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Thermal Structure of Flames in
Metal Particle Suspensions
Michael Soo
Department of Mechanical Engineering
McGill University
Montreal, Quebec
December 2016
Supervisors:
Professors Jeffrey Bergthorson and David Frost
A thesis submitted to McGill University in partial fulfillment of the requirements of the

degree of Doctor of Philosophy.
© Michael Soo, 2016

Abstract
Understanding the combustion behavior of reactive particle suspensions is central to the goal
of predicting and tailoring the performance of metalized explosives and propellants. The
mass fraction of metal in these energetic compositions can exceed 20%, leading to the metal
burning as a dense suspension in the gaseous products of a hydrocarbon fuel matrix. The
combustion characteristics in dense particle suspensions are often extrapolated from those
measured from isolated, single particles or dilute suspensions. However, these characteristics
depend on the temperatures and composition of the gas which are altered during the reaction
of the particle suspension.
A simple model is explored to demonstrate how particle concentration may affect com-
bustion time, reaction regime, and thermal structure in the suspension for a zero-dimensional
reactor and for one-dimensional flame propagation. Unlike the majority of models previously
developed for particle combustion, no external parameters are imposed, such as particle igni-
tion temperature, combustion time, or the assumption of either kinetic- or diffusion-limited
particle combustion regimes. Instead, it is demonstrated that these characteristics can be
functions of the particle mass concentration, and that the a priori imposition of these char-
acteristics from single-particle combustion data may result in erroneous predictions.
There are very few experimental techniques developed to determine combustion charac-
teristics in dense suspensions. The determination of key parameters such as reaction regime,
and burning time in suspension combustion is difficult due to the inability to isolate and
observe individual particles. Instead, the particle combustion characteristics must be de-
termined from diagnostics on the bulk flame. A flat flame in a suspension of micron-sized
aluminum fuel and gaseous oxidizer is stabilized on a counterflow burner to provide a one-
dimensional geometry for use with line-of-sight optical diagnostics. An imaging emission
spectroscopy and a broadband-laser absorption spectroscopy technique are developed and
applied to the flat flame to assess the regime of particle combustion in the flame. These tech-
niques provide a method for determining the combustion time of particles in the suspension.
i
Abrégé
Comprendre la combustion de suspensions de particules réactives est essentiel pour prédir

et adapter la performance des explosifs et des propergols métallisés. La fraction massique
du métal dans ces mélanges énergetiques peut excéder 20% et ce dernier brûle ainsi en tant
que suspension dense dans les produits gazeux de la matrice d’hydrocarbures du carburant.
Les charactéristiques de ces suspensions denses de particules sont souvent extrapolées à
partir de celles mesurées sur des particules isolées ou de suspensions diluées. Cependant, ces
charactéristiques dépendent des températures et de la composition du gaz qui sont modifiées
pendant la réaction de la suspension des particules.
Un modéle simple, développé dans cette thése, explore et démontre comment la con-
centration des particules peut affecter le temps de combustion, le régime de réaction et la
structure thermique d’une suspension pour un réacteur de dimension zéro ainsi que dans
la propagation d’une flamme unidimensionnelle. A la différence de la plupart des modles
de combustion de particules actuels, ce modéle n’impose aucun paramétre externe comme
la température d’allumage, le temps de combustion ou la supposition d’un régime-limite
cinétique ou de diffusion. Au contraire, les résultats démontrent que ces charactéristiques
peuvent être des fonctions de la concentration massique des particules et qu’une imposition
a priori de ces charactéristiques à partir de la combustion de particules uniques peut résulter
en prédictions erronées.
Très peu de techniques expérimentales permettent la mesure de charactéristiques de com-
bustion des suspensions denses. La détermination de paramètres-clés tels que le régime de
réaction ou le temps de combustion de la suspension est difficile car présentement, on est
incapable d’isoler et d’observer les particules individuellement. Les charactéristiques de
combustion des particules doivent donc être déterminées grâce aux diagnostics de lensem-
ble de la flamme. Une flamme plate dans la suspension de micro-particules d’aluminium et
d’oxydant gazeux est stabilisée sur un brûleur à contre-courant, résultant en une géometrie
unidimensionnelle qui permet une portée optique pour les diagnostics. Des techniques de
spectrométrie de formation d’images d’émission et de spectrométrie d’absorption à bandes
larges ont été développées et appliquées sur la flamme plate pour déterminer le régime de
ii
combustion des particules dans la flamme.
iii
Acknowledgments
I would like to thank Prof. Jeffrey Bergthorson and Prof. David Frost for their guidance in
the completion of the PhD project and for their countless hours editing and critiquing my
work.
I would also like to thank Dr. Samuel Goroshin whose unique vision and understanding
of metal combustion provided inspiration and guidance for the work in this thesis.
The technical advice of Prof. Andrew Higgins and Prof. Nick Glumac was invaluable for
presentations and in the completion of the diagnostic setups.
My colleagues and co-authors, Philippe Julien, Jan Palecka, James Vickery, and Keishi
Kumashiro, deserve a special thanks for their comradery and research efforts. I addition-
ally owe a debt of gratitude to the rest of the official and unofficial metal flames students
for keeping things interesting during my time at McGill and University of Illinois Urbana-
Champaign.
My thanks also go to my family: Jake, Pip, Sheila, and David.
iv
Contributions of the Author
Section 1.4 of the Introduction:

I developed the original analysis of the heterogeneous ignition theory using the steady
thermal states presented here.
Chapter 2 Publication [1]:

Soo, M., Goroshin, S., Bergthorson, J.M., Frost, D.L. Reaction of a particle suspension
in a rapidly-heated oxidizing gas. Propellants, Explosives, Pyrotechnics, 2015. 40(4):604-612.
I performed the analysis for the understanding of heterogeneous ignition. I wrote the
derivation to the governing equations and the assumptions. The coding was completed with
assistance from Keishi Kumashiro during a summer undergraduate research project whom I
supervised. I performed the analysis of the model and wrote the paper. David Frost, Jeffrey
Bergthorson, and Samuel Goroshin provided research guidance and editorial review.

Soo, M.J., Kumashiro, K., Goroshin, S., Frost, D.L., Bergthorson, J.M. Thermal struc-
ture of flames in non-volatile fuel suspensions. Proceedings of the Combustion Institute, 2017.
36(2):2351-2358.
I derived the set of governing equations and assumptions. The coding of the model was
completed with assistance from Keishi Kumashiro during his undergraduate thesis project.
We analyzed the data together. I wrote the paper. David Frost, Jeffrey Bergthorson, and
Samuel Goroshin provided research guidance and editorial review.

Soo, M.J., Goroshin, S., Glumac, N., Kumashiro, K., Vickery, J., Frost, D.L., Bergthor-
son, J.M. Emission and laser absorption spectroscopy of flat flames in aluminum suspensions.
Combustion and Flame, 2017. 180:230-238.
v
I developed the diagnostic setup and wrote the spectral processing codes. Experiments
were run with help from Keishi Kumashiro and James Vickery. James Vickery wrote the
codes to analyze reference burning velocity from the Particle Image Velocimetry technique. I
analyzed the data and wrote the paper. David Frost, Jeffrey Bergthorson, Samuel Goroshin,
and Nick Glumac provided research guidance and editorial review.
vi
Appendix D: Laser Absorption Diagnostic [4]:
Soo, M., Glumac, N. Ultraviolet absorption spectroscopy in optically dense fireballs using
broadband second-harmonic generation of a pulsed modeless dye laser. Applied Spectroscopy,
2014. 68(5):517-24.
In the process of constructing the laser absorption setup used for the publication in
Chapter 4, I developed a method to extend the visible broadband dye laser technique to
produce to broadband, ultraviolet (UV) laser light. I performed the experiments, developed
the spectral models, and wrote the paper. Nick Glumac provided research guidance and
editorial review. While the publication provides an overview of the diagnostic used in [3] and
the novel UV technique may be important for future diagnostic developments, the subject of
the paper is considered peripheral to the main body of the thesis. It is, therefore, included
as supplemental material.
vii
List of Figures
1.1 Combustion in condensed-phase fuel suspensions, classified according the fuel

volatility. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2 Classifications of combustion mode based on thermodynamics equilibrium cal-
culations from the analysis of [5]. . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3 The expected modes of metal particle combustion from [5]. . . . . . . . . . . 8
1.4 Thermal structure for the two limiting kinetic and diffusion regimes for het-
erogeneous and vapor-phase modes of combustion. A) the kinetic limit, B)
the diffusion limit for a heterogeneously burning particle, and C) the diffusion
limit for a vapor-phase burning particle. . . . . . . . . . . . . . . . . . . . . 13
1.5 General S-curve form for a particle. . . . . . . . . . . . . . . . . . . . . . . . 14
1.6 S-curves for a range of particle sizes. At a critical size, ignition degenerates,
and the particle reaction is limited to the kinetic regime. . . . . . . . . . . . 15
1.7 S-curves simulating particle burnout at a set gas phase temperature.(Left)
Particle ignites and transitions critically to the kinetic regime during burnout.
(Right) Particle ignites and transitions smoothly to the kinetic regime during
burnout. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.1 Temperature and oxidizer concentration profiles adjacent to the particle sur-
face for different combustion regimes. . . . . . . . . . . . . . . . . . . . . . . 28
2.2 (Left) Semenov diagram of the single particle ignition and extinction. (Right)
dependence of the particle temperature (Ts ) on gas temperature (Tg ) illustrat-
ing disappearance of the critical ignition and extinction points below some
critical particle size (unstable regimes are marked with dashed lines). The
temperatures are scaled by the activation temperature Ta = Ea /Ru . . . . . . 30
2.3 Dependence of the ignition temperature on particle size. Note that below a
critical value of the particle radius of 1.9 μm ignition is impossible. . . . . . 31
viii
2.4 Time histories of the temperature (scaled to the activation temperature Ta ),
radius and normalized Damköhler parameter for a single particle with differ-
ent sizes injected into a hot oxidizing gas flow illustrating the different pos-
sible reaction regimes: a) a small particle (1 μm radius) that oxidizes within
the kinetic regime, b) an intermediate sized (7 μm) particle that ignites and
quenches, and c) a large particle (20 μm) that ignites and burns within the
diffusive regime. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.5 Reaction of an instantaneously heated suspension of solid fuel particles with
a solid fuel concentration of 200 g/m3 with three different particles sizes, re-
sulting in combustion regimes that are a) kinetically-limited, b) intermediate,
and c) diffusively-limited. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.6 Dependence of combustion time on particle size at different solid fuel concen-
trations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.7 Dependence of combustion time on concentration of the solid fuel for particle
sizes of 4 and 10 μm. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.8 The transformation of the range of particle sizes and concentrations (shaded
area) where 95% of the particle radius is burned within 500 ms with a 20%
and 40% increase of the cooling rate. . . . . . . . . . . . . . . . . . . . . . . 37
3.1 Modified Semenov diagram illustrating particle ignition (I) at some critical
temperature (Tg0 for r2 ) and transition to near the diffusion limit (D). Ex-
tinction (E) occurs as the particle shrinks and undergoes the reverse transition
to the kinetic limit (K). Stable states are shown by (•) while unstable states
are denoted by (◦). The heat production curve is solid, and the heat loss curve
is dashed. Inset: ignition temperature as a function of particle size showing
critical radius below which ignition is impossible [1]. . . . . . . . . . . . . . . 46
3.2 Particle temperature and radius history of a particle injected into a hot oxdiz-
ing gas at temperature Tg burning in a predominantly diffusive combustion
regime (r0 rcrit ), an intermediate regime (r0 ∼ rcrit ), and a kinetic combus-
tion regime (r0 < rcrit ) [1]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.3 Flame structure profiles for three different particle sizes in a fuel-lean flame
(φ = 0.5). Top: gas and particle temperature non-dimensionalized by Ta =
Ea /Ru ; Middle: normalized oxidizer mass fraction, Y , and particle radius,
r/r0 ; Bottom: reaction heat release rate, q̇, and Da∗ . The arrow indicates
direction of propagation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
ix
3.4 Flame structure profiles for three different particle sizes in a fuel-rich mixture
(φ = 1.5). The same variables are shown as in Fig. 3.3. . . . . . . . . . . . . 50
3.5 Burning velocity, ub , as a function of particle size for different equivalence
ratios. Hatched area corresponds to regions where unstable flame propagation
is observed. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.6 Burning velocity as a function of equivalence ratio for different initial particle
sizes. The expanded view shows the intersections of burning velocities for lean
equivalence ratios for various particle sizes. . . . . . . . . . . . . . . . . . . . 52
3.7 Instantenous profiles of gas and particle temperatures and Da∗ at different
instances in time over a single oscillation period of an oscillating flame. The
units of t are seconds. The arrow indicates the direction of propagation. . . . 52
3.8 Comparison of computed burning velocity to semi-empirical asymptotic Zel-
dovich and Frank-Kamenetskii (kinetic) and modified Mallard-Le Chatelier
(diffusive) flame models. The semi-empirical models are normalized to the
numerical model at r0 = 1 μm for the kinetic model and r0 = 25 μm for the
diffusive model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.1 Stabilized Bunsen flames in methane-air and metal-air suspensions from [5]. . 56
4.2 a) Photograph of a flat flame in an aluminum-air suspension, b) schematic
of the counterflow flame burner and side view of the laser sheet and dust
concentration laser probe and c) top-view schematic of the imaging-emission
and laser-absorption spectroscopy setups including simultaneous imaging and
concentration measurement. . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
4.3 Particle size distribution and SEM image of Valimet H-2 Aluminum. The
particle sizing results are provided by the manufacturer. . . . . . . . . . . . . 65
4.4 (Left) Greyscale-inverted spectrogram of the aluminum atomic lines from
aluminum-air flame with a (non-inverted) blown-up region of the self-reversal
region in the inset. (Right) Intensity profiles of the spectrum taken at three
different locations: (1) post-flame zone, (2) reaction zone, (3) pre-heat zone.
The comparison of the emission line thickness to the instrument resolution
function is also shown. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
4.5 (Left) Greyscale-inverted spectrogram of the aluminum atomic lines from the
aluminum-methane-air flame showing no self-reversal. (Right) Intensity pro-
files of the spectrum taken at three different locations: (1) post-flame zone,
(2) reaction zone, (3) pre-heat zone. The comparison of the emission line
thickness to the instrument resolution function is also shown. . . . . . . . . . 68
x
4.6 Absorption spectrograms of the Al I atomic lines for aluminum-air and aluminum-
methane air flames. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
4.7 (Left) inverted spectrogram of the AlO B−X Δν = −1 band sequence across
the flame. (Right) Spectra from two locations in the flame showing the opti-
cally thick and optically thin regions. . . . . . . . . . . . . . . . . . . . . . . 71
4.8 Flame temperatures measured using AlO molecular spectra (• and ◦) in com-
parison to equilibrium calculations (lines) at different initial aluminum parti-
cle concentrations. The predicted mole fraction of gaseous aluminum vapor
in equilibrium is also shown. . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.9 (Top) schematic of the micro-scale emission and absorption of aluminum vapor
from the flat flame that is integrated along the line of sight to the spectrometer.
(Bottom) Schematic of self-reversal. Hot zone emission of linewidth w1 is
partially absorbed by cold zone with linewidth of w2 where w1 > w2 . . . . . . 74
C.1 Temperature profiles of the simplified Zeldovich and Barenblatt model. . . . 99

C.2 Relative concentration profiles of the simplified Zeldovich and Barenblatt model.100
C.3 Relative difference between solutions computed at different spatial step-sizes. 101
D.1 Schematic of the entire setup for the absorption measurement. A pulsed
Nd:YAG (355 nm) pumps a dye cell in a grazing incidence configuration. The
modeless dye beam is then focused onto a BBO-I crystal, and the resulting
UV beam is collimated and separated from fundamental and passed through
the combustion chamber. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
D.2 Spectral bandwidth of the second harmonic for different focal lengths of the
lens used to focus the fundamental beam onto the nonlinear crystal. . . . . . 107
D.3 (top) Spectral bandwidth of modeless dye beam with Coumarin 450 as the
dye averaged over several pulses. (below) The spectral profile of the second
harmonic. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
D.4 NO spectrum at low concentration from continuously pulsed laser (20 Hz)
integrated over 1 second compared to spectrum simulated by LIFBASE at
T = 300 K. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
D.5 NO spectrum under optically thick conditions from a single pulse compared
to spectrum simulated by LIFBASE at T = 300 K. . . . . . . . . . . . . . . 111
D.6 Al atomic line absorption in EBWs taken in a series of experiments at different
times after bridge wire initiation. . . . . . . . . . . . . . . . . . . . . . . . . 112
D.7 The absorption spectrum of MgF in flash powder combustion fit with a 3000
K simulation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
xi
D.8 The absorption spectrum of AlF in flash powder combustion fit with a 2800 K
simulation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
D.9 Second order spectrum of AlF with a simulation at 2800 K. . . . . . . . . . . 115
xii
List of Tables
2.1 Numerical values of gas and solid-fuel parameters. . . . . . . . . . . . . . . . 29
3.1 Numerical values of gas and solid-fuel parameters. . . . . . . . . . . . . . . . 49
C.1 Effect of spatial step-size on calculated burning velocity. . . . . . . . . . . . 101
xiii
List of symbols
Description Dimension*
α Thermal diffusivity of the gas L2 T−1
β Convective mass transfer coefficient of a particle LT−1
γ Mass of fuel consumed per unit mass of oxidizer consumed
κ Pre-exponential factor of surface reaction rate LT−1
λ Thermal conductivity of the gas MLT−3 Θ−1
λI Thermal conductivity of the gas at the solid-gas interface MLT−3 Θ−1
ρg Gas phase density ML−3
ρs Mass density of a particle ML−3
φ Fuel-air equivalence ratio
ξ Flame-fixed coordinate L
ω̇ Rate of depletion of oxidizer divided by Cu /ρg0 ML−3 T−1
ω̇f Rate of depletion of fuel per unit volume ML−3 T−1
ω̇p Rate of depletion of oxidizer per particle MT−1
ω̇eff Rate of depletion of fuel per unit surface area ML−2 T−1
τr Reaction time T
A Surface area of a particle L2
B Particle, or fuel, concentration ML−3
C Oxidizer concentration in the bulk gas – suspension case ML−3
Cs Oxidizer concentration at the particle surface ML−3
cg Specific heat capacity of the gas phase L2 T−2 Θ−1
cs Specific heat capacity of the solid phase L2 T−2 Θ−1
D Mass diffusivity of oxidizer L2 T−1
DI Mass diffusivity of oxidizer at solid-gas interface L2 T−1
Ea Activation energy ML2 T−2
Da Damköhler number
Da∗ Normalized Damköhler number
G Mass burning flux ML−2 T−1
h Convective heat transfer coefficient of a particle MT−3 Θ−1
j Oxidizer diffusion flux to the particle surface ML−2 T−1
k Rate of surface reaction LT−1
keff Effective rate of reaction LT−1
r Reaction zone thickness L
L Characteristic length L
* L: length, T: time, M: mass, Θ: temperature, N: moles.
xiv
Description Dimension
Le Lewis number
ms Mass of a particle M
N Number density of particles L−3
Nu Nusselt number
pg Gas phase pressure ML−1 T−2
q Heat of reaction per unit mass of fuel L2 T−2
Q˙R Rate of heat production per particle/unit surface area ML2 T−3 / MT−3
Q˙L Rate of heat loss per particle/unit surface area ML2 T−3 / MT−3
q̇ Normalized heat production profile across the flame
q̇I Volumetric rate of heat transfer between the phases ML−1 T−3
q̇r Volumetric heat production rate ML−1 T−3
R Specific gas constant L2 T−2 Θ−1
Ru Universal gas constant M L2 T−2 Θ−1 N−1
r Particle radius L
rcrit Critical particle radius for ignition L
rmin Minimum particle radius for reaction L
Sh Sherwood number
Sf Burning velocity LT−1
Ta Activation temperature Θ
Tad Adiabatic flame temperature Θ
Tg Gas phase temperature Θ
Tig Ignition temperature Θ
Ts Solid phase temperature Θ
t Time T
tb Combustion time (of a single particle) T
u Flow velocity in the laboratory reference frame LT−1
ub Burning velocity LT−1
v Flow velocity in the flame-fixed reference frame LT−1
w Rate of oxidizer concentration per particle per unit surface area ML−2 T−1
x Density-weighted coordinate L
x Spatial coordinate L
xf Flame front position in the density-weighted coordinate space L
Y Normalized oxidizer mass fraction
z Generic Arrhenius pre-exponential factor Reaction dependent
xv
Subscripts
Description
0 Initial or at a fixed value
stoich At stoichiometry
u In the unburned mixture (for flame study)
ox Oxidizer
I At the interface between the particle and gas
xvi
Contents
Abstract i
Abrégé ii
Acknowledgements iv
Contributions of the Author v
List of Figures viii
List of Tables xiii
List of Symbols xiv
1 Introduction 1
1.1 Motivations for the Study of Metal Combustion . . . . . . . . . . . . . . . . 1
1.1.1 Historical Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.2 Modern Metal Combustion Applications . . . . . . . . . . . . . . . . 3
1.2 Classification of Combustion in Metal Fuel Suspensions . . . . . . . . . . . . 4
1.3 Modes of Metal Particle Combustion . . . . . . . . . . . . . . . . . . . . . . 5
1.4 Particle Ignition and Reaction Regimes . . . . . . . . . . . . . . . . . . . . . 8
1.4.1 Defining Ignition for Particles . . . . . . . . . . . . . . . . . . . . . . 8
1.4.2 Heterogeneous Heat of Reaction and Heat Loss Rates . . . . . . . . . 10
1.4.3 Steady-State S-Curve Analysis . . . . . . . . . . . . . . . . . . . . . . 11
1.4.4 Particles Burnout in Mixed Regimes . . . . . . . . . . . . . . . . . . 16
1.5 Scope of Thesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2 Reaction Onset and Combustion in a Particle Fuel Suspension 20

2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
xvii
2.2 Publication: Publication: Reaction of a Particle Suspension in a Rapidly-
Heated Oxidizing Gas, Propellants, Explosives, Pyrotechnics [1] . . . . . . . 24
2.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.2.2 Model Formulation and Results . . . . . . . . . . . . . . . . . . . . . 26
2.2.3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3 Flame Propagation in Particle Suspensions 39

3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.2 Publication: Thermal Structure and Burning Velocity of Flames in Non-
volatile Fuel Suspensions, Proceedings of the Combustion Institute [2] . . . . 42
3.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.2.2 Model Formulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.2.3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.2.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
4 Combustion Diagnostics in Particle Fuel Suspensions 56

4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.2 Publication: Emission and Laser Absorption Spectroscopy of Flat Flames in
Aluminum Suspensions, Combustion and Flame [3] . . . . . . . . . . . . . . 60
4.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
4.2.2 Experimental Methods . . . . . . . . . . . . . . . . . . . . . . . . . . 63
4.2.3 General Features of the Emission and Absorption Spectra . . . . . . . 66
4.2.4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
4.2.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
5 Conclusions 79
5.1 Synopsis of Contributions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5.2 Direction of Future Research . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
A Zero-dimensional Induction Combustion in a Fuel Suspension: Governing

Equations 84
A.1 Particle Energy Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
A.2 Particle Mass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
A.3 Bulk Gas Oxidizer Continuity . . . . . . . . . . . . . . . . . . . . . . . . . . 86
A.4 Gas Thermal Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
xviii
B One-dimensional Flame Propagation in a Fuel Suspension: Governing
Equations 88
B.1 Equation of State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
B.2 Momentum Conservation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
B.3 Gas Phase Continuity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
B.4 Density-Weighted Coordinate . . . . . . . . . . . . . . . . . . . . . . . . . . 89
B.5 Temperature Dependence of Gas and Solid Phase Properties . . . . . . . . . 90
B.6 Gas Phase Thermal Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
B.7 Oxidizer Continuity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
B.8 Solid Phase Continuity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
B.9 Solid Phase Thermal Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
C Validation of Numerical Methods 98

C.1 Code Verification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
C.2 Demonstration of Grid-Independence . . . . . . . . . . . . . . . . . . . . . . 101
D Laser Absorption Diagnostic 102

D.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
D.2 Diagnostic Setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
D.2.1 Dye Laser Configuration . . . . . . . . . . . . . . . . . . . . . . . . . 105
D.2.2 Second Harmonic Generation . . . . . . . . . . . . . . . . . . . . . . 105
D.3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
D.3.1 Stationary NO Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
D.3.2 Time Resolution in Exploding Bridge Wires . . . . . . . . . . . . . . 110
D.3.3 Metal-Teflon Flash Powders . . . . . . . . . . . . . . . . . . . . . . . 111
D.3.4 Spectroscopic Model for AlF and MgF . . . . . . . . . . . . . . . . . 111
D.3.5 MgF Detection in Dispersed Flash Powder Combustion . . . . . . . . 113
D.3.6 AlF Detection in Dispersed Flash Powder Combustion . . . . . . . . 113
D.4 Summary and Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
Bibliography 116
xix
Chapter 1
Introduction
1.1 Motivations for the Study of Metal Combustion

1.1.1 Historical Perspective
The scientific study of the combustion of metal powders in gaseous suspensions has been
historically motivated by two practical applications: energetic materials and industrial safety.
In energetic materials applications, the high volumetric energy density of metal powder fuels
makes them attractive to add to explosive and propellant formulations to increase the overall
energy output. Typically, for propellant formulations, metal powders are added in high mass
loadings up to nearly 20% by weight [6]. This leads to the suspension of metal particles
burning in the gaseous products of the hydrocarbon fuel matrix. For explosives, similar to
propellants, metal fuels are added to increase both the blast energy and, in some cases, to
enhance the blast effect. Blast enhancement is accomplished by explosively dispersing the
metal particles into the surrounding air, which burn behind the blast wave enhancing the
local pressure [6].
Influential developments in the science of metal combustion for energetic materials began
during the mid 20th century. After World War II, the Office of Naval Research (ONR) in
the United States, realizing the importance of aerospace superiority, began to fund the
development of advanced propulsion systems, including jet engines, rockets, and ramjets.
The effort, known as Project SQUID, consisted of a primary contract between the U.S. Navy
and Princeton University [7, 8, 9]. Princeton was then tasked with awarding subcontracts
to other participating groups and universities. After the 1950s, the scope of Project SQUID
shifted away from applied research on propulsion system development to focus more on basic
research problems involving the conversion of energy to thrust. It was during this period of
Project SQUID that several fields of modern combustion science were developed, including
1
the field of metal combustion.
Notable research efforts in metal combustion during Project SQUID and other similar
programs were carried out by researchers such as Brzustowski and Glassman [10], Friedman
and Maček [11], and Markstein [12]. Many of the theories and concepts developed in those
research efforts form the basis of our understanding of metal combustion today. Perhaps
the most well known of these efforts is the understanding of modes of combustion for metal
particles developed by Glassman [13]. Parts of his analysis are covered in this thesis in the
section entitled, Modes of Metal Particle Combustion.
It is also important to note the contributions of the Soviet scientists from the same
era. Information about the development of Soviet metal combustion research appears to be
available in closed literature [14]. However, deducing from the open translated literature, it
is likely that intense research efforts began sometime after U.S. efforts, in the 1960s at the
Semenov Institute of Chemical Physics [15]. It is clear that much of the basic understanding
of metal combustion from the Soviet perspective was formed out of concepts from reactor
theory and heterogeneous combustion concepts developed by prominent researchers such as
Zel’dovich [16], Frank-Kamenetskii [17], and Semenov [18], just to name a few.
Despite the significant overlap of the science in metal combustion developed in both the
U.S.A. and the U.S.S.R., certain core concepts developed in the Soviet literature are often
omitted from modern English texts when covering metal combustion. Particularly absent
from modern literature is a comprehensive analysis of heterogeneous particle ignition and
combustion as it relates to metal combustion. To the author’s knowledge, there is no single
text that fully covers these concepts. The basic principles are outlined in several fundamental
works by Vulis [19], Frank-Kamenetskii [17], Khaikin [20], and Merzhanov [21], and partial
reproductions of the theory can be found scattered throughout textbooks on heterogeneous
combustion [22, 23]. It is for this reason that a section, entitled Particle Ignition and Reaction
Regimes, devoted to the often omitted key concepts, is included in this introduction. This
theory also forms the basis of the models for combustion in particle suspensions presented
in this thesis.
The other prominent application of metal combustion research is industrial safety. Even
before the development of metal fuels for energetic materials, it was well known that dusts
from the process industries suspended in air (plastics, foods, metals, etc.) could cause highly
energetic, uncontrolled explosions. A survey of dust explosions from 1900-1956, published
by the National Fire Protection Association, found over a thousand instances of dust ex-
plosions over several industries [24]. Almost one tenth of those explosions resulted from the
combustion of metal dusts.
Much of the understanding of metal combustion encountered in the process industries is
2
centered around the idea that combustion in metal dusts should be treated as a reaction wave
propagation phenomenon. This is in contrast to much of fundamental research in metal com-
bustion for energetic materials, which has mainly focused on the combustion characteristics
of large, isolated individual particles [25]. A large body of research devoted to understanding
dust explosions has focused on studies of flames in dust suspensions [26, 27, 28]. The first
fundamental study of reaction wave propagation in metal suspensions was mainly through
the efforts of Hans Cassel at the U.S. Bureau of Mines, where he found that a flame could be
stabilized in flowing metal suspensions similar to hydrocarbon fuels [29]. Cassel recognized
that, in the suspension, the collection of closely spaced particles could cause self-heating
of the suspension and thereby accelerate the rates of reaction for the individual particles.
He termed this phenomenon the “cooperative mechanism”, realizing that the combustion
characteristics of the particles in the suspension would change compared to the combustion
of a single, isolated particle [30]. This was also understood by Soviet scientists, and can be
seen in the early fundamental theoretical work on combustion in suspensions by Rumanov
and Khaikin [31]. This led to the pursuit of metal combustion science in the context of
the basic principles that were developed for flame propagation and combustion in reactors
similar to studies of gas-phase fuel combustion [29, 26]. To date, the bodies of research from
Goroshin et al. [32, 33, 34, 35] and King [36] represent some of the most comprehensive
studies of flames in metal suspensions since Cassel’s initial research. The basic principles of
combustion in metal suspensions outlined in these studies are reviewed in the introductions
of Chapters 2 and 3 presented in this thesis.
1.1.2 Modern Metal Combustion Applications

After the initial push from Project SQUID, there were occasional bursts of research in metal
combustion for materials synthesis [37], underwater propulsion [38], as well as continued
efforts to understand metal combustion for propellants, explosives and industrial safety.
More recently, interest in metal combustion was revived during the 1990s and 2000s as a
result of advances in nanotechnology [39]. The accessibility of nano-powders and nano-
material synthesis opened up several new research possibilities. It was predicted that the
high specific surface area of nano-sized metals would lead to higher reactivity and enhance
combustion characteristics of energetic materials [39].
Several new ideas for applications of metal combustion emerged during this period. Re-
search from underwater propulsion using metal-water suspensions was revisited and led to
the creation of environmentally friendly, nano-aluminum/ice rocket propellants [40, 41]. As
a prototype demonstration, a small rocket using aluminum-ice (ALICE) propellant was suc-
3
cessfully launched in 2009 [42].
During the late 2000s, It was also proposed that metal nano-particles could be used as
clean energy carriers for sustainable energy generation [43]. The combustion of metals with
air produces no carbon emissions, and metal fuels have high energy and power densities.
The solid oxide products can be collected and recycled back into metal fuels. Beach et al.
initially proposed injecting powder suspensions into internal combustion engines (ICEs) to
produce power [43]. However, this study did not consider that solid metal oxide products
would be incompatible with internal combustion systems similar to coal [44]. Later, it
was proposed that flames in metal suspensions could be used to provide sustained heat to
external combustion engines for power generation and transportation applications [5]. A
similar concept was also proposed for combustion of metal-water suspensions [45].
Despite over 50 years of sporadic research efforts, the progress in the science of metal
combustion has lagged far behind in comparison to the understanding of gaseous and liq-
uid hydrocarbon fuel combustion. This can be partially attributed to the numerous, often
disconnected, interpretations of the physics that govern combustion in metal particle sus-
pensions. This is especially true of the connection between experimental and theoretical
studies of single particles versus suspensions of particles. The goal of this introduction is to
bring together some of the important core concepts from the literature which serve as the
background knowledge required to understand results in the thesis.
1.2 Classification of Combustion in Metal Fuel Suspen-

sions
The overall combustion behavior in condensed-phase fuel suspensions can be classified ac-
cording to the ability of the fuel to volatilize and premix with the gaseous oxidizer. Fuels
can be placed on a scale according to the predominant combustion behavior in the droplet
or particle suspension, ranging from purely homogeneous combustion (similar to gaseous fu-
els) to purely heterogeneous combustion, as qualitatively shown in Fig. 1.1. Highly volatile
droplet or particle fuels such as plastics, organic dusts, and liquid hydrocarbons will be able
to evaporate after some relatively small pre-heating, before combustion can occur. The gasi-
fied fuel can then premix with the oxidizing gas, leading to a fuel system where homogeneous
combustion phenomena dominate. For fuels like coals or slurry fuels (e.g. liquid hydrocar-
bons mixed with metal powders [46]), where part of the fuel material will volatilize and
premix with the oxidizing gas, there are both heterogeneous and homogeneous components
to the combustion behavior, leading to a more or less “hybrid” fuel system [47, 48, 49]
4
The least volatile fuels are generally metal and metalloid powders. For the purposes
of brevity in this thesis, the term metals is also meant to include metalloids. Metals, in
general, have relatively high volatilization temperatures, and the reactions of metal gases
with several oxidizers are nearly unactivated [50, 51]. Accordingly, metal vapor is not able
to appreciably premix with the bulk oxidizer before reacting, and the combustion of the
fuel system will be more heterogeneous in nature. These classifications are important for
understanding the overall general treatment of combustion of metal suspensions both from
a theoretical perspective and for designing experimental approaches.
Figure 1.1: Combustion in condensed-phase fuel suspensions, classified according the fuel
volatility.
The overall more heterogeneous nature of combustion is what separates metal suspensions
from other condensed-phase fuels. As an example, most flames in liquid hydrocarbon sprays
exhibit typical behaviors of homogeneous combustion. This is due to the fact that the
liquid droplets rapidly vaporize in the preheat zone of the flame leading to mostly gas phase
combustion in the reaction zone [52].
1.3 Modes of Metal Particle Combustion

Despite the overall heterogeneous behavior of combustion in metal suspensions, there can be
similarities to hydrocarbon fuels in the way (i.e. the mode) some metal particles burn. The
differences in the physical properties of the metals, such as the volatility of the metal and
its oxide, the heat of reaction, and the oxidizer properties, can lead to a variety of modes
of particle combustion. This is why, as will be explained, the different metal fuels listed in
Fig. 1.1 are not placed in the same location on the scale of combustion classification.
The modes of combustion can be established when the kinetic reaction rate of the metal
with the oxidizer is fast in comparison to diffusive transport, leading to the combustion of the
particle being limited by diffusion. This is generally true for very large particles but, as will be
shown in the following section, this assumption does not necessarily hold for small particles.
In the case of purely diffusion-limited combustion, the highest temperature that can be
achieved is the stoichiometric adiabatic flame temperature of the metal with the oxidizing
5
gas [53]. In one of the early studies of metal combustion for solid propellant research,
Glassman [13] realized that many burning metals with non-volatile oxides as products would
have a flame temperature limited to the evaporation or dissociation point of the condensed-
phase oxides, since the heat of gasification of the oxide exceeded the heat released in the
reaction. This basic idea has historically served as a basis for the classification of modes of
metal particle combustion [54].
In Glassman’s analysis, the boiling points of the metal fuel are compared to the “dissoci-
ation point” or “boiling point” of the oxide (with the underlying assumption that this is the
flame temperature) to determine the mode of combustion. In the case that the dissociation
point exceeds the boiling point of the metal, the metal droplet can begin to boil, and the
evaporating metal burns in a micro-diffusion flame enveloping the droplet, similar to the
combustion of a droplet of hydrocarbon fuel [53]. This concept is known as Glassman’s cri-
terion for the vapor-phase combustion of metals. In the case where the dissociation point is
less than the boiling point of the metal, combustion is expected to proceed heterogeneously
on the surface of the particle.
However, the definition for the “dissociation point” of the oxide is vague, since at any
given temperature, there may be some partial pressure of dissociated sub-oxide gases in
equilibrium with the condensed-phase oxide. Furthermore, different initial conditions (initial
temperature, oxygen concentration, pressure, etc.) can change the so-called dissociation
point. In the 1990s Steinberg et al. [55] published a sensible argument that Glassman’s
approach was only appropriate if the oxide undergoes a first-order phase transition. The
limitation of the definition for a dissociation point was acceptable at the time of Glassman’s
analysis because it predated the existence of robust, numerical thermodynamic equilibrium
solvers. A more modern analysis of the mode of combustion for metal particles [55, 5]
can be accomplished through the use of tools such as the NASA chemical equilibrium code
(CEA) [56]. The author agrees with the approach of Steinberg et al., however, in a series of
comments and responses by both Glassman [57] and Stienburg et al. [58], Glassman defended
his original analysis and refused to concede.
Steinberg et al. reasoned that the maximum temperature for the reaction of the particle
and oxidizer is the stoichiometric adiabatic flame temperature [55]. Comparing the boiling
point of the metal to the flame temperature, and the partial pressure of the gaseous oxides
predicted in equilibrium, can provide a more complete analysis of the combustion mode [5].
The partial pressure of the gaseous oxides predicted from equilibrium calculations in the
NASA CEA code are plotted against the ratio of the flame temperature to metal boiling
temperature in Fig. 1.2. The calculations were performed using the constant enthalpy and
pressure assumption at atmospheric pressure in air for stoichiometric mixtures of different
6
metals. Stoichiometry is defined as the quantity of reactants required to create products
without any excess of reactant. It should be noted that the notion of a stoichiometric mixture
is loosely defined. The product species are a result of equilibrium itself and, in general, cannot
be known a priori. Here, stoichiometry is calculated based on the assumption of complete
oxidation of the metal to the stable metal oxide indicated in Fig. 1.2.
Figure 1.2: Classifications of combustion mode based on thermodynamics equilibrium cal-

culations from the analysis of [5].
When the ratio of flame temperature to the metal boiling temperature is above unity,
the so-called Glassman criterion is met and it is predicted that the particle will burn in
a lifted micro-diffusion flame similar to a hydrocarbon droplet. A schematic of this type
of vapor-phase combustion is shown as mode A in Fig. 1.3. According to the analysis in
Fig. 1.2, metals such as magnesium or aluminum are predicted to burn in this mode.
When the flame temperature is less than, or close to, the boiling point of the metal, it
is likely that the metal will not readily evaporate and combustion must proceed heteroge-
neously. There are two modes associated with heterogeneous combustion of the particle. In
the case where the reaction forms gaseous oxides or sub-oxides, the oxides will then diffuse
away from the reaction zone at the particle surface and condense (if they are able) in a zone
lifted from the particle as shown as mode B in Fig. 1.3. Due to the high partial pressure of
oxides predicted in equilibrium, a metal like boron is predicted to burn in this mode. The
second mode of heterogeneous combustion can occur when the partial pressure of gaseous
oxides is low and only condensed-phase oxides can form. The oxide will then form a shell on
the particle surface as shown as in mode C on Fig. 1.3. When the density of the oxide is lower
than the density of the metal, this shell will be porous according to the Pilling-Bedworth
law [59], and diffusion of oxygen through the oxide layer will not significantly inhibit the
7
combustion of the particle. As shown in Fig. 1.2, iron is expected to have only condensed
phase oxides, leading to combustion mode C.
Figure 1.3: The expected modes of metal particle combustion from [5].
The existence of multiple modes of combustion that depend on the properties of the
particle fuel and gaseous oxidizer is the reason that the metal fuels listed in Fig. 1.1, though
having more heterogeneous combustion behavior overall, have been separated on the combus-
tion behavior scale. In air at atmospheric temperature and pressure, metals like aluminum
and magnesium can burn in the vapor-phase, and metals like iron will undergo purely het-
erogeneous combustion. This can be controlled by varying the oxidizing environment which
controls the flame temperature. The mode of combustion is important for developing the-
oretical models of different fuel types and, as will be explored in Chapter 4, interpreting
results from experimental investigations.
1.4 Particle Ignition and Reaction Regimes

1.4.1 Defining Ignition for Particles
In Glassman’s analysis, the mode of combustion is established after reaction rates become
fast compared to diffusive transport. In order to reach this state, the rate of heat produced
in the reaction must first be sufficient to overcome the heat loss to the surroundings (due
to molecular diffusion, radiation, etc.), which requires some initial heating of the particle.
When the heat production rate from an activated reaction is sufficient to overcome heat
losses, the thermal state of the particle can experience a criticality known as “ignition”. The
particle heat production goes into thermal runaway as the heat production rates become
fast compared to loss rates, allowing the transition to a stable, diffusion controlled rate of
8
reaction. After ignition occurs, the predicted modes of particle combustion, discussed in the
previous section, can be established.
The word “ignition” is often used colloquially to describe the initiation of a reaction
leading to self-sustained combustion in an energetic material or particle fuel cloud. This
leads to the use of terms like “minimum ignition energy”, “ignition temperature” or “ignition
delay”, often loosely defined, to describe the initiation of a reaction [24, 60]. However, in
the context of the combustion of particles, “ignition” has a historical and precise definition
that is often lumped together with these general, colloquial terms for reaction onset. As will
be made apparent in the work of this thesis, the consistent use of terminology is imperative
for correctly describing and understanding the phenomena that occur in the combustion of
single, isolated particles and in suspensions.
The overall non-volatile nature of combustion in metal suspensions means that ignition
will occur heterogeneously due to the reaction at the particle-gas interface. This differs from
the type of ignition resulting from the reaction of volatilized components at some distance
away from the condensed-phase surface, known as homogeneous ignition. Homogeneous
ignition is more applicable to hydrocarbon droplets and fuels with more volatile components,
like coal [22].
While classic heterogeneous ignition and combustion theory does not precisely describe
the ignition and combustion of some metal particles, especially particles with a protective
oxide layer (e.g. aluminum [20]), or more volatile fuels (e.g. sulfur [61]), it does provide an
understanding of the combustion physics for metal particles as a minimalistic approach. The
simplicity of the model makes it a valuable tool for developing an intuition of the expected
changes in combustion behavior as a function of the various physical and thermodynamic
properties of the fuel and oxidizing gas.
Heterogeneous ignition theory is an extension of non-adiabatic Semenov thermal explo-
sion theory [18], and was first applied by Vulis [19] and Frank-Kamenetskii [17] to study
coal char particle combustion. The results of their analysis are carefully repeated in Yarin
and Hestroni [22] and pieces of the heterogeneous ignition analysis can be found in several
books [23, 62]. The primary appeal of the theory is the possibility of understanding ignition,
extinction, and the steady thermal combustion regimes of a particle by examining the heat
generation and heat loss functions, without examining the transient processes. As will be
shown, the ignition and extinction phenomena for a heterogeneously burning particle is anal-
ogous to the critical ignition and extinction phenomena that are associated with the classic
analysis of a well-stirred reactor [19, 63]. The goal of this section is to present some of the
key elements of the theory, related to the ignition, extinction, and the changing regimes of
combustion, that are important to understand the thermal structure in the combustion of
9
particle suspensions.
1.4.2 Heterogeneous Heat of Reaction and Heat Loss Rates

Following the approach outlined by Vulis [19] and Frank-Kamenetskii [17], the overall reac-
tion rate of a heterogeneously burning single particle in an oxidizing gas is governed by the
competition between oxidizer transport to the particle surface and the kinetic reaction rate
at the particle surface. For simplicity, the following assumptions are made: (i) the particle is
spherical, (ii) the Biot number is small, (iii) the contributions of Stefan flow are negligible,
and (iv) the particle is always in quasi-static equilibrium where the reaction rate is equal
to the rate at which oxidizer reaches the surface. This approach assumes that the gaseous
diffusion field between the reacting particle surface and the surrounding gas, in the boundary
layer surrounding the particle, adjusts to the changing boundary conditions at the particle
surface and within the bulk gas instantaneously. As will be shown later in Chapter 2, in the
case where the reaction kinetics satisfy a first order equation, the effective reaction rate can
be expressed in terms of the combined rates of the diffusion and kinetics as
kβ
ω̇eff = C0 (1.1)
k+β
where ω̇eff is the mass of particle reacting per unit surface area per unit time, and C0 is
the mass concentration of oxidizer in the bulk gas far from the particle surface. The kinetic
term, k, is given by the Arrhenius expression,
k = κ0 exp(−Ea /Ru Ts ) (1.2)
where κ0 is the pre-exponential factor, Ea is the activation energy, Ru is the universal gas
constant, and Ts is the particle temperature.
The term β is the mass transfer coefficient between a particle and the gas. In the absence
of Stefan flow, the mass transfer coefficient takes the simple form of
ShD0
β= (1.3)
2r
Here D0 denotes the oxidizer diffusivity at the particle-gas interface, and r is the particle
radius. For a spherical particle that is stationary relative to the gas, the exact solution to
the steady-state spherical diffusion equation yields a Sherwood number (Sh) equal to 2.
The resulting expression for the heat release rate, assuming a stoichiometric mass coeffi-
cient of unity for the particle fuel and oxidizer, is
10
kβ
Q̇R = qAω̇eff = qA C0 (1.4)
k+β
where q is the heat of reaction and A is the particle surface area.
For simplicity, molecular conductivity is assumed to be the dominant mechanism of heat
loss from the particle, and radiative losses are ignored. For small Biot numbers, the heat
loss rate is described by the simple conductive cooling rate expression
Q̇L = hA(Ts − Tg ) (1.5)
where Tg is the bulk gas temperature, and the heat transfer coefficient for a spherical particle
is h = Nuλ0 /2r where λ0 is the interfacial thermal conductivity and the Nusselt number (Nu)
is equal to 2 for conditions of a spherical particle that is stationary relative to the gas.
The time dependent energy equation for a particle can be written in terms of the sum of
the heat-generation source and heat-loss sink terms:
d(mTs )
cs = Q̇R − Q̇L (1.6)
dt
Similar to the analysis of a well-stirred reactor, these heat source and sink terms can be
analyzed to find the steady regimes of combustion for the particle. The time derivative in
Eq. 1.6 is set to zero, and the heat generation rate Q̇R is set equal to the heat loss rate Q̇L . It
is important to note that this analysis requires the assumption of steady particle mass. The
changing mass in the reaction of the particle affects the generation and loss terms through
the changing radius, and, naturally, steady combustion states do not truly exist when the
particle is being consumed in the reaction. Nonetheless, the assumption that the mass of
the particle changes slowly compared to the time to reach a predicted state provides a way
to analyze potential states of particle combustion. It is potential in the sense that a burning
particle must transiently shift from its current state towards the predicted steady state, and,
during that transition, the particle mass change may be sufficient such that the predicted
state is never reached. However, as will be later shown in Chapter 2, the time dependent
solutions taking into account particle burn out match the qualitative predictions from the
simple steady-state analysis.
1.4.3 Steady-State S-Curve Analysis

One particularly illuminating variation on the analysis of heat generation and heat loss rates
is the determination of steady-state particle temperature as a function of the initial tem-
perature of the gas. This is of practical value for realistic fuel systems where dispersed
11
particles may experience a range of gas temperatures. In experimental practice, the analysis
is valuable because particle combustion is most often studied by providing an initial gas tem-
perature source such as a flame or shock tube [11, 64, 65], and particle and gas temperatures
can be measured from a variety of diagnostics as outlined in Chapter 4.
Equating Eq. 1.4 and Eq. 1.5, the equation can be rearranged to find the difference
between the particle temperature Ts and the gas temperature Tg :

D0 k(Ts ) qC0
Ts − Tg = (1.7)
α k(Ts ) + β(r) c g ρg
Here, the expression is altered to include the thermal diffusivity of the gas α = λ0 /ρg cg
where ρg and cg are the density and the heat capacity of the gas respectively. For simplicity
of the analysis, the Lewis number Le=α/D0 is assumed to be unity.
Written in this way, it is clear that the relative values of the particle-temperature-
dependent k term and particle-size-dependent β term will alter the steady state temper-
ature of the particle compared to the gas temperature. The competition between these two
terms admits two asymptotic temperature states. As diffusive rates become fast compared
to kinetic rates (β k), the temperature separation of the particle and gas approaches zero
and the particle and gas will assume the same temperature in what is known as the kinetic
limit. As kinetic rates become fast compared to diffusive rates (k β), the separation of
temperatures approaches the following expression:
qC0
Ts − Tg = (1.8)
cg ρg
The right hand side term in Eq. 1.8 is equivalent to the temperature rise in the gas if all
the oxidizer in the gas is consumed in the reaction [17]. This implies that the upper limit on
the particle temperature, assuming a Lewis number of unity, is the stoichiometric, adiabatic
flame temperature as previously stated in the section on combustion modes. This is known
as the diffusion limit. In the case of the heterogeneously burning particle, the maximum
temperature at the particle surface is expressed as
qC0
Tstoich = Tg + (1.9)
c g ρg
The local thermal structure of the particle will depend on both the reaction regime and
the mode of particle combustion. A particle burning in the kinetic limit will not apprecia-
bly exceed the gas phase temperature as shown in Fig. 1.4A, and therefore, the predicted
vapor-phase modes of particle combustion discussed in the previous section cannot develop.
Particles burning in the kinetic limit must burn heterogeneously.
12
In the case where the diffusion limit is reached, the predicted modes of combustion can be
established. A heterogeneously burning particle will have a thermal structure similar to the
schematic of Fig. 1.4B, where the particle temperature assumes the stoichiometric adiabatic
flame temperature.
The theoretical treatment of ignition and combustion for a vapor-phase burning particle
are discussed elsewhere [63, 22] and are beyond the scope of this work. In order make
a comparison to heterogeneous combustion, however, the general thermal structure of a
metal particle burning in the vapor-phase diffusion limit is shown in Fig. 1.4C. Similar to
heterogeneous combustion, the maximum temperature reached is the stoichiometric adiabatic
flame temperature. This temperature occurs at the diffusion flame lifted from the particle
surface due to the evaporating metal vapor from the boiling droplet.
Figure 1.4: Thermal structure for the two limiting kinetic and diffusion regimes for hetero-
geneous and vapor-phase modes of combustion. A) the kinetic limit, B) the diffusion limit
for a heterogeneously burning particle, and C) the diffusion limit for a vapor-phase burning
particle.
Equation 1.7 can then be solved to map the steady-state particle temperature as a func-
tion of the initial gas temperature as shown for a general case in Fig. 1.5. The temperatures
are normalized to the stoichiometric, adiabatic temperature in Eq. 1.9. The interplay be-
tween the kinetic and diffusion rates produces the classic S-curve forms observed in the
analysis of the well-stirred reactor [63, 19]. A change in gas temperature adjusts the heat
loss rates for the particle, similar to the way the Damköhler number adjusts the relative rates
13
of heat release and flow rates of cold reactants into the reactor. The particle temperature
state is similar to the final temperature state of the reactor. Higher reaction rates push the
combustion regime closer to the diffusion limit for the particle or to the intensely burning
branch for the well-stirred reactor [63].
1.0 diffusion limit Ts = Tstoich

0.9
regime
diffusion
0.8
0.7
0.6 2
Ts/Tstoich
0.5
it
ignition
0.4 n e ti c lim
ki
extinction
T
T = g
s
0.3
1
me
0.2 egi
tic r
kine
0.1
0.0
0.0 0.1 0.2 0.3 0.4 0.5
Tg/Tstoich
Figure 1.5: General S-curve form for a particle.
The upper branch of the S-curve, close to the diffusion limit on Fig. 1.5, is termed the
“diffusion regime”. The lower branch, close to the kinetic limit, is termed the “kinetic
regime”. The S-curve analysis shows that at some critical gas temperature, labeled point 1
on Fig. 1.5, the stable temperature state of the particle shifts discontinuously from the
kinetic regime up to a stable point in the diffusion regime, and is what is classically defined
as particle “ignition”. This is marked by a large increase in particle temperature compared
to the gas. The critical gas temperature at which ignition can occur is termed the “ignition
temperature”.
Ignition is defined as the discontinuous transition from a stable state in the kinetic regime
to a stable state in the diffusion regime at a critical temperature. The extinction point,
labeled point 2 on Fig. 1.5, is the critical point at which the reverse transition occurs. It is
noted that the extinction temperature will always be lower than the ignition temperature,
which implies that, after particle ignition, the burning rate is somewhat resistant to changes
in the temperature of the surrounding medium.
In many experimental studies that focus on the combustion of single particles, a heat
source, such as a flame [11] or the reflected shock in a shock tube [64], is provided to induce
ignition of the particles. The underlying assumption in many of these experiments is that,
14
after ignition, the gas temperature of the medium has little effect on the combustion rates
of the particles. The degree to which this assumption is true is a function of the various
physical and chemical properties of the particle and gas mixture. In particular, it is of interest
to determine how particle size affects this assumption, as it is an adjustable parameter in
practical fuel systems. The importance of particle size is reflected in the extensive literature
devoted to the experimental investigation of the ignition and combustion characteristics of
particles of different sizes [25].
The qualitative S-curves for a large range of initial particle sizes are plotted in Fig. 1.6
and provide a way to assess the expected burning behavior and the validity of the assumption
that, after ignition, the particle will burn essentially independently from the surrounding gas.
For larger particles shown on curve 1 of Fig. 1.6, the gas temperature at which ignition
occurs is lower than smaller particles, the maximum temperature is closer to the diffusive
limit, and the extinction points may not be physical* . This implies that, for a large enough
particle, a significant portion of the combustion occurs near the diffusion limit, and it is
more likely that the particle will not be able to reach the extinction point, until very close to
burnout. After ignition, a particle burning in the asymptotic diffusion limit has a reaction
rate essentially independent of any changes to surrounding gas temperature.
1.0
diffusion regime
0.9 large r0 1
2
0.8 e
egim
i netic r
3 k
0.7 no real
extinction extinction 4
0.6 point point
ignition/extinction small r0
Ts/Tstoich
0.5 degeneration
no criticality
0.4 Tg
Ts=
0.3
ignition
0.2 points
e
0.1 egim
tic r
kine
0.0
0.0 0.1 0.2 0.3 0.4 0.5
T /T
g stoich
Figure 1.6: S-curves for a range of particle sizes. At a critical size, ignition degenerates, and
the particle reaction is limited to the kinetic regime.
As initial particle sizes decreases, as shown for curve 2 on Fig. 1.6, the ignition and ex-
*A non-physical solution would occur when the extinction temperature is a negative value in contrast to
an imaginary value.
15
tinction temperature points begin to move closer together. This suggests that, after ignition,
a changing gas temperature can possibly alter the burning state during combustion, shifting
the particle from the diffusion regime back to the kinetic regime. It is also important to
note that even after ignition and transition to the diffusion regime, the maximum particle
temperature begins to depart significantly from the purely diffusive limit. Particles in this
size range will burn transiently in mixed regimes of combustion (often referred to as the
transition regime [66]) as both the kinetic and the diffusive rates are important in shaping
the burning behavior.
For very small particles shown for curves 3 and 4 on Fig. 1.6, the ignition and extinction
points can coincide, leading to the degeneration of the ignition phenomenon. At some critical
particle size, the criticalities of ignition and extinction, leading to discontinuous stable-state
transitions, will disappear, and the particle temperature will be a continuous function of
the gas temperature. In this case, the boundaries between the diffusion and kinetic regimes
becomes ill-defined.
After the degeneration of ignition, the particle will no longer burn as a micro-diffusion
reactor with a reaction rate isolated from changes in the gas temperature. The reaction
rate becomes a continuously varying function of both the gas and particle temperatures.
These behaviors are, overall, more consistent with the description of the kinetic regime than
the diffusion regime. Therefore, after ignition degeneration occurs, the entire “stretched”
S-curve is considered to be in the kinetic regime as shown for curves 3 and 4 on Fig. 1.6.
Even in this redefined kinetic regime, it is important to note that the temperature of
the particle can still overshoot the gas temperature by some degree. However, this temper-
ature separation will be a continuous function of the gas temperature, and no critical gas
temperature exists.
1.4.4 Particles Burnout in Mixed Regimes

While the combustion of particles that burn in the diffusive or kinetic limit is relatively
straight forward, the burning dynamics of a particle in the mixed regimes is not as clear.
As previously stated, the steady state analysis can only provide information about potential
states, since particle burnout is not taken into account. However, the S-curve analysis can
still provide a picture of how a particle in the transition regime may burn by examining
the predicted stable states of decreasing initial particle sizes at a set gas-phase temperature.
This, in essence, simulates particle burnout at a given gas-phase temperature.
Combustion in mixed regimes can occur in two scenarios. The first scenario is shown in
the left hand side of Fig. 1.7, and demonstrates a situation where at time t1 the initial gas-
16
1 = t0 1 = t0
t
1 r
1
= r0 t
1 r
1
= r0
ignition and transition ignition and
to diffusion regime transition to
diffusion
regime
T = T0 Tg = T0
g
0 0
1 1
t = t1+ t t = t1+ t
2 r
2
< r1 2
r
2
< r1
Ts/Tstoich
Ts/Tstoich
mixed regime
combustion mixed regime
combustion
0 0
1 1
t = t2+ t t = t2+ t
3
r < r2 3
3
r
3
< r2
extinction and transition non-critical transition
to kinetic regime to kinetic regime
0 0
0.0 0.1 0.2 0.3 0.4 0.5 0.0 0.1 0.2 0.3 0.4 0.5
/
T T
g stoich
T /T
g stoich
Figure 1.7: S-curves simulating particle burnout at a set gas phase temperature.(Left) Par-
ticle ignites and transitions critically to the kinetic regime during burnout. (Right) Particle
ignites and transitions smoothly to the kinetic regime during burnout.
phase temperature is relatively low, on the order of the ignition temperature. The particle
can ignite and begins to burn in the diffusion regime. As the particle begins to burn out
at t2 , the final temperature departs from the diffusion limit as the nontrivial dependence on
kinetic rates becomes more pronounced. Finally, at t3 where the particle size has further
reduced, the extinction point is reached and the particle sharply transitions to the kinetic
regime and the remainder of the burnout occurs in this regime.
In the second scenario shown in the right hand side of Fig. 1.7, the particle temperature
is initially set high compared to the ignition temperature. Here, the particle is able to ignite
and begins to burn in the diffusion regime. As the particle size decreases, the relatively high
gas temperature prevents the extinction point from being reached and the transition to the
kinetic regime will occur smoothly during burnout.
As will be shown in Chapter 2, the solutions to the transient problem including particle
burn out will yield similar results. This analysis can provide a qualitative understanding of
how the particle behaves in induced temperature fields or in the self-induced temperature
field resulting from the cooperative mechanism in the reacting suspension.
17
One disadvantage of the steady-state analysis is that it does not provide a feeling for
the relative reaction rates at different particle sizes. The thermal S-curve analysis gives
the impression that particles that ignite experience faster burning rates due to the higher
temperatures realized in the diffusion limit. The real picture is more complicated due to
interplay between particle burnout and the regimes of combustion and is best analyzed
through the transient problem discussed in Chapter 2.
The other important aspect about the steady state analysis, discussed briefly in the
context of potential states above, is that the predicted stable states are reached over an
infinite time scale. From a practical standpoint, most applications and experiments require
ignition and combustion to occur in a relatively constrained timeframe. As such, the trends
predicted in this analysis (e.g. ignition temperature as a function of particle size) may not
reflect the trends observed in practice. The time dependent problem is more suitable for
the examination of combustion within a set timeframe. Overall, this makes the steady state
analysis less useful as a predictive tool and more important as a method of understanding
the expected regimes of particle combustion.
1.5 Scope of Thesis

The papers in this manuscript-based thesis are presented in their logical order. The basic
theoretical principles of heterogeneous combustion are established in simple models, then
experimental techniques are developed to verify the theory.
The first paper in Chapter 2 develops a model of particle suspension combustion in
an adiabatic, zero-dimensional reactor. This extends the understanding of heterogeneous
ignition theory explained in the introduction to a time dependent model that examines
combustion of both single particles and suspensions. The second paper in Chapter 3 extends
the reactor model to one-dimensional flame propagation in the suspension.
The two modeling papers included in Chapters 2 and 3 have introductions which overview
heterogeneous particle ignition in context of the basic Semenov-type analysis used in the
classic texts of Vulis [19] and Frank-Kamenetskii [17]. However, after these papers were
written, it was clear that the results of the models and experiments did not readily correlate
with the classic heterogeneous ignition explanation. As the models and experiments focus on
the thermal structure of the flame, it became necessary to explain heterogeneous ignition in
context of steady thermal states as opposed to reaction states (See Section 2.2.2 and 3.2.2).
It is for this reason that Section 1.4 includes the basic theoretical principles of heterogeneous
particle combustion explained in context of a steady thermal regime analysis.
The final paper in Chapter 4 applies the understanding developed in the theoretical
18
papers to the development of experimental diagnostics to examine the structure of particle
flames. Key combustion characteristics are extracted using novel diagnostic approaches.
The paper also highlights some of the fundamental difficulties encountered in diagnostic
development for heterogeneous combustion.
The laser diagnostic used in Chapter 4 is outlined in the original work in Appendix D.
In the course of constructing the broadband laser technique for the paper in Chapter 4, a
novel experimental method to produce broadband, ultraviolet laser light was developed, and
a paper was published. This technique may be important for future diagnostic developments
in particle flames as discussed in the conclusions. However, the subject of the paper is
peripheral to the main subject of the thesis. It is, therefore, included as a supplemental
material.
The final chapter presents the conclusions and summarizes the key contributions of the
thesis.
19
Chapter 2
Reaction Onset and Combustion in a

Particle Fuel Suspension
2.1 Introduction
In dense suspensions of particles, the particle reaction rate can be accelerated by self-heating
of the mixture. This phenomenon was originally termed the “cooperative mechanism” by
Cassel [30], and subsequent literature uses terms such as “collective” effects [34, 67] or
“cloud” combustion [36] to describe the same phenomenon. This thesis will refer to the self-
heating phenomenon as “collective” effects for disambiguation. It is important to distinguish
the collective effect from “group combustion” (unfortunately, also sometimes called “cloud
combustion”), which refers to the phenomenon where burning suspensions of volatile droplets
or particles form a single flame around the whole group of particles or around clusters of
particles [68, 63, 69]. In this scenario, diffusion of oxidizer into the suspension dominates
the combustion behavior.
The basic principle of the collective effect is that heat released in the reaction is trans-
ferred from the particles to the gaseous medium in the suspension. In turn, the rising gas
temperature increases the particle reaction rates, leading to faster heat release rates. The
feedback mechanism causes the reaction to proceed explosively, after some delay time, due
to the exponential dependence of Arrhenius kinetics on temperature. After this onset of
reaction, the fuel or oxidizer is rapidly consumed. This is the same mechanism by which a
premixed gaseous fuel mixture undergoes thermal explosion. The primary difference between
the thermal explosion in a gaseous fuel mixture and a particle fuel suspension is the heat and
mass transport processes between the particles and gas that affect the combustion behavior.
There is an unfortunate naming convention for gaseous fuels to call the process of thermal
20
explosion “ignition” or “self-ignition” [16]. This can be confusing when referring to ignition
of individual particles, defined in the previous chapter, which can also take place in the
suspension. To avoid confusion, the thermal explosion of a particle suspension resulting
from self-heating is referred to here as “reaction onset”.
Two types of combustion in particle suspension flows are examined in this thesis. The
first type of combustion is termed induction combustion [16]. Conceptually, this type of
combustion can occur in a uniformly-heated, stationary fuel suspension within a reaction
vessel. It also describes a case where a uniform particle-oxidizer flow (assuming negligible
velocity slip) is moving and reacting at sufficiently high rates such that molecular heat
transfer upstream of the flow can be neglected. In the laboratory reference frame, if the
flow is heated instantaneously at some point x = 0, a reaction front will stabilize at some
distance downstream. In a stationary coordinate system relative to a moving section of the
particle flow, the reaction occurs strictly due to self-heating and particle ignition, and heat
does not have time to be transported from other layers of the flow. The initial conditions
of the suspension must allow the reaction to proceed to completion after a relatively short
period of time. This would require that the mixture be rapidly pre-heated. For the sake
of simplicity in the explanation, the gas dynamic effects are ignored. The subject of gas
dynamic interaction leading to a detonation wave in the suspension is beyond the scope of
this thesis and is discussed elsewhere in the literature [70].
Induction combustion neglects spatially dependent transport which greatly simplifies the
theoretical treatment of the problem. In the stationary reference frame of a section of moving
suspension flow, this effectively reduces to an adiabatic, zero-dimensional reactor problem.
The closest practical realization of the inductive mode of combustion for particle suspensions
is in metalized explosives. After detonation, the metal particle suspension is rapidly dispersed
into the hot detonation product of the hydrocarbon matrix. If the onset of reaction occurs
fast enough, conductive heat transfer to other parts of the dispersed suspension may be
relatively inconsequential. This can also be realized by the rapid dispersal and combustion
of particles behind a shock as examined in shock tube experiments [66, 65].
The induction regime of combustion is likely to also have some applicability to combustion
that occurs in rocket motors or ramjet type propulsion. However, in most applications,
turbulent or laminar diffusion processes in the flow are non-negligible. Heat from the reaction
zone, initiated at some point in the flow, is diffused upstream into the fresh fuel mixture
causing a reaction wave to propagate in the suspension. Reaction wave propagation driven
by diffusion, or flame propagation, is the second type of combustion that can be realized in
a particle suspension and is discussed in Chapter 3.
The additional transport processes in flame propagation complicate the theoretical treat-
21
ment of the problem. It follows logically that the first steps to a theoretical understanding
of flames in suspensions should be through the analysis of the simpler induction mode of
combustion. Induction combustion for a heterogeneously burning particle suspension was
theoretically investigated by Soviet scientists in several classic papers. The primary purpose
of those papers was to examine the effects of particle size and particle concentration on
the critical conditions for reaction onset [67, 71, 72, 73]. The parameters of particle size
and concentration were considered of special importance since these parameters are easily
adjusted in practical fuel systems.
The Soviet work focused on how reaction onset was affected by the interaction of heat
transport between the reacting particle and gas and the effect of self-heating from the sus-
pension. However, absent from the literature is a clear understanding of how the particles
in the suspension burn after reaction onset. The interplay between the physics of particle
ignition and collective effects leads to changes in the burning behavior and thermal structure
of particles during burnout. These changes in burning behavior are functions of particle size
and concentration. The dynamics of particle ignition can lead to a shift in the regime of
combustion as the particle size decreases during burnout, as demonstrated with the steady
state analysis in Chapter 1. In the diffusion regime of combustion, the relative insensitiv-
ity of the particle burning rate to changes in the gas temperature also can also lead to a
non-intuitive response of the burning suspension to heat loss. The lack of understanding of
particles burning in the intermediate regime in suspensions is the primary motivation for
the paper included in the following section. Within the context of the simple physics of
heterogeneously burning particles in a suspension, the basic reaction behaviors expected in
metal suspensions can be understood.
In the paper, a time dependent theoretical model is employed to examine a stationary
particle fuel suspension rapidly introduced into a uniform, high temperature oxidizing gas.
The theoretical treatment of the reactive suspension is analogous to the adiabatic explosion
problem from classic Semenov theory for reactive gases. The model tracks the particle and
gas energy and the mass of particles and oxidizer as they are consumed in the reaction. The
paper is meant to be an extension of the understanding provided in the early work by the
Soviet scientists. While the early studies often employed a set of simplifications meant to
ease the analytical treatment of the problem, the application of analytical tools to treat the
fully coupled set of time dependent governing equations is limited. Moreover, the physical
intuition is often obscured by analytical approximations (e.g. [72]). For simplicity in this
thesis, the equations are solved strictly by numerical methods. Despite this, it is important
to distinguish this model as a “minimalistic model” as it does not predict any particular fuel
system. It is, instead, meant to demonstrate the basic combustion physics when including
22
particle burnout in heterogeneously burning suspensions. A derivation of the governing
equations is provided in Appendix A.
23
2.2 Publication: Publication: Reaction of a Particle
Suspension in a Rapidly-Heated Oxidizing Gas, Pro-
pellants, Explosives, Pyrotechnics [1]
Michael Soo, Samuel Goroshin, Jeffrey M. Bergthorson, and David L. Frost
Abstract
The reaction of a suspension of solid particles in a rapidly-heated oxidizing gas is relevant to
metalized explosives and propellants, as well as to combustion of solid fuel-particle suspen-
sions in premixed-gaseous-fuel clouds encountered in accidents within the mining and process
industries. A simplified model is considered, using a constant-volume approximation, which
assumes that non-volatile particles react heterogeneously via a one-step surface reaction. The
resulting unified particle reaction rate includes both kinetic and diffusive reaction resistances.
It is shown that the onset of the chemical reaction in a rapidly heated particulate suspension
may occur by two different physical mechanisms. The first mechanism, realized in a dilute
suspension of particles, is defined by the ignition of a single particle, i.e., by the critical
phenomenon associated with the rapid transition from a kinetically- to diffusively-limited
reaction regime. The second mechanism dominates the reaction onset in a dense particulate
suspension and occurs in a similar manner to the reaction onset in a rapidly-heated homo-
geneous gas mixture, where the highly-activated reaction occurs in an explosion-like manner
after some time delay and preheating. Unlike the single particle ignition phenomenon, the
second mechanism lacks criticality and is not limited to particles above a certain size. The
interplay between these two reaction-onset mechanisms leads to a nontrivial dependence of
the total reaction time on the particle size and solid-fuel concentration within the suspension.
Keywords
Particle Combustion, Ignition, Burning Time, Metalized Explosive
2.2.1 Introduction
A suspension of reactive solid fuel particles dispersed within hot oxidizing gases may be
formed, for example, following the detonation or deflagration of a metalized energetic ma-
terial or during an accidental explosion in a coal mine or the process industries [24]. In the
24
first example, the reaction time for the energetic material is typically much shorter than the
characteristic time for heat exchange between the particles and the combustion products,
hence the particle suspension may be treated as if it were suddenly exposed to a hot oxidiz-
ing atmosphere. Measures of the performance of the energetic material, such as the work
done by the expanding products and blast wave for an explosive, or the specific impulse of a
propellant, will depend critically on the subsequent reaction delay and combustion time of
the solid-fuel suspension. The overall system performance may be tailored by choosing ap-
propriate particle sizes and other system parameters as guided by the available experimental
data and predictions from theoretical models.
Historically, most of the information on solid-fuel reactivity has been obtained from
laboratory experiments using relatively large single particles, with sizes ranging from tens
to hundreds of microns. In the experiments, the particles are typically either injected into
an oxidizing flow produced by a hydrocarbon flame [11], or heated by the gas behind a
reflected shock within a shock tube [74]. The experimental results are then used to construct
models that are extended to predict the combustion behavior of much smaller particles and
of dense particulate suspensions that are common in practical particle-fuel systems. The
underlying assumption made when extrapolating to practical energetic materials is that
the combustion physics on which the models are built do not change with particle size or
concentration. However, the validity of these assumptions is theoretically questionable and
difficult to justify, especially in light of recent experiments using nano-sized particles [75, 76]
and with large particle concentrations [48, 47, 77].
Experiments in which a small amount of aluminum powder was injected into a shock
tube and heated by a reflected shock have indicated that the aluminum particle combus-
tion regime shifts from being predominantly diffusion controlled to a kinetically-controlled
reaction regime when the particle size is reduced to a value below about ten microns [78].
In contrast with isolated single particles, the reaction of a particle suspension modifies the
ambient gas environment by reducing the concentration of oxidizer and increasing the tem-
perature, which in turn influences the particle combustion rate [30]. The combustion regime
for a particle suspension with a given initial particle size may change as the particles burn
out and may also differ from the combustion regime of an isolated particle with the same
size.
Recent experimental observations of flames in hybrid combustible gas-solid fuel mixtures
have shown that the combustion physics of the solid suspension depends critically on the
initial mass concentration of the solid fuel [47]. For the case of aluminum particles, the
particle combustion regime within a methane-air-aluminum flame changes rapidly when the
particle concentration reaches a critical threshold value of about 150 g/m3 [47], shifting from
25
a relatively slow oxidation regime, characteristic of an isolated single particle within the same
gaseous environment, to a relatively fast reaction regime associated with a flame front. An
analogous transition is also observed in suspensions of iron powder in methane-air mixtures
indicating that the phenomenon is of a general nature and is not fuel specific [77]. These
results also suggest that the common practice of introducing externally-defined parameters,
such as ignition temperature, ignition delay, and burn time, obtained from single-particle
experiments into reaction models for metalized energetic compositions may be inadequate
for cases in which a dense particle suspension is formed.
The goal of the present paper is to use a simple, transparent model to describe the
characteristics of the combustion of fuel particle suspensions and to illustrate how distinct
combustion phenomena may arise that do not occur during the combustion of a single par-
ticle. The model does not represent a comprehensive description of the combustion of a
specific fuel, but rather demonstrates, in general terms, how the mass concentration of a
solid fuel can influence the reaction behavior and combustion regime of the particle suspen-
sion with different particle sizes. To accomplish this, it is assumed that the particles undergo
a purely heterogeneous reaction with a gaseous oxidizer through one-step surface Arrhenius
kinetics which avoids the complications introduced by phase transitions, multistage kinetics,
and the complex thermodynamics typical of “real” systems [79]. Through this analysis, it
is theoretically shown that the general terms ignition temperature, combustion time, and ig-
nition delay, adapted from combustion models for large single particles, may be inadequate
to describe the complex phenomena associated with the combustion of particle suspensions
and for small particle sizes.
The presented work illustrates the diverse combustion characteristics associated with
adiabatic, constant-volume combustion of a stationary particle suspension for a particular
choice of values for the reaction rate and other physical parameters associated with the solid
and gaseous components. The effect of applying a rate of heat loss is also examined to
illustrate how the combustion of a suspension might behave in a real system subject to, for
example, expansion cooling. However, systematic parametric analysis of possible combustion
phenomena that may arise in different experimental situations following detonation and
deflagration events is beyond the scope of the present work.
2.2.2 Model Formulation and Results

Kinetic-Diffusion Reaction Rate
The general treatment of heterogeneous reactions governed by the competition between

transport and kinetic rates, and the associated thermal regimes and critical nature of regime
26
change, is thoroughly investigated in the classical work of Frank-Kamenetskii [17] and further
analyzed in Vulis [19]. A similar approach is applied here in a simplified form to analyze
and interpret different reaction regimes for the case of a single particle and a particulate
suspension.
As stated above, it is assumed that oxidizer consumption rate by chemical reaction on
the particle surface is described by a single-step first-order Arrhenius reaction, i.e.,
dm
= Cs A k (2.1)
dt
−Ea
k= κ0 exp (2.2)
Ru T s
Here, Cs is the concentration of the oxidizer at the particle surface, A is the particle
surface area, and k is the kinetic reaction rate, which depends on the activation energy Ea
and the particle temperature Ts . Following the assumption made by Frank-Kamenetskii
of quasi static equilibrium [17], the concentration of the oxidizer at the particle surface Cs
is found from the balance between the rate of consumption of the oxidizer by the chemical
reaction in Eq. 2.1 and the rate of transport of the oxidizer to the particle surface by molecular
diffusion and convection, i.e.,

β
A Cs k = A β (C0 − Cs ) → Cs = C0 (2.3)
k+β
where β is the mass-transfer coefficient between a particle and the gas, per surface area,
and C0 is the volumetric concentration of the oxidizer in the flow. By introducing the
expression for Cs from Eq. 2.3 into Eq. 2.1, the unified reaction rate, taking into account
both the kinetic reaction and diffusion “resistances”, may be written as
dm
= A C0 β Da∗ (2.4)
dt
where Da∗ = k/(k + β). The normalized Damköhler parameter Da∗ is related to the
traditional Damköhler number, Da= k/β, by the expression Da∗ = Da/(1 + Da). The value
of Da∗ is close to unity when the reaction rate is controlled by the diffusion of the oxidizer
(i.e., the diffusion regime where k β) and approaches zero when the rate of particle
oxidation is determined by Arrhenius surface reaction rate (i.e., the kinetic regime where
β k).
For the sake of simplicity, the contribution of the Stefan convective flow [17] to the
heat and mass transfer between the particle and the gas is neglected. The Stefan flow is
negligible when the concentration of the oxidizer in the flow is low and/or the volume of
27
reacted gas oxidizing on particle surface is closely matched by the volume of the gaseous
reaction products formed. In the absence of the Stefan flow, the mass and heat exchange
coefficients between a particle and the gas take the following simple form:
ShD0
β= (2.5)
2r
Nuλ0
h= (2.6)
2r
Figure 2.1: Temperature and oxidizer concentration profiles adjacent to the particle surface
for different combustion regimes.
where the Nusselt (Nu) and Sherwood (Sh) numbers are calculated assuming spherical
particles which are stationary relative to the gas (Nu=Sh=2). At Lewis numbers close to
unity, and under the particle lumped-capacitance assumption, the profiles of the temperature
field and oxidizer concentration around a particle are similar in all oxidation regimes, as
shown in Fig. 2.1.
In the diffusion-limited stationary reaction regime, the concentration of the oxidizer at
the particle surface is close to zero, and the particle temperature is close to the maximum
adiabatic flame temperature of the stoichiometric mixture [19]. In the kinetically-limited
regime, where diffusion is much faster than the rate of chemical reaction, the oxidizer con-
centration at the particle surface is close to the concentration within the bulk flow and
the temperature difference between the particle and gas does not exceed one characteristic
temperature interval, ΔT ≤ Ru Tg0 2
/Ea [19, 16].
28
Ignition of a Single Particle
The transition from the kinetically-limited to the diffusion-limited reaction regime occurs as
a discontinuous jump at a critical particle temperature and is the classic definition of the
ignition of a particle. The corresponding critical gas temperature is denoted the ignition tem-
perature. The reverse discontinuous transition from diffusion-limited to kinetically-limited
reaction is called extinction. The Semenov thermal ignition diagram, shown in Fig. 2.2(left)
adapted for the kinetic/diffusive particle reaction rate, qualitatively illustrates both the crit-
ical ignition and extinction points for a single particle and the subsequent transition into
stable regimes. It is important to note that once ignition occurs (i.e., the jump to the
diffusion-limited burning regime), the particle will also undergo extinction and return to the
kinetically-limited burning regime when it reaches a critical size due to particle burnout.
This is not reflected in the classical particle ignition theory which is only formulated to de-
termine ignition temperatures and stationary states and ignores the changing particle mass
with time [22]. With the inclusion of time-dependent particle burnout, for large initial par-
ticle sizes, the mass of the extinguished particle is negligibly small in comparison to the
initial mass. However, for decreasing initial particle sizes, extinction occurs more rapidly
after ignition, leading to a non-negligible mass of the extinguished particle which burns in
the kinetically-limited regime.
Property Value Property Value

λ0 0.0238 W1 m−1 K−1 T0 300 K
cg 1010.08 J1 kg−1 K−1 cs 978.56 J1 kg−1 K−1
D0 2.01 × 10−5 m2 s−1 κ0 70 m1 s−1
ρg 0 1.172 kg1 m−3 ρs 2700 kg1 m−3
Tg0 2100 K γ 1.12
C0 0.27 kg1 m−3 q 3.10×107 J1 kg−1
α0 2.01 × 10−5 m2 s−1 Ea /Ru 15 000 K
Table 2.1: Numerical values of gas and solid-fuel parameters.
There is a critical particle size for which the ignition and extinction temperatures coincide,
illustrated in Fig. 2.2(right), leading to the existence of a limit where the particle is unable
to ignite at any gas temperature. The breakdown of the ignition criticality is derived from
the particle ignition conditions and reflects the dependence of the particle temperature on
the gas temperature for the classical stationary model for particle ignition. Below this
critical size, there is no ignition temperature as the particle temperature is a monotonically
increasing function of the gas-phase temperature and is not significantly different from the
gas temperature which is expected in a purely kinetically-limited combustion regime.
29
The particular set of numerical values for the thermodynamic and transport constants
of the gas and solid phase used to calculate the curves in Fig. 2.2(right) are shown in
Table 2.1 and are also used in the subsequent examples in this paper. The values of the
thermodynamic parameters are typical for metal fuels, and with the particular values of
the reaction constants chosen, both the diffusion and kinetic combustion regimes occur with
micron-sized particles, where the molecular mean free path is still much smaller than the
particle radius and, therefore, Knudsen diffusion effects can be neglected.
Figure 2.2: (Left) Semenov diagram of the single particle ignition and extinction. (Right)
dependence of the particle temperature (Ts ) on gas temperature (Tg ) illustrating disappear-
ance of the critical ignition and extinction points below some critical particle size (unstable
regimes are marked with dashed lines). The temperatures are scaled by the activation tem-
perature Ta = Ea /Ru .
The ignition temperature calculated from the balance between the rates of heat produc-
tion and heat loss and their derivatives is plotted in Fig. 2.3 as a function of particle size.
It is evident that the particle ignition temperature increases with decreasing particle size,
reflecting the fact that the heat loss per unit particle surface area increases proportionally to
1/r. For the set of numerical parameters chosen, the heat loss rate exceeds the heat produc-
tion rate for any particle temperature when the particle size is below a critical size of about
1.9 μm, and ignition, or a transition to diffusion-limited combustion, becomes impossible.
If a particle below this limiting size is injected into a hot oxidizing gas it will heat
slightly above the gas temperature and will undergo oxidation within the kinetic reaction
regime without igniting. The time history of the temperature and radius of a single particle
is plotted in Fig. 2.4 for three different particle sizes corresponding to different combus-
tion regimes. The smallest particle undergoes a stable kinetically-limited oxidation process
(Fig. 2.4A). The largest particle ignites leading to a stable diffusive combustion regime with
30
Figure 2.3: Dependence of the ignition temperature on particle size. Note that below a
critical value of the particle radius of 1.9 μm ignition is impossible.
Da∗ near unity, which then quenches when the particle size is less than 10% of the initial
value (Fig. 2.4C). For an intermediate particle diameter, an intermediate transient regime
occurs in which the particle ignites, but extinguishes prior to reaching a fully-developed
diffusive-combustion regime (Fig. 2.4B).
The length of the kinetically-limited reaction “tail” depends exponentially on the ambient
gas temperature and, thus, is usually very long for single particles or for a dilute suspension
in which the self-heating of the mixture is negligible. In the transient combustion regime
observed in Fig. 2.4B, the time for complete oxidation of the particle in the kinetic regime
is usually much longer than for larger particles.
It should be noted that the particle size defining the border between the diffusion- and
kinetically-limited combustion regimes is not only a function of the reaction parameters
but also depends on the heat exchange coefficient between the particles and gas. As an
example, the detonation of metalized explosives typically results in much larger gas-particle
slip velocities, in comparison with metalized propellants that undergo deflagration, resulting
in a shift of the border between the two regimes towards larger particle sizes [80].
Reaction of a Dense Particulate Suspension
The dynamics of the solid-fuel reaction change completely if the initial concentration of
the solid fuel is sufficient to significantly influence the gas temperature through the particle
heating and subsequent heat release by the particle reaction. The effective reaction rate
derived in the previous section is given in Eq. 2.7. The algebraically reduced conservation
of energy equations describing the change of the particle temperature Ts by heat from the
reaction and convective heat loss to the gas is given in Eq. 2.8 and its changing radius r
31
Figure 2.4: Time histories of the tempera- Figure 2.5: Reaction of an instanta-
ture (scaled to the activation temperature neously heated suspension of solid fuel
Ta ), radius and normalized Damköhler particles with a solid fuel concentration
parameter for a single particle with differ- of 200 g/m3 with three different parti-
ent sizes injected into a hot oxidizing gas cles sizes, resulting in combustion regimes
flow illustrating the different possible re- that are a) kinetically-limited, b) interme-
action regimes: a) a small particle (1 μm diate, and c) diffusively-limited.
radius) that oxidizes within the kinetic
regime, b) an intermediate sized (7 μm)
particle that ignites and quenches, and c)
a large particle (20 μm) that ignites and
burns within the diffusive regime.
32
due to mass consumption is given in Eq. 2.9. These must be supplemented with equations
describing the time dependent temperature of the gas Tg heated convectively by the particles
shown in Eq. 2.10 and the depletion of the oxidizer mass concentration C due to the reaction
shown in Eq. 2.11.
kβ Sh D2r0 κ0 exp( R−E a

u Ts
)
keff = = (2.7)
k+β κ0 exp( R−E a
u Ts
) + Sh D2r0
dTs 3γ C Ts dr 3 λ0 Ts − Tg
= keff − 3 − Nu (2.8)
dt c s ρs r r dt 2 cs ρs r2
dr γ
= − keff C (2.9)
dt ρs
dTg 3 Bα0
= Nu(Ts − Tg )r (2.10)
dt 2 ρs r03
dC 3B
= − 3 keff r2 C (2.11)
dt ρs r0
The governing equations are written with a constant volume approximation and the
assumption that the pressure increase does not change the reaction kinetics or the heat and
mass transfer constants. The exclusion of the gas-dynamic effects that are specific to a
particular experimental situation allows us to focus primarily on the effect of particle mass
concentration B in the combustion dynamics of the suspension.
The time histories of the particle temperature, radius, concentration and the normalized
Damköhler parameter are determined by numerically integrating equations 2.7—2.11 with
the assumption that the initially cold particle suspension is suddenly exposed to a hot gas.
The results are shown in Fig. 2.5 for the same three particle sizes considered for the reaction
of a single particle in Fig. 2.4. For the purposes of this illustration, we assume that the
fuel suspension is lean with a mass concentration of 200 kg/m3 , corresponding to about
two-thirds of the stoichiometric value and with an initial gas temperature of 2100 K, which
is characteristic of hydrocarbon flames.
As seen from Fig. 2.5A for a small particle size, in contrast with a single particle, the
dense suspension of kinetically-reacting particles undergoes a rapid reaction onset and a cor-
responding sharp temperature increase. Although this behavior has the appearance of an
ignition event, the rapid rise of the reaction rate of the small particles within the suspension
lacks criticality as the value of the Damköhler parameter does not exceed 0.2 and, thus, the
combustion process remains close to the kinetically-limited reaction regime. The nature of
33
the sharp reaction onset in this case is analogous to that of a reactive gas mixture heated
under adiabatic conditions. After a certain delay time during which the mixture slowly
oxidizes, the reaction proceeds rapidly in an explosion-like manner reflecting the self accel-
erating nature of Arrhenius kinetics at high activation energies and large heats of reaction.
The adiabatic reaction delay time in this case can be estimated using the same well-known
formula for gaseous mixtures if the reaction delay time is significantly longer than the particle
heating time [16].
For large particles, which have the ability to ignite and burn within the diffusion-limited
regime, there is a complex interplay between the onset of the reaction due to the particle
cloud effect and the individual particle ignition (Fig. 2.5C). The calculations indicate that, for
any given particle concentration, the cloud effect leading to a reduction in the reaction delay
diminishes with increasing initial particle size, where eventually the suspension combustion
will behave in a similar fashion to the single particle. For suspensions of intermediate-sized
particles, the diffusive-combustion regime is followed by extinction and kinetically-controlled
combustion of the remaining fuel similar to the case of a single particle (Fig. 2.5B). However,
unlike a single particle, the transition to the kinetically burning branch of the suspension
does not result in a long kinetic-reaction particle-burnout “tail” but proceeds rapidly due to
much higher gas temperatures.
An important parameter for practical particle combustion applications is the sum of the
delay and reaction times which indicates how rapidly the solid fuel energy is released for a
particular energetic system. This is denoted for sake of brevity as the “combustion time”.
The combustion time calculation is limited to the point when 95% of the particle radius is
consumed in order to exclude the disproportional contribution of the long, kinetic-reaction
“tail” during which a relatively small amount of fuel is consumed after particle extinction.
The dependence of the combustion time on particle size is plotted in Fig. 2.6 for different
solid fuel concentrations.
From Fig. 2.6, the overall combustion time of a single particle initially rises with parti-
cle radius, but then sharply drops after the initial particle size crosses a critical threshold
at which point the particle burns primarily in a diffusion-limited regime. After this drop,
the combustion time slowly increases for increasing particle sizes although this is not read-
ily apparent on the semi-log vertical scale on Fig. 2.6. The fraction of the particle mass
that burns in the fast diffusive regime increases with particle size within this size range,
compensating for both the increased heating and reaction times. With an increase in fuel
concentration within the suspension (and therefore gas temperature), the advantage of the
diffusion-combustion regime diminishes and, for high particle concentrations, the overall
combustion time increases monotonically with particle size.
34
Figure 2.6: Dependence of combustion time on particle size at different solid fuel concentra-
tions.
The same interplay between kinetically- and diffusively-limited combustion regimes at

different fuel concentrations explains why the combustion time dependence with respect to
concentration intersects for two different particle sizes, as shown in Fig. 2.7. At low fuel
concentrations and, thus, lower gas temperatures, the large particles have an advantage.
They can ignite and burn faster in the diffusion regime than kinetically-reacting particles
at lower temperatures. At high fuel concentrations and, thus, high gas temperatures, the
advantage of the diffusive combustion disappears and small particles react more rapidly due
to their higher specific surface area.
Figure 2.7 also exhibits an initial sharp drop in the overall combustion time with an
increase in the fuel concentration for both particle sizes. The combustion time for a suspen-
sion of 4 μm particles reacting primarily in the kinetic mode decreases by about an order
of magnitude in contrast with a single particle. The exponential dependence of the reaction
delay time on the gas temperature, which is proportional to the fuel concentration, is a clear
demonstration of the “cloud” or “collective” effect on the combustion process. The drop in
combustion time will be even stronger if the increase of the heat and mass transfer coeffi-
cients with temperature and pressure are taken into account. Accounting for the cloud effect
may explain the extremely low combustion times observed experimentally for aluminum par-
ticles burning within the products of metalized explosives that are difficult to reconcile with
the much longer times derived from experiments with single particles [81]. The recently
proposed hypothesis [82, 83] that the short reaction times are due to the cracking of the
35
Figure 2.7: Dependence of combustion time on concentration of the solid fuel for particle
sizes of 4 and 10 μm.
protective alumina shell by a shock wave resulting in faster oxidation kinetics cannot explain
why combustion times of the same order are observed during the detonation of aluminum
suspensions in air where the shock pressure is lower by almost three orders of magnitude
[84]. In addition, it is well known that protective oxide films can swiftly re-establish on the
metal surface if the conditions are not optimum for the particle ignition [85].
Reaction of a Suspension in a Cooling Gas
In a real experimental situation, the system is non-adiabatic and the temperature of the
gas decreases with time due to heat loss or may fall sharply due to the expansion of the
gas products as in the case of a detonation event. Modeling the complex flow dynamics of
explosive formulations is outside the scope of this paper but, in the context of the present
model, the general considerations of what may occur during the combustion of a suspension
in such a system can be examined through the addition of a simple convective cooling rate
of the gas phase as shown in Eq. 2.12 which is a modified form of Eq. 2.10, i.e.,
dTg 3 Bα0
=− Nu(Ts − Tg )r − hw (Tg − T0 ) (2.12)
dt 2 ρs r03
Here, the hw is an arbitrary heat transfer coefficient, and T0 is the ambient temperature.
The addition of the cooling rate in this simple form is not connected to any particular
experimental situation, but serves to qualitatively demonstrate the type of analysis that can
36
be performed to find optimum particle sizes for a given particle loading. The introduction
of the cooling rate affects the ability of the particles to react to completion before the gas
temperature drops below the point at which the reaction rate is negligible. The cooling
of the gas may also lead to a longer reaction onset time in which case the particles will
never react within the given time frame. Among several parameters, including the initial gas
temperature and reaction constants, the major factors affecting the reaction completeness
within a given time are the particle size and mass concentration of the fuel within the
suspension. Although the particle size has long been recognized as a critical parameter, the
fuel concentration within the suspension is typically neglected. To analyze this situation, a
criterion is set such that if burnout of 95% of the particle radius does not occur within the
assigned time frame, then it is considered to be unburned. The resulting combinations of
particle size and concentration for which particle burnout occurs (shaded regions) are plotted
in coordinates of particle size vs. mass concentration in Fig. 2.7 for three different cooling
rates. Particle sizes below 1 μm were not considered in the calculation.
Figure 2.8: The transformation of the range of particle sizes and concentrations (shaded
area) where 95% of the particle radius is burned within 500 ms with a 20% and 40% increase
of the cooling rate.
This is by no means a comprehensive analysis of the model as the set reaction time window
and cooling rates are arbitrary, but it does show that the outcomes are not necessarily
37
intuitive. The resulting particle size/concentration combinations for both the lowest and
intermediate cooling rates indicate that at lower concentrations, it is actually more beneficial
to use larger particle sizes since the smaller, more kinetically-limited particles do not burn
to completion. In the intermediate case, at low concentrations, there is an isolated “island”
of large particle sizes that burnout. This island continually shrinks with increasing cooling
rate until, for a certain range of concentrations, there will only be a very small range of
optimum particle sizes. In the case of the highest cooling rate, it is seen that only relatively
small particle sizes have the ability to react to completion.
2.2.3 Conclusion
The primary conclusion of the present work is that the onset of the chemical reaction in
a rapidly heated particulate suspension may occur by two different physical mechanisms.
The first mechanism, realized in a dilute suspension of particles, is defined by the ignition
of a single particle, i.e., by the critical phenomenon associated with the rapid transition
from a kinetically- to diffusively-limited reaction regime. The second mechanism dominates
the reaction onset in a dense particulate suspension and occurs in a similar manner to the
reaction onset in a rapidly-heated homogeneous gas mixture, where the highly-activated
reaction occurs in an explosion-like manner after some delay and self-heating. Unlike the
ignition phenomenon, the second mechanism lacks criticality and is not limited to particles
above a certain size. The interplay between these two reaction onset mechanisms leads to a
nontrivial dependence of the total reaction time on the particle size and fuel concentration
within the suspension.
Acknowledgments
Special thanks to Keishi Kumashiro for his help in the formulation of the governing equa-
tions. Support for this work was provided by the Defense Threat Reduction Agency under
contract HDTRA1-11-1-0014 (program manager Suhithi Peiris), the NSERC CREATE on
Clean Combustion Engines, and a McGill Engineering Doctoral Award.
38
Chapter 3
Flame Propagation in Particle

Suspensions
3.1 Introduction
With the possible exception of metalized explosives, a direct implementation of the purely in-
duction mode of combustion is not likely to be encountered in practical applications especially
where controlled energy release is required. Although the induction mode of combustion for
gaseous fuels was found to be hydrodynamically stable [16], from an engineering perspective,
it is technically impractical. To maintain a stable reaction front in the induction regime for
high speed flows, the reaction onset in the suspension must carefully controlled. The expo-
nentially dependent nature of Arrhenius kinetics on the initial temperature demands precise
regulation of the initial conditions to maintain a steady reaction front. In practice, this
would be difficult to maintain.
The most encountered type of combustion in metal suspensions will be a transport driven
reaction wave, or flame. The transport of heat from the reaction zone into the fresh mixture
permits the propagation of the flame even if the mixture is initially cold. It should be noted
that there is also the possibility of an intermediate regime between the induction and the
flame propagation types of combustion. The intermediate regime was proposed by Zel’dovich
for gaseous fuels, and a similar principle may apply to combustion of heterogeneous fuel
suspensions [16]. However, this is beyond the scope of the thesis.
For gaseous fuel flames, the most typical method of transport is turbulent or laminar
diffusion. This also applies to flames in suspensions of particles [26, 86]. Additionally, for
particle flames, radiative transport can also play a role in flame propagation. Unlike gaseous
fuel flames which only emit and absorb radiation at discrete wavelengths, condensed-phase
39
species can emit and absorb broadband radiation. When the radiation absorption path length
becomes comparable to the diffusion driven flame thickness, then the role of radiation in
driving the flame cannot be neglected [31]. However, such conditions are unlikely to occur at
the typical stoichiometric concentrations, pressures, and particle sizes typically encountered
in metal flames at the laboratory scale. The radiation absorption path length approaches
tens of centimeters while the flame thickness is on the order of millimeters [86, 87, 88]. This
implies that for small-scale flames, radiation acts as a heat loss mechanism. In large-scale
flames, such as those investigated in [86], the flame and radiative transport scales can be
separated, and the influence of radiation is to preheat the fresh fuel mixture ahead of the
diffusion driven flame. In this sense, despite some possible disagreement in the literature
[89, 90], radiation should only play a secondary role and is neglected in this thesis.
For flame propagation, one of the most valuable measurable parameters to characterize
the combustion is the laminar burning velocity. The laminar burning velocity results from
the combination of reaction onset, transport between the particle and gas, and diffusive
transport in the suspension flow. The laminar burning velocity is somewhat of an idealized
case as it is experimentally difficult to remove the influence of effects such as turbulence,
flame stretch, and heat loss [88]. Nevertheless, the trends in laminar burning velocity as a
function of the various thermodynamic and physical parameters provide an insight into the
fundamental nature of self-sustained combustion in particle fuel systems.
Flames in particle suspensions have an important secondary parameter that gaseous fuel
flames lack. The role of transport between the particles and gas is not generally reflected
by typical combustion characteristics such as burning velocity or flame thickness. However,
as demonstrated in the introduction and in Chapter 2, the dynamics of transport lead to
different thermal regimes of combustion. The kinetic and diffusive regimes are functions
of the heat and mass transport rates between the particles and gas and are characterized
by changes in the temperature state of the particles relative to the gaseous medium. This
indicates that the thermal structure is also an important measurable parameter as it is a
direct consequence of the regime of combustion. It is for this reason that the paper in the
following section focuses not only on the burning velocity but also the thermal structure of
flames in suspensions. An introduction into the experimental study of thermal structure in
particle flames is covered in Chapter 4.
In many ways, the results of the zero-dimensional model in Chapter 2 provide insight
into the behavior of flame propagation. Similar to gaseous flames, the burning velocity in
the suspension is expected to a follow a simple relation, obtained from dimensional analysis,
formulated as

Sf ∝ α/τr (3.1)
40
Where Sf is the burning velocity, α is the thermal diffusivity and τr is the characteristic
reaction time. From the model in Chapter 2, it is clear that the characteristic reaction time
changes with both concentration and particle size. For this reason, it is expected that the
interplay between the kinetic and diffusive regimes of combustion seen in the burning time
behavior should also manifest similarly in the flame behavior.
There is no clear understanding in the literature of the fundamental behavior of flame
propagation in suspensions of particles that can burn in mixed regimes of combustion. The
dynamics between the particle reaction regimes and the diffusion of heat and gaseous species
in the suspension flow can lead to non-intuitive behavior of the thermal structure and burning
velocity of the flame. This lack of understanding motivates the need for a simple model of
flame propagation in heterogeneously burning suspensions.
In the paper presented in the next section, the inductive model of combustion from
Chapter 2 is extended to model a time dependent, adiabatic, one-dimensional laminar flame
including the dynamics of heterogeneous ignition and combustion. The governing equations
are again treated numerically. As stated previously, the lack of asymptotic analysis or
analytical solution should not diminish the importance of the physical understanding that
can be obtained from this simple model. A derivation of the governing equations is provided
in Appendix B.
The flame study is not meant to be parametric and focuses mainly on the effects of
initial particle size and concentration. The model also bears some resemblance to previous
models of flame propagation in coal suspensions in the literature [26, 91]. The models use the
principles of heterogeneous combustion of particles, outlined in Section 1.4, as the basis of the
particle reaction. However, those models add several assumptions in an attempt to simulate
combustion of coal, specifically. In the results of these models, the general physics resulting
from the heterogeneous reaction and self-heating of the mixture is obscured. The simple
model presented here is compared to the classic Zel’dovich expression for burning velocity
[16] for a kinetically limited reaction and the Goroshin expression for burning velocity [32] in
a diffusion limited particle suspension. The model is meant to bridge these two asymptotic
models to demonstrate the behavior of particles burning in the intermediate regime within
a flame.
41
3.2 Publication: Thermal Structure and Burning Ve-
locity of Flames in Non-volatile Fuel Suspensions,
Proceedings of the Combustion Institute [2]
Michael J. Soo, Keishi Kumashiro, Samuel Goroshin, David L. Frost, Jeffrey
M. Bergthorson
Abstract
Flame propagation through a non-volatile solid-fuel suspension is studied using a simplified,
time-dependent numerical model that considers the influence of both diffusional and kinetic
rates on the particle combustion process. It is assumed that particles react via a single-
step, first-order Arrhenius surface reaction with an oxidizer delivered to the particle surface
through gas diffusion. Unlike the majority of models previously developed for flames in
suspensions, no external parameters are imposed, such as particle ignition temperature,
combustion time, or the assumption of either kinetic- or diffusion-limited particle combustion
regimes. Instead, it is demonstrated that these parameters are characteristic values of the
flame propagation problem that must be solved together with the burning velocity, and that
the a priori imposition of these parameters from single-particle combustion data may result
in erroneous predictions. It is also shown that both diffusive and kinetic reaction regimes can
alternate within the same flame and that their interaction may result in non-trivial flame
behavior. In fuel-lean mixtures, it is demonstrated that this interaction leads to certain
particle size ranges where burning velocity increases with increasing particle size, opposite
to the expected trend. For even leaner mixtures, the interplay between kinetic and diffusive
reaction rates leads to the appearance of a new type of flame instability where kinetic and
diffusive regimes alternate in time, resulting in a pulsating regime of flame propagation.
Keywords
Two-phase flames, particle combustion regime, ignition, extinction, instability
3.2.1 Introduction
Understanding the mechanisms controlling flame propagation in suspensions of non-volatile
particles is crucial to obtaining efficient combustion of metallized propellants, slurry fuels,
42
pulverized coal, and powdered metals as carbon-free chemical energy carriers [5]. It is also
necessary for the mitigation of catastrophic explosions in coal mines or in process industries
that involve handling metallic dusts and other combustible solid powders.
Like gas flames, flames in particulate suspensions at the laboratory scale are primarily
driven by molecular heat diffusion and have comparable burning velocities [5]. Nevertheless,
they exhibit several significant differences in their structure and behavior from homogeneous
flames due to their multiphase nature.
The main distinctive feature of a flame in a solid suspension is the ability of particles
to ignite–that is, to transition from a combustion regime limited by reaction kinetics to a
regime limited by diffusion of the oxidizing gas towards the particle surface, or in the case
of evaporating particles, towards the micro-flame enveloping each individual particle.
After ignition, the temperature of the particle or micro-flame can exceed the gas tem-
perature by several hundred degrees, often surpassing the adiabatic flame temperature for
fuel-lean mixtures. The particle combustion rate in the diffusion combustion regime is a
weak, non-Arrhenius, function of gas temperature. Unlike gas flames, the width of the flame
reaction zone in particle suspensions can span a large temperature range and can be compa-
rable to, or even exceed, that of the preheat zone [32]. The existence of diffusion micro-flames
within a global flame-front (in effect, flames within the flame), which are insensitive to the
bulk gas temperature, makes dust flames resistant to heat loss [5, 92, 17, 19] and also serves
to maintain a constant burning velocity with increasing fuel concentration in fuel-rich mix-
tures [33]. The ability of particles to ignite, together with low ignition temperatures, may
result in much wider flame propagation limits for particle suspensions than for gaseous fuels.
Despite the overall qualitative understanding of the crucial role of the particle combus-
tion regime on burning velocity and thermal structure, the theoretical description of flames
in particulate suspensions has been limited to simple semi-empirical models that postulate
either purely diffusion or purely kinetic modes of particle combustion [33, 52]. The diffu-
sive combustion models presume that particles within the suspension ignite and transit to
the diffusion regime instantaneously when they reach the ignition temperature of a single,
isolated particle. The common assumption is that, after ignition, the particle within the
suspension will have a combustion time equal to that of an isolated single particle. Using
this approach, particle ignition temperature and combustion time are considered to be ex-
ternal parameters that are independent of the flame-propagation mechanism. As such, they
often are taken from experiments with individual particles or calculated using theoretical
models for single particle combustion. These assumptions are useful for estimation, but are,
in general, not justified and may lead to erroneous predictions. In reality, the particle igni-
tion temperature, particle reaction time, and the actual regime of particle combustion are all
43
characteristic values of the flame propagation problem directly linked to the burning velocity
eigenvalue. Moreover, the particle combustion regime may alternate throughout the flame.
For example, the particle may start to react in a kinetically limited regime, then transit to a
diffusion-dominated combustion mode, before returning to a kinetics-dominated mode [92].
As a result, a non-negligible fraction of the particle mass may be consumed during both
diffusive and kinetic combustion, leading to a complex dependence of the burning velocity
on particle size and concentration, as demonstrated in this study.
In this paper, the thermal structure of a flame in a particulate suspension is investigated
using a simplified, transparent model that assumes that non-volatile solid fuel particles react
via a single-step Arrhenius surface reaction with gaseous oxidizer delivered to the particle
surface by diffusion. Besides incorporating heterogeneous reaction kinetics, the model does
not impose the particle combustion mode or any other external combustion parameters. The
flame propagation problem is solved numerically in a non-stationary formulation developed
by Spalding [93]. This approach avoids the difficulties inherent in a steady-state formulation
and permits the investigation of flame stability, which has led to the discovery of a new type
of oscillating flame in heterogeneous mixtures.
3.2.2 Model Formulation

Combined Kinetic-Diffusive Reaction Rate
Following the quasi-stationary approach of Frank-Kamenetskii [17], the overall reaction rate
per unit surface area of a particle in an oxidizing gas, accounting for both kinetic and diffusion
“resistances” can be written as
kβ
ω̇eff = γ C0 (3.2)
k+β
where ω˙eff is the particle mass consumption per unit surface area, γ is the stoichiometric coef-
ficient, and C0 is the concentration of oxidizer in the bulk gas far from the particle surface [1].
The kinetic term, k, is the overall Arrhenius surface reaction rate, k = κ0 exp (−Ea /Ru Ts ),
where κ0 is the pre-exponential factor, Ea is the activation energy, and Ru is the universal
gas constant. β is the mass transfer coefficient between a particle and the gas.
For simplicity, the contribution of Stefan flow to the heat and mass transfer between the
particle and the surrounding gas is assumed to be negligible. Stefan flow is small when the
molecular weight of the reaction products is close to that of the consumed oxidizer or when
the initial oxidizer concentration is relatively low [17]. In the absence of Stefan flow, the
mass transfer coefficient takes the simple form, β = ShDI /2r. Here, DI denotes the oxidizer
diffusivity at the particle-gas interface, and r, the particle radius. For a spherical particle
44
that is stationary relative to the gas, the exact solution to the steady-state diffusion equation
yields a Sherwood number, Sh, equal to 2 [17].
The reaction rate in Eq. 3.2 can then be written in terms of the normalized Damköhler
number, Da∗ , which is related to the traditional Damköhler number, Da = k/β, by Da∗ =
Da/(1 + Da) [1]. The resulting expression for the heat release rate per unit particle surface
area is:
QR = q ω̇eff = qγβDa∗ C0 (3.3)
where q is the heat of reaction.

This formulation naturally incorporates the two limiting kinetic and diffusive regimes.
In a kinetically controlled regime (β k), Da∗ approaches zero. In the diffusion-limited
regime (k β), the reaction rate is primarily limited by diffusive transport of oxidizer, and
Da∗ approaches unity.
Ignition and Combustion of a Single Particle
The reaction of a suspension of particles within the flame is fundamentally different from
the reaction of an isolated single particle [1]. However, mapping the reaction regimes for a
single particle is crucial to understanding this difference and interpreting the flame structure
in a suspension. The interplay between kinetic and diffusion reaction rates of heterogeneous
chemical reactions leading to the processes of ignition and extinction was first investigated by
Frank-Kamenetskii [17] and then analyzed further by Vulis [19]. Their analyses are adapted
here in a simplified form to interpret the reaction behavior of a single particle injected into
a hot oxidizing gas.
The modified Semenov diagram shown in Fig. 3.1 plots the reaction heat release rate
that accounts for both kinetic and diffusive rates as a function of the particle temperature,
Ts . At low temperatures, the reaction rate increases exponentially with Ts due to Arrhenius
kinetics. At high temperatures, Da∗ approaches unity and the reaction rate in Eq. 3.3
becomes practically independent of temperature. If the heat loss from radiation is negligible,
as is the case for moderate temperatures and small particles, then the heat loss rate is
proportional to the temperature difference between the particle and gas and is plotted in
Fig. 3.1 as straight lines: QL = h(Ts − Tg ). Here h is the heat transfer coefficient, given by
h = NuλI /2r, where λI is the thermal conductivity of the gas at the gas-solid interface. The
Nusselt Number, Nu, is equal to 2 for a spherical particle that is stationary relative to the
gas [17].
At some critical gas temperature, known as the ignition temperature, the heat loss and
the heat release curves become tangent (point I on Fig. 3.1). The particle starts to accu-
45
r
1 r
2
diffusion limit
D
Heat production/loss
E
Q
l
T
i
K I
r
Q crit r
0
r
T
g0 T
s
Figure 3.1: Modified Semenov diagram illustrating particle ignition (I) at some critical tem-
perature (Tg0 for r2 ) and transition to near the diffusion limit (D). Extinction (E) occurs
as the particle shrinks and undergoes the reverse transition to the kinetic limit (K). Stable
states are shown by (•) while unstable states are denoted by (◦). The heat production curve
is solid, and the heat loss curve is dashed. Inset: ignition temperature as a function of
particle size showing critical radius below which ignition is impossible [1].
mulate heat and promptly transitions from a predominantly kinetic combustion regime to a
predominantly diffusive regime with temperatures close to the adiabatic temperature of the
stoichiometric mixture (point D). Once ignited, the burning particle inevitably extinguishes
when its radius reduces to the point (r1 ) where the heat loss and heat release curves become
tangent again, albeit at a higher particle temperature (point E). After extinction, the par-
ticle will transit to a kinetic burning regime (point K). For large particles, the extinction
radius is small in comparison to the initial particle size, and, thus, the residual particle mass
at extinction is negligible since m ∼ r3 . For smaller particles, the mass of the extinguished
particle may not be negligible relative to the initial particle mass. If the initial particle size is
reduced even further, the slope of the heat loss curve becomes so steep that tangency of the
heat release and heat loss curves becomes impossible. Below this critical radius, the particle
cannot ignite at any gas temperature (see inset in Fig. 3.1) [1].
The particle temperature history for three different initial sizes injected into a hot oxi-
dizing gas is illustrated in Fig. 3.2. The first case (r0 rcrit ) corresponds to a large particle
that undergoes heating, then ignites and reacts to completion almost entirely in the diffu-
sive regime. The second case (r0 ∼ rcrit ) corresponds to an intermediate-sized particle that
ignites but extinguishes soon afterwards without achieving full-fledged diffusive combustion.
After extinction, the particle continues to react in the kinetic regime at a temperature close
to the gas temperature. The third case (r0 < rcrit ) corresponds to a particle whose size is
below the critical value, and, as such, reacts entirely in the kinetic regime without ignition.
46
T
s r
0
>> rcrit
r
T
g
r
0
~ rcrit
r
0
< rcrit
Figure 3.2: Particle temperature and radius history of a particle injected into a hot oxdizing
gas at temperature Tg burning in a predominantly diffusive combustion regime (r0 rcrit ),
an intermediate regime (r0 ∼ rcrit ), and a kinetic combustion regime (r0 < rcrit ) [1].
This analysis shows that the particle reaction regime is a strong function of the particle
radius as well as the surrounding temperature and oxidizer concentration. In a flame, a re-
acting particle with constantly changing radius is exposed to rising temperature and falling
oxidizer concentration fields that are functions of the burning velocity. Therefore, postu-
lation of the particle reaction regime and “ignition temperature” and “combustion time”
parameters is, generally, unjustified in flame modeling. As demonstrated in this paper, only
by solving the flame propagation problem as a whole can the particle combustion regime and
other fundamental flame parameters be determined.
Governing Equations and Numerical Method
The flame propagation problem is cast in a time-dependent formulation, based on the method
developed by Spalding [93], and solved numerically. This method has been used to analyze
gas-phase flames [94]. Smoot et al. also used this method to model flames in coal dust-air
mixtures [26], but no attempt was made to draw general conclusions beyond the specifics of
coal combustion.
The model presented here employs several simplifying assumptions: (i) the solid fuel
can be modelled using the continuum approach described in [95, 96], (ii) the velocity slip
between the particles and gas is negligible, (iii) the molecular weight and heat capacity of
the products and oxidizer are similar, and (iv) the solid particles do not undergo any phase
transitions [97]. All of these are second-order effects.
The governing equations for the flame are simplified by introducing a density-weighted
x
coordinate, x, which is related to the physical coordinate, x , by x = 0 [ρg (x̄ )/ρg0 ]dx̄ [93].
47
In this coordinate system, the continuity equation is automatically satisfied, and advection
effects induced by thermal expansion of the gas are absent. Once found, the solution in
x-space can be transformed into x -space, as described by Margolis [98].
For simplicity, the temperature dependences of transport and kinetic properties are cho-
sen to eliminate thermal expansion effects. With these assumptions, the governing equations
can be reduced to the following expressions for the gas-phase temperature (Eq. 3.4), particle
temperature (Eq. 3.5), particle mass, ms (Eq. 3.6)), and normalized oxidizer mass fraction,
Y = Yox /Yox,0 (Eq. 3.7). The combined kinetic-diffusion reaction rate, ω̇eff , is given by
Eq. 3.2.
∂Tg ∂ 2 Tg
ρg0 cg = λ0 2 + N0 Ah(Ts − Tg ) (3.4)
∂t ∂x
∂
cs (ms Ts ) = Aq ω̇eff Y − Ah(Ts − Tg ) (3.5)
∂t
∂ms
= −Aω̇eff Y (3.6)
∂t
∂Y ∂ 2Y N0 ω̇eff A
= D0 2 − Y (3.7)
∂t ∂x γρg0
Here, A is the instantaneous particle surface area, cs and cg are the solid and gas-phase
specific heats, D0 and λ0 are the bulk mass diffusivity and thermal conductivity of the gas,
respectively, ρg0 is the initial gas density, and N0 is the initial particle number density. The
numerical values for the thermodynamic, transport and reaction properties used are given
in Table 1. These values are similar to those for an aluminum particle in air, but the model
is not meant to describe aluminum combustion in particular. The reaction parameters are
chosen such that the switch from kinetics- to diffusion-dominated particle combustion can
be observed in the micrometer particle size range.
The equations were numerically integrated in MATLAB by the method of lines using
a second-order finite difference formulation and a multi-step, variable order, implicit time
integration scheme [99]. The integration was performed over an effectively semi-infinite
domain with an adiabatic and impermeable hot wall condition [98]. Because long-term
solutions were of interest, the exact initial conditions used in this study turned out to be
immaterial [16].
3.2.3 Results and Discussion

Flame Thermal Structure
After an initial transient period, a steady-state flame, propagating at a constant speed,

typically develops. As discussed below, for some values of φ and r0 , no steady-state solution is
48
λ0 , λ i 0.02 W1 m−1 K−1 Ea /Ru 15 000 K
cg 1010 J1 kg−1 K−1 cs 979 J1 kg−1 K−1
D0 , DI 2.0 × 10−5 m2 s−1 κ0 70 m1 s−1
ρg 0 1.17 kg1 m−3 ρs 2700 kg1 m−3
γ 1.12 q 3.10×107 J1 kg−1
C0 0.27 kg1 m−3
Table 3.1: Numerical values of gas and solid-fuel parameters.
observed. Steady-state flame profiles of gas and particle temperatures, oxidizer mass fraction
and particle radius are shown for the fuel-lean case (φ = 0.5) in Fig. 3.3 for three different
initial particle sizes corresponding to overall kinetic (r0 = 1 μm), diffusive (r0 = 10 μm),
and intermediate (r0 = 4 μm) particle combustion regimes.
0.6 0.6 0.6
0.5 r = 1 m r = 4 m 0.5 r = 10 m
0 0.5 0 0
0.4 0.4 0.4
0.3 0.3 0.3

a
T/ T
0.2 T 0.2 0.2

s
0.1 T 0.1 0.1

g
0.0 0.0 0.0

1.0 1.0 1.0
Yand
0.5 0.5 0.5

r
0
r/r
Y
0.0 0.0 0.0
1.0
q
1.0 1.0
Da*
Da* and
0.5 q 0.5 0.5
0.0 0.0 0.0

-4 -2 0 2 4 -4 -2 0 2 4 -4 -2 0 2 4
x (mm) x (mm) x (mm)
Figure 3.3: Flame structure profiles for three different particle sizes in a fuel-lean flame
(φ = 0.5). Top: gas and particle temperature non-dimensionalized by Ta = Ea /Ru ; Middle:
normalized oxidizer mass fraction, Y , and particle radius, r/r0 ; Bottom: reaction heat release
rate, q̇, and Da∗ . The arrow indicates direction of propagation.
For small particle sizes, the flame structure is similar to that of a homogeneous gaseous
flame. The gas and particle temperatures remain close to each other throughout the flame,
and the reaction zone is thin and located near the point where the temperature reaches the
adiabatic flame temperature of the mixture.
In contrast, the flame structure for large particles is significantly different. After ignition,
the particles attain a temperature close to the adiabatic flame temperature of the stoichio-
metric mixture, which greatly exceeds that of the fuel-lean mixture. In addition, the reaction
zone is wide, encompassing a large gas temperature range. There is also a slight lag of the
particle temperature profile behind the gas temperature in the flame preheat zone.
In the case of intermediate particle sizes, particles ignite, but then extinguish before
49
achieving full-fledged diffusion-limited combustion. Thus, the particle temperature surpasses
the adiabatic flame temperature of the mixture, but does not reach that of the stoichiometric
mixture. In contrast to the reaction of a single particle of the same size, the kinetic reaction
time after the transition back to the kinetic combustion mode is relatively short due to the
high flame temperatures and, thus, does not significantly increase the overall combustion
time.
Flames in fuel-rich suspensions, as shown in Fig. 3.4, have a different structure to that
of fuel-lean mixtures, since the limiting reactant changes from the solid fuel, which has a
negligible mass diffusivity, to the oxidizing gas, which readily diffuses across the flame. The
primary difference is that the temperature of the particles after ignition does not exceed
the adiabatic flame temperature of the mixture. The reason for this is that the temperature
separation between particles and gas in the diffusive combustion regime is proportional to the
concentration of the oxidizer in a particular location, which falls to zero as the temperature
rises. Due to complete oxidizer consumption at the end of the combustion zone and, therefore,
a negligibly small reaction rate, the value of Da∗ remains constant after the oxidizer is
depleted.
0.6 0.6 0.6
0.5 r0 = 1 m 0.5 r
0
=4 m 0.5 r
0
= 10 m
0.4 0.4 0.4
0.3 0.3 0.3

a
T/T
0.2 Ts 0.2 0.2
0.1 Tg 0.1 0.1
0.0 0.0 0.0

1.0 1.0 1.0
Yand
0.5 r 0.5 0.5
Y
0
r/r
0.0 0.0 0.0

q
1.0 1.0
Da* 1.0
Da* and
0.5 q 0.5 0.5
0.0 0.0 0.0

-4 -2 0 2 4 -4 -2 0 2 4 -4 -2 0 2 4
x (mm) x (mm) x (mm)
Figure 3.4: Flame structure profiles for three different particle sizes in a fuel-rich mixture
(φ = 1.5). The same variables are shown as in Fig. 3.3.
Burning Velocity
The burning velocity is calculated based on the flame-front displacement as a function of

time. The burning velocity is plotted in Fig. 3.5 as a function of initial particle size for
different equivalence ratios. The general trend for stoichiometric, rich, and somewhat lean
mixtures is that the burning velocity increases monotonically with decreasing particle size.
50
This is simply due to the increasing specific reaction surface area with decreasing particle
size. In contrast, this dependence becomes non-monotonic for very lean mixtures. For
equivalence ratios below φ = 0.4, there is also a region where the burning velocity curves
split into two separate branches between which no steady solution exists.
10
8
4
ub (cm/s)
0 2 4 6 8 10
r
0
( m)
Figure 3.5: Burning velocity, ub , as a function of particle size for different equivalence ratios.
Hatched area corresponds to regions where unstable flame propagation is observed.
The nontrivial dependence of the burning velocity on particle size in lean mixtures is
the result of the intricate interplay between the kinetic and diffusive particle combustion
modes. Because of the relatively low flame temperatures in lean mixtures, the combustion
time of a larger particle reacting diffusively can be shorter than that of a smaller particle
reacting kinetically. This behavior is counter-intuitive, but is a direct consequence of the
ability of large particles to ignite and burn with temperatures much higher than the adiabatic
flame temperature of the lean mixture. The appearance of “flames within the flame”, results
in higher reaction rates for suspensions of larger particles that offset, and potentially even
overcome, the reduced specific reaction surface area as compared to finer suspensions. This
behavior can be seen first as a plateau in the dependence of burning velocity on particle
radius (Fig. 3.5, φ = 0.4) and then a decline as particle size decreases (Fig. 3.5, φ < 0.4).
It can also be seen in Fig. 3.6 as intersections of the burning velocity versus equivalence
ratio curves for different particle sizes. As the particle size is increased, eventually the
effect of decreasing specific reaction surface area again dominates, and the burning velocity
decreases with increasing particle size. These trends have been observed experimentally in
the combustion of coal suspensions [26] and liquid sprays [100], although no clear physical
explanation was given at the time.
51
4
r =1 m
0
3 =3 m
ub (cm/s)
r
10 0
0
=6 mr
2 r = 10 m
0
r
0
=1 m 1
0.30 0.32 0.34 0.36 0.38 0.40
ub (cm/s)
5
r= 10 m
0
0
2 4 6 8 10
Figure 3.6: Burning velocity as a function of equivalence ratio for different initial particle
sizes. The expanded view shows the intersections of burning velocities for lean equivalence
ratios for various particle sizes.
Kinetic-Diffusive Instabilities
For equivalence ratios below φ = 0.4, there is a region where no steady-state flame propa-
gation occurs (see hatched area of Fig. 3.5). Instead, these flames oscillate both in terms of
burning velocity and flame structure. An example of instantaneous profiles of particle and
gas temperature, and Da∗ at different instances over a single oscillation period are shown in
Fig. 3.7 for an equivalence ratio of φ = 0.4 and initial particle size of r0 = 4 μm.
0.4 = 0.325 r =
0
4 m T
s
T
g
0.3
a
T/T
0.2 T
ad
t
3
= 0.70
t = 0.63 t = 0.80
0.1 2 4
t = 0.97
t
1
= 0.45 5
0.0
t
3
0.4
*
0.2 t
Da
t 4
t 2
1
t
5
4 8 12 16 20
x (mm)
Figure 3.7: Instantenous profiles of gas and particle temperatures and Da∗ at different in-
stances in time over a single oscillation period of an oscillating flame. The units of t are
seconds. The arrow indicates the direction of propagation.
The gas temperature is observed to oscillate about the adiabatic flame temperature, while
the particle temperature oscillates with a much greater amplitude than that of the gas. At
52
t3 , the combustion regime is more diffusive, as indicated by the large temperature separation
and Da∗ , while at t1 and t5 , the regime is more kinetic, as indicated by the low values of
temperature separation and Da∗ .
At first glance, these oscillations resemble the well-known thermo-diffusive flame insta-
bility often observed in homogeneous gas [101] and quasi-homogeneous solid mixtures [102],
and also recently observed in aluminum dust flames [103]. The physical mechanisms un-
derlying the thermo-diffusive instability and the heterogeneous pulsating flame shown here
are, however, fundamentally different. In homogeneous mixtures, pulsations are induced by
changes in the gas molecular transport properties (Lewis number), activation energy, and
overall heat production, as required by the thermo-diffusive instability criteria formulated
by Matkowsky and coworkers [104, 105]. In the particle flame, the fuel has zero diffusivity,
and, for a fixed equivalence ratio, the gas-phase transport, kinetic parameters, and overall
heat production are fixed. In particular, they do not change with particle size. Instead,
the cause of the observed instability is evidently rooted in the processes of particle ignition
and extinction that are, indeed, very sensitive to particle size. Thus, it may be called a
kinetic-diffusive instability, reflecting the fact that the particle combustion regime in the
pulsating flame oscillates between diffusive and kinetic combustion modes. This interesting
new phenomenon will be studied in detail in subsequent work.
Comparison to Semi-Empirical Flame Models
Most existing models for flames in suspensions are semi-empirical and postulate either a
purely kinetic or purely diffusive regime of particle combustion. Plots of the normalized
burning velocity versus particle size predicted by such models are compared with the result
of the current numerical simulations in Fig. 3.8 for the lean mixture with an equivalence
ratio of φ = 0.3.
2.5 current model

0.30 kinetic regime
2.0 diffusive regime
1.5
ub (cm/s)
1.0
0.5
0.0
5 10 15 20 25
r
0
( m)
Figure 3.8: Comparison of computed burning velocity to semi-empirical asymptotic Zeldovich

and Frank-Kamenetskii (kinetic) and modified Mallard-Le Chatelier (diffusive) flame models.
The semi-empirical models are normalized to the numerical model at r0 = 1 μm for the kinetic
model and r0 = 25 μm for the diffusive model.
53
For the case of the purely kinetic regime, the burning velocity is calculated using an
analytical expression formulated by Zeldovich and Frank-Kamenetskii, modified for a com-
bustible mixture with a single-step, first order heterogeneous surface reaction [16]. The result
is normalized to match that of numerical simulations for the smallest particles, which burn
in the kinetic regime.
The burning velocity in the case of the purely diffusive regime is calculated using an
expression given in [32, 33] that requires two externally defined combustion parameters: the
ignition temperature and combustion time of the single particle. Ignition temperatures at
different particle sizes are calculated using the Semenov ignition criterion as shown in Fig. 3.1
and have a dependence with particle size similar to that shown in the inset of Fig. 3.1. The
particle combustion time is calculated using a simple diffusive reaction model that predicts
a tc ∼ r02 dependence [106]. The result of the purely diffusive model is normalized to match
that of the numerical simulations for the largest particles, which burn in the diffusive regime.
As can be seen in Fig. 3.8, these semi-empirical models only qualitatively predict the
asymptotic behavior of burning velocity on particle size where the combustion regimes are
either purely kinetic or diffusive. Over a wide particle size range, where diffusion and kinetic
rates are comparable, these models cannot capture the physics of the flame propagation and
yield erroneous results.
3.2.4 Conclusion
The comprehensive analysis of flame propagation in non-volatile particle suspensions pre-
sented in this paper has a historical parallel. It can be compared with the replacement of
the semi-empirical Mallard-Le Chatelier flame model, based on the notion of ignition tem-
perature and reaction time as external parameters, to flame models developed in the 20th
century based on the Arrhenius reaction law. Here, it is similarly shown that the particle
ignition temperature, particle reaction time, and regime of particle combustion are, in gen-
eral, characteristic values of the flame problem that must be solved for together with the
burning velocity. Moreover, this analysis demonstrates that the thermal structure of flames
in suspensions is defined primarily by the interplay between kinetic and diffusive reaction
modes that also yields non-trivial dependence of the burning velocity on particle size. This
interplay leads to the emergence of a new type of pulsating instability that is related to the
process of ignition and extinction of particles within the flame.
54
Acknowledgments
Support for this work was provided by the Defense Threat Reduction Agency under contract
HDTRA1-11- 1-0014, the NSERC CREATE on Clean Combustion Engines, and a McGill
Engineering Doctoral Award. Additional funding was provided by the Panda Faculty Schol-
arship in Sustainable Engineering & Design and a William Dawson Scholarship.
55
Chapter 4
Combustion Diagnostics in Particle

Fuel Suspensions
4.1 Introduction
As outlined in Chapters 2 and 3, there are several similarities between combustion in metal
suspensions and gaseous fuels. For example, a stationary reaction wave can be established
in a flowing suspension of metal particles similar to a gaseous fuel flow. A visual comparison
of Bunsen flames in different metal fuels compared to a hydrocarbon fuel is shown in Fig. 4.1
and reveals the similarities of their structure. It logically follows that the experimental study
of combustion in metal fuels should be similar to the study of gaseous fuels.
Figure 4.1: Stabilized Bunsen flames in methane-air and metal-air suspensions from [5].
The measurement of parameters such as burning velocity, suspension reaction time, and
thermal structure of the flame is essential to understanding metalized fuel systems. Experi-
mental approaches which investigate the combustion of single particles can only probe a small
56
portion of the physics that govern the burning behavior in dense fuel loadings. This requires
experimental approaches to study either the induction type or flame type of combustion in
suspensions.
Induction type combustion of metal particles has been previously studied at low [107]
and moderate particle concentrations [65] in optically accessible shock tubes. Induction
combustion has also been studied by introducing suspension flows into furnaces [30]. These
types of experiments are useful for determining reaction onset time or critical reaction onset
temperature (in the presence of heat loss). Typically, the luminosity from the hot particles, or
resonant emission from a gaseous species involved in the combustion, is used as an indication
of reaction onset. The radiance of emission in both cases should exhibit a strong dependence
on temperature [78].
The reaction times for single particles (or dilute suspensions) also can be measured in
shock tubes [108]. The duration of luminous intensity is a generally acceptable measure-
ment for combustion time if the particles burn primarily in the diffusion regime. However,
if extinction and transition back to the kinetic regime occurs, as shown in the model of
Chapter 2, the subsequent decrease in luminosity may falsely register as particle burnout.
For induction combustion of dense suspensions, the measurement of reaction time is more
difficult in practice. To perform systematic experiments, care must be taken to maintain a
uniform dispersion of particles and uniform heating of the suspension.
The flame type of combustion in suspensions is more suitable for the investigation of
reaction time and, generally, other combustion parameters. Unlike induction combustion,
where the initial heating must be precisely regulated, only a uniform suspension flow is
required for a flame. The initiation of the reaction in the suspension flow will establish a
reaction wave that can propagate automatically on its own.
However, even for flames, the direct measurement of combustion characteristics is not
a trivial task. The laminar burning velocity is difficult to measure, even in gaseous fuel
flames, as effects from flame stretch and heat losses are difficult to overcome experimen-
tally. Moreover, the variation in the particle size and morphology, as well as effects from
agglomeration, can greatly affect burning velocity measurements, making data even between
different batches of powder difficult to compare. This issue was addressed in a recent pub-
lication where burning velocities in suspensions of a single batch of aluminum powder were
measured using different methodologies [109]. The burning velocities measured from coun-
terflow flat flames [109], Bunsen flames [33], spherically expanding flames [103], and flames
propagating in tubes [33] exhibited significant scatter. These results reflect the still rudi-
mentary understanding of flames in heterogeneously burning suspensions, and more research
is required to assess the effects of the flame geometry.
57
The overall flame thickness and reaction zone thickness are also important parameters
which describe the fundamental length scales of the combustion phenomenon [63]. Similar
to gaseous fuel flames, it was reasoned that a measurement of quenching distance could
provide an estimate of the characteristic flame thickness [88]. This led to the development
of a methodology for determining quenching distance in dust flames [33]. However, the
overall flame thickness represents both the reaction and diffusion processes, while the reaction
zone thickness is related only to the characteristic reaction time of the suspension. From
dimensional analysis, the suspension reaction time τr should be related to the burning velocity
Sf and the characteristic reaction zone thickness r , by the simple relation:
τr ∝ r /Sf (4.1)
A measurement of the reaction zone requires an additional diagnostic to measure the

zone of the majority of heat release within the flame. In gaseous flames, the reaction zone
thickness has been measured by laser diagnostic techniques to a fairly high degree of accuracy
[110]. However, no such diagnostics have yet been applied to flames in particle suspensions.
The state-of-the-art for measurements of thermal structure in particle flames is perhaps
just as primitive as the measurements of burning velocity and flame thickness. The use
of intrusive diagnostics like thermocouples are often ineffective because they disrupt the
suspension flow [88]. Moreover, the multiple temperature environment cannot be probed in
this manner. The preferred techniques are non-intrusive optical diagnostics which are more
suitable to the combustion environment in suspensions.
The high luminosities of condensed phase combustion lend to the prevalence of emission-
based techniques [111, 112, 34]. Laser absorption techniques also appear to be suitable since
a probe beam of sufficient power should be able to pass through the high scattering envi-
ronment [113], although the measurement is path averaged. There is also some tendency
to try to apply off-the-shelf diagnostics developed for gaseous combustion directly to metal
fuel combustion. However, most advanced techniques developed for gaseous flames are of-
ten difficult, if not impossible, to apply to in suspensions due to the presence of condensed
phase material. For example, the application of standard Coherent anti-Stokes Raman Spec-
troscopy (CARS) to metalized propellants requires significant modifications in the presence
of particles [114].
Overall, there is a lack of suitable experimental diagnostic techniques to accurately de-
termine many of the combustion characteristics of flames in particle suspensions. Moreover,
the utility of common diagnostic techniques applied to particle flames has not yet been fully
assessed. These current experimental limitations serve as the primary motivation for the
paper in the following section.
58
The goal of the paper is to examine the implementation of emission and laser absorp-
tion diagnostics to stabilized, flat flames in aluminum suspensions. The stationary flame is
convenient as it avoids the difficulties of implementing optical and spectral diagnostics to a
non-stationary reaction wave or for highly transient induction combustion. The paper also
highlights some the key difficulties in the interpretation of data from these measurements.
The experimental techniques are used to resolve the multiple temperature nature of the
flame expected for combustion in the diffusion regime. Additionally, the study attempts to
use the laser absorption and emission spectroscopy technique to determine the reaction zone
thickness. This measurement, combined with other measured parameters, is used to extract
the reaction time of the suspension.
A more thorough explanation of the absorption technique used in the paper is presented
in Appendix D.
59
4.2 Publication: Emission and Laser Absorption Spec-
troscopy of Flat Flames in Aluminum Suspensions,
Combustion and Flame [3]
Michael Soo, Samuel Goroshin, Nick Glumac, Keishi Kumashiro, James
Vickery, David L. Frost, Jeffrey M. Bergthorson
Abstract
Imaging emission spectroscopy, spatially resolved laser-absorption spectroscopy, and particle
image velocimetry (PIV) are applied to a flat flame stabilized in a suspension of micron-sized
aluminum. The results from the combination of diagnostics are used to infer the combustion
regime of the particles and to estimate the characteristic combustion time of the suspension.
It is observed that the reaction zone of the flame in stoichiometric aluminum-air suspensions
exhibits strong self-reversal of the atomic aluminum emission lines. These lines also exhibit
high optical depths in both emission and absorption spectroscopy. The strong self-reversal
and high optical depths indicate high concentrations of aluminum vapor within the reaction
zone of the flame at multiple temperatures. These features provide evidence of the formation
of vapor-phase micro-diffusion flames around the individual particles in the suspension. In
aluminum-methane-air flames, the lack of self-reversal and lower optical depths of the alu-
minum atomic lines indicate the absence of vapor-phase micro-diffusion flames, and point
to a more heterogeneous, and likely kinetically-controlled, particle combustion regime. The
reaction zone thickness is estimated from the spatially resolved profiles of aluminum reso-
nance lines in both absorption and emission through the flame. The emission measurements
yield a reaction zone thickness on the order of 1.7±0.3 mm in aluminum-air flames, and the
absorption measurements yield a thickness on the order of 2.3±0.5. It is demonstrated that
the combination of the combustion zone thickness measurement, flame temperatures deter-
mined from molecular AlO emission spectra, and particle velocity measurements from the
PIV diagnostic permits an estimation of the burning time in the suspension. The burning
time in stoichiometric aluminum-air suspensions using the suite of diagnostics is estimated
to be on the order of 0.7 milliseconds.
Keywords
aluminum; suspensions; spectroscopy; flames
60
4.2.1 Introduction
Micron-sized metal powders, particularly aluminum, are common energetic additives to pro-
pellants and explosives. The mass fraction of metal in these energetic compositions can
exceed 20%, meaning that the metal burns as a dense suspension in the gaseous products
of a hydrocarbon fuel matrix. Understanding the combustion behavior of metal particles
in a dense suspension is central to the goal of predicting and tailoring the performance of
metalized explosives and propellants. Metals are also increasingly being investigated for use
as recyclable fuels [5, 115, 45], which would be burned in dense suspensions to achieve high
power densities and ensure flame stability.
The combustion physics of a dense suspension of micron-sized particles can differ con-
siderably from the combustion of large, individual, isolated particles, which have been the
dominant subject of experimental work in metal combustion [25]. While large particles
burn primarily in a diffusion-controlled regime of combustion, combustion of micron- and
submicron-sized particles can be limited by heterogeneous kinetics or they can burn in a
transitional diffusion-to-kinetic regime [78]. The combustion characteristics measured from
single particle studies, such as combustion time and combustion regime, are often extrap-
olated to particles in the dense suspensions encountered in the majority of practical fuel
systems. However, these characteristics are also functions of ambient temperature and oxi-
dizer concentration and, therefore, will depend on the fuel particle concentration [2, 1]. The
extrapolation of characteristic combustion data from single-particle studies to dense metal
suspensions, where temperatures can exceed 3000 K, will, in general, result in erroneous pre-
dictions. Thus, it is imperative to have experimental techniques to determine combustion
characteristics of bulk reacting suspensions.
In our previous work, stabilized Bunsen-type flames were used to study combustion char-
acteristics of aluminum and iron suspensions in oxygen and in the products of hydrocarbon
flames [48, 109, 116, 33]. Other studies have used freely-propagating flames in tubes [117] or,
more recently, transparent latex balloons [86], to study flame propagation speeds, laminar
burning velocities, and the formation of instabilities. The burning velocities measured in
these studies permit a more realistic estimation of the characteristic combustion time of the
suspension compared to experiments with individual particles.
However, the determination of key combustion characteristics in suspensions of metal par-
ticles is difficult due to the inability to isolate and observe individual particles in the cloud.
Optical diagnostic techniques to extract these parameters must be tailored to the specific
nature of metal suspension combustion which can be optically dense, contain multiple tem-
peratures, have intense luminosity, and cause strong multiple scattering. These phenomena
are not often encountered in hydrocarbon combustion systems and largely prevent the use
61
of “off-the-shelf” approaches to the study of combustion in suspensions.
Tailoring standard diagnostic techniques to metalized suspensions is often not straight for-
ward. For example, recent studies show that coherent anti-Stokes Raman scattering (CARS)
for gas temperature measurements in heavily metalized propellant flames may only be fea-
sible with the use of femtosecond and picosecond laser pulses [114]. Using a technique like
planar laser induced florescence (PLIF) to study the combustion of individual burning alu-
minum particles [118] is not realistic for quantitative measurements in suspensions due to
the high particle number density. However, PLIF may still be useful as an imaging technique
in these multi-phase environments [119].
Emission spectroscopy was previously applied to aluminum Bunsen flames to compare
temperatures from gaseous AlO band spectra and condensed-phase continuum emitters, in
an attempt to diagnose the particle combustion regime in the suspension and to compare
temperatures to equilibrium calculations [34]. Line-of-sight integrated emission measure-
ments from the cylindrically symmetric Bunsen flame cones required the use of a reverse
Abel transform to reconstruct the radial profiles of spectral emission intensity to determine
the thermal structure of the flame and the width of the combustion zone. The high opti-
cal thickness of both the condensed phase spectra and the AlO molecular bands, however,
rendered the Abel reconstruction performed in [34] unreliable. The experiment was further
complicated by the presence of strong multiple scattering of light by aluminum and alu-
minum oxide particles, which contaminated local emission spectra with the radiation from
different regions of the flame. The accuracy of temperature measurements using continuum
and molecular AlO spectra was also found to be insufficient to resolve the temperature dif-
ference between diffusively burning particles and the bulk flame temperature in the fuel-rich
flames [34]. Due to these difficulties, the study was not able to draw definite conclusions
about the regime of particle combustion in the suspension.
In the present study, a counterflow dust burner is used to create a flat aluminum dust
flame with a one dimensional flame geometry that eliminates the need for spatial reconstruc-
tion using the Abel transform. Using the flat flame, an emission diagnostic technique that
permits the direct qualitative determination of the regime of aluminum particle combustion
in dense suspensions is demonstrated. The technique is based on the spectroscopic detection
of self-reversal of the atomic aluminum emission lines that occurs due to inhomogeneous
metal vapor temperatures near the micro-diffusion flames that surround the aluminum par-
ticles and in the bulk gas of the suspension. The diagnostic technique is also used to measure
the combustion zone thickness. The length of the region where the lines are self-reversed
serves as a measurement of the reaction zone and largely avoids the difficulties of interpreting
the emission spectra in the presence of multiple scattering.
62
These measurements are compared to those obtained using a complementary diagnos-
tic technique of spatially resolved absorption spectroscopy to detect the aluminum resonant
lines. Using a broadband laser as a spectral source, the effects of multiple scattering are
greatly reduced, and the length of the region where aluminum is detected serves as a mea-
surement of the reaction zone. Combined with a particle image velocimetry (PIV) technique
for estimating the particle residence time in the combustion zone and temperatures measured
from AlO molecular spectra, the suite of diagnostics permits the characteristic combustion
time of a dense aluminum suspension to be estimated.
4.2.2 Experimental Methods

Counterflow Burner and Aluminum/Gas Mixtures
The spectroscopic study is performed on flat aluminum dust flames stabilized using a coun-
terflow dust burner (see Fig. 4.2a). The design of the apparatus is described in [109], where
it was used to measure burning velocities in aluminum clouds using a PIV technique. For
this study, the apparatus is modified to increase the flame planarity. The coaxial flow nozzle
on the opposing jet in [109] is removed in order to eliminate recirculation of the combustion
products on the flame periphery because it interferes with concentration and spectral mea-
surements. The air in the coaxial flow around the bottom nozzle is also replaced with inert
nitrogen to prevent formation of the diffusion flame often enveloping flat flames at fuel-rich
conditions.
Concentration of the particles is monitored by a laser attenuation probe described in
previous work [47]. In the present study, the laser beam probe passes just above the exit of
the bottom nozzle as shown in Fig. 4.2. An attempt was made to keep the concentration of
aluminum in the suspension stable at around 300 g/m3 for all measurements. Considering the
accuracy of the dust concentration measurements, the actual concentration varies between
270 and 330 g/m3 .
The combustion in the aluminum suspension is studied in two gaseous environments: air
and a stoichiometric methane-air mixture. The gas flow rates are monitored using factory
calibrated electronic flow meters and rotameters. The oxygen concentration in aluminum-
methane-air mixtures is monitored by an in-situ oxygen analyzer (Oxigraf) to determine the
equivalence ratio.
Aluminum Powder
Unlike our previous studies of stationary aluminum dust flames that used Ampal 637 alu-
minum (Ampal, Inc.) with nodular shaped particles with a size around 6 μm [48, 109, 33],
63
Figure 4.2: a) Photograph of a flat flame in an aluminum-air suspension, b) schematic of
the counterflow flame burner and side view of the laser sheet and dust concentration laser
probe and c) top-view schematic of the imaging-emission and laser-absorption spectroscopy
setups including simultaneous imaging and concentration measurement.
the present study employs H-2 aluminum powder produced by Valimet Inc. (Stockton, CA)
with spherical particles and a narrow particle size distribution. The particle size distribution
in the H-2 powder from laser diffraction measurements is provided by Valimet and shown in
Fig. 4.3. The arithmetic mean diameter (d10 ) in the H-2 aluminum powder is reported to be
around 4.2 μm.
Emission Imaging Spectroscopy Setup
The general schematic of the imaging spectroscopy setup is shown in Fig. 4.2c. The setup
consists of a 250 mm focal length spherical lens that images the flame onto the entrance slit of
an imaging spectrometer with a focal length of 0.3 m equipped with a CCD array. Due to the
internally recessed focal plane of the instrument, the CCD array detector is coupled to the
spectrometer by a de-magnifying image relay consisting of two imaging lenses (50 mm Nikkor
f /1.4 and 35 mm Nikkor f /2). The detector is a CCD camera with a 4032 (w)×2688 (h)
pixel chip (Starlight Xpress SXVR H35) and 9 μm square pixels. Only a 2006×1336 pixel
segment of the CCD array is used as it affords faster image readout.
The spectrometer is installed with a 3600 gr/mm UV holographic grating. The spec-
trometer entrance slit width is set to 50 μm permitting an overall spectral dispersion of
64
Figure 4.3: Particle size distribution and SEM image of Valimet H-2 Aluminum. The particle
sizing results are provided by the manufacturer.
0.004 nm/pixel covering a spectral bandwidth of about 8 nm with an instrument resolution

of about 0.03 nm. For the measurements of the AlO molecular band spectrum, the holo-
graphic grating was replaced by a 1200 gr/mm ruled grating. This permits a spectral range
of about 40 nm with an overall spectral dispersion of about 0.02 nm/pixel and an instrument
resolution of about 0.16 nm.
Absorption Spectroscopy Setup
In order to perform absorption spectroscopy of the atomic aluminum vapor, a Q-switched

Nd:YAG laser at the 3rd harmonic (Quantel Ultra) is used to pump a modeless dye laser to
produce a beam with broadband spectral output as outlined in previous publications [113, 4].
The dye used is a mixture of Exalite 398 and Exalite 389 (Exciton) at concentrations of
0.36 g/l and 0.17 g/l, respectively, dissolved in reagent grade acetone. The pulse energy used
in the present experiments is measured to be less than 0.5 mJ per pulse with a broadband
spectral output of nearly 8 nm centered near 395 nm. The broadband dye cell output covers
both of the Al I doublet (2 S1/2 → 2 Po1/2,3/2 ) emission lines at 394.4 and 396.15 nm.
The beam is expanded (focal length f = −25 mm), collimated (f = 50 mm), and then
focused into a narrow “sheet” using a cylindrical lens (f = 300 mm). The sheet is passed
through the flame and is focused several inches past the center of the flame in order to reduce
the light collected from the flame emitters. The laser sheet is refocused, using a cylindrical
lens, onto the slit of a customized spectrometer with a 0.45 m focal length installed with an
1200 gr/mm grating. The spectrometer is coupled to a CCD array by a de-magnifying image
relay constructed from aspheric lens (f = 50 mm) and a UV imaging lens (f = 25 mm). The
CCD is an EM-CCD (Rolera EM-C2) camera with a sensor size of 1004×1002 pixels and
65
a pixel size of about 8 μm. This permits a dispersion of 0.02 nm/px and an approximate
instrument resolution of 0.12 nm covering a bandwidth of about 16 nm. The camera trigger
is synchronized to the laser pulse and the integration time of the camera is minimized to
gate the laser pulse signal and minimize collection of the flame emission.
Particle Image Velocimetry (PIV) Setup
A particle image velocimetry technique is used to determine the velocity of the aluminum
particles as they enter the flame preheat zone. The details of the PIV technique and the
specific difficulties for dust flames are discussed in a previous publication [109]. The beam
from a 532 nm wavelength, 5 W continuous-wave laser (Dragon Lasers) is formed into a
narrow light sheet using the same set of optical elements as in the laser absorption setup.
The illuminated particles in the sheet are filmed at a frame rate of approximately 15000 fps
by a Photron SA-5 camera through a macro lens with a 532±2 nm narrow bandpass filter
(Andover).
4.2.3 General Features of the Emission and Absorption Spectra

As practically no intrusive probes can be used for measurements inside flames of particulate
suspensions, only optical methods, and specifically optical spectroscopy, can provide both
qualitative and quantitative information on the flame structure. The present paper focuses
primarily on the qualitative analysis of the spatially resolved aluminum atomic spectra that
permits determination of the particle combustion regime in the flame and the estimation of
the characteristic reaction time of suspension. Analysis of the other flame spectral charac-
teristics is left to future work.
This study also highlights some of the specific difficulties encountered in optical diagnos-
tics of flames in metal fuel suspensions, such as multiple light scattering by the condensed-
phase media and large optical flame thickness. These effects, rarely encountered in gas-phase
combustion, can easily be overlooked when applying similar spectroscopic methods to com-
bustion of condensed-phase fuels.
Aluminum Atomic Line Emission Spectra
A sample emission spectrogram of the two strong atomic Al I lines at 394.4 nm and 396.15 nm
emitted from the aluminum-air flame is shown in Fig. 4.4(left). The spectral intensity profiles
at three flame locations are shown in Fig. 4.4(right). Two weak atomic lines observed near
393 nm are identified on the spectrogram as neutral Fe lines that are present due to iron
impurities in the aluminum powder.
66
Figure 4.4: (Left) Greyscale-inverted spectrogram of the aluminum atomic lines from
aluminum-air flame with a (non-inverted) blown-up region of the self-reversal region in the
inset. (Right) Intensity profiles of the spectrum taken at three different locations: (1)
post-flame zone, (2) reaction zone, (3) pre-heat zone. The comparison of the emission line
thickness to the instrument resolution function is also shown.
The Al atomic lines in the flame reaction zone appear to be strongly broadened. The
observed broadening beyond the instrument resolution considerably exceeds the expected
linewidth from Doppler-, collisional-, etc., broadening mechanisms and can only be attributed
to strong self-absorption. The broadening effect of self-absorption is synonymous with large
optical thickness and indicates high concentrations of the emitting/absorbing aluminum
vapor species. In addition to the line broadening by self-absorption, the Al lines also demon-
strate self-reversal in the flame reaction zone (see zone 2 in Fig. 4.4). The phenomenon
of line self-reversal can occur only in the presence of a temperature gradient of the emit-
ting/absorbing media along the line of sight [120], and is often observed in spectroscopic
studies of plasmas [121] and widely used in astrophysics to infer the structure of stellar
atmospheres [122].
Self-reversal is often observed in multi-temperature media due to the dependence of
the atomic line broadening on temperature. The intensity profile of a resonance line, in
both emission and absorption, from the hot atomic vapor will have a wider half-width than
the colder regions of atomic vapor. The difference in line half-widths as well as emission
intensity at different temperatures causes the observed atomic line on a spectrograph to be
more strongly absorbed, by the colder atoms, in the center of the line than on the wings.
The resulting profile of the emission line on a spectrometer is “caved-in” at the center, as
shown for zone 2 of Fig. 4.4. The observation of line self-reversal, in general, requires not
only temperature gradients in the emitting/absorbing media but will also only be apparent
67
at sufficiently high optical depths with sufficiently high resolution of the spectral instrument.
The conditions for the observation of line self-reversal have several other nuances which are
outlined and discussed in [120].
In stark contrast to the results for the aluminum-air flame shown in Fig. 4.4, the results
for aluminum-methane-air flames, shown in Fig. 4.5, indicate the absence of self-reversal of
the aluminum lines in any region of the flame. The aluminum lines are also much thinner than
in aluminum-air flames, with the line half-width nearly the same as that of the instrument
function.
Figure 4.5: (Left) Greyscale-inverted spectrogram of the aluminum atomic lines from the
aluminum-methane-air flame showing no self-reversal. (Right) Intensity profiles of the spec-
trum taken at three different locations: (1) post-flame zone, (2) reaction zone, (3) pre-heat
zone. The comparison of the emission line thickness to the instrument resolution function is
also shown.
Taking into account the similar flame geometries and light path lengths through the
flames in both mixtures, the observed differences in line-widths suggest a much higher op-
tical thickness of aluminum lines in aluminum-air suspensions compared to the aluminum-
methane-air mixture which, in turn, is indicative of a much larger concentration of aluminum
vapor in aluminum-air flames. The plausible explanation for why line self-reversal is, or is
not, observed in aluminum-air and aluminum-methane-air flames is further discussed in the
Discussion section.
Aluminum Atomic Line Absorption Spectra
A typical image of the absorption spectrogram through the flame is shown in Fig. 4.6 for
both air and methane-air oxidizing mixtures. The spectral profile of the modeless dye laser
68
exhibits a relatively strong noise level, as was observed in previous studies [113]. There are
also variations in intensity along the spatial axis due to the non-uniform beam profile of
the laser. Variable attenuation from particles in the medium and small imperfections in the
spectrometer slit also create striations in the laser intensity along the spatial coordinate.
Despite this non-uniformity, the laser sheet technique can still yield a relatively clear picture
of the line-of-sight spatial profiles of Al absorption lines, permitting a reconstruction of
spatial distribution of aluminum vapor concentration in the flame.
The emission spectrograms in Fig. 4.4 and Fig. 4.5 reveal long zones of aluminum vapor
emission along the spatial coordinate compared to the absorption spectrograms in Fig. 4.6.
The absorption measurements reveal a zone of aluminum vapor less than a couple of millime-
ters in length while the emission measurements indicate that aluminum vapor can apparently
be observed well above and below the flame zone even near the cold, dispersion nozzle. The
observed difference can be explained by the strong multiple scattering of light emitted from
the combustion zone by both the unburned aluminum particles in the preheat zone and nano-
sized oxides in the post-flame zone. In contrast to the emission measurement, the highly
directional laser absorption measurements shown in Fig. 4.6 are not strongly affected by the
scattered light and, thus, provides a more realistic measurement of the location of aluminum
vapor in the flame.
Figure 4.6: Absorption spectrograms of the Al I atomic lines for aluminum-air and aluminum-
methane air flames.
The spatial variations of the laser beam intensity in Fig. 4.6 also reveal an interesting
69
phenomenon showing that light at wavelengths near the resonance wavelength bends upward
or downward along the spatial axis in the aluminum-air flame. This can also be observed,
albeit to a lesser extent, in the aluminum-methane-air spectrogram.
The bending observed here is qualitatively similar to the effect observed in the com-
bined spectroscopic and interferometric technique known as the Hook Method which exploits
anomalous dispersion near the resonance lines to measure concentration of species [123]. In
the present study, the observed light bending is also due to anomalous dispersion but without
the interference fringes seen in the hook method. In these spectrograms, the combustion of
the aluminum particles in the flame produces a strong spatial gradient of aluminum vapor.
At high aluminum vapor concentrations, anomalous dispersion causes pronounced deviations
in the refractive index of the medium at wavelengths near the aluminum resonance lines.
The strong spatial concentration gradients, and corresponding gradients in refractive index,
lead to a pronounced lensing effect where the flame essentially behaves as a gradient index
lens for the laser light frequencies around resonance lines. The lensing effect stretches the
spatial appearance of aluminum lines and makes the interpretation of the spatial intensity
profiles of absorption spectra difficult.
Nevertheless, the degree of lensing that occurs and the width of the absorption line give
direct qualitative indication of the amount of aluminum vapor in the reaction zone. It can be
easily seen that the spectrogram for aluminum-air flames exhibits a stronger lensing effect,
as well as much wider absorption lines, compared to aluminum-methane-air flames. This
confirms the results from emission spectroscopy, where considerably higher concentrations of
aluminum vapor are observed in aluminum-air flames in comparison to aluminum-methane-
air flames.
Molecular Emission Spectra of AlO
The previous spectral study of the Bunsen aluminum dust flame attempted to use the AlO
emission spectrum and the condensed phase continuum spectrum to derive spatial distribu-
tions of temperatures in the flame [34]. The present results, however, indicate that strong
multiple scattering of the light in two-phase metal flames makes spatial interpretation of
the emission spectra unreliable. At best, the emission measurements can only indicate the
maximum temperature in the flame, since emission intensity is strongly weighted to higher
temperatures [124].
The measurement of condensed-phase temperatures, by fitting the continuum spectrum to
a Planck distribution, relies on the choice of an appropriate spectral emissivity function of the
aluminum oxide emitters, which, in general, is a strong function of wavelength, temperature,
and the optical depth [125, 126]. As shown in the literature, a small deviation in emissivity
70
data can lead to large scattering in temperatures, often reaching several hundred degrees
[108]. Due to these difficulties, we have opted to derive gas temperatures only from AlO
molecular spectra in this study. As in previous work [34], the temperature is found by fitting
a simulated spectral intensity distribution in the AlO B−X Δν = −1 band sequence to the
experimentally measured spectral intensity.
The AlO B−X Δν = −1 band sequence emitted by the aluminum-air flame is shown in
Fig. 4.7. Similar to the Al atomic lines, the AlO molecular lines become optically thick in the
flame zone (Fig. 4.7(right), zone 1). Away from the flame, the spectrum is optically thin,
and, thus, fits reasonably well with a simulation based on optically thin approximations
commonly used in literature [107]. In the optically thick zone, a temperature fitting of
the AlO band sequence becomes much less accurate. The effect of optical thickness is to
enhance the weak lines at the expense of the stronger features. This effect typically skews
fits to higher temperature as shown in Fig. 4.7(right) (zone 1). Here the observed spectrum
is compared to optically thin spectra simulated using the ExoMol line list for the AlO B−X
transition simulated in the PGopher software [127, 128]. It appears that even when optical
thickness is accounted for in the model, the relative line intensities become less sensitive to
temperature leading to considerable uncertainty in measurements.
Figure 4.7: (Left) inverted spectrogram of the AlO B−X Δν = −1 band sequence across
the flame. (Right) Spectra from two locations in the flame showing the optically thick and
optically thin regions.
The light emission observed from the cold, pre-flame zone (below zone 3 on Fig. 4.4 and
Fig. 4.5) is due to multiple scattering of light from the reaction zone in flame. Scattered light
71
from the flame, in general, will have traveled a smaller distance through the reaction zone in
comparison to the light from the flame traveling along the optical axis and is, consequently,
an optically thinner version of the spectrum from the flame zone. Due to the strong bias
of resonant emission to high temperatures, measurement using scattered light generally can
only indicate the maximum temperature of AlO in the flame. In the present experiment,
measurements of temperatures at different locations on the spectrogram outside of the com-
bustion zone yield nearly the same temperatures regardless of the location, even in the cold
zone upstream of the flame.
Comparison of Flame Temperatures Derived from AlO Spectra with Equilibrium

Calculations
The resulting temperatures derived from the optically thin AlO spectra are plotted in Fig. 4.8
together with adiabatic flame temperature, and equilibrium concentrations of aluminum
vapor calculated with the NASA CEA code [56].
Equilibrium calculations predict close to 400 K temperature difference between aluminum-
air and aluminum-methane-air flames, while the actual measured temperature difference is
considerably smaller. The average temperature measured in aluminum-air flames is about
3370 K while the average temperature measured in aluminum-methane-air flames is found to
be about 3170 K, with an estimated measurement accuracy of about ±150 K in both cases
[107].
It needs to be noted that equilibrium calculations predict higher concentrations of alu-
minum vapor in aluminum-methane-air mixtures in comparison to aluminum-air mixtures.
The emission and absorption spectroscopy results show the exact opposite behavior. The
possible explanation for the difference between the measurements and equilibrium calcula-
tions is discussed in the Discussion section.
4.2.4 Discussion
Al Emission Self-reversal and the Regime of Combustion in the Flame
In the majority of models in the literature [129], diffusion limited combustion of aluminum
particles is similar to hydrocarbon droplet combustion during which aluminum vapor gen-
erated by the evaporating aluminum droplet reacts with oxygen in a thin gas-phase flame
enveloping the droplet at the distance of several droplet radii. The temperature of such
micro-diffusion flames, lifted from the particle surface, is close to the adiabatic temperature
of the stoichiometric aluminum mixture with oxidizer. It can be several hundred degrees
72
3800 0.08
aluminum-air
aluminum-methane-air
3600
3400 0.06
Adiabatic Temperature (K)

3200
Al (g) mole fraction

3000
0.04
2800
2600
0.02
2400
2200
0.00
100 200 300 400
3
Al particle concentration (g/m )
Figure 4.8: Flame temperatures measured using AlO molecular spectra (• and ◦) in compar-
ison to equilibrium calculations (lines) at different initial aluminum particle concentrations.
The predicted mole fraction of gaseous aluminum vapor in equilibrium is also shown.
higher than the temperature of the evaporating aluminum droplet and the average temper-
ature of the gas between the reacting particles.
The existence of diffusion micro-flames around the particles leads to local micro-gradients
of aluminum vapor concentration and temperature within the suspension. The high reac-
tivity of aluminum vapor with various oxidizers [50, 130], generally prevents the formation
of a premixed aluminum-oxidizer mixture, such that the aluminum vapor can only exist
in the bulk gas of a fuel-rich mixture once the oxidizer has been nearly consumed. For
nearly stoichiometric mixtures, a small amount of aluminum vapor forms due to natural
dissociation process of aluminum sub-oxides at high temperatures. Traversal of the light
emitted by micro-diffusion flames through colder aluminum vapor in the space between the
flame and the particle surface, and in the bulk gas, leads to the self-reversal (“caving”) of
aluminum lines. This self-reversal results from the different half-width of the Al lines at
different temperatures, as illustrated in Fig. 4.9.
The existence of diffusion micro-flames around the particles leads to local micro-gradients
of aluminum vapor concentration and temperature within the suspension. The high reac-
tivity of aluminum vapor with various oxidizers [50, 130], generally prevents the formation
of a premixed aluminum-oxidizer mixture, such that the aluminum vapor can only exist
in the bulk gas of a fuel-rich mixture once the oxidizer has been nearly consumed. For
nearly stoichiometric mixtures, a small amount of aluminum vapor forms due to natural
dissociation process of aluminum sub-oxides at high temperatures. Traversal of the light
emitted by micro-diffusion flames through colder aluminum vapor in the space between the
73
flame and the particle surface, and in the bulk gas, leads to the self-reversal (“caving”) of
aluminum lines. This self-reversal results from the different half-width of the Al lines at
different temperatures, as illustrated in Fig. 4.9.
Figure 4.9: (Top) schematic of the micro-scale emission and absorption of aluminum vapor
from the flat flame that is integrated along the line of sight to the spectrometer. (Bottom)
Schematic of self-reversal. Hot zone emission of linewidth w1 is partially absorbed by cold
zone with linewidth of w2 where w1 > w2 .
Self-reversal of aluminum atomic lines was also observed in our previous work on spec-
troscopy of aluminum Bunsen-type conical flames [34], where the lines were also often caved-
in below the intensity of the continuous spectrum. This lineshape was believed to be caused
by the macro-temperature gradients along the line-of-sight due to the cylindrical flame ge-
ometry, where light emitted from the flame front travels through cooling combustion prod-
ucts containing residual aluminum vapors due to the fuel-rich combustion. The use of the
flat flame in the present work precludes the existence of macro-scale temperature gradients
along the line-of-sight, suggesting that the observed strong self-reversal of aluminum lines in
aluminum-air flames is the result of the micro-scale temperature gradients of the aluminum
vapors inside the lifted micro-diffusion flames that surround burning aluminum droplets. It
is interesting to note that the self-reversal of aluminum and magnesium atomic lines was first
noticed during a spectroscopic study of the combustion of burning magnesium ribbons and
aluminum foils, which was also interpreted as evidence of a diffusion-dominated combustion
regime due to the presence of multiple temperatures [10].
The diffusion regime of combustion causes high concentrations of aluminum vapors in
the space between the aluminum droplet and the micro-diffusion flame, and these vapors
74
are insulated by the flame from the oxidizers within the bulk gas. The observed large
optical depths of Al emission and absorption lines indeed indicate very high aluminum vapor
concentrations in aluminum-air flames and point to a diffusion-limited flame mode. In this
regime of particle combustion, there is no macro-equilibrium state for a given flame cross
section, and the temperature and integrated concentrations of gaseous aluminum in the
flame can exceed the predicted equilibrium values of the bulk mixture. A similar conclusion
was also made by in the study of laminar diffusion flames in aluminum suspensions, where
the high optical depth of the atomic Al lines was also attributed to the existence of micro-
diffusion flames [131].
In contrast to aluminum-air flames, no line self-reversal was observed in aluminum-
methane-air flames. In addition, the atomic Al lines emitted by these flames are generally
optically thin, with the line half-width on the order of the instrument resolution. The ab-
sence of the line self-reversal, and lower concentration of aluminum vapors indicated by the
weak broadening of Al lines, suggest that, unlike in aluminum-air flames, lifted diffusion
micro-flames do not form in aluminum-methane-air suspensions. This observation points
to a heterogeneous, and most likely kinetically-limited, combustion mode of aluminum in
the hydrocarbon combustion products. The disparity between the equilibrium calculations
that predict similar concentrations of aluminum vapor in both mixtures, shown in Fig. 4.8,
and the large difference in the spectroscopically measured concentrations is explained by the
different modes of combustion in each mixture. A shift to kinetically dominated combustion
in methane-air mixtures is consistent with the conclusions of our previous hybrid aluminum-
methane Bunsen flame studies [48, 47]. While a detailed analysis as to why the change in
combustion regime occurs is beyond the scope of the present work, it is not surprising tak-
ing into account the slower rates of heterogeneous aluminum reactions with CO2 , CO, and
H2 O [25], as well as higher rates of molecular heat transfer in the media containing water
molecules and the hydrogen produced by the aluminum-water reaction.
The Width of the Flame Reaction Zone
The thickness of the combustion zone in the flame can be estimated from the spatially re-
solved spectrogram of aluminum vapor lines in both emission and absorption. As mentioned
previously, the strong multiple scattering of the light by unreacted aluminum particles and
nano-sized oxide products makes the determination of the location of the aluminum vapor
from the intensity of the emitted light unreliable. This causes the luminous zone of the flame
to be much larger than the reaction zone thickness. It is possible, however, to use a spatially
resolved measurement of the self-reversed line, when it is present, as a method to estimate
the flame thickness. The presence of self-reversal on the emission spectrogram is not as
75
affected by multiple scattering since, in order for self-reversal to occur, light must traverse
a significant path along the optical axis through the flame zone. Therefore, self-reversal is
practically not present in the scattered light.
A self-reversed line appears as a double-peaked spectral feature with a local minimum
at the central resonance wavelength. The ratio of the intensity at the local minimum at the
line center to the peak intensity on either side of the line is a measure of the relative degree
of self-reversal. When this ratio is unity, self-reversal is weak either due to low optical depth
or small temperature gradients within the medium. When this ratio is close to zero, the self-
reversal phenomenon is strong, indicating temperature gradients and typically high optical
depths. The value of this spectral intensity ratio subtracted from unity measured along the
spatial axis of the spectrogram is a peaked function with a half-width that serves as an
estimate for the flame thickness. The average “self-reversal width” measured for the 396.15
nm Al I line in aluminum-air mixtures over several spectrograms indicates a combustion zone
thickness on the order of 1.7±0.3 mm. The reported error represents the standard deviation
over the measurements.
The intensity of absorption at the central line wavelength was measured in relation to
the unabsorbed and unperturbed baseline laser spectrum intensity, taken far from the flame
zone and away from wavelengths demonstrating the lensing effect. The width of the resulting
spatial distribution of intensity in the atomic line center is used as an estimate of the combus-
tion zone thickness. Using this method, a combustion zone thickness in aluminum-air flames,
averaged from five spectrograms, is estimated to be about 2.3±0.5 mm, i.e. about 25% larger
than the estimate given by the method of the line self-reversal but not significantly different
given the uncertainties in each measurement.
The estimated length of aluminum vapor in aluminum-methane-air flames of about
1.5±0.7 mm using this method may reflect only part of the combustion zone length where
the particles burn in the intermediate diffusion-to-kinetic regime as discussed in recent works
[2, 1]. Aluminum absorption lines could also be an indication of hot aluminum-vapor in the
equilibrated bulk gas predicted by thermodynamics (see Fig. 4.8). This observation would
suggest that the length of aluminum vapor lines reflects cooling of the products and has no
correlation with the particle combustion zone.
Estimation of the Suspension Combustion Time
The characteristic reaction time of the suspension can be estimated by dividing the length
of the flame reaction zone by the average velocity of the burning particles traversing it. The
velocity at which the particles enter the flame is determined from the axial velocity profiles
of the particles measured by the PIV technique, where aluminum particles also play the role
76
of the flow tracers. The particles slow down as they approach the stagnation surface and
their velocity reaches a minimum as they enter the preheat zone of the flame [132]. After this
point, the gas expands due to heating and particles accelerate (see [109]). Due to the very
small velocity slip estimated between the H-2 aluminum particles and the gas, the measured
particle minimum velocity practically coincides with the velocity of gas and, therefore, is
the burning velocity of the flame. Indeed, the measured values of the minimum particle
speed in stoichiometric methane-air flames using low loadings of H-2 aluminum particles
exhibited values very close to the methane-air burning velocities reported in the literature
[133], indicating that the slip between the H-2 particles and the gas is small.
The PIV technique cannot track the reacting particles in the flame as they are rapidly
obscured by nano-sized oxide combustion products. As a result, the particle velocity at the
end of the combustion zone was estimated by multiplying the entrance speed by the gas
expansion coefficient calculated by a ratio of the flame temperature and room temperature.
The average minimum particle speed and, therefore, burning velocity in aluminum-air flames
is measured to be about 48±6 cm/s. The measured burning velocity for H-2 Valimet powder
is considerably higher than the measured burning velocities of 6 μm Ampal-637 powder of
about 35 cm/s [109]. This observation corresponds to the expected, inversely proportional,
dependence of the flame burning velocity on particle size [2]. The particles are assumed to
accelerate constantly to their maximum velocity set by the expansion ratio, which is deter-
mined from the average flame temperatures measured by the AlO spectra (Fig. 4.8). The
average particle velocity is determined to be ≈295 cm/s for flames in aluminum-air suspen-
sions. This gives an estimate for the characteristic reaction time for a nearly stoichiometric
aluminum-air suspension of about 0.6 ms using the flame thickness determined by the line
self-reversal method and about 0.8 ms using the flame thickness profiles found by spectral
absorption.
As mentioned previously, the length of aluminum lines measured in aluminum-methane-
air flames are not directly related to the flame combustion zone and, therefore, some other
markers that can indicate heterogeneous and kinetically-controlled aluminum combustion
will need to be developed in future studies.
It should also be noted that the methods of flame thickness measurement in the aluminum-
air flames are biased toward the combustion of larger particles which would be expected to
produce more aluminum vapor from the micro-diffusion flames and to have comparatively
longer burning times. The zone of the majority of heat release may be much smaller in
comparison to the zone of aluminum vapor and, thus, it is likely that the flame thickness
and combustion time are shorter than currently estimated.
77
4.2.5 Conclusion
Flat flames in aluminum-air and aluminum-methane-air suspensions, stabilized using a coun-
terflow burner, are investigated using imaging emission spectroscopy, laser-absorption spec-
troscopy, and PIV. It is demonstrated that the combination of these optical techniques can
be used to extract the combustion characteristics of particles in dense suspensions where
isolating and observing individual particles is nearly impossible.
The emission diagnostics show that aluminum-air flames exhibit strong self-reversal of
atomic aluminum resonance lines in the combustion zone as well as high optical depths in
both emission and absorption spectra. Both of these observations are attributed to aluminum
particles burning in a diffusion-controlled combustion regime with the formation of lifted
micro-diffusion flames around the particles. In contrast, the aluminum resonance lines in the
aluminum-methane-air flames show no self-reversal and are more optically thin in both emis-
sion and absorption spectra, indicating more heterogeneous, and likely kinetically-controlled,
aluminum combustion. The combination of combustion zone thickness measurements from
spatially resolved emission and absorption spectra, the flame temperatures derived from
AlO molecular spectra, and the particle velocities measured by PIV provide the necessary
information to estimate the combustion time of the particle suspension. The estimated char-
acteristic combustion time of the aluminum-air suspension is found to be in the range of 0.6
to 0.8 ms.
The diagnostic approach outlined in this paper provides a methodology for studying
particle combustion at more realistic particle loadings encountered in practical fuel systems.
These diagnostics are important for understanding burning behavior and the contribution of
particle energy release to the flow field in dense suspensions.
Acknowledgments
Support for this work was provided by the Defense Threat Reduction Agency under contract
HDTRA1-11- 1-0014 and a McGill Engineering Doctoral Award. Additional funding was
provided by the Panda Faculty Scholarship in Sustainable Engineering & Design and a
William Dawson Scholarship.
78
Chapter 5
Conclusions
5.1 Synopsis of Contributions

The goals of scientific research in metal combustion should be focused on understanding the
combustion behavior of metal fuel systems. In most practical scenarios, metal combustion
occurs in dense suspensions of powders. Nevertheless, many experimental and theoretical
studies tend to focus on the combustion of single, isolated particles. It is often assumed that
the combustion characteristics of single particles can be used to anticipate the combustion
behavior at dense fuel loadings. As demonstrated in this thesis, however, the combustion
behavior of individual particles may not be similar to combustion in suspensions. It is for
this reason that both experimental and theoretical approaches to metal combustion need to
examine the effect of particle concentration on the combustion behavior.
In the first part of this thesis, combustion in a suspension of heterogeneously burning
particles is investigated using a simple, transparent theoretical model. It is argued that the
general underlying physical behaviors of metal combustion are driven by the heterogeneous
nature of the particle reaction and the fundamental mechanisms of mass and heat transport.
A simple theoretical treatment is used to examine combustion of single particles, induction
combustion in the suspension, and one-dimensional flame propagation in the suspension.
Several important scientific contributions to the field of metal combustion are presented
in the context of this simple theoretical approach. The fundamental theory of heterogeneous
ignition and extinction is explained using the thermal states analysis presented in Section 1.4.
This simple analytical treatment of heterogeneous particle ignition is illuminating because
it analytically provides an intuition of the effect of parameters like particle size and initial
temperature on the regimes of combustion. The analysis shows how ignition, i.e., the critical-
state transition from the kinetic regime to the diffusion regime, changes the thermal regimes
of the particle combustion. The analysis also demonstrates how particles that are able to
79
ignite and burn in the diffusion regime are resistant to heat loss in the gaseous medium.
For particles that burn in mixed regimes between the kinetic and diffusion limits, the effects
of particle burnout and changes in the regime of combustion are made apparent from the
analysis of potential stable states. This method of explaining heterogeneous ignition theory
provides insight into the features of the intermediate regime of combustion for particles
beyond the simple analysis often included in textbooks [22, 23]. One critical aspect of this
analysis is that it shows a critical particle size, below which the process of ignition degenerates
and the particle must burn in the kinetic regime.
The model of induction combustion in a suspension in Chapter 2 builds on the analysis
of Section 1.4 and provides a physical intuition of the effect of particle concentration on
combustion. The primary result of this model is that the combustion behavior of the sus-
pension is governed by two physical mechanisms. The first mechanism is the particle ignition
phenomenon which can occur even in dilute suspensions. The second mechanism dominates
the reaction behavior in dense suspensions and occurs due to the collective effect of the
particles, where reaction proceeds in an explosion-like manner, after some delay, through
self-heating. The interplay between these two mechanisms leads to a nontrivial dependence
of the reaction time on the particle size and particle concentration.
The extension of the induction combustion model to the one-dimensional flame in Chapter
3 provides insight into the basic behavior of heterogeneous flames. The model is meant
to replace the asymptotic, semi-empirical models of particle flames based on the notion
of ignition temperature and reaction time as external parameters. It is shown that the
particle ignition temperature, particle reaction time, and regime of particle combustion are
characteristic parameters of the flame comparable to the burning velocity eigenvalue. In
this sense, they cannot be determined independently. Similar to the induction combustion
analysis, the thermal structure of flames in suspensions is defined primarily by the interplay
between kinetic and diffusion reaction regimes that yield a non-trivial dependence of the
burning velocity on particle size. This interplay between reaction onset due to self-heating
and the criticality of the ignition process leads to the prediction of a new type of pulsating
instability that is related to subsequent ignition and extinction processes of particles within
the flame.
In light of the understanding from the simple heterogeneous combustion models, it is
clear that combustion characteristics change not only as a function of particle size but also
particle concentration. The second part of the thesis experimentally examines stabilized
flames in aluminum suspensions in order to determine the fundamental combustion param-
eters. It is demonstrated that a combination of diagnostic techniques can be used to extract
the combustion characteristics of the suspension where isolating and observing individual
80
particles is nearly impossible. The techniques developed in this study overcome some of
the specific problems associated with multiple scattering and optically thick environments
encountered in dust flames.
The diagnostic study contributes an application of spatially resolved emission and laser
absorption spectroscopy to determine the presence of the diffusion regime of combustion
in the suspension. This technique is based on the detection of atomic aluminum line self-
reversal which occurs due to the presence of multiple temperatures in the medium due to
the lifted vapor-phase diffusion-flames around the aluminum particles. The spatially resolved
emission and absorption technique also permits a novel measurement of the combustion zone
thickness. Combined with the flame temperatures derived from AlO molecular spectra, and
the particle velocities measured by PIV, the combustion time of the particle suspension is
estimated. These diagnostics are an important first step for understanding burning behavior
and the contribution of particle energy release to the flow field in dense suspensions.
5.2 Direction of Future Research

The simple formulation for the heterogeneously reacting particle suspension can provide
basic physical intuition of the effect of various parameters on the combustion characteristics.
While the focus in this thesis was to examine the effect of particle size and concentration,
a parametric study is also possible. The minimalistic model can be extended to include the
effects encountered in realistic systems. For instance, the effects of expansion cooling, initial
temperature, and pressure may be of significant importance in the combustion behavior of
practical metal fuel systems. A more thorough examination of the flame instability discussed
in Chapter 3 is also required to determine the conditions of manifestation. This type of
model, despite having no apparent analytical solution, is relatively easy to implement in
practice and requires little computational power. This makes it a valuable tool for studying
fundamental physics of combustion in suspensions.
In the literature, there is some tendency for models of heterogeneous combustion to
claim quantitative prediction capability [79, 26]. This type of mentality likely stems from
the impression that the field of heterogeneous/metal combustion is as developed as the fields
of computational fluid dynamics and gaseous combustion physics. It is true that, over the
years, several advanced computational tools have been developed to model flames in gaseous
fuels [134, 135]. The inclusion of experimentally verified chemistry and physics into the flame
model permits an understanding of the flame structure as a function of various operating
conditions. The degree to which these models match experimental conditions is a testament
to the decades of experimental and theoretical research efforts in gaseous fuel combustion
81
that form the basis of these predictive codes.
It is the author’s opinion that quantitatively predictive models of reactive flow in solid fuel
suspensions are not yet within reach. Despite the advanced computational tools available,
the physical complexity of real heterogeneous fuel combustion, compared to gaseous fuels,
requires several theoretical and experimental considerations beyond what has currently been
studied. Fundamental investigations are still required to determine the important physics of
the problem, how the physics affect the flame structure, and how the flame structure varies
as a function of different operating conditions.
The minimalistic model presented in this thesis is a single step in the direction towards
understanding realistic particle fuels. It is based on the fundamental considerations of flame
propagation and the heterogeneous nature of the reaction and heat transfer. However, there
are several neglected physics which may not be negligible for real fuels. For example, phase
changes, the dynamics of heat and mass exchange between the particle and gas, and contribu-
tions of Stefan flow may affect the combustion behavior significantly. It is also of significant
interest to understand the combustion behavior of a polydisperse suspension, or a suspension
of agglomerates, as encountered in realistic systems.
The diagnostic approaches proposed in this thesis also provide direction for future exper-
imental research in flows of reactive suspensions. While more qualitative measurements are
reported, the measurements are less important than the proposed direction and methodology.
Future diagnostic developments for combustion in suspensions must address fundamental is-
sues, such as the presence of multiple temperatures, strongly scattering media, and high
optical depths. This requires a paradigm shift in the way flames in particle suspensions are
studied experimentally compared to gaseous flames.
The laser absorption technique used in this thesis has several possible extensions. As
discussed in Chapter 4, emission measurements tend to represent the highest temperatures
which are more closely related to particle or micro-flame temperatures. There is currently
a lack of a diagnostic which can probe the ambient gas temperature that is also suitable
for dust combustion environments. It may be possible to measure the gas temperature in
absorption by probing a molecular species that should be present mostly in the bulk gas.
This prospect is discussed in Appendix D in the discussion of the laser diagnostic technique.
The “hooking” effect in the laser absorption spectrogram observed at high optical depths
in Chapter 4 can also be extended to a quantitative measurement. This effect, though per-
haps detrimental to the measurements in the paper, can be utilized in a different manner to
determine the concentration gradient of aluminum vapor in the flame [136]. This can possi-
bly provide another method to determine flame thickness that can verify the measurements
in absorption and the self-reversal profiles.
82
The spatially resolved laser absorption technique is able to work around the effect of
scattering to determine the profiles of aluminum vapor in the flame. However, scattering
may still affect the measurement to some degree and may not be negligible at larger scales. A
few possible ways to remove scattering include ballistic imaging techniques [137] and X-ray
radiography [138].
These proposed diagnostics are just a few of several possible solutions that may be able to
overcome the specific problems associated with dust flames. Continued efforts are required
to model the appropriate physics, combined with experimental techniques and diagnostics to
verify the predictions. With continued scientific developments, the field of metal combustion,
and heterogeneous combustion in general, may one day reach the level of understanding of
conventional hydrocarbon fuels.
83
Appendix A
Zero-dimensional Induction
Combustion in a Fuel Suspension:
Governing Equations
This section presents the governing equations for adiabatic, induction combustion (or a zero-
dimensional reactor) of a mono-sized fuel suspension. The equations are written in the frame
of reference of a uniform, stationary suspension and are only functions of time, t. Here, the
theoretical treatment of induction combustion in a heterogeneously burning fuel suspension
is meant to be analogous to the problem of adiabatic thermal explosion in a gaseous fuel
mixture from classic Semenov theory. It is assumed that the gas is heated instantly to
some temperature at t = 0. The kinetic and thermodynamic parameters are assumed to be
pressure/temperature independent for simplicity. These simplifications focus the model on
the behavior of the suspension combustion due to the particle concentration and particle
burnout alone.
A.1 Particle Energy Equation

The model assumes the particles have no radial variations of temperature within the particle
(i.e. treated as a lumped capacitance). This implies a high rate of heat transfer inside the
particle compared to the heating rate at the surface due to convection. The validity of
this condition is determined by examining the Biot number Bi=h /λp where h is the heat
transfer coefficient, is the length scale (r in the case of a spherical particle) and λp is the
conductivity of the particle. For a spherical particle of radius r in a stationary flow, h can
be estimated by h = λ0 /r where λ0 is the conductivity of the gas. The Biot number then
84
takes the form of Bi = λ0 /λp . For most metals and oxidizers, Bi 1, and therefore, this
assumption is appropriate.
Because all particles in the suspension are the same, only the energy equation for a single
particle is required and takes the form
d
cs (mTs ) = Q̇R − Q̇L (A.1)
dt
where Ts is the particle temperature and Q̇R and Q̇L are heat gained due to the surface
reaction and heat lost due to convection to the gas, respectively. The heat capacity cs is
assumed to be constant, but the mass m = 43 πr3 ρs changes during particle burnout.
Defining the heat of reaction per unit mass of fuel as q, the rate of heat released may be
expressed as:
Q̇R = qAγ ω̇eff (A.2)
where γ is the stoichiometric ratio (i.e. the mass of fuel consumed per unit mass of oxidizer
consumed), A is the instantaneous surface area of the particle, and ω̇eff is the particle reaction
rate per unit surface area combining both the kinetic and diffusive terms, as discussed in
Chapter 1 and 2. The reaction rate in this model takes the form of
kβ
ω̇eff = keff C = C (A.3)
k+β
where k is defined by Eq. 2.3 and β is defined by Eq. 2.5, and C is the instantaneous oxidizer
concentration in the bulk gas. This formulation assumes quasi-stationary conditions where
the reaction rate on the particle surface must be equal to the rate at which oxidizer is diffused
to the surface [17]. It is also assumed that the contributions from Stefan flow are negligible.
This assumption is reasonable when the concentration of the oxidizer in the flow is low or
the volume of oxidizer reacting on the particle surface is similar to the volume of products
formed.
The term Q̇L takes the same form as Eq. 2.6. The final form of the solid phase energy
conservation equation is
d
cs (mTs ) = qAγ ω̇eff − hA(Ts − Tg ) (A.4)
dt
where h =Nuλ0 /2r, Nu= 2, and m = 43 πr3 ρs . Differentiating the left hand side of Eq. A.4
using the product rule, and using the expression found in Eq. A.5, Eq. A.4 reduces to the
expression in Eq. 2.8.
85
A.2 Particle Mass
The particle mass consumed in the reaction is removed from the particle and the resulting
oxide is assumed to be gaseous. This assumption simplifies the treatment of the particle
mass equation. In this case, the continuity equation for the particle is
dm
= −γAω̇eff (A.5)
dt
Equation A.5 reduces to Eq. 2.9 shown in Chapter 2. The particle is allowed to shrink
until a size where rmin /r0 = 1 × 10−6 . This condition prevents the solution of the equation
set from breakdown at r = 0.
A.3 Bulk Gas Oxidizer Continuity

It is assumed that the molecular weight of the gaseous oxide products are close to that of
the oxidizer. Hence, there is no net generation or consumption of the total gas mass, since
the oxide replaces the oxidizer species as it is consumed in the reaction. The equation for
the consumption of oxidizer takes the form
dC
= −N Aω̇eff (A.6)
dt
where N is the number density of particles and is related to the particle concentration B by
N N
B= = 4 3 (A.7)
m0 3
πr0 ρs
where r0 is the initial particle size.

The expression in Eq. A.6 algebraically reduces to the expression in Eq. 2.11.
A.4 Gas Thermal Energy

The particles are assumed to have a negligible volume contribution and the volume of gas
can be treated independently from the particles. The validity of this assumption can be
determined by examining the ratio of the volume of particles to the volume of gas which
is given by the expression B/ρs . This volume ratio is typically less than 1% for metals at
stoichiometric concentrations.
In the adiabatic system, the rate of change of the energy of the gas is equal to the rate
of energy transferred by convection to/from the well-mixed solid-phase. Thus, the equation
86
for the gas energy takes the form
dTg
ρg0 cg = N Q̇L = N hA(Ts − Tg ) (A.8)
dt
where ρg0 is the gas density and cg is the specific heat of the gas. Using the relation in
Eq. A.7, Eq. A.8 algebraically reduces to Eq. 2.10.
87
Appendix B
One-dimensional Flame Propagation

in a Fuel Suspension: Governing
Equations
This section presents the governing equations for a flame in a mono-sized particle suspension
propagating in a single spatial coordinate, x , and time, t. The model is analyzed in the paper
of Chapter 3. The model consists of one equation of state and six conservation equations
for 1) the momentum, 2) the overall continuity of the gas, 3) the thermal energy of the gas
phase, 4) the continuity of the oxidizer, 5) the continuity of the solid fuel, and 6) the thermal
energy of the solid phase. Several simplifications and assumptions, outlined in this appendix,
are applied to the equations in order to simplify the solution.
B.1 Equation of State

The gas phase is treated as an ideal gas mixture comprised of an oxidizer and an inert
component. Hence,
pg = ρg RTg (B.1)
where pg is the gas phase pressure; ρg is the gas phase density; Tg is the gas phase tempera-
ture; and R is the specific gas constant.
B.2 Momentum Conservation

The model only considers deflagrations, and as such, the Mach numbers encountered are
small. In addition, viscous forces are assumed to be negligible. In this limit, the momentum
88
equation can be integrated to yield simply [139]:
pg ≈ const. (B.2)
Combining this with the equation of state, it is found that
1
ρg ∝ . (B.3)
Tg
In addition, it is assumed that the particles experience negligible velocity slip with respect to
the gas. Thus the particle number density, N , changes according to the gas density. Hence,
1
N∝ . (B.4)
Tg
B.3 Gas Phase Continuity

It is assumed that the molecular weight of the products are close to that of the oxidizer.
Hence, there is no net generation or consumption of the gas phase, so that the equation of
overall continuity of the gas phase is as follows:
∂ρg ∂
+ (uρg ) = 0 (B.5)
∂t ∂x
where u is the x -component of the flow velocity.
B.4 Density-Weighted Coordinate

The governing equations are simplified by introducing a density-weighted coordinate, x,
defined as follows: x
ρg (x̄ , t)
x(x , t) = dx̄ . (B.6)
0 ρg0
where ρg0 is the gas density at the unburned temperature, Tu . The dimension of x, as with
x , is length. By definition,
∂x ρg

= (B.7)
∂x ρg0
and
∂x ρg ρg
=− u+ u . (B.8)
∂t ρg0 ρg0 x =0
89
where x = 0 identifies the boundary of the semi-infinite domain, which is in contact with
the burnt gas. One can always choose a reference frame that is stationary with respect to

the burnt gas such that ux =0 = 0, and,
∂x ρg
= − u. (B.9)
∂t ρg0
It then follows that the t and x derivatives transform as follows
∂ ρg ∂

→ (B.10)
∂x ρg0 ∂x
∂ ρg ∂ ∂
→− u + . (B.11)
∂t ρg0 ∂x ∂t
With this transformation, proposed initially by Spalding [93], the equation of continuity of
the gas phase is automatically satisfied, and advection effects due to the thermal expansion
of the gas are eliminated.
B.5 Temperature Dependence of Gas and Solid Phase

Properties
In order to completely remove the effects of thermal expansion from the governing equations,
a number of simplifying assumptions regarding the temperature dependence of certain prop-
erties are made. The bulk mass diffusivity and thermal conductivity of the gas are assumed
to have temperature dependences of D ∝ Tg2 and λ ∝ Tg , respectively, while the mass diffu-
sivity and thermal conductivity at the particle-gas interface are assumed to have temperature
dependences of DI ∝ Tg and λI = constant, respectively. In addition, the pre-exponential
factor is assumed to have a temperature dependence of κ ∝ Tg .
As explained in B.2, the gas density and particle number density, N , are inversely propor-
tional to the gas temperature. Hence, the temperature dependence of the following combined
parameters cancel out such that:
λρg = λ0 ρg0 (B.12)

Dρ2g = D0 ρ2g0 (B.13)
κ/DI = κ0 /DI0 (B.14)
N κ = N0 κ 0 (B.15)
κρg = κ0 ρg0 (B.16)
90
where the subscript 0 denotes evaluation at the initial—or unburned—temperature, Tu .
B.6 Gas Phase Thermal Energy

It is assumed that, within the gas phase, Fourier’s law of heat conduction applies, and that
heat transfer due to radiation, inter-diffusion, and the Dufour effect are all negligible. The
gas phase thermal energy balance for a differential control volume can then be stated as:

∂ ∂ ∂ ∂Tg
(cg ρg Tg ) + (ucg ρg Tg ) = λ + q˙I . (B.17)
∂t ∂x ∂x ∂x
where cg is the specific heat capacity of the gas. Because the gas and solid phases are,
in general, not in thermal equilibrium, heat transfer occurs between the phases. This is
accounted for by q˙I , which is the volumetric heat transfer rate between the phases. Further
assuming that the gas phase is calorically perfect, this equation, after expanding the first
two derivative terms, becomes:

∂ρg ∂ρg ∂u ∂Tg ∂Tg ∂ ∂Tg
cg T g + cg Tg u + cg Tg ρg + cg ρg + c g ρg u = λ + q˙I (B.18)
∂t ∂x ∂x ∂t ∂x ∂x ∂x
which may be re-arranged as

∂ρg ∂ρg ∂u ∂Tg ∂Tg ∂ ∂Tg
cg T g + u + ρg + c g ρ g + c g ρg u = λ + q˙I . (B.19)
∂t ∂x ∂x ∂t ∂x ∂x ∂x
The expression enclosed by the square brackets is identically zero by Eq. B.5, and, thus, the
energy balance simplifies to:

∂Tg ∂Tg ∂ ∂Tg
cg ρg + c g ρg u = λ + q˙I . (B.20)
∂t ∂x ∂x ∂x
Applying the transformation to the density-weighted coordinate space, x, Eq. B.20 becomes:

∂Tg ρg ∂ ρg ∂Tg
c g ρg = λ + q˙I . (B.21)
∂t ρg0 ∂x ρg0 ∂x
Invoking Eq. B.12, this simplifies to:
∂Tg λ0 ∂ 2 T g q˙I
cg = + . (B.22)
∂t ρg0 ∂x2 ρg
91
Defining α0 = λ0 /(cg ρg0 ),
∂Tg ∂ 2 Tg q˙I
= α0 2 + . (B.23)
∂t ∂x ρg c g
The interphase heat transfer term, q˙I , is simply the heat transfer by convection between
a single particle and the surrounding gas multiplied by the number density of particles:
q˙I = N hA(Ts − Tg ). (B.24)
Here, h is the convective heat transfer coefficient between the particle and gas, and A is
the surface area of the particle. Since the particles are spherical, A = 4πr2 , where r is
the instantaneous particle radius. Denoting the mass per particle as m and the particle
concentration as B, the number density can be re-written as follows:
B
N= . (B.25)
m
By dimensional analysis, h may be given by:
hd
Nu = (B.26)
λI
provided effects due to Stefan flow are negligible [17]. Here, the particle diameter, d, has
been taken as the characteristic length. For a spherical particle that is stationary relative to
the surrounding gas, it can be shown that Nu = 2. Thus,
λI
h= . (B.27)
r
Invoking the invariance of N/ρg , the effect of thermal expansion may be eliminated from the
interphase heat transfer term:
∂Tg ∂ 2 Tg N0
= α0 2 + 2πλI r(Ts − Tg ). (B.28)
∂t ∂x cg ρg0
In accordance with Eq. B.25,

B0
N0 = (B.29)
m0
where B0 is the initial mass concentration of the solid phase; and m0 is the initial mass per
particle. Assuming that, initially, all particles have the same radius, r0 ,
3B0
N0 = (B.30)
4πρs r03
92
where ρs is the density of the solid, here assumed constant. Thus, the final reduced form of
the gas-phase thermal energy equation is:
∂Tg ∂ 2 Tg 3B0 λI
= α0 2 + r(Ts − Tg ). (B.31)
∂t ∂x 2ρs cg ρg0 r03
B.7 Oxidizer Continuity

The oxidizer is treated as a gas that diffuses through the bulk gas phase according to Fick’s
law. Hence,
∂ ∂ ∂Y
(ρg Y ) + ρg uY − ρg D = −ω̇. (B.32)
∂t ∂x ∂x
where Y is the normalized mass fraction of oxidizer, and ω̇ is the rate of depletion of oxidizer
per unit volume normalized with Cu /ρg0 . The oxidizer continuity is formulated in terms of Y
because it is independent of gas expansion, unlike the oxidizer concentration, C. Y is related
to C by Y = ρg0 C/ρg Cu , where Cu is the unburned oxidizer concentration. Expanding the
derivatives,

∂ρg ∂ ∂Y ∂Y ∂ ∂Y
Y + Y (ρg u) + ρg + ρg u − ρg D = −ω̇ (B.33)
∂t ∂x ∂t ∂x ∂x ∂x
and rearranging,

∂ρg ∂ ∂Y ∂Y ∂ ∂Y
Y + (ρg u) + ρg + ρg u − ρg D = −ω̇. (B.34)
∂t ∂x ∂t ∂x ∂x ∂x
The expression in the square brackets vanishes by Eq. B.5. Hence, the equation for oxidizer
continuity simplifies to:

∂Y ∂Y ∂ ∂Y
ρg + ρg u = ρg D − ω̇. (B.35)
∂t ∂x ∂x ∂x
Introducing the density-weighted coordinate, x,

∂Y ρg ∂ ρ2g ∂Y
ρg = D − ω̇. (B.36)
∂t ρg0 ∂x ρg0 ∂x
Invoking Eq. B.13, and rearranging,
∂Y ∂ 2Y ω̇
= D0 2 − . (B.37)
∂t ∂x ρg
93
The rate of depletion of oxidizer per unit volume, ω̇, is related to the rate of depletion of
oxidizer per particle, ω̇p , by:
ρg0
ω̇ = N ω̇p . (B.38)
Cu
where ω̇p = Akeff Cu where Cu is the concentration of oxidizer in the unburned gas, which,
expressed in terms of Y , is:
ρg
ω̇p = Akeff Cu Y (B.39)
ρg0
Therefore,
ω̇
= N Akeff Y. (B.40)
ρg
The effective rate of reaction per unit particle surface area, keff can be written as
−1
κr Ea
keff =κ + exp . (B.41)
DI Ru T s
Finally, invoking Eqs. B.14 and B.15, and noting that A = 4πr2 , the equation of oxidizer
conservation reduces to:
−1
∂Y ∂ 2Y 2 κ0 r Ea
= D0 2 − 4πN0 κ0 r + exp Y. (B.42)
∂t ∂x DI0 Ru T s
B.8 Solid Phase Continuity

A fundamental assumption of the model is that the particle, or fuel, concentration is suffi-
ciently high so that the solid phase behaves as a continuum in the classical sense. However,
no bulk diffusive transport takes place within the solid phase. Thus, the species balance for
the solid phase takes the following form:
∂B ∂
+ (uB) = −ω̇f . (B.43)
∂t ∂x
where ω̇f is the rate of depletion of fuel per unit volume. It is related to the rate of depletion
of oxidizer per particle, ω̇p , by:
ω̇f = N γ ω̇p (B.44)
where γ is the mass-based stoichiometric ratio—that is, the mass of fuel consumed per unit
mass of oxidizer consumed. Invoking Eq. B.25,
∂ ∂
(N m) + (uN m) = −N γ ω̇p . (B.45)
∂t ∂x
94
Expanding the derivatives,
∂N ∂N ∂u ∂m ∂m
m + mu + mN + N + N u = −N γ ω̇p . (B.46)
∂t ∂x ∂x ∂t ∂x
Invoking the invariance of N/ρg ,
N0 ∂ρg N0 ∂ρg N0 ∂u ∂m ∂m
m + m u + m ρg + N + N u = −N γ ω̇p (B.47)
ρg0 ∂t ρg0 ∂x ρg0 ∂x ∂t ∂x
Rearranging,

N0 ∂ρg ∂ρg ∂u ∂m ∂m
m + u + ρg + N + N u = −N γ ω̇p . (B.48)
ρg0 ∂t ∂x ∂x ∂t ∂x
The expression enclosed by the square brackets is identically zero by Eq. B.5, and the solid
phase continuity equation simplifies to:
∂m ∂m
N + N u = −N γ ω̇p . (B.49)
∂t ∂x
Dividing through by N ,
∂m ∂m
+ u = −γ ω̇p . (B.50)
∂t ∂x
∂m
= −γ ω̇p (B.51)
∂t
or −1
∂m ρg κ 0 r Ea
= −γ4πr Cu κ
2
+ exp Y. (B.52)
∂t ρg0 DI0 Ru T s
As the particles are spherical, m = 43 πr3 ρs . Hence,
∂m ∂r
= 4πr2 ρs . (B.53)
∂t ∂t
Finally, combining this equation with Eq. B.16, the equation of solid phase continuity
simplifies to: −1
∂r γCu κ0 κ0 r Ea
=− + exp Y. (B.54)
∂t ρs DI0 Ru T s
95
B.9 Solid Phase Thermal Energy
Starting from the assumption that the solid phase is a continuum with no bulk diffusive
transport, the thermal energy balance of solid phase for a differential control volume is:
∂ ∂
(cs BTs ) + (ucs BTs ) = q˙r − q˙I (B.55)
∂t ∂x
where q˙I is the same interphase heat transfer term as in the gas phase energy equation; and
q˙r is the heat released by the reaction per unit volume. Invoking Eq. B.25,
∂ ∂
(cs N mTs ) + (ucs N mTs ) = q˙r − q˙I . (B.56)
∂t ∂x
Assuming that the solid phase heat capacity is constant and expanding the derivatives,
∂N ∂ ∂ ∂
cs mTs + cs mTs (uN ) + cs N (mTs ) + cs uN (mTs ) = q˙r − q˙I . (B.57)
∂t ∂x ∂t ∂x
Invoking the invariance of N/ρg and rearranging,

N0 ∂ρg ∂ ∂ ∂
cs mTs + (ρg u) + cs N (mTs ) + cs uN (mTs ) = q˙r − q˙I . (B.58)
ρg0 ∂t ∂x ∂t ∂x
The expression in the square brackets vanishes by Eq. B.5, and thus,
∂ ∂
cs N (mTs ) + cs uN (mTs ) = q˙r − q˙I . (B.59)
∂t ∂x
Defining the heat of reaction per unit mass of fuel as q, the rate of heat released per unit
volume may be expressed as:
q˙r = N qγ ω˙p . (B.60)
Combining equations B.24, B.59, and B.60,
∂ ∂
cs N (mTs ) + cs uN (mTs ) = N qγ ω˙p − N hA(Ts − Tg ). (B.61)
∂t ∂x
As with the derivation for the solid phase continuity equation, the number density turns out
to be a common factor for all the terms of the solid phase energy equation. Therefore,
∂ ∂
cs (mTs ) + cs u (mTs ) = qγ ω˙p − hA(Ts − Tg ). (B.62)
∂t ∂x
96
∂
cs (mTs ) = qγ ω˙p − hA(Ts − Tg ). (B.63)
∂t
Expanding the derivative,
∂Ts ∂m
cs m + cs T s = qγ ω˙p − hA(Ts − Tg ). (B.64)
∂t ∂t
Using Eq. B.51,

∂Ts
cs m = γ ω̇p (q + cs Ts ) − hA(Ts − Tg ). (B.65)
∂t

−1
Recalling that ω̇p = Aκρg ρCg0u κr
DI
+ exp Ea
Ru T s
Y , m = 43 πρs r3 , A = 4πr2 , and h = λrI ,
−1
1 ∂Ts Cu κr Ea λI
cs ρs r = γρg κ + exp (q + cs Ts ) − (Ts − Tg ). (B.66)
3 ∂t ρg0 DI Ru T s r
Finally, invoking Eq. B.16, and rearranging, the equation of solid phase thermal energy
conservation simplifies to:
−1
∂Ts 3γ κ0 r Ea q Y λI T s − T g
= κ0 Cu + exp + Ts −3 . (B.67)
∂t ρs DI0 Ru T s cs r c s ρs r 2
97
Appendix C
Validation of Numerical Methods
The governing equations of the models in Chapters 2 and 3 are integrated using MATLAB.
The set of governing equations in Chapter 2 is integrated using MATLAB’s native ordinary
differential equation (ODE) solvers. The flame model is integrated using the method of lines,
which is a general technique for the solution of time-dependent partial differential equations
[99]. In this method, the spatial derivatives are replaced with algebraic approximations, and
this results in a system of initial value ordinary differential equations. The resulting system
can then be integrated using the native ODE solvers in MATLAB.
The governing equations considered here were integrated using a second-order finite dif-
ference formulation together with a a multi-step, variable-order, implicit time integration
method based on the code provided in [99]. In order to validate this method, the solutions
are compared to benchmark studies in the literature that use a similar time dependent flame
models.
C.1 Code Verification

To verify the code, a classical flame propagation problem with a well known solution was
fed into it. The problem is that of one-dimensional, laminar flame propagation through a
homogeneous gaseous mixture characterized by the concentration of a single deficient species
with no heat losses. The solution produced by the current numerical method is compared
to that found by Zeldovich and Barenblatt [94].
The governing equations of this model are as follows:
∂n ∂ 2 n
− 2 = −zn exp (−Ea /Ru T ) (C.1)
∂t ∂x
∂T α ∂ 2T Q
− 2
= zn exp (−Ea /Ru T ) (C.2)
∂t D ∂x c
98
2500
t=8
t = 10
2000 t = 12
t = 14
1500
T [◦ C]
1000
500
0
5 10 15 20 25
x
(a) Output of code used for thesis. (b) Solution presented in [94].
Figure C.1: Temperature profiles of the simplified Zeldovich and Barenblatt model.
where n is the concentration of the deficient species, normalized with the initial concen-
tration; T is the temperature; α is the thermal diffusivity of the mixture; D is the mass
√
diffusivity of the deficient species; x = y/ D, where y is the coordinate normal to the
flame front; z is the pre-exponential factor; Ea is the activation energy; Ru is the universal
gas constant; Q is the heat of reaction; and c is the specific heat of the mixture. Like the
governing equations presented in this thesis, this is a system of so-called reaction-diffusion
equations. Thus this problem is mathematically similar and serves as a useful benchmark
for the numerical method used.
The evolution of the solution is observed over a semi-infinite domain (0 ≤ x < ∞) with
the following auxiliary conditions:
for x > 0, t = 0, n = 1 and T = T0

for x = 0, t ≥ 0, n = 0 and T = T0 + Q/c.
In accordance with [94], the equations are numerically integrated with the following values
for the mixture properties: T0 = 300 ◦ C; Q/c = 2 × 103 ◦ C; Ea /Ru = 1.5 × 104 K; z = 104
s−1 ; and α/D = 2. The results are shown in Figs. C.1 and C.2. The corresponding flame
profiles presented in [94] are juxtaposed for comparison. It is readily seen that the code
satisfactorily reproduces the solution presented by Zeldovich and Barenblatt.
99
1
0.9
t=8
t = 10
0.8 t = 12
t = 14
0.7
0.6
n [-]
0.5
0.4
0.3
0.2
0.1
0
5 10 15 20 25
x
(a) Output of code used for thesis. (b) Solution presented in [94].
Figure C.2: Relative concentration profiles of the simplified Zeldovich and Barenblatt model.
100
0.09 0.15
Solid phase temperature Solid phase temperature
0.08
Gas phase temperature Gas phase temperature
0.07
Oxidizer concentration Oxidizer concentration
0.06 0.1
Relative difference
Relative difference
0.05
0.04
0.03 0.05
0.02
0.01
0 0
0 0.01 0.02 0.03 0.04 0.05 0.06 0 0.005 0.01 0.015 0.02 0.025 0.03
x [m] x [m]
(a) Fuel-lean case. (b) Fuel-rich case.
Figure C.3: Relative difference between solutions computed at different spatial step-sizes.
C.2 Demonstration of Grid-Independence

For the grid-convergence study, the effect of the spatial step-size on the flame profile and
burning velocity was found for representative fuel-lean (φ = 0.5) and fuel-rich (φ = 1.5)
cases. The spatial step-size used for all solutions was 10−4 m. The time integration method
used was adaptive and, thus, did not allow parametric variation of the temporal step-size.
The relative difference between solutions for step-sizes of 10−4 m and 5×10−5 m is plotted
in Fig. C.3 for both the lean and rich cases. The plots show that halving the spatial step-size
yields a relative difference of less than 9 % in the lean case and less than 15 % in the rich
case. This result is satisfactory because only qualitative results are of interest in this study.
Table C.1 summarizes the results for the burning velocity. The relative difference in both
cases is less than 0.5 %. Thus, in terms of burning velocity, the step-size used is more than
satisfactory.
φ Spatial step-size ub Relative difference

0.5 10−4 m 3.7916 cm/s
0.5 5 × 10−4 m 3.7921 cm/s 0.014 %
1.5 10−4 m 4.65 cm/s
1.5 5 × 10−4 m 4.67 cm/s 0.4 %
Table C.1: Effect of spatial step-size on calculated burning velocity.
101
Appendix D
Laser Absorption Diagnostic
This section outlines the broadband absorption technique utilized in Chapter 4 of the thesis.
While only broadband visible light was required for the measurements in that paper, an
extension of the diagnostic technique to produce broadband ultraviolet (UV) light is required
for future work as discussed in the Direction of Future Research section of the conclusion.
The original work in the following section was published by the present author in [4] and
outlines both the construction and characteristics of the broadband laser system developed
for the diagnostics used in Chapter 4 and a novel system to extend the technique to the UV.
Ultraviolet (UV) Absorption Spectroscopy in Optically

Dense Fireballs Using Broadband Second Harmonic
Generation of a Pulsed Modeless Dye Laser, Applied
Spectroscopy [4]
D.1 Introduction
Combustion measurements within the fireballs generated by explosives and other energetic
materials have several diagnostic hurdles owing to the multiphase dynamics, the high tem-
peratures, short time scales, and high optical depths of the combustion event. Explosives
are often enhanced by the addition of solid phase fuels like metal particles which create
high temperature environments of particulate and gas phases within the fireball. The rel-
evant diagnostic time scales within explosives systems are typically on the order of several
microseconds necessitating diagnostics which can be performed with this time resolution.
One of the key diagnostic capabilities is the characterization of temperatures within
102
the fireball and the ability to monitor chemical species that evolve during the combustion.
Optical techniques are more robust within the high temperature, multiphase environments
where mechanical probes methods are difficult to implement due to temperature limitations
and slow response time. In fireballs containing reactive particles, it is possible that the
temperatures of the solid phase and gas phase may be different due to kinetically limited
and diffusion limited particle reactions. Spectroscopic diagnostics may be able to analyze the
possible separation of particle and gas temperatures by examining the gas phase components
of the flame thereby demonstrating the regimes of particle combustion.
The high luminosities of fireballs of energetic materials lend to the prevalence of emission
based diagnostics. The condensed phase temperature is often determined by using optical
pyrometry or by fitting the continuum from the condensed phase to a Planck distribution,
and this technique has been used as a temperature diagnostic in energetic materials in many
studies [108, 34]. There is also precedent for using metal salt tracers to introduce vaporized
atomic species into flames to determine electronic excitation temperatures which can be
extended to diagnostics of explosives [111]. Lewis et al. have shown that by using atomic
tracer elements seeded into explosives that a gas phase temperature can be measured from the
relative intensities of the resulting atomic lines in the emission spectrum of the fireball [140].
Emission from the diatomic species present in the combustion of energetic materials (e.g.
AlO) can also be fit to theoretical transitions to determine temperatures and concentrations
[124].
Emission spectroscopy measurements probe upper (excited) electronic states, and, in
many cases, especially when the upper state is strongly populated by exothermic reactions,
the population distribution in the upper state is not representative of the more abundant
ground state molecules [111]. In general, a temperature derived from an emission measure-
ment should be checked for rotational/vibrational equilibrium or by comparing to an ab-
sorption measurement. In the particular case of optically thick fireballs, it has been shown
that the detonation products of gram scale and higher experiments that the attenuation
lengths are on the order of a few centimeters implying that the temperatures derived from
the emission measurements may be only representative of the outer edge of the fireball [141].
The preferred measurement, in these cases, would be to probe the ground state in ab-
sorption which provides quantifiable information on species concentration and temperature,
though the measurements are path averaged. However, absorption measurements in fireballs
are difficult owing to the intense luminosity of the fireball and the high intensity and co-
herence required from a broadband source to penetrate the fireball in order to perform the
measurement.
The limitations of emission spectroscopy have prompted several experiments to probe
103
of the inside of explosive fireballs. Lewis et al. found no significant difference in apparent
temperatures measured by emission spectroscopy of the interior and the outer edge of an
RDX explosive cloud revealing the possibility of temperature uniformity throughout the
fireball at certain times during the combustion [142]. Carney et al. demonstrated the use
of a booster optical amplifier to measure the absorption of water vapor in the near-infrared
(NIR) and obtained a line-of-sight temperature measurement in a high explosive [143].
In previous work, Glumac was able to show proof-of-concept experiments using a modeless
dye laser as a spectral source for absorption spectroscopy measurements in optically thick
fireballs [113]. Modeless dye lasers offer a widely tunable, relatively high bandwidth (≈1-
10 nm) coherent source and have moderate divergence and high power. In optically thick
regions, there is difficulty in passing sufficient signal to a detector from other broadband
sources due to the scattering of the light. The dye laser offers an intense, directional beam
allowing the strong rejection of the fireball luminosity and sufficient signal at the detector
even at 98% attenuation.
Dye beam wavelengths are limited to above the near-ultraviolet (UV) due to the nature
of the available dyes. A great number of important diatomic and atomic transitions occur
below these wavelengths necessitating broadband UV spectral sources that can access the
transitions. The advantage of dye lasers is that almost any visible wavelength can be reached
by the appropriate selection of dye. By utilizing broadband second harmonic generation
(SHG) of the dye laser beam using a nonlinear crystal, the wavelength range can be extended
into the deep UV. Absorption measurements of several more atomic and diatomic species
become possible for diagnostics ranging from the transitions found in hydrocarbon flames
(e.g. OH, CN, NO) to those associated with the combustion of energetic materials (e.g. Ni,
Fe, BO, AlCl). In this work, energetic systems are examined, and a stationary gas of NO is
used to calibrate the diagnostic. Time resolution of the diagnostic is demonstrated by probing
Al atomic line absorptions in exploding bridge wires (EBW). Finally, the diagnostic is used
to obtain spectra from diatomic species of metal-fluorocarbon reactions (MgF and AlF) in
dispersed flash powders which are of recent interest to enhance combustion performance in
energetic materials [144, 145]. We fit the spectra to a model in order to confirm the species
and yield path averaged temperatures.
104
D.2 Diagnostic Setup
D.2.1 Dye Laser Configuration
The schematic of the entire setup is shown in Fig. D.1. A frequency tripled, compact
neodymium-doped yttrium aluminum garnet (Nd:YAG) laser (Quantel) at 355 nm with 5 ns
pulses at 20 Hz is used as the pump for the dye laser. The maximum power available from
the laser is approximately 60 mJ per pulse. The built in flash-lamp/Q-switch delay on the
laser is used to adjust the power to pump the dye with 2-4 mJ per pulse which produces
sufficient dye laser energy for the experimental setup.
The custom dye laser configuration is demonstrated in previous work by Glumac to
produce a modeless beam with about 5% efficiency [113]. The 355 nm Nd:YAG beam is
passed through a cylindrical lens to produce a horizontally spread beam and then focused
down in the vertical direction by a second cylindrical lens onto a quartz dye cuvette 40
mm in length. The cuvette is tilted at a 20 degree angle to minimize etaloning effects. A
full reflecting mirror is placed at one end of the laser cavity approximately 10 cm from the
cuvette, though for a modeless laser this distance may vary without much consequence. The
laser has no output coupler, and the front end is empty aside from an iris to prevent stray
light and an achromatic collimating lens with a focal length of 175 mm to counteract the
moderate divergence of the beam.
In cases where higher power and better beam shape is desired, Glumac shows that a
partially reflecting mirror may be used at the front end of the cavity as long as the cavity is
designed with very low finesse [113]. Modeless dye lasers designed for broadband coherent
anti-Stokes Raman spectroscopy (CARS) utilize Bethune dye cells and pass the initial dye
beam through an amplifier to change the beam shape and divergence [146]. The power of
the pump beam may be increased by using a flowing dye cell since stationary dyes tend to
degrade quickly under high pump powers. The advantage of the modeless configuration is
the broadband character which is found to have a much smoother spectral distribution of
intensity [113]. The power of the dye beam produced by an empty cavity front end and
a stationary dye cell is found to be sufficient for the systems examined in this work. The
Coumarin 450, 460, and 540 (Exciton) dye laser pulse energies are measured to be 0.1 0.2
mJ per pulse for a pump beam energy of 2-4 mJ.
D.2.2 Second Harmonic Generation

The wavelengths produced by dye lasers are limited to wavelengths above 330 nm for Nd:YAG
pumped dyes. To extend deeper into UV spectrum to access a much greater number of
105
Figure D.1: Schematic of the entire setup for the absorption measurement. A pulsed Nd:YAG
(355 nm) pumps a dye cell in a grazing incidence configuration. The modeless dye beam is
then focused onto a BBO-I crystal, and the resulting UV beam is collimated and separated
from fundamental and passed through the combustion chamber.
species, the beam can be passed through a non-linear crystal for SHG. Critical phase match-
ing to the non-linear crystal allows for efficient SHG of a monochromatic beam by simply
rotating the crystal to the optimum angle determined by the crystal cut. Wavelengths in a
broadband beam which are outside the phase-matching bandwidth, determined by the thick-
ness of the crystal and the diameter of the beam incident on the crystal, will typically have
very low SHG efficiencies. The beta barium borate (BBO) type I, 7mm crystal with a cut
angle of 52 degrees (Radiant Dyes) used in this study theoretically has less than 0.1 nm of
phase matching bandwidth at the desired wavelengths for NO absorption. Shorter crystals
will theoretically provide higher spectral bandwidth at the expense of conversion efficiency.
The broadband nature of ultra-short laser pulses has led to the development of several
techniques for increasing the phase matching bandwidth in crystals using chromatic disper-
sion of the fundamental beam [147, 148, 149, 150]. Due to the relatively low power of the dye
beam in this experimental setup, the use of any method of increasing the bandwidth which
requires a significant loss in power is generally not desired. Dispersive elements can cause
significant losses due to reflections of the required polarization for SHG in the nonlinear
106
crystal at the surfaces of the dispersive element.
Unlike the large bandwidth of ultra-short pulses (typically around 100 nm), the band-
width of the second harmonic pulse in the present experiments is only few nanometers in
wavelength since the bandwidth of the fundamental dye beam has only around 10 nm of
bandwidth at maximum. Previous studies indicate that by simply creating a strong focusing
condition of the fundamental beam into the crystal, a significant bandwidth in the frequency
doubled beam can be achieved at a fraction of the signal loss compared to dispersive methods
[151, 152]. To demonstrate this in the current experiment, the spectral bandwidth of the
SHG of a Coumarin 540 dye beam under different focusing conditions is plotted in Fig. D.2.
The crystal is first rotated to the central phase matching angle of the dye beam, and the
lenses are varied without changing the crystal angle. The tight focus decreases the effective
interaction length thereby increasing the spectral bandwidth.
Figure D.2: Spectral bandwidth of the second harmonic for different focal lengths of the lens
used to focus the fundamental beam onto the nonlinear crystal.
Without spectral dispersion, the fundamental dye beam is focused onto the crystal with
a 50 mm focal length achromatic lens. The crystal is then rotated until the second harmonic
appears and adjusted to the desired spectral position. The combined fundamental and
second harmonic beams are then re-collimated using a UV fused silica (UVFS) 25 mm focal
length plano-concave lens. It is found in previous studies under strong focusing condition,
the UV beam emerges nearly collimated in the horizontal direction [148]. The re-collimating
lens allows the collimation of the beam in the vertical direction but causes divergence in
the horizontal direction necessitating cylindrical correction optics to shape the beam in
the horizontal direction (see Fig. D.1). The combined fundamental and second harmonic
emerging from the crystal are first passed through a UVFS dispersion prism with an apex
107
angle of 60 degrees to separate the fundamental from the second harmonic and then shaped
with a UVFS cylindrical inverse telescope consisting of a 75 mm and 25 mm focal length
UVFS plano-convex cylindrical lens. The resulting beam is approximately 5 mm in diameter
as seen on a UV viewing card. The spectral profiles of an example dye beam (Courmarin 450
at 920 μmol/L concentration in ethanol) and the second harmonic are shown in Fig. D.3.
The pulse energy from the second harmonic of the Coumarin 450, 460, and 540 dye beam is
determined to be 1-5 μJ per pulse.
Figure D.3: (top) Spectral bandwidth of modeless dye beam with Coumarin 450 as the dye
averaged over several pulses. (below) The spectral profile of the second harmonic.
After passing through the combustion chamber, the UV beam is focused onto the 50
μm slit of a customized 1260 mm focal length Czerny-Turner SPEX 1250 spectrometer with
deviation angle of 11 degrees and a 3600 grooves/mm UV holographic grating (Optomet-
rics). The detector used for NO absorption is a GARRY 3000 which is a CCD line array of
3000 pixels each 7×200 μm. The approximate resolution achieved by this spectrometer is
approximately 0.01 nm full-width-half-maximum (FWHM) determined by the FWHM of an
elemental calibration line over a range of about 4 nm on the detector. The detector used in
flash powder tests is a Hamamatsu C7041 CCD array with 1044×255 pixels each 25×25 μm
with an approximate resolution of 0.013 nm FWHM over about a 4 nm range. The spectrum
108
is binned over the entire chip. Even at low dye beam powers, the generated SHG UV beam
is sufficient to saturate the spectrometer detectors with a single pulse.
D.3 Results and Discussion

D.3.1 Stationary NO Gas
The diagnostic is first calibrated with the NO A←X (0,0) transition in the 226 nm to 227
nm range, the fundamental dye beam is created by pumping a solution of Coumarin 460
(Exciton) in ethanol at 0.005 mol/L. The resulting spectral bandwidth of the UV beam
generated from the strong focusing of the dye beam onto the crystal is approximately 1.5 nm
at FWHM. The spectral position on the detector is calibrated using a Ni-Ne hollow cathode
lamp (Azzota) and checked against the position of the strong NO transitions. A test system
of NO is generated in a sealed chamber with fused silica windows using a continuous electric
arc discharge in air. The electrodes are mounted within a 5 cm wide sealed chamber with
quartz windows. The amount of NO produced in the chamber is correlated to the duration
of the arc.
The laser is set to pulse continuously (20 Hz), and integration time is set to one second
on the detector in order to obtain an averaged spectrum over the 20 pulses. A reference
spectrum is first taken in the empty chamber. An optically thin spectrum of NO is obtained
by producing an arc for five seconds or until only a slight absorption feature is qualitatively
observed in the raw spectrum. The resulting spectrum and comparison to the LIFBASE
simulation[153] is shown in Fig. D.4. Good agreement is shown between the simulation and
resulting averaged spectrum from several laser shots in the optically thin limit.
A single pulse measurement is then taken in a high concentration of NO to simulate
conditions in an optically dense fireball medium. The detector is set to a two second inte-
gration time and a reference pulse averaged over ten pulses taken in the empty chamber. An
arc is then produced in the chamber for 30 seconds until the absorption signal is noticeably
visible over the noise from the laser, and a second pulse is recorded. The transmittance from
the single pulse measurement is plotted in Fig. D.5. A simulation of the NO absorption
spectrum is provided by LIFBASE for comparison using the resolution of 0.013 nm obtained
by spectrometer calibration and set to room temperature at 300 K. The single pulse ab-
sorption measurement produces a high signal to noise spectrum across a 1 nm region with
approximately 30 well resolved rotational lines. A comparison of the optically thick with an
optically thin LIFBASE spectrum shows clearly the effects of optical depth in the spectrum,
which enhance weaker lines at the expense of stronger ones.
109
Figure D.4: NO spectrum at low concentration from continuously pulsed laser (20 Hz)
integrated over 1 second compared to spectrum simulated by LIFBASE at T = 300 K.
D.3.2 Time Resolution in Exploding Bridge Wires

The ability to time resolve species absorption in the UV is demonstrated in the vapor cloud
produced by an aluminum EBW. Previous work [113] showed that Al concentration in an
exploding bridgewire cloud varies strongly over the first millisecond after breakdown. The
same dye mixture used in the stationary NO gas measurement is used to probe the spectral
range from 226 nm to 227 nm. To create aluminum bridge wires, aluminum foil is cut into
thin strips approximately 0.5 mm wide × 25 μm thick. The thin strips are then clamped
between two electrodes set approximately 1 cm apart. The center of the UV beam is then
positioned approximately 1 cm above the bridgewire. The electrodes are then connected to
a Teledyne RISI FS-43 fireset synchronized to the laser pulse output by a delay generator
(Quantum) to allow for measurements at different times after the bridgewire initiation. An
optical beam shutter (Thor Labs) is placed in front of the combustion chamber and connected
to the pulse generator. Several single shot experiments are conducted with the absorption
probe beam passing through the cloud at different times after breakdown. Before each wire
is initiated, a reference pulse averaged over ten pulses is taken.
The resulting spectra for aluminum absorption lines at 200 s increments after the ini-
tiation of the bridge wire are shown in Fig. D.6. Two atomic absorption lines, the Al I
(2 Po1/2 →2 D3/2 ) transition at the lower wavelength and the Al I (2 Po3/2 →2 D5/2 ) transition at
the upper wavelength,[154] are apparent in the spectrum. It is seen initially that after the
explosion, the absorption lines are extremely broad while gradually thinning out at later
times. The broadening is attributed to the increase in equivalent width due to the optically
110
Figure D.5: NO spectrum under optically thick conditions from a single pulse compared to
spectrum simulated by LIFBASE at T = 300 K.
thick spectrum. The observed linewidth far exceeds the expected pressure, Doppler, and
Stark broadened linewidths in the bridgewire environment.
D.3.3 Metal-Teflon Flash Powders

Flash powders mixed with PTFE powder are used to examine fluorinated metal species in
absorption in a solid fuel combustion environment. The spectrum of AlF is examined in a
flash powder a powder of containing KClO4 /PTFE/Al (57/10/33 by wt. %). The spectrum
of MgF is examined in a flash powder containing KClO4 /PTFE/Mg (40/10/50 by wt. %).
An EBW is used to disperse and ignite the powders. A tungsten bridgewire with 0.005 cm
diameter (McMaster Carr) is attached between the electrodes in the combustion chamber.
Testing the tungsten wire in the same manner as described in the previous section revealed no
absorption features in the regions of interest at any time after the initiation of the bridgewire
making it an ideal candidate for dispersing powders. A piece of non-conductive tape is placed
directly under the bridgewire to support a small pile of flash powder (5 mg) that rests on
top of the wire. The bridge wires are initiated and spectrum recorded in the same manner
as described in the previous section.
D.3.4 Spectroscopic Model for AlF and MgF

The procedure for calculation of line positions and intensities used in this study is outlined
in Arnold et al. utilizing the approximation to the Voigt profile provided in the reference
[155]. The spectroscopic constants for the aluminum AlF A1 Π←X1 Σ+ transition are taken
111
Figure D.6: Al atomic line absorption in EBWs taken in a series of experiments at different
times after bridge wire initiation.
from Rowlinson and Barrow [156]. The Franck-Condon factors for the first five vibrational
levels of the Δν=0 transitions are taken from Liszt and Smith [157]. Due to the nearly
vertical nature of the transition, factors for five subsequent vibrational levels are estimated
to be unity. Spectroscopic constants for the magnesium MgF B2 Σ+ ←X2 Σ+ transition are
taken from Huber and Herzberg [158]. Frank-Condon Factors for the first five levels of the
the Δν=0 transition were taken from Maheshwari et al. [159]. Expressions for Hönl-London
factors for both molecules are taken from Kovács [160]. The calculation of the absorption
coefficients is outlined by Luque and Crosley [153].
The classical Beer’s law expression is used to describe the absorption. There are five
adjustable parameters for the simulation of absorption spectrum taking into account the
optical thickness: the temperature, a factor of non-resonant absorption/scattering, a factor
of the amount of light that passes through the absorbers, an effective product of the number
density and path length, and the effective resolution. The slit function of the spectrometer
setup is approximated as a Lorentzian function. The transmittance is plotted as a function
of the wavelength. The fitting parameters are the same as described in previous work in
modeling the AlO absorption spectrum [107]. The model is meant to be primarily used to
verify the species being probed. The quantitative accuracy of the temperature measurement
is not assessed in this work.
112
D.3.5 MgF Detection in Dispersed Flash Powder Combustion
The MgF B2 Σ+ ←X2 Σ+ Δν=0 bandhead is observed at 268.85 nm. In order to reach this
transition, a Coumarin 540 dye at 0.0035 mol/L concentration is used to produce the fun-
damental beam. The UV pulse energy is measured to be 3 μJ. The spectral position on
the detector is calibrated using the atomic lines produced by a Fe-Ne hollow cathode lamp
(Analyte). The spectral bandwidth after doubling is approximately 2 nm with a profile
similar to the bandwidth in Fig. D.2. The combustion of the dispersed magnesium flash
powder provides moderate optical thickness of the MgF spectrum at times 500-600 s after
the initiation of the tungsten EBW. The resulting spectrum is shown in Fig. D.7 along with
the simulation at 3000 K with an effective resolution of 0.015 nm. Despite the path averaged
nature of the measurement, a fair fit to the spectrum is obtained using a single temperature.
Figure D.7: The absorption spectrum of MgF in flash powder combustion fit with a 3000 K
simulation.
D.3.6 AlF Detection in Dispersed Flash Powder Combustion

The AlF A1 Π←X1 Σ+ Δν=0 transition is observed with a strong absorption feature with a
peak at 227.4 nm. The same Courmarin 460 dye used for the aluminum bridge wire tests is
used to produce the fundamental beam. The crystal is angle adjusted to center the beam
in the 227 to 228 nm region of interest for AlF. The resulting pulse energy is approximately
1 μJ. The spectral position is calibrated by the Ni-Ne hollow cathode lamp. Measurements
of AlF are taken approximately 800-1000 μs after the initiation of the EBW, and produce
noticeably optically thick spectrum. There is considerable difficulty in obtaining an optically
113
thin spectrum since the highly optically thick signal rapidly decays to negligible signal. An
example spectrum of the AlF transition is shown in Fig. D.8 with a simulation at 2800 K
with an effective resolution of 0.015 nm. There is disparity of the model in the blue-degraded
absorption feature at 227.4 nm possibly due to an unaccounted source of broadening or from
the relative uncertainty of the spectroscopic constants in the literature.
Figure D.8: The absorption spectrum of AlF in flash powder combustion fit with a 2800 K
simulation.
The intensity and coherence of the UV beam allows for easy alignment of the spectrometer
in the second order of the grating. In the second order, the dispersion and resolution are
more than doubled. The theoretical instrument resolution becomes 0.0026 nm with a range
of 1.4 nm. The second order spectrum is shown in Fig. D.9. It is observed that pulse noise is
increased. Although the majority of the rotational lines are too closely spaced to be resolved,
a new feature appears in the main spectrum at about 227.5 nm which also appears in the
simulated spectrum. The second order spectrum is again fit to a temperature of 2800 K.
Absorption Saturation
High pulse intensities can optically pump the absorption medium so that sufficient population
in the in excited state may cause non-linear absorption effects. Full saturation is considered
when the excited state population is driven by the laser radiation to match the ground
state. In this scenario, the medium becomes effectively transparent to the laser light and no
absorption will take place.
The limiting pulse energy is determined for NO A2 Σ←X2 Π(0,0) absorption as an example.
The spectral range of the laser is considered from 226 nm to 229 nm. A beam radius of 2.5
114
Figure D.9: Second order spectrum of AlF with a simulation at 2800 K.
mm and a pulse width of 5 ns are assumed. The calculated maximum pulse energy at which
the excited state population reaches 25% is found to be approximately 0.4 mJ. In cases of
higher pulse energy, an increase in the beam radius can reduce the overall beam intensity
allowing for greater pulse energy at a small expense of spatial resolution in the measurement.
D.4 Summary and Conclusions

The use of a modeless dye laser as a spectral source for an absorption measurement is
extended into the UV beyond the limitations of pumped dye beams by using broadband
SHG. Absorption measurements of the NO A2 Σ←X2 Π(0,0) transition and atomic lines in
aluminum EBWs are used to calibrate the diagnostic showing convergence in the optically
thin limit over multiple pulses and to demonstrate microsecond time resolution in a series
of experiments. The diagnostic is used to probe the fireballs of flash powders dispersed by
EBWs to examine the optically thick AlF A1 Π←X1 Σ+ transition, and the MgF B2 Σ+ ←X2 Σ+
transition. A single temperature is derived by fitting simulations of the diatomic transitions
to the experimental data. A simple analysis of the laser intensity where saturation effects
may not be negligible is given for a two level system for wavelengths near NO and AlF
transitions.
It is found in this setup that the pulse noise and pulse variation do not degrade the
absorption measurement significantly. The average standard deviation in amplitude over the
laser pulse spectrum for a sample of ten pulses is found to be 15-20%. The noise level of a
single pulse, however, is estimated to be 5-10%. Improvements in the measurement can be
made by splitting the beam before the combustion chamber and acquiring a simultaneous
reference measurement using an array detector as demonstrated by Glumac [113]. Other
broadband laser sources such as femtosecond lasers may offer superior noise characteristics,
115
though currently, these tend to be more expensive than the dye based approach.
A strong focusing condition of the fundamental dye beam onto the crystal is found to
be sufficient to produce approximately 1-3 nm of bandwidth. The SHG beam is able to
saturate the detector in a single pulse and provides enough signal to be used for a single
shot measurement in the second order of a grating. This diagnostic provides a simple tool
for obtaining a path averaged measurement and overcoming the difficulties of absorption
spectroscopy in explosive fireballs and other optically thick combustion systems as shown
in previous studies using the visible spectrum of dyes [113]. Several atomic and diatomic
species can be accessed for measurement by careful selection of dyes and crystals. Following
the assumption of approximately a 2 cm attenuation length from previous studies of optical
depth in fireballs [141] and assuming a pulse energy around 10 mJ max, the technique is
estimated to be able to scale up to a 20 cm path length.
116
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Thermal Structure of Flames in

Metal Particle Suspensions

Department of Mechanical Engineering

A thesis submitted to McGill University in partial fulﬁllment of the requirements of the

© Michael Soo, 2016

Comprendre la combustion de suspensions de particules réactives est essentiel pour prédir

Section 1.4 of the Introduction:

Chapter 2 Publication [1]:

Chapter 3 Publication [2]:

Chapter 4 Publication [3]:

1.1 Combustion in condensed-phase fuel suspensions, classiﬁed according the fuel

C.1 Temperature proﬁles of the simpliﬁed Zeldovich and Barenblatt model. . . . 99

2.1 Numerical values of gas and solid-fuel parameters. . . . . . . . . . . . . . . . 29

3.1 Numerical values of gas and solid-fuel parameters. . . . . . . . . . . . . . . . 49

C.1 Eﬀect of spatial step-size on calculated burning velocity. . . . . . . . . . . . 101

* L: length, T: time, M: mass, Θ: temperature, N: moles.

Contributions of the Author v

List of Figures viii

List of Tables xiii

List of Symbols xiv

2 Reaction Onset and Combustion in a Particle Fuel Suspension 20

3 Flame Propagation in Particle Suspensions 39

4 Combustion Diagnostics in Particle Fuel Suspensions 56

A Zero-dimensional Induction Combustion in a Fuel Suspension: Governing

C Validation of Numerical Methods 98

D Laser Absorption Diagnostic 102

1.1 Motivations for the Study of Metal Combustion

1.1.2 Modern Metal Combustion Applications

1.2 Classiﬁcation of Combustion in Metal Fuel Suspen-

1.3 Modes of Metal Particle Combustion

Figure 1.2: Classiﬁcations of combustion mode based on thermodynamics equilibrium cal-

1.4 Particle Ignition and Reaction Regimes

1.4.2 Heterogeneous Heat of Reaction and Heat Loss Rates

k = κ0 exp(−Ea /Ru Ts ) (1.2)

Q̇L = hA(Ts − Tg ) (1.5)

1.4.3 Steady-State S-Curve Analysis

1.0 diffusion limit Ts = Tstoich

Figure 1.5: General S-curve form for a particle.

1.4.4 Particles Burnout in Mixed Regimes

1.5 Scope of Thesis

Reaction Onset and Combustion in a

2.2.2 Model Formulation and Results

The general treatment of heterogeneous reactions governed by the competition between

Property Value Property Value

Table 2.1: Numerical values of gas and solid-fuel parameters.

Reaction of a Dense Particulate Suspension

kβ Sh D2r0 κ0 exp( R−E a

The same interplay between kinetically- and diﬀusively-limited combustion regimes at

Reaction of a Suspension in a Cooling Gas

Flame Propagation in Particle

3.2.2 Model Formulation

where q is the heat of reaction.

Ignition and Combustion of a Single Particle

Governing Equations and Numerical Method

3.2.3 Results and Discussion

After an initial transient period, a steady-state ﬂame, propagating at a constant speed,

Table 3.1: Numerical values of gas and solid-fuel parameters.

0.6 0.6 0.6

0.4 0.4 0.4

0.3 0.3 0.3

0.2 T 0.2 0.2

0.1 T 0.1 0.1

0.0 0.0 0.0