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Explosive

Degradation: Products
of Detonation and
Combustion
Martin Braithwaite
RMCS, Cranfield University,
Shrivenham, Swindon, SN6 8LA.
Brief CV
Cambridge University Chemical kinetics PhD

UBC (Canada), USC, U Colorado (Boulder) laser induced


chemistry, molecular energy transfer

ICI UK mainly explosives and explosion safety and


performance

Cranfield University William Penney Professor of


Chemical Physics theoretical shock and detonation
studies: energetic materials safety gas and dust explosions
PFM1 Mines studies at RMCS, Cranfield
University
Conduct a technical analysis of predicted combustion and
detonation products of the PFM1 series APM and the effects
of liquid explosive degradation and migration

- combustion and detonation products (MB) awaiting data

- degradation and migration (SGM) in progress


acidic medium/ slow oxidation/ physical state
Prediction of Combustion and Detonation
products and by-products
Some difficulties
multicomponent munitions
polymer, shell, peripheral material
the whole chemistry of the device has to
be included
disparate processes detonation, combustion etc
time scales, role of air/ late reaction,
smouldering
complex mechanisms
a-priori chemical rates probably not available
for complex mixtures of materials
Combustion and Detonation
Combustion
slow process governed by conductive/ convective or
radiative heat transfer/ turbulence

Detonation
shock dynamics fast
disintegration of donor charge
governed largely by small product molecules

Also
Thermal Explosion
Explosion Related Hazards in Potentially
Reactive Systems
Explosion Related Hazards in Potentially
Reactive Systems
Explosives combustion pathways

Temperature
Impact
t Compression
T cook off
Shear
t pulsed laser Hot spot Shock to
detonation
Deflagration transition
Deflagration to SDT
detonation
transition Pressure build up Strong shock
DDT
Detonation
PFM constituents

Explosive
Cl(NO2)2C-CH2-O-CH2-O-CH2-C(NO2)2Cl - 50 %
Bis (2-chloro-2,2-dinitroethyl)formal
CH3-O-C(=O)-CH2-CH2-C(NO2)3 - 20%
Methyl 4,4,4-trinitrobutylate
CH3-C(=O)-O-CH2-C(NO2)3 - 20 %
2,2,2 Trinitroethyl acetate
(NO2)3C-CH2-O-CH2-O-CH2-C(NO2)3 - 10 %
Bis-(2,2,2-trinitroethyl)formal
PFM constituents contd
Other significant mine components
(Explosive is only 50% of 80 gm)
Mine
Steel 5.4 g
Al alloy 15 g
Rubber 1.2 g
Polyethylene 10.5 g

Cassette
Polyethylene
Assorted chlorinated rubbers etc

Information kindly provided by Taron Inc (Montreal, Canada)


Description - Detonation
Thermodynamics
to 30 GPa, 6000 K

Chemical and Transport kinetics


Partial/ non-ideal detonation
Reactions during adiabatic expansion

Shock Compression
hydrodynamic control
shock velocities to 10 km/s
Ideal Detonation

Chapman Jouguet Detonation


1-D process
Chemical, mechanical and thermal equilibrium in
products
No energy or momentum losses
Chapman Jouguet condition

Thermodynamic Problem:
multiphase multi-component chemical equilibrium
at high temperatures and densities
DETONATION - 1 - DIMENSIONAL

Reaction
Zone

Undisturbed Disturbed Explosion Unreacted


Air Air Products Gas

shock wave

material Discontinuity -
interface velocity
gradient

mechanical )
thermal ) equilibrium
C J state chemical )
IDEAL DETONATION
S
Pressure
VN

Pcj
CJ
W
E

O
Vcj Vo Volume

Reactant Hugoniot - locus of accessible PV points


Product Hugoniot

Reactant Rayleigh line - CJ


Reactant Rayleigh line

CJ - Chapman - Jonguet Detonation


S - Strong (overdriven) Detonation
W - Weak
E - Constant volume Explosion
- Von Neumann Spike
VN
Thermodynamics of Detonation Products - multi-
component, multi-phase (solid/fluid mixtures)
EoS - Intermolecular contribution

Empirical Full/ Partial


Fluid
Chemistry explicit/ implicit
Semi Empirical
Solid
Fundamental

5 m EoS - Intramolecular contribution


ideal
tabulated/ experimental
Ideal Detonation Computer Programs
EoS (fluid/ solid) - inter/ intra molecular contributions

Chemical Equilibrium Algorithm

Calculation Options

Databases
ingredient explosives
product thermodynamics

Windows/ GUI etc


Typical High (Secondary) Explosives
LLNL Code, CHEETAH
LLNL Detonation Modeling
Cavity collapse site

Shock Main
reaction site

Adiabatically Jet impact


compressed and position
heated vapour

Viscous flow

Initial wall
position
PFM Fume C1.62 H2.05 N1.25O3.18Cl0.28
VOD high 7km/s +, likely small dcrit
OB 15%

Toxic Detonation products CO, HCl, HCN, NH3

Based on earlier experimental work (Ornellas, LLNL:


Volk, ICT) + some thermodynamic considerations

Nb (i) HCN is comparatively stable in air and not very soluble


(ii) relative quantities of CO/ HCN/ NH3 confinement dependent
(iii) confinement dependence
Description - Combustion
Thermodynamics
Modest pressures , 4000 K

Chemical and Transport kinetics


Partial combustion/ sympathetic detonation
Reactions during adiabatic expansion
Known difficult chemistry in O2 negative systems

Heat transfer with chemical reaction

Role of air and other fuels/ possible dominance by polymer


contribution
Reported Russian work toxic products
Gas
NO 1240
NH3 11
H2S 110
HCl 12454
CO 6356 nb HCN oxidized (none reported) high NO suggests
SO2 189 high temperature (direct of thermal source)
Dust NO-NO2 conversion slow
PbO 115
Al2O3 48172
AlCl3 31525 Reports highlight HCN, Al2O3, Pb salts nb O2 negative
AlN 12591 polluted zone - 0.29-6.8 km 1 box
0.92-21.6 km 10 boxes
Conclusions

Detonation/ Combustion fume for multi-component


disparate phases not amenable to prediction alone

Worst case scenarios are readily available but could


greatly exaggerate problem

Perceived current lack of data precludes detailed


assessment
Suggestions/ recommendations

Experimental trials at various scales


Oxygen Balance explosive system sensitized AN
based emulsion care NOx
Contained detonation (in vessel, underwater) +
treatment plant nominally transportable

Reservations about underground mining use would


create severe fume problem underground