March 22-24, 2004

Symposium on Interdisciplinary Shock Wave Research

Sendai, Japan

Equation of state of energetic materials for unreacted compression

K. Nagayama1 , S. Kubota2 1 Department of Aeronautics and Astronautics, Faculty of Engineering, Kyushu University, Hakozaki, Higashiku, Fukuoka 812-8581 Japan. e-mail: nagayama@aero.kyushu-u.ac.jp 2 Research Institute for Explosion Safety, Institute of Advanced Industrial Science and Technology, Sakura, Tsukuba, Ibaraki 305-8569 Japan.

Abstract. Thermodynamic model is presented to predict the unreacted shock Hugoniot compression curve for energetic materials. Model theory is applied to explain the non-linear shock velocity-particle velocity data for single crystal PETN explosive. It is based on the speculation that for weak shock compression, dynamic properties such as wave velocity or excitation of vibrational modes is determined solely by the weak interaction of large organic molecules of the energetic materials. Very few vibron modes have inuence on the dynamic properties. The shock compressed state of these materials is supposed to be far from thermal statistical equilibrium in the above sense. With increasing shock pressure, energy transfer between phonon and vibron modes proceeds, which equilibrates the excitation of all vibrational modes, and tends to equilibrium. This tendency should also be seen in the curved feature of the shock-particle velocity Hugoniot as is given by the data for various energetic materials. According to the Slater model for the Grneisen parameter, Hugoniot parameters and vibrational mode u excitation are related to each other. A quadratic shock-particle velocity Hugoniot function based on the thermodynamic relationship together with the Slater model is used to predict PETN Hugoniot. Model and the available data shows a good agreement.

1. Introduction
Enormous amounts of experimental data and theoretical calculations have been made for the understanding of the detonation phenomena of condensed phase high explosives (Gibbs & Popolato 1980, Mader et al. 1982, Dobratz 1985). Equation of state (EOS) for the detonation product gases is one of the important research topics, which attracts many researchers (Zukas & Walters 1997, Fickett & Davis 1979, Mader 1998, Cheret 1993). Various kinds of calculations (Shaw, Ree et al., Pastine, Shaw) have been made to aim at the collection of information on the basic features of the phenomena, although the experimental data set may not be precise enough to evaluate the theories. 377

8.0

Shock Velocity - km/s

P ETN
Us UsEx p

7.0

6.0

5.0

4.0

3.0

2.0 0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Particle Velocity - km/s

Fig. 1 Published Hugoniot data for PETN from Los Alamos Shock Hugoniot Data. Solid line is a theoretical model calculation.

Equation of state or shock Hugoniot for unreacted energetic materials is another major topic. Although shock Hugoniot measurement of several energetic materials have been published (Marsh 1980), precision or reproducibility of the data is not very good compared with that of inert materials. The reason is considered to be the possibility of onset of partial reaction at the shock front that will increase the detonation velocity. Information on the above two EOS is quite fundamental for numerical simulation of detonation phenomena. This paper presents a theoretical model to obtain the shock Hugoniot function for energetic materials based on the minimum set of experimental data other than Hugoniot data. The key idea of the present method is that this kind of material is a molecular crystal consisting of relatively large molecules. Weak shock compression of these materials will excite phonon mode vibration exclusively, and almost no excitation of vibron modes. The situation is similar to that of polymeric materials (Nagayama & Mori 1998). In this sense, the shock compressed state of materials is not in thermal equilibrium. Modeled shock Hugoniot function together with predicted Gr neisen parameter gives a sucient information for EOS u of the unreacted phase of high explosives.

2. Unreacted shock Hugoniot of energetic materials and thermal non-equilibrium model

Figure 1 shows the published Hugoniot data for single crystal PETN. This suggests the following: (i) shock velocity-particle velocity relationship is non-linear and Hugoniot slope decreases with compression, (ii) data scatter is seen to be rather large, although the experimental situation might be as good as similar shock experiments of inert solids. Data scatter can be explained by the contribution of a partial reaction expected to occur at the shock front. In other words, complete no reaction at the shock front of energetic 378

intramolecular interaction

intermolecular interaction

Fig. 2 Schematic illustration of compression characteristics of typical energetic materials.

materials is not very easy to realize. Partial reaction is expected to increase shock pressure thereby increasing shock velocity. By this consideration, the lower periphery of the data might be close to the accurate values. This point is discussed again in a later section by the comparison of the theoretical model with the experimental data. Curvature of the Hugoniot curve is sometimes expressed by the word softening. Some materials may have structural phase transition under high pressure. Softening is a confusing word, since shock velocity increases monotonically with particle velocity as shown in Fig. 1. Although the slope decreases with particle velocity, the slope does not represent material strength, but its change. In this sense, the decrease in slope does not mean softening of the material, but the rate to hardening decreases with compression. In the next section, we will propose a new explanation of this behavior. Consider shock compression of a material consisting of large molecules containing relatively a large number of atoms, such as the most energetic materials or polymeric materials. One may note that the van der Waals interaction of these molecules is much weaker than that of bonding which is responsible for constructing the molecules. Compressibility of the substance is determined, therefore, almost solely by the interaction potential of molecules, and not by the intramolecular interaction. In the case of weak shock compression, the excited vibrational modes together with volume compression is expected to be phonon modes associated with the interaction of molecules. This is because weak compression of a substance shortens weaker spring between molecules. Here we assume that no modes of vibron are not excited for very weak shock compression. This is the problem of nite relaxation time of the energy transfer between phonon modes to vibron modes. This situation is schematically shown in Fig. 2. In this model, volume compressed states themselves and the induced vibration or thermal internal energy should be produced by the same force eld, shock Hugoniot compression curve and the thermal 379

state variables are closely related with each other. Particularly, thermal states are described by the Gr neisen parameter. In the present model, the shock Hugoniot compression curve u given by the nonlinear mechanical properties of volume compression, is determined by the excited vibrational states. In this sense, the Hugoniot function at the weak shock limit might be reected by the compression property of molecular crystal which has almost no relationship with molecular structure. According to statistical mechanics, the distribution of the excited states of phonons and vibrons obeys the Bose-Einstein distribution, and the expectation value of the number of vibrons is much smaller than that of phonon number due to the large value of the vibron frequency. The number of modes of vibron is expected to be very large, so that the contribution of vibron excitation to the values of specic heat or thermodynamic Grneisen u parameter is quite large even at room temperature. On the other hand, shock compression shows a peculiar property dierent from the above equilibrium properties. The dierence of shock process and equilibrium states is that in the very short time of shock process, almost no energy transfers from the phonon modes to vibron modes. As a result, a feature of phonon vibrational modes can be seen in the initial slope of the shock Hugoniot. The present image of a weak shock compression is based on the experimental observation of relatively large slope of the Hugoniot of energetic materials or of polymeric materials. Value of the slope is larger than 2. Non-dimensional number Hugoniot slope and the Grneisen parameter has been discussed by various theoretical models. We will u calculate the Gr neisen parameter of PETN based on the Slater model, which is compatible u with the Debye model for the specic heat of a crystalline substance. Two similar theoretical models for the Gr neisen parameter have been proposed so far, but the dierence between u them has been proved to decrease with compression. According to the Slater model, the initial slope of the Hugoniot and the Gr neisen u parameter are connected by the relation, dus 2 |0 dup 3

0 = 2

(1)

where , us and up denote the Gr neisen parameter, shock velocity and the particle velocity, u respectively, and sux 0 denotes the initial state. If the initial Hugoniot slope is equal to 2.5, the Gr neisen parameter at the initial state is u 0 = 4.33 (2)

This value is much larger than the value of the thermodynamic Gr neisen parameter u estimated by the thermal data of PETN. This large Grneisen parameter is explained by u the phonon mode Gr neisen parameter which is the one corresponding to a very weak nonu linear spring by van der Waals force between large molecules. Experimental data show that the Hugoniot slope is seen to decrease with compression, although the data themselves had relatively large scatter. The change in Hugoniot slope can be explained as follows: with increasing shock strength, temperature or amplitude of vibration increases, then the 380

non-linearity of the vibration increases which makes the energy transfer between phonon and vibron modes faster, thus the energy distribution is approaching thermal equilibrium. Hugoniot slope changes due to the approach to equilibrium. Apparently, the Grneisen u parameter will decrease with compression. The discussion will be similarly applicable both to energetic materials and polymeric materials.

3. Non-linear Hugoniot for energetic materials and evaluation of Grneisen parameter u

Assumptions of the previous section lead to the conclusion that the unreacted shock Hugoniot for energetic materials is inherently non-linear. Here we assume that the shock velocityparticle velocity Hugoniot for energetic materials is given by the following quadratic equation

Us = A + Bup + Cu2 p

(3)

where A, B, C are material constants to be determined. Coecient C is expected to be negative. In the following, we will propose a method to determine these three coecients basically not using the measured Hugoniot data. We will also focus our discussion on the Hugoniot of crystalline energetic material. The Hugoniot of porous materials will be obtained by theoretical models for porous bodies, once the Hugoniot of a crystalline solid is established. Procedures to obtain three parameters are given below: (i) This parameter should be equal to bulk sound velocity, which is calculated by the measured longitudinal and transverse sound velocity of the substance. (ii) This parameter has no dimension and is related to the Gr neisen parameter at u the initial state. The value is assumed to be given by Eq.(1) by the Slater model. As assumed previously, the Gr neisen parameter at the initial state should correspond to that u of the phonon Grneisen parameter having the value of 3-5. The non-equilibrium nature u of the materials of a molecular solid with relatively large molecules can also be seen in the pressure dependence of the ultrasonic sound velocity. High-pressure study of high polymers have produced a large Gr neisen parameter which really be explained by the phonon mode u Grneisen parameter. In the case of energetic materials, a similar high pressure measurement u of ultrasonic velocity can provide the phonon Gr neisen parameter and a theoretical model u such as the Slater model gives the coecient B. (iii) Coecient C: This parameter expresses the approach from a thermally non-equilibrium weak shock state to an equilibrium shock state. Thermodynamic Gr neisen parameter at u the initial equilibrium state for PETN is given to be 1.0, calculated by equilibrium properties. As noted, the initial non-equilibrium Gr neisen parameter has a value around 3-5, u which will decrease with approaching thermal equilibrium. A negative value of coecient C gives the result that the Grneisen parameter decreases with compression as the model u predicts. 381

As the amplitude of vibration of phonon frequency, non-linearity of vibration or intermediate modes accelerates the excitation of vibron modes, which is the vibration of carbon frame, and/or of various molecular components, the vibron mode excitation then triggers the decomposition reaction. We will determine the value C by the following principle. That is, the value C is given so that the Gr neisen parameter reaches its equilibrium value at the u so-called von Neuman spike point. The von Neuman spike point is the state that chemical reaction will begin without any other additional disturbance. This means that at the state vibron mode, other vibrational modes will be fully excited to ensure the onset of reaction. In other words, the state is apparently a thermal equilibrium state. The spike point is the shock compressed state with the condition that the shock velocity is equal to detonation velocity, and at that point the calculated Gr neisen parameter is equal to the value of its u equilibrium value. This is the condition for the value C to be determined. With compression, the Gr neisen parameter is known to decrease. In this model, howu ever, the value at spike point is set equal to that at the initial state with thermal equilibrium. Since we have no further information on how the Gr neisen parameter decreases with presu sure. With these three procedures, we can predict the unreacted shock Hugoniot for energetic materials. For this purpose, we have to calculate the Gr neisen parameter for the quadratic u Hugoniot function. In the following, we will describe the method to calculate the Grneisen parameter along u the quadratic shock Hugoniot curve. The procedure itself has been published previously. As shown later, the dierential equation governing the non-linear Hugoniot function is extremely complicated. We derived here the governing equation for the arbitrary Hugoniot function. As already explained, we assumed the Slater model for the Gr neisen parameter behavior, u but in the case of other theoretical model, the calculation procedure is almost the same. In the Slater model, the ratio of the volume derivative of cold pressure and of the second derivative appears in the formulation. Thermal pressure can be included to the pressure derivative, since the Slater approximation should not be aected appreciably by adding the thermal contribution. We have proposed a simple procedure of calculating the Gr neisen u parameter by a modied Slater model using pressure instead of cold pressure. By this method, we combine the thermodynamic identity
2 u2 dus dus (us up ) p [us + up ] dus dup us up dup us up dup

a2 = H

(4)

with the Slater approximation 1 us up d1na2 H =+ + )H ( dus 3 2[us up du ] dup p to obtain a dierential equation for the Gr neisen parameter u 2 dus 2us dus 2 d = 2 dus [2 ] + [( 2 ) dup 3 up dup up dup dup 382 (5)

dus 1 u2 d2 us du 3 2 s ] [ p + ( + 2) dus us up us up dup du2 p d2 us du2 p dus dup

us d us du2
p

dus us up dup

2( 1 ) dus 3 ] up [ us dup + 2( 1 ) dus 3 ] us (us up ) dup

(6)

d2 u5 du2 p
dus us up dup

This is the equation used to obtain the volume dependence of the Gr neisen parameter by inu tegrating it over particle velocity. In this sense, integration will be made along the Hugoniot compression curve whose coecients themselves are unknown and are to be determined. It is obvious by inspecting Eq.(6) that the initial state of up =0 is a singular point of the dierential equation. In order to integrate Eq.(6) avoiding this singular point, it is necessary to derive an asymptotic formula around the initial singular point. The asymptotic relationship can be derived in the form of a quadratic equation. Since Eq.(6) contains the information on the Hugoniot by several derivatives of the us -up Hugoniot function, it is possible to use any complicated form of the Hugoniot function to integrate Eq.(6). Eq (6) was integrated by using parameters of PETN to obtain the Gr neisen parameter u up to the von Neumann spike point. This calculation was repeated by assuming three parameters of us -up Hugoniot for PETN until the value of the Gr neisen parameter at u the spike point is equal to the thermodynamic equilibrium value at room temperature zero pressure state. The estimated three parameters of Hugoniot function for PETN are A = 2.32(km/s), B = 2.333, C = 0.13(s/km). Value of A is chosen to be the bulk sound velocity whose value is available from measured longitudinal and transverse sound velocity. We have no high pressure data for sound velocity to evaluate the value of B for PETN, then in this calculation, we assumed the value of the Grneisen parameter equal to 4 and the value of B is calculated by the Slater model. In u this calculation, only the value of C is a parameter to be determined in the above process. The result is shown in Fig. 1. The estimated Hugoniot curve is shown as a solid line. Agreement between data and the model theory seems very good. It is noted again that the model does not require Hugoniot data except for the sound velocity. As discussed in the previous section, a relatively large data scatter might stem from slight but partial reaction at the shock front, and the unreacted shock Hugoniot curve is more likely to be the lower limit of the data set. The model theory again shows a good prediction of this behavior. Slight deviation of this behavior at the higher shock strength indicates that the value of the Grneisen parameter at the spike point may not be equal to that at the thermodynamic u value but be lower than that, since the spike point is the point of a fairly compressed state of solid explosive material. Even so, the present model gives a very good approximation of the unreacted shock Hugoniot for energetic material. The calculated value of the Gr neisen parameter decreases rather rapidly and smoothly u 383

to a very small value up to the spike point volume. Estimated spike point parameters are : PN = 45.7(GP a), VN = 0.36(cm /g), us = 8.30(km/s), up = 3.10(km/s). (8)
3

(7)

4. Conclusion
We have developed a simple evaluation method to predict the unreacted shock Hugoniot compression curve for energetic materials. The present model is based on the fact that weak shock compression leads to the exclusive excitation of phonon modes that cannot be converted to vibron modes. Predicted crystalline PETN Hugoniot agrees well with experimental data. Volume dependence of the Grneisen parameter evaluated in the present model does u not correspond to the normal compression behavior. For example, the unreacted Hugoniot for low density explosive can be explained by the temperature dependent Gr neisen u parameter. The eort in this direction is now under way. Acknowledgement. Authors wish to thank Dr. M. Yoshida and his group for the interests during the course of this work.

References
Gibbs TR, Popolato A (ed) (1980) LASL Explosive Property Data, ed. Univ. Calif. Press. Mader CL, Johnson JN and CraneLos SL (ed) (1982) Alamos Explosives Performance Data, ed. Univ. Calif. Press. Dobratz BM (1985) LLNL Handbook of Explosives. UCRL-52997, Lawrence Livermore National Laboratory. Zukas JA, Walters WP (1997) Explosive Eects and Applications Springer-Verlag, p 115 Fickett W, Davis WC (1979) Detonation Univ. Calif. Press, Berkeley, p. 68 Mader CL(1998) Numerical Modeling of Explosives and Propellants, 2nd edition CRC Press, p. 31 Cheret R (1993) Detonation of Condensed Explosives Springer-Verlag, New York. Shaw MS Proc. 11th Det. Symp., Oce of Naval Res., U.S. Gov. Printing Oce, p. 933 Ree FH, Viecelli JA, van Thiel M Proc. 11th Det. Symp., p. 942 Pastine DJ Proc. 11th Det. Symp., Oce of Naval Res., U.S. Gov. Printing Oce, p. 1088 Shaw MS Proc. 9th Det. Symp., Oce of Naval Res., U.S. Gov. Printing Oce, p. 452 Marsh SP (ed) (1980) LASL Shock Hugoniot Data, Berkeley, Univ. of California Press. Nagayama K, Mori Y (1998) J. Appl. Phys. 84 : 6592

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