Equation of state and reaction rate for condensed-phase explosives

B. L. Wescott, D. Scott Stewart, and W. C. Davis

Citation: J. Appl. Phys. 98, 053514 (2005); doi: 10.1063/1.2035310

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 JOURNAL OF APPLIED PHYSICS 98, 053514 共2005兲

Equation of state and reaction rate for condensed-phase explosives

B. L. Wescott
Department of Theoretical and Applied Mechanics, University of Illinois at Urbana–Champaign,
Urbana, Illinois 61801
D. Scott Stewarta兲
Department of Mechanical and Industrial Engineering, University of Illinois at Urbana–Champaign,
Urbana, Illinois 61801
W. C. Davis
Los Alamos National Laboratory, Los Alamos, New Mexico 87545
共Received 22 February 2005; accepted 19 July 2005; published online 8 September 2005兲
The wide-ranging equation of state is a nonideal equation of state based on empirical fitting forms
argued from thermodynamic considerations that yield the proper physical features of detonation.
The complete equation of state forms are presented and the equation of state and a reaction rate are
calibrated for the condensed-phase explosive PBX-9502. Experimental overdriven Hugoniot data
are used to calibrate the products equation of state off the principal isentrope passing through the
Chapman-Jouguet state. Shock Hugoniot data are used to calibrate the reactants equation of state.
The normal detonation shock speed-shock curvature data 共Dn − ␬兲 from rate-stick measurements and
shock initiation data from wedge tests are used to calibrate the reaction rate. Simulations are carried
out that predict detailed particle velocity transients that are measured experimentally with embedded
electromagnetic gauge measurements from gas-gun experiments. Multidimensional simulations of
steady detonation in a right circular cylinder rate stick are carried out and compared with
experiment. © 2005 American Institute of Physics. 关DOI: 10.1063/1.2035310兴

I. INTRODUCTION Although these equations of state are based on the plane,

More than a century ago Chapman1 and Jouguet2 inde-
pendently proposed a model of detonation. Their model as-
sumes that the chemical reaction supporting the detonation
takes place instantly, and that the detonation propagates as a
constant speed plane wave. With that model, they were able
to compute detonation speeds that were in close agreement
with experimental values for detonation in gases. As an
equation of state for the product gases, they assumed a mix-
ture of ideal gases with p␷ / RT ⬵ 1. Since the density of their
mixtures was low, 0.001 g / cm3 ⬍ ␳ ⬍ 0.01 g / cm3, molecular
interaction did not contribute to the internal energy of the
mixture. Detonating solid explosives have a density nearer
2.5 g / cm3 at the end of the reaction zone. Then p␷ / RT
⬵ 15, and the interaction energy is large compared with the
thermal energy. Early attempts to find better equations of
state were made by Becker3 and Taylor.4 Since then, many
empirical equations of state have been proposed. Some of
these forms are reviewed by Fickett and Davis5 and Davis.6
One that merits mention is the Jones-Wilkins-Lee 共JWL兲7
equation of state. It has been widely used because it can be
made to agree well with experiment. All of these equations
of state describe the detonation products. They are used to
calculate both the detonation state, called the Chapman-
Jouguet 共CJ兲 state, and the work that the subsequent expan-
sion of the detonation products does on the surroundings.
a兲
Author to whom correspondence should be addressed; electronic mail:
dss@uiuc.edu
steady model, they are often used to describe more compli-
cated systems.
These empirical detonation-product equations of state
must be experimentally calibrated for each explosive and for
each initial density. A more general approach is to develop,
from experiments, an equation of state for each molecular
species expected in the products: nitrogen, water, carbon di-
oxide, etc. Then by developing mixing rules for how a mix-
ture of such products behaves, one then calculates the equa-
tion of state for the products of any explosive. This approach
eliminates the need for calibration experiments with each
particular explosive. The equilibrium composition of the
products is calculated by minimizing the free energy of the
mixture. The concept is simple, but its application is tedious.
Well-known equations of state of this type are BKW,8 JCZ,9
9 10
TIGER, and CHEQ. Some forms are reviewed by Fickett and
Davis.5 Such equations of state are for the Chapman-Jouguet
model of plane detonation with instantaneous reaction.
A number of equation of state 共EOS兲 forms are used to
model the unreacted explosive. The linear Us − U p 共Mie-
Gruneisen兲 EOS is often used in modeling shock waves in
solids. A linear relationship between the shock velocity and
the particle velocity behind the shock represents the Hugo-
niot of many solids quite well; a useful approximation ␳⌫
= ␳0⌫0 = const 共Ref. 11兲 provides a simple relationship for
⌫共␷兲. The Walsh mirror image EOS 共Ref. 12兲 is based on the
experimental observation that in the p − u plane the isentropic
expansion curve is approximately coincident with the re-
flected shock Hugoniot. With this assumption an expression
for the pressure on the principal isentrope can be derived and

0021-8979/2005/98共5兲/053514/10/$22.50 98, 053514-1 © 2005 American Institute of Physics

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053514-2 Wescott, Stewart, and Davis J. Appl. Phys. 98, 053514 共2005兲

used to calibrate an EOS form. Typically the reaction zone is
a mixture of the detonation products and unreacted explosive
with pressure and temperature equilibrium. The HOM equa-
tion of state in Ref. 8 is essentially a combination of the
linear Us − U p EOS for the unreacted explosive and BKW
equation of state for the products with temperature and pres-
sure equilibrium. For further discussion of the various equa-
tions of state used to model explosives, see Refs. 5 and 6.
The Chapman-Jouguet model is not a good approxima-
tion for sharply curved detonation waves or for explosives
with long reaction zones that cannot be considered instanta-
neous. Insensitive high explosives and blasting agents are
often far from the CJ model. To compute such reaction zone
effects requires both a continuum equation of state 共one
equation of state for each particular composition兲 and a rate
law that governs the transition from one composition to an-
other. The assumptions for such a model are 共1兲 the details of
the chemistry need not be considered so that one composi-
tion variable is adequate 共the mass fraction of products兲 and
共2兲 the pressure and particle speed are the same for reactants
and products. Examples can be found in the work of Mader,8
Tarver and co-workers,13,14 and many others. The EOS de-
scribed herein is of this type. An additional assumption is
needed to bring closure to the equation of state of the mix-
ture. This assumption is usually that the temperature is the
same for reactants and products.
Computations of the flow with a resolved reaction zone
can be very demanding. A very fine mesh is required to solve
the equations accurately. Problems with one-dimensional
haves as strongly nonideal in its applications. The EOS and
reaction rate have an important role when this nonideal be-
havior must be predicted in numerical simulations.
Section II contains a detailed description of the EOS
forms and their calibration, along with the discussion of the
mixture rules and some suggestions for expedient closure of
the mixture equations. Section III concerns the reaction rate
and its calibration at high and low pressures. Section IV
presents some conclusions.
II. WIDE-RANGING EQUATION OF STATE
A. Detonation products
Davis15–17 developed an EOS with the correct physical
behavior of adiabatic ␥ 共dimensionless sound speed兲 and
Gruneisen gamma ⌫, the quantities entering into the Euler
equations. The forms for E p共p , ␷兲 and p p共E , ␷兲 are
␷
E p共p, ␷兲 = Esp共␷兲 + 关p − psp共␷兲兴 共1兲
⌫ p共 ␷ 兲
and
⌫ p共 ␷ 兲
p p共E, ␷兲 = psp共␷兲 + 关E − Esp共␷兲兴, 共2兲
␷
where p is the pressure, E the specific internal energy, ␷ the
specific volume, and the superscript s indicates that the func-
tion is defined on an isentrope, here the one passing through
the CJ state. The subscript p denotes the detonation-products
EOS. Further, from Ref. 16

冋 册
symmetry can be done well. Some problems with two- a/n
dimensional symmetry, such as those with a simple cylindri- 1 1
共␷/␷c兲n + 共␷/␷c兲−n
cal or slab geometry, can also be done. Fully three- 2 2 k − 1 + F共␷兲
psp共␷兲 = pc , 共3兲
dimensional problems are still too demanding. 共␷/␷c兲k+a k−1+a
The wide-ranging equation of state presented here is
based on the empirical fitting forms calibrated from the ex- 2a共␷/␷c兲−n
perimental measurements of Hugoniot curves, isentropes, F共␷兲 = , 共4兲
共␷/␷c兲n + 共␷/␷c兲−n
and thermodynamic properties. The EOS is a complete equa-
tion of state with values for temperature and entropy in ad- ⌫ p共␷兲 = k − 1 + 共1 − b兲F共␷兲, 共5兲
dition to the usual values for pressure and specific volume.
There are no experimental data for the thermal properties, so
the values assumed for them must be considered estimates.
The EOS has been made to be thermodynamically consistent. Esp共␷兲 = Ec
冋 1
2
1
共␷/␷c兲n + 共␷/␷c兲−n
2
册 a/n

The reaction rate is calibrated for quasisteady behavior such
as shock curvature versus normal detonation speed relation-
ships obtained from rate-stick experiments, as well as time-
dependent measurements of shock initiation. The reaction
rate as presented is limited to sharp shock wave input, no
attempt has been made in this work to model other phenom-
ena such as burning in a closed vessel, slow compression, or
dead-pressing effects.
We present a general set of forms for the EOS and reac-
tion rate but we show the efficacy of the forms by illustrating
their properties for PBX-9502, a well-studied explosive.
PBX-9502 is a plastic-bonded composite of 95% TATB par-
ticles with a binder of 5% Kel-F 800 pressed to near maxi-
mum density. PBX-9502 is remarkably insensitive to acci-
dental initiation by shock or flame. This useful property
depends in part on the long reaction zone in this explosive,
and the long reaction zone usually makes the explosive be-
, 共6兲
共␷/␷c兲k−1+a
p c␷ c
Ec = , 共7兲
k−1+a
where pc, ␷c, a, k, n, and b are used to calibrate to experi-
mental data.
B. Calibration
Calibration of the products EOS, that is, determining
values for the adjustable parameters k, b, a, n, ␷c, and pc to
find a best fit to all the experimental data, is based on a few
simple requirements. First, the principal isentrope must pass
through the CJ point determined from experiment. Second,
the principal isentrope and the Rayleigh line must be tangent
at the CJ state. Third, the total energy from expansion down
the isentrope must be the total chemical energy liberated by

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053514-3 Wescott, Stewart, and Davis J. Appl. Phys. 98, 053514 共2005兲

TABLE I. Calibration input parameters.

DCJ pCJ ␳0 e0 E0 eg
共mm/ ␮s兲 共GPa兲 共g / cm3兲 共kJ/ cm3兲 共kJ/g兲 共kJ/ cm3兲 k ␣

7.730 28.0 1.895 7.07 3.731 5.010 1.3 1.150

the explosive. Fourth, adiabatic gamma ␥ at large volume

where the value is k must be the ideal-gas value for the
products. Fifth, the energy from the expansion down the pg = pc
1
k − 1 + F共␷g兲 2
G共␷g兲 冋 册
a/n

, 共12兲
k−1+a 共␷g/␷c兲k+a
isentrope must be partitioned between a high-pressure part
above 0.1 GPa where useful work-driving metal is done and
where
the low-pressure part that accounts for the rest of the chemi-
cal energy. Sixth, Gruneisen gamma ⌫ must be adjusted in G共␷兲 = 共␷/␷c兲n + 共␷/␷c兲−n , 共13兲
the high-pressure region to describe the Hugoniot curve for
overdriven detonations that are far from the principal isen-
2
trope. These six requirements determine the six adjustable DCJ
␥CJ = ␳0 − 1, 共14兲
parameters. pCJ
The fifth requirement, concerning the partitioning of en-
ergy between a high-pressure region and a low-pressure re-
␷0␥CJ
gion, merits discussion. It amounts to adjusting the shape of ␷CJ = . 共15兲
the principal isentrope. Detailed measurements of the isen- ␥CJ + 1
trope, either from direct experiments or from simulations of
Equations 共8兲 and 共9兲 are the definitions of ␥ and pressure
experiments that have precisely known measurements of the
evaluated at the CJ point, respectively. Equations 共10兲 and
motion, are not available. An approximation must be used. It
共11兲 are the total chemical energy and Gurney energy of the
has been found that a useful approximation is relating the
explosive, respectively. Equation 共12兲 is the pressure at the
energy in the high-pressure part to the Gurney energy,18 usu-
cutoff dividing the high-pressure part of the isentrope used in
ally obtained by measuring the expansion of a tube filled
calculating the Gurney energy and the low-pressure part.
with explosive 共the cylinder test兲. The ratio of the energy
Finally, the parameter b is used to fit the products EOS
under the isentrope to the Gurney energy is denoted here by
off the principal isentrope to the overdriven Hugoniot data.
␣; it has been found that for high-density explosives 1.1
The detonation-product Hugoniot equations for pressure
⬍ ␣ ⬍ 1.2. Here, in Eq. 共11兲 ␣ is chosen as the ratio of eg
pH共␷兲, particle velocity U p共␷兲, and shock velocity Us共␷兲 are
共measured experimentally兲 to an energy calculated from a
calibrated equation of state that has been found accurate
2⌫ p共␷兲关E0 − Es共␷兲兴 + 2psp共␷兲␷
enough to be useful,16 the JWL EOS as given by Dobratz and p H共 ␷ 兲 = , 共16兲
Crawford19 yields ␣ = 1.15. There are slight disagreements 关⌫ p共␷兲 + 2兴␷ − ⌫ p共␷兲␷0
about the values for the input parameters in the published
papers. The values chosen for this calibration are listed in UHp 共␷兲 = 冑pHp 共␷兲共␷0 − ␷兲, 共17兲
Table I.

冑
The equations to be solved simultaneously for the adjust-
able parameters are pHp 共␷兲␷20
UsH共␷兲 = . 共18兲
共␷0 − ␷兲
4an
␥CJ = k + F共␷CJ兲 + , 共8兲 These U p共␷兲 and Us共␷兲 equations are used to calibrate b.
关k − 1 + F共␷CJ兲兴G共␷CJ兲2 Here the experimental overdriven data in Ref. 20 are used,
the calibrated Hugoniot is shown with the experimental data

冋 册
in Fig. 1. The tangent at the lowest point on the curve is
a/n
1 horizontal and its location is fixed by the CJ point. The pa-
G共␷CJ兲
k − 1 + F共␷CJ兲 2 rameter b adjusts the EOS in the high-pressure region 共right
pCJ = pc , 共9兲 end of the curve兲. Also included in Fig. 1 is the supracom-
k−1+a 共␷CJ/␷c兲k+a
pression data 共circles兲 for LX-17, another TATB-based ex-
plosive, from Green et al.21 Table II gives derived values
used in the calibration and the resulting calibrated param-
pCJ共␷CJ/␷c兲 1
␳ 0E 0 = − pCJ共1 − ␷CJ/␷0兲, 共10兲 eters are shown in Table III.
k − 1 + F共␷CJ兲 2 Most hydrodynamics calculations require that only cer-
tain mechanical properties, such as p, ␷, and E, be deter-
mined from the EOS forms. However, sometimes tempera-
p g共 ␷ g/ ␷ 0兲 ture T or even the entropy S is required. The wide-ranging
␳ 0E 0 − ␣ e g = , 共11兲
k − 1 + F共␷g兲 EOS is a complete EOS, with temperature given by

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053514-4 Wescott, Stewart, and Davis J. Appl. Phys. 98, 053514 共2005兲

TABLE III. Calibrated product parameters.

␷c pc C␷
a n 共cm3 / g兲 共GPa兲 b 共J/kg K兲

0.8592 2.521 0.9884 1.307 0.58 725

prs共␷兲 = p̂ 冋兺 3

j=1
共4By兲 j
j!
+C
共4By兲4
4!
+
y2
共1 − y兲4
, 册 共25兲

with y = 1 − ␷ / ␷0 and p̂ = ␳0A2 / 4B, where A and B are deter-

mined from experimental shock Hugoniot data. The subscript
r denotes the detonation reactants EOS. This form for the
principal isentrope results from a truncated expansion of the
exponential function 共derived from Walsh mirror image
assumption12兲, prs共␷兲 = p̂关exp共4By兲 − 1兴, for ␷ ⬍ ␷0.
The reactant EOS form of Ref. 24 introduced C to cali-
FIG. 1. Us − U p Hugoniot curves for the PBX-9502 products and reactants brate the EOS for ␷ Ⰶ ␷0. Parameter C modifies the last term
EOS and the experimental data 共Refs. 20–23兲.
retained in the series and allows adjustment of the shock
Hugoniot at high pressures, much like b in the products EOS.
E − Esp共␷兲 C is chosen to ensure that the products and reactants Hugo-
T p共E, ␷兲 = Tsp共␷兲 + , 共19兲 niot curves do not cross at high pressures. The reactant isen-
C␷
trope in Ref. 24 retained five terms, here four terms of the
where the temperature on the principal isentrope is expansion are retained and an additional term is added. The

冋 1
2
1
共␷/␷c兲n + 共␷/␷c兲−n
2
册
共a/n兲共1−b兲 last term in Eq. 共25兲 is included to yield the proper behavior
in the limit as ␷ → 0. Further,

冕
Tsp共␷兲 = Tc , 共20兲 y
共␷/␷c兲k−1+a共1−b兲
Ers共␷兲 = ␷0 prs共ȳ兲dȳ + E0 , 共26兲
0
2−ab/n pc␷c
Tc = , 共21兲
k − 1 + a C␷ ⌫r共y兲 = ⌫r0 + Zy, 共27兲
and where R = 共k − 1兲C␷. The entropy can be obtained from
the complete EOS form ⌫r0 = ␤c20/C p , 共28兲

E p共S, ␷兲 = Esp共␷兲 + C␷TSp共␷兲 exp 冋 冉 冊 册 S−

C␷
Ssp
−1 , 共22兲 Z = 共⌫sc − ⌫r0兲/y max , 共29兲

where Ssp is the entropy on the principal isentrope. 2

y max = . 共30兲
⌫ p共y max兲 + 2
C. Detonation reactants Setting ⌫sc = ⌫ p共y max兲 ensures that the shock compression
12
Davis developed a complete EOS for unreacted explo- limit for the products is the same as the reactants. Also, ␤ is
sives. Stewart et al.24 modified the definition of the principal the thermal-expansion coefficient, C p the specific heat at
isentrope to allow for calibration at high pressures. The constant pressure, and c0 = 2.5 the bulk sound speed are given
forms for Er共p , ␷兲 and pr共E , ␷兲 are in Table IV. The reactant temperature on the reference isen-
trope is
␷
Er共p, ␷兲 = Ers共␷兲 +
⌫ r共 ␷ 兲
关p − prs共␷兲兴, 共23兲
Trs共␷兲 = T 0e −Zy
冉冊
␷
␷0
−共⌫r0+Z兲
. 共31兲
⌫ r共 ␷ 兲
pr共E, ␷兲 = prs共␷兲 + 关E − Ers共␷兲兴, 共24兲 The specific heat at constant volume is assumed to have a
␷ linear dependence on the change in entropy from a reference
where the pressure on the principal isentrope is isentrope ⌬S, as in Ref. 12,

TABLE II. Derived values. TABLE IV. Reactant calibration input parameters.

␷0 ␷CJ pg ␤ Cp T0 c0
共cm3 / g兲 共cm3 / g兲 共GPa兲 ␥CJ 共K−1兲 共J/kg K兲 共K兲 共km/s兲

0.5277 0.3972 0.1 3.044 132⫻ 10−6 1010 293 2.5

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053514-5 Wescott, Stewart, and Davis J. Appl. Phys. 98, 053514 共2005兲

TABLE V. Calibrated reactant parameters.

A C␷0
共mm/ ␮s兲 B C ⌫r0 ⌫sc y max Z 共J/kg K兲

1.75 5.2 0.1 0.8168 1.022 0.6620 0.3093 979

pH共␷兲 = ␳0UHp 共␷兲UsH共␷兲. 共40兲

The products and reactants Us − U p are plotted together and C
is chosen such that the two Hugoniot curves do not cross at
high pressures, as seen in Fig. 1. The Us intercept of the
reactant Hugoniot is below the bulk sound speed value of
c0 ⬇ 2.5 km/ s, this is consistent with the experimental shock
Hugoniot measurements of PBX-9502 in Ref. 22. Figure 2 in
the p − ␷ plane includes both Hugoniot curves and the Ray-
leigh line. Shown in Table V are the calibrated reactant pa-
rameters.
FIG. 2. p − ␷ Hugoniot curves for the PBX-9502 products and reactants Finally the reactant temperature Tr共E , ␷兲 is set. As in
EOS, the Rayleigh line, and experimental data 共Refs. 20 and 22兲.
Ref. 12 ␣st in Eq. 共32兲 is determined if a temperature at a
point off of the reference isentrope is known. Here EN − E0
C␷ = C␷0 + ␣st共S − Ss兲. 共32兲 = 共1 / 2兲uN2 = 4.02⫻ 106 J / kg and with the shock temperature
chosen to be TN = 1600 K. Equation 共36兲 can be solved itera-
Here ␣st is introduced to calibrate the shock temperature, and
tively for ␣st at ␷ = ␷N 共the von Neumann point兲. For this
C␷0 is obtained from the thermodynamic relationship
choice of TN the resulting values are given in Table VI.
C␷ = C p共1 + ␤⌫T兲−1 共33兲
yielding C␷0 = 979
J / kg at T = 293 K. The temperature off the
reference isentrope is given by E. Mixture equation of state

Tr共S, ␷兲 = Trs共␷兲 冋 C␷0 + ␣st共S − Srs兲

C␷0
册 1/␣st
. 共34兲
The conservation laws give the total specific internal en-
ergy but no information about how that energy is apportioned
between the reactants and the products.15 In the complex
Thus the complete form for the internal energy is given by region of a detonation reaction zone the basic assumptions of

Er共S, ␷兲 = Ers共␷兲 +
C␷0TrS共␷兲
1 + ␣st
再冋 1+
␣st
C␷0
共S − Srs兲 册 共1+␣st兲/␣st energy partitioning are detailed in Ref. 24 and two limiting
closure models are discussed. Two closure models used are
as follows:24

−1 , 冎 共35兲
•

•
Temperature equilibrium: most likely valid when the
reaction is nearly complete,
isentropic expansion of the reactant 共no heat transfer兲:
and using Eq. 共34兲 to eliminate the entropy yields

再冋 册 冎
most valid near the shock,
1+␣st
C␷0TrS共␷兲 Tr where both enforce pressure equilibrium 共p = pr = p p兲 and
Er共T, ␷兲 = Ers共␷兲 + −1 . 共36兲
1 + ␣st Trs共␷兲 equal particle speed. In the real physical reaction zone the
energy will be apportioned somewhere between these limit-
Solving for Tr共E , ␷兲 the reactant temperature is

再 冎
ing cases.
1/共1+␣st兲
1 + ␣st For an unsupported Zel’dovich–von Neumann–Doring
Tr共E, ␷兲 = Trs共␷兲 关E − Ers共␷兲兴 + 1 . 共37兲
C␷0Trs共␷兲 共ZND兲 reaction zone, Fig. 3 shows a plot of temperature
versus progress variable for the two limiting cases of closure
of the mixture EOS. The upper and lower curves show tem-
D. Calibration of reactants EOS perature for products and reactants with no heat transfer, and
the central solid curve shows the temperature for thermal
The reactant EOS is calibrated against the experimental equilibrium. For the reaction-rate calibration that follows we
shock Hugoniot data of Dick et al.22 The parameters A and B use temperature equilibrium Tr = T p. The equilibrium of the
are calibrated with the reactant Hugoniot equations

UsH共␷兲 = 冑 2 关␷/⌫r共␷兲兴prs共␷兲 − Ers共␷兲

y共␷兲 共␷/␷0兲关2 + ⌫r共␷兲兴/⌫r共␷兲 − 1
, 共38兲
TABLE VI. Calibrated reactant thermal parameters.

TN ⌬S C␷N
共K兲 ␣st 共J/kg K兲 共J/kg K兲
UHp 共␷兲 = UsH共␷兲y共␷兲, 共39兲
1600 0.7331 2118 2531
and

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053514-6 Wescott, Stewart, and Davis J. Appl. Phys. 98, 053514 共2005兲

TABLE VII. Calibrated rate parameters.

kI kIG kDG kB ␳c
共1 / ␮s兲 共1 / ␮s兲 共1 / ␮s兲 共1 / ␮s兲 a 共g / cm3兲

105 29 70 0.85 0.214 2.74

last term is burn out to completion. The last term is moti-

vated by Seitz et al.28 who found that the detonation reaction
zone was comprised of a fast reaction that consumes the bulk
of the explosive, followed by a much slower reaction to
completion. Here we have replaced Heaviside functions 共or
instantaneous switches used in the earlier I&G models兲 with
smooth functions tanh functions in ␭ , S共␭兲. The functions
have analytic derivatives and facilitate further analysis in the
detonation theory that depend on the functional form of the
rate, such as stability analysis and detonation shock dynam-
FIG. 3. Temperature in the reaction zone for plane steady ZND detonations
ics. The reaction rate is given by
for two different closure models: thermal equilibrium and isentropic expan-
sion of the reactants.
r = rISI共␭兲 + rGSG共␭兲 + 关1 − SG共␭兲兴rB . 共44兲

temperatures in the reactants and products is a root-finding However, the rate differs from I&G in that there are two
problem in ⌽ = ␷r / ␷ p, the ratio of partial volumes, such that different pressure sensitivities in the growth term, one for
Tr = T p and p p = pr. shock initiation and another for full detonation, thus allowing
The assumption of perfect mixing gives the matching of a wide variety of experiments with one set of
parameters. This also allows the simulation of problems with
␷ = 共1 − ␭兲␷r + ␭␷ p , 共41兲 both shock initiation and highly curved detonation waves.
The transition between the two pressure sensitivities depends
⌽␷ ␷
␷r = , ␷p = , 共42兲 on the shock density and therefore the growth term is
␭ + 共1 − ␭兲⌽ ␭ + 共1 − ␭兲⌽
rG = 兵rIGW共␳SH兲 + rDG关1 − W共␳SH兲兴其. 共45兲
E共p, ␷,␭兲 = 共1 − ␭兲Er共p, ␷r兲 + ␭E p共p, ␷ p兲. 共43兲
The function W共␳SH兲 switches between the initiation and
detonation growth terms and similar to S共␭兲 is a tanh func-
III. REACTION RATE tion. The forms of the individual rate components are

Once the EOS is calibrated as described in Sec. II E, a

reaction rate can be proposed with parameters that can be
rI = kI 冉 ␳
␳0
7
冊
− 1 − a 共1 − ␭兲2/3H
␳
␳0
−1−a , 冉 冊 共46兲
calibrated to experimental measurements. We were unable to
find a simple reaction rate for PBX-9502 that led to model
predictions that simultaneously matched the data obtained
from a variety of experiments, such as shock initiation and
rIG = kIG 冉 冊 p
pCJ
4.5
␭1/3共1 − ␭兲, 共47兲

冉 冊
quasisteady curved detonation waves. The observation that a 2
more complex rate form is required for PBX-9502 seems to p
rDG = kDG ␭1/3共1 − ␭兲, 共48兲
be in agreement with the previous work for TATB-based ex- pCJ
plosives. Ignition and growth 共I&G兲 was initially developed
to model shock initiation, more recently I&G has been ap-
plied to detonation conditions.25 However, the parameters rB = kB 冉 冊 p
pCJ
共1 − ␭兲1/2 , 共49兲
used for the I&G model differ between shock initiation and
detonation conditions.14,25–27 One set of parameters is not 1
available that models nonideal explosives, such as those con- SI共␭兲 = 兵1 − tanh关200共␭ − 0.025兲兴其, 共50兲
2
taining TATB, under a wide range of conditions. Here we
develop a combined rate that models the shock initiation and
detonation conditions with one set of parameters. A reaction 1
SG共␭兲 = 兵1 − tanh关30共␭ − 0.9兲兴其, 共51兲
rate is proposed for PBX-9502 of a form motivated by igni- 2

再 冋 冉 冊册冎
tion and growth. Current ignition and growth models contain
three terms to model explosives such as TATB.14 1 ␳SH
The reaction rate is written in a form than resembles W共␳SH兲 = 1 − tanh 50 −1 . 共52兲
2 ␳c
ignition and growth, where the first term is an ignition term
that represents hot spot formation, the second term represents The calibrated reaction-rate constants are shown in Table
the growth of these hot spots in the main reaction, and the VII.

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053514-7 Wescott, Stewart, and Davis J. Appl. Phys. 98, 053514 共2005兲

FIG. 4. Run-to-detonation distance vs input shock pressure for the cali- FIG. 5. Normal detonation shock speed-shock curvature 共Dn − ␬兲 relation for
brated reaction rate and the experimental data 共Refs. 22, 27, and 29兲. the calibrated rate and experimental data at 25 ° C 共Ref. 30兲.

A. PBX-9502 reaction-rate calibration tance for a one-dimensional shock to detonation experiment兲.

Calibration of the reaction rate involves a procedure that Pop-plot data are determined from either wedge tests or from
simultaneously matches a set of available experimental data, gas-gun experiments. In gas-gun projectile experiments a
such as that for shock initiation and Dn − ␬ data. First one flier plate is accelerated down a long barrel and impacts a
assumes that r = rISI共␭兲 + rIG and calibrates the reaction rate fixed block of explosive. To simplify the simulation, the ex-
against shock initiation data. To do this, time-dependent, periment was reversed and a block 共slab geometry兲 of explo-
one-dimensional numerical simulations of the shock initia- sive at initial pressure and density is translated and impacts a
tion experiment are carried out. More detailed information rigid wall. In order to match the logarithmic slope of the
on the shock initiation simulations is given in Sec. III B. In run-to-detonation distance versus shock input pressure PBX-
these simulations the shock input pressure to the explosive is 9502, the pressure exponent 4.5 was needed to match the
known and the distance to detonation is recorded. The pa- experimental data. Figure 4 shows a comparison of Pop-plot
rameters kI and kIG and the exponent on the pressure in the data generated from the results of simulation compared
initiation growth term are adjusted to match the slope and against the wedge test and gas-gun data of Ref. 22 and the
intercept in the shock pressure versus run-to-detonation dis- more recent gas-gun data of Refs. 27 and 29.
tance plot as in Fig. 4. The pressure exponent is used to
adjust the slope and kIG is varied to match the intercept. Once C. Dn − ␬ relation and curvature
a shock initiation fit is obtained, the rate is assumed to be
r = rISI共␭兲 + rDGSG共␭兲 + 关1 − SG共␭兲兴rB and the rate is calibrated Quasisteady experiments such as rate sticks provide ex-
to the Dn − ␬ data. The constant kB is adjusted to match the perimentally determined Dn − ␬ relations for ␬ ⬎ 0 as de-
slope of the Dn − ␬ relation for ␬ ⬍ 0 and ␬ ⬇ 0 and kDG is
adjusted to match the Dn − ␬ for ␬ ⬎ 0. Smooth transition
function SG共␭兲 switches the reaction rate from rG to rB in the
vicinity ␭ = 0.9. The experimental Dn − ␬ relation for PBX-
9502 has a pronounced change in slope at ␬ slightly greater
than zero, as seen in Fig. 5 and the transitional value of ␭
= 0.9 was chosen to match the location of this change in
slope. Finally, ␳c in Eq. 共52兲 is set ensuring the proper failure
diameter and the turning point in the Dn − ␬ curve. Figure 6
shows the plane steady ZND detonation profile that corre-
sponds to the calibrated EOS and reaction rate, under these
conditions the shock density is the von Neumann spike den-
sity and W共␳SH = ␳N兲 ⬇ 0. In Fig. 6, n is the distance from the
lead shock to a point in the reaction zone as a function of the
progress variable ␭, where n = 0 mm at the shock and n
= 2.9 mm at complete reaction.

B. Shock initiation
FIG. 6. Profile of a ZND detonation wave for the calibrated EOS; 共a兲 pres-
A Pop plot is a log-log plot of the input shock pressure sure, 共b兲 volume, 共c兲 velocity, and 共d兲 distance from the shock into the
versus the distance to detonation 共or run-to-detonation dis- reaction zone.

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053514-8 Wescott, Stewart, and Davis J. Appl. Phys. 98, 053514 共2005兲

FIG. 7. Particle velocities u p at gauge locations from a gas-gun experiment, FIG. 8. Particle velocities u p at gauge locations from a gas-gun experiment,
compared with a simulation using the calibrated model, uflier = 2.766 km/ s compared with a simulation using the calibrated model, uflier = 3.118 km/ s
共Refs. 27 and 29兲. 共Refs. 27 and 29兲.

the experimentally measured wave forms at the two different

scribed in Ref. 30. Converging detonation experiments such
impactor velocities. The discrepancy in the von Neumann
as those in Ref. 31 provide Dn − ␬ relations for ␬ ⬍ 0. Mea-
spike is due in part to the EM gauge response time.27 These
surements from these experiments provide detonation veloci-
two simulations are indicated in Fig. 4, where it is seen that
ties and wave shapes. Wave shape data are then fitted to an
the uflier = 2.766-km/ s shot develops in a slightly shorter dis-
analytic form that assumes Dn = Dn共␬兲. The experimental
tance than the fit and the uflier = 3.118-km/ s shot is slightly
data fits for PBX-9502 for ␬ ⬍ 0 and ␬ ⬎ 0 match at ␬ = 0.31
longer distance than the fit. Figure 9 shows the calculated
For the calibrated wide-ranging EOS and reaction rate used
temperature profiles at the gauge locations for the uflier
here, the Dn − ␬ relation is calculated by using a shooting
= 2.766-km/ s simulation. The simulations can be regarded as
method to integrate the reaction zone structure from the
a predictions of a model that uses the wide-ranging EOS and
sonic point to the shock and to determine the nonlinear ei-
reaction rate, as all the calibration parameters have previ-
genvalue relation, as described by Stewart et al.32 For the
ously been set. The agreement of the calculations to the EM
extension for ␬ ⬍ 0, they assume that reaction is complete
gauge experiments is a prediction and not primarily due to
共␭ = 1兲 at the sonic point. The calculated Dn − ␬ relation is
the fitting of the EM gauge data 共although one anticipates the
compared to the experimental fit of the Dn − ␬ relation de-
need for minor adjustments in the reaction rate that can be
rived from the experimental data at T0 = 25 ° C given in Refs.
construed as additional calibration of the model兲.
30 and 31. Figure 5 shows a comparison of the Dn − ␬ rela-
tionships from the experimental fit and the final combined E. Multidimensional simulations
calibrated reaction rate.
To determine the final value of ␳c and to fully test the
calibrations the calibrated EOS and reaction rate have been
D. Gas-gun up wave forms
One-dimensional gas-gun experiments measure particle
velocities and record transient behavior of the reaction zone
structure during the initiation process. Electromagnetic 共EM兲
gauges are used to measure particle velocity 共u p兲 in blocks of
explosives that are impacted with a flier plate, see Sheffield
et al.33 for detailed information. A one-dimensional multima-
terial simulation code GFM2, written by Aslam,34 and em-
ploying the ghost fluid method,35 was used to simulate the
initiation behavior predicted by the wide-ranging EOS and
reaction rate and the results are compared against EM gauge
measurements of Gustavsen et al.27,29 In the simulation, the
Kel-F impactor was modeled with a Mie-Gruneisen EOS,
where ␳0 = 2.14 g / cm3 and Us = 1.99+ 1.76u p km/ s.36 Com-
parisons of experiment and simulation are shown for two
different impactor velocities and hence input pressures. Fig-
ure 7 corresponds to uflier = 2.766 km/ s and Fig. 8 corre-
sponds to uflier = 3.118 km/ s. There is excellent agreement FIG. 9. Temperature profiles from simulation at the gauge locations from a
between the simulated particle velocity u p wave forms and gas-gun experiment, uflier = 2.766 km/ s.

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053514-9 Wescott, Stewart, and Davis
FIG. 10. Detonation phase speed vs inverse rate-stick radius, the diameter
effect curve, for the calibrated reaction rate and experimental data 共Refs. 30
and 40兲.
implemented in a multimaterial simulation code.37 The mul-
timaterial simulation code is a combination of three high-
order solvers, a single fluid hydrocode, a level set algorithm
to track the interface, and the ghost fluid method to provide
fluid-fluid coupling across the interface. In each material re-
gion a high-order shock capturing scheme is used to solve
the Euler equations, see Ref. 38 for more details. The hybrid
narrow-band level set representation is described in Ref. 39.
The narrow band is used to update the position of the level
contours as well as the ghost values needed in the ghost fluid
method 共GFM兲. The details of the combined implementation
of these three solvers and their use with nonideal equations
of state are detailed in Ref. 37.
Numerical simulations were performed on a variety of
rate-stick diameters and at two different resolutions. The
PBX-9502 was modeled using the wide-ranging EOS and
reaction rate described in this paper. The confinement was a
low-density fluid with a polytropic EOS, where ␳0
= 0.1 g / cm3 and ␥ = 1.4. Measurements of the detonation
phase speed in different diameter rate sticks can be combined
to obtain a diameter effect curve as has been done with ex-
periments. Figure 10 shows the D0共R兲 curve compared with
experimental velocity curves.30,40 The simulation results are
comparable to experiments30,40 for a resolution of ⌬x
= 0.025 mm and fall between the two results. Finer resolution
lowers the failure diameter and increases the phase speed, as
is expected.
IV. CONCLUSIONS
We have proposed a wide-ranging equation of state and a
reaction rate law that describe PBX-9502. The equation of
state was calibrated to fit the shock and product Hugoniot
curves that fit experimental data. The reaction law model was
calibrated to fit Dn − ␬ and shock initiation data. Particle ve-
locity wave forms from EM gauge measurements are pre-
dicted with excellent agreement. The forms and procedures
are simple enough that they can be modified for other explo-
sives. Parameters for condensed explosives with more ideal
performance such as PBX-9501, PETN, PBXN-9, and ni-
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J. Appl. Phys. 98, 053514 共2005兲
tromethane have also been developed, and the results con-
firm the straightforward application of the constitutive forms
and procedures presented here for use with other explosives.
Current work involves applications of this model to detona-
tion diffraction and detonation-material interaction problems.
Further work including stability analysis, sensitivity of the
model to numerical resolution once implemented in simula-
tion codes, and improvements including dead-pressing ef-
fects will be investigated.
ACKNOWLEDGMENTS
This work has been supported by Los Alamos National
Laboratory, DOE/LANL 3223501019Z and U.S. Air Force
Research Laboratory, Munitions Directorate F08630-00-1-
0002. Los Alamos Report No. LA-UR-04-6054. Special
thanks to S. Yoo 共UIUC兲 for his help with the multidimen-
sional simulations. Comments and feedback from J. Bdzil, L.
Hill, and T. Aslam in regard to the rate modeling are appre-
ciated.
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