an induction delay of about 1.4 s, which is quite different from that deduced from pressure dependency, but in better agreement with experiment. However, a tungsten wall provides a reflected shock of about 19 GPa in NM and T~1700 K corresponding to an induction delay of about 0.27 s. This should lead to the quick initiation of NM from the reflected shock. A similar behavior has been obtained by HIGGINS et al. who saw light emission in sensitized nitromethane after reflection on a steel wall. Different equations of state give very different quantitative results, especially about temperature and induction delay, but the qualitative behavior described here is nearly the same in any case. The material of the entrance face has also an influence on the shock temperature in the explosive. However, this influence is smaller than that of the reflection material and has the opposite tendency. The study in the (P,u) plane shows that pressure and particle velocity in the explosive are as low as c of the entrance material is far from that of the explosive. Then, for a given specific heat, this is the same tendency for the temperature. Then we can expect that chemical reactions are initiated after the reflected shock in the same manner as an incident shock, but in the opposite way. It should lead to a continuous reactive zone converging in a backward superdetonation. When the backward superdetonation reaches the reflected shock, they merge in a backward detonation that is a retonation. We can notice that this retonation runs in a medium not at rest but with initial velocity and pressure. Then, from different initial shock levels, we can obtain different backward detonation (retonation) regimes from an explosive. The characteristics network obtained from our hydro-calculations provides very useful information about the shock to

detonation transition from reflected shock. The C- characteristic network (Fig. VI and VII ) is very similar to the former C+ characteristic network obtained from the incident shock initiation.

FIGURE VI. C- CHARACTERISTICS NETWORK FOR A SHOCK TO DETONATION TRANSITION FROM A REFLECTED SHOCK. CONCLUSION In the present paper, we have tried to understand some properties of the superdetonation. We have given some explanations on its birth, on the behavior of its characteristic curves in the (x,t) coordinates, and we described how a backward superdetonation may occur. We also explained how these main features depend on temperature, and cannot be explained by pressure based chemical kinetics. We pointed out that the effect called desensitization may be an artifact simply explained by the normal effect of temperature, even in the case of heterogeneous explosives.

Although it is not the purpose of the present paper, we can notice that it does not seem possible to obtain a retonation (in the sense clearly described by DING JING et al.14 ) from an incident shock with our chemical kinetics scheme.

dx = U ( x, t ) dt

with U(x,t) = u-c, u, or u+c in any cell of the (x,t) grid. For that purpose, we assume:
U ( x, t ) = w + ax t

with three parameters: w, a, and . The solution of the differential equation is: x= w (t ) + (t ) a 1 a

FIGURE VII. C- CHARACTERISTICS NETWORK FOR A SHOCK TO DETONATION TRANSITION FROM A REFLECTED SHOCK (ZOOM).

where is an integration constant (calculated from given x0 and t0). For any point of the grid (x0,t0), we use U0=U(x0,t0), U0'=U/x=[U(x0+x,t0)we choose a point U(x0,t0)]/x, (x1,t1=t0+t) such that x1~ x0+ U0.(t1-t0) and use U1=U(x1,t1). From the knowledge of (x0,t0),U0, U0', (x1,t1) and U1, we calculate the four constants w, a, , and and then deduce all the characteristics curves in the cell (x0<x<x0+x , t0<t< t0+t). Although our assumption requires a thin (x,t) grid, it provides a coherent patchwork as seen in Fig III, IV, VI, VII.

REFERENCES
1. B. LEAL-CROUZET, G. BAUDIN, H.N. PRESLES "Shock Initiation of Detonation in Nitromethane", Comb. and Flame 122:463-473 (2000). 2. A.J. HIGGINS, F.X. JETT, A.C. YOSHINAKA, J.H.S. LEE, F. ZHANG "Detonation Initiation in Preshocked Liquid Explosives" 12th APS Conference on SCCM, ATLANTA (2001) to be published. 3. A.J. HIGGINS, F.X. JETT, A.C. YOSHINAKA, F. ZHANG "Initiation of Detonation in Liquid Explosives by a

This study is a part of a larger project including forthcoming experiments. It is expected to give new information on chemical kinetics and equations of state.
APPENDIX I: BUILDING OF CHARACTERISTIC CURVES FROM HYDROCALCULATIONS

A Lagrangian hydro-calculation provides velocity and sound speed for given (x,t). With this information, the problem to obtain the characteristic curves is to solve the differential equation:

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