Combustion Analysis of Nanoenergetic Materials
Transcript of Combustion Analysis of Nanoenergetic Materials
NEEM MURI
Combustion Analysis of Nanoenergetic Materials
Richard A. YetterYoni MalchiJustin SabourinGrant A. Risha (Penn State Altoona)Steven F. Son (Purdue University)The Pennsylvania State University
Tim Foley, Bryce Tappan, Blaine AsayLos Alamos National Laboratory
NEEM MURI Research Areas and Progress
• Flame spread across thin fuel films of nano metallic particles. • Combustion of nAl with O2/Ar mixtures• Combustion of nAl with CO2, CO, N2O, and N2
• Combustion of nano metallic particles and flame propagation through quasi-homogeneous mixtures of nano metallic particles and liquid and gaseous oxidizers.
• Combustion of nAl/liquid H2O• Combustion of nAl/H2O/H2O2• Combustion of nAl/CH3NO2• Initial studies on nB/H2O/H2O2
• Combustion of nano metallic particles and flame propagation through quasi-homogeneous mixtures of nano metallic particles and solid oxidizers.
• Combustion of nano Al/MoO3 thermites• Combustion of nano Al/CuO thermites• Initial studies on the combustion of nano Si with variuos oxidizers
• Mixing of nano thermites
NEEM MURI
Flame spread across thin fuel films of nano metallic particles
NEEM MURI Flame Spread Experimental Setup
Vox
h
NEEM MURI Three Consecutive Modes of Combustion
1. Surface Burn
2. Bulk Bed Burn
3. Cellular Flames
NEEM MURI Fingering Combustion with Nano-Aluminum: Below Pecrit
20% O2 – 80% Ar
Pe = voxh/DO2
NEEM MURI Effect of Oxygen Content
0
10
20
30
40
50
60
70
0 40 80 120
Flam
e Fr
ont V
eloc
ity, v
f (cm
/s)
Oxygen Percentage
NEEM MURI Effect of Particle Diameter
0.0
1.0
2.0
3.0
4.0
20 40 60 80 100 120 140
y = 3.6e+3 * x^(-2.0)
Flam
e Fr
ont V
eloc
ity (v
f ) (c
m/s
)
Diameter of Particle (dp ) (nm)
NEEM MURI Changing Oxidizer
CO CO2 N2O
NEEM MURI
Combustion of nano metallic particles and flame propagation through quasi-homogeneous mixtures of
nano metallic particles and liquid and gaseous oxidizers
NEEM MURI Characteristics of Al Particles
16.5-84.02.2130 nmb
26.1-74.02.780 nmb
26.53.07681.01.980 nmb
25.8-84.01.680 nmb
41.23.00868.02.150 nmb
54.13.20554.33.138 nma
Surface Area
[m2/g]
ParticleDensityc
[g/cm3]
Active AlContent [%]
Oxide LayerThickness
[nm]
ParticleDiameter
[nm]
aManufactured by Technanogy, LLCbManufactured by NanotechnologiescMeasured using a pycnometer
100 nm
NEEM MURI Sample Preparation & Packing Densities
Increasing φ
Increasing Dp
38nm nAlφ = 0.5
38nm nAlφ = 1.0
1.351±0.020130b1.001.331±0.10680b1.00
1.39550b1.000.731±0.01638a1.250.726±0.02838a1.001.055±0.01838a0.751.478±0.03038a0.671.384±0.03038a0.50
Packing Density [g/cm3]Particle Diameter [nm]Equivalence Ratio
aManufactured by Technanogy, LLC; bManufactured by Nanotechnologies
NEEM MURI Video of nAl/H2O Combustion 38nm Diameter Particles
NEEM MURI rb vs Pressure
1
10
0.1 1 10
nAl (38 nm) and Liquid WaternAl (38 nm) and Liquid Water / Poly-ALi
near
Bur
ning
Rat
e [c
m/s
]
Chamber Pressure [MPa]
φ = 1.0
0.1
1
10
0.1 1 10
Bur
ning
Rat
e [c
m/s
]
Pressure [MPa]
rb [cm/s] = 4.5*(P[MPa])0.47
ADN* CL-20*
HNF*
JA2#HMX* * Altwood, 1999
# Kopicz, 1997
NEEM MURI
0.5
1
1.5
2
2.5
3
3.5
4
40 50 60 70 80 90 100
Burn
ing
Rat
e [c
m/s
] or [
g/cm
2 -s]
Particle Diameter [nm]
Pnom
= 3.65 MPa
φ = 1.00
rb [cm/s] = 122.7*(D[nm])-1
150
mb [g/cm2-s] = 165.4*(D[nm])-1
Burning Rate vs Dp
NEEM MURI Mass Burning Rate & Tad vs φ
0
5
10
15
500
1000
1500
2000
2500
3000
3500
0.4 0.6 0.8 1 1.2 1.4
Mas
s B
urni
ng R
ate
[g/c
m2 -s
]
Adiabatic Flam
e Temperature [K
]
Equivalence Ratio
No Al2O
3 Coating
45.7 wt% Al2O
3 Coating
Dp = 38nmP = 3.65 MPa
0.001
0.01
0.1
1
0.4 0.6 0.8 1 1.2 1.4
Pro
duct
Spe
cies
Mol
e Fr
actio
ns
Equivalence Ratio
Al2O
3(a)
H
Al2O
3(L)
H2
Al
H2O
No Al2O
3
Coating
NEEM MURI Efficiency vs Pressure
0
20
40
60
80
100
0 20 40 60 80 100 120 140Pressure [atm]
Dp = 38 nm
φ = 1.0
NEEM MURI Al/H2O/H2O2 Combustion
P = 3.6MPa, φ = 1, Dp = 38nm, Oxidizer mass ratio = 32%H2O2/65%H2O
NEEM MURI Burning Rates for Al/H2O/H2O2Mixtures
1
10
0.1 1 10
nAl - (90%H2O+10%H
2O
2)
nAl - (75%H2O+25%H
2O
2)
nAl-H2O
Mas
s B
urni
ng R
ate
[g/c
m2 -s
]
Pressure [MPa]
Dp =38 nm
φ = 1.0
0
10
20
30
40
50
60
70
0 5 10 15 20 25 30 35
Line
ar B
urni
ng R
ate,
r b [cm
/s]
Hydrogen Peroxide Fraction [mass %]
Pnom
= 3.6 MPa
φ = 1.0D
p = 38 nm
0
5
10
15
20
25
0.4 0.6 0.8 1 1.2 1.4
nAl-(90%H2O+10%H
2O
2)
nAl-H2O (Risha et al. 2006)
Mas
s B
urni
ng R
ate
[g/c
m2 -s
]
Equivalence Ratio
φ = 1.0P
nom = 3.6 MPa
Dp =38 nm
NEEM MURI Al/H2O/H2O2 Combustion
P = 3.6MPa, φ = 1, Dp = 38nmOxidizer mass ratio = 35%H2O2/65%H2O0
1020304050607080
0 0.5 1 1.5 2 2.5 3 3.5 4Time [s]
Pinitial
= 1 atm
Dp = 38nm
10% H2O
2
35% H2O
2
NEEM MURI
Combustion of nano metallic particles and flame propagation through quasi-homogeneous mixtures
of nano metallic particles and solid oxidizers
NEEM MURI Combustion of Al/MoO3
NEEM MURI Propagation Speeds of Al/MoO3 in Capillary Tubes
400.00
600.00
800.00
1000.00
1200.00
15 20 25 30 35 40 45 50 55
Pro
paga
tion
Vel
ocity
(m/s
)
Mass nAl (%)
Stoichiometric is 31.6% nAl
2600
2800
3000
3200
3400
3600
3800
4000
0
1
2
3
4
5
20 25 30 35 40
T
Total Gas
Adi
abat
ic T
empe
ratu
re (K
) Total Gas P
roducts (mol/kg)
Mass nAl (%)
Stoichiometric is 31.6% nAl
PeakVelocity38% nAl
Mo meltsat 2896K
time between images is 13.8 μs
NEEM MURI Propagation of Al/MoO3 Mixtures in Small Tubes and Channels
700
800
900
1000
1100
1200
0 500 1000 1500 2000 2500
V = 1090.3 - 0.1508/d R= 0.99351
Pro
paga
tion
Vel
ocity
(m/s
)
1/Diameter (m-1)
100
200
300
400
500
600
700
1000 2000 3000 4000 5000 6000 7000 8000 9000
300 μm slots500 μm slots
V = 945.66 - 0.21408/dh R= 0.9691
Pro
paga
tion
Vel
ocity
(m/s
)
1/dh (m-1)
Quartz Capillary Tubes SS Micro Channels
NEEM MURI Effect of Al2O3 Nanoparticles on Al-CuO Nano-scale Thermite
Objectives• Gain control over reaction velocity• Understand effect of lowering flame temperature by adding a heat sink into the
material• Does lowering the flame temperature also hinder gas production which is the
proposed mechanism for propagation?• Understand the relation between gas production and reaction velocity –
convective mechanismExperiments• Constant volume combustion, burn tray propagation, burn tube propagation
NEEM MURI Al/CuO Combustion and Propagation
10-1
100
101
102
103
0 2 4 6 8 10 12
dP/d
t (M
Pa/m
s)
% Al2O3
00.20.40.60.8
11.21.4
0 2 4 6 8 10 12
y = 0.113 * e^(0.231x) R2= 0.993
Indu
ctio
n Ti
me,
t i (ms)
% Al2O3
0
0.2
0.4
0.6
0.8
1
1.2
0
100
200
300
400
0 5 10 15 20
PeakPressure
Two PointVelocity
Pea
k P
ress
ure
(MP
a)Tw
o Point V
elocity (m/s)
% Al2O3
0
2
4
6
0 300 600
0%5%10%15%
Pos
ition
(cm
)
Time of Arrival (µs)
633 m/s570 m/s
Burn TubeSteady propagation at 0 and 5% Al2O3Accelerating wave at 10 and 15% Spinning instability at 20%
Closed bomb and Burn TrayChange in reaction wave at 5% Al2O3Strong correlation between gas production and velocity
Closed Bomb Burn Tray Burn Tube
NEEM MURI Al/CuO Combustion
0
0.2
0.4
0.6
0.8
1
0 5 10 15 20 25 30
Total gasAl2O gasCu gasAl gasN2 gasAl liquidAlN solid
Pro
duct
Con
cent
ratio
n (m
ol/k
g)
% Al2O3
0
500
1000
1500
2000
0 10 20 30
CalculatedPeakPressure (psi)
AvgerageExperimentalPeakPressure (psi)
Pre
ssur
e (p
si)
% Al2O3
• Al-CuO nano-scale thermite is relatively sensitive to the addition of Al2O3
• Hinders gas production leading to lower pressures and reaction velocities
• Burn tube shows a steady velocity for 0% and 5%, acceleration for 10% and 15%, and an unstable regime at 20% added Al2O3
• Constant volume equilibrium calculations predict gas production dropping with added aluminum oxide and peak pressures match
• Adding aluminum oxide lowers the flame temperature, which hinders the gaseous products and weakens the convective mechanism
4
8
12
16
20
0 5 10 15 20 25 30
Total condensed phaseCu LiquidAl2O3 liquid
Pro
duct
Con
cent
ratio
ns (m
ol/k
g)
% Al2O3
NEEM MURI Silicon Combustion
2600
2800
3000
3200
3400
3600
3800
4000
0
50
100
150
5 10 15 20 25 30 35 40Mass Fraction Al (%)
2600
2800
3000
3200
3400
3600
3800
4000
0
50
100
150
5 10 15 20 25 30 35Mass Fraction Si (%)
Si/AP Si/CuO Si/Bi2O3
2600
2800
3000
3200
3400
3600
3800
4000
0
20
40
60
80
100
120
140
10 15 20 25 30 35 40 45
Tem
pera
ture
(K) P
ressure (atm)
MassFraction Al (%)
T T T
PP
P
Al/MoO3 Al/CuO Si/CuO
NEEM MURI Electrostatic Self Assembly of Nano Thermites
C
OH
O Al C N+
CH3
CH3
CH3 Cl-
C CS-
O
O
O HS
H+
Metal oxide
• Functionalize surface of nano-particles with ligands to charge the particles
• Allow particles to self-assemble for improving mixing on the nano-scale
A.M. Kalsin, M. Fialkowski, M. Paszewski, S.K. Smoukov, K.J.M. Bishop, B.A. Grzybowski, Electrostatic Self-Assembly of Binary NanoparticleCrystals with a Diamond-Like Lattice, Science, 23 Feb. 2006
CuOAl
HS(CH2)11SO3H orHS(CH2)10COOHThiol with sulfonic acid
(CH3)N(CH2)10COOHCarboxylic acid with tri methyl ammonium chloride
NEEM MURI Summary
• Completed studies on flame spread of nAl and different oxidizers.
• Completed studies on the combustion of Al/H2O mixtures.
• Completed studies on channel diameter effect on propagation of nano thermite Al/MoO3 system.
NEEM MURI Available Publications
nAl Flame Spread“Nano-Aluminum Flame Spread with Fingering Combustion Instabilities,” Malchi, J. Y., Yetter, R. A., Son, S.
F., and Risha, G. A., Proceedings of the Combustion Institute, 31, in press, 2006.“Flat Flame Spread Over a Bed of Nano-Aluminum Powder,” Malchi, J. Y., Yetter, R. A., and Son, S. F.,
33rd International Pyrotechnics Seminar, Fort Collins, Colorado, July 16-21, 2006.“Nano-Aluminum Flame Spread with O2/CO/CO2/N2O, and N2 Oxidizers,” Malchi, J.Y., Yetter, R.A., and
Son, S.F., Combustion and Flame, in preparation, 2006.
nAl/H2O/H2O2 Combustion“Combustion of Liquid Water Combustion of Aluminum Particles with Steam and Liquid Water,” G. A. Risha,
Y. Huang, R. A. Yetter, V. Yang, S. F. Son and B. C. Tappan, AIAA Paper 2006-1154.“Combustion of Nano-Aluminum and Liquid Water,” Risha, G. A., Son, S. F., Yetter, R. A., Yang, V., and
Tappan, B. C., Proceedings of the Combustion Institute, 31, in press, 2006.“Combustion and Conversion Efficiency of Nanoaluminum-Water Mixtures,” Risha, G. A., Son, S. F.,
Tappan, B. C., Yang, V., and Yetter, R. A., 33rd International Pyrotechnics Seminar, Fort Collins, Colorado, July 16-21, 2006.
“Combustion of nano-aluminum, hydrogen peroxide, and liquid water mixtures,” J.L. Sabourin, G.A. Risha, R.A. Yetter, S.F. Son, and B.C. Tappan, JANNAF APS-CS-PSHS Joint Meeting, 2006.
“nAl-Liquid Water Combustion and Conversion Efficiency,” Risha, G. A., Son, S. F., Tappan, B. C., Yang, V., and Yetter, R. A., Combustion Flame, in preparation, 2006.
Nano Thermite Combustion“Combustion of Nanoscale Al/MoO3 Thermite in Microchannels,” S. F. Son, T. J. Foley, R. A. Yetter, M. H.
Wu, and G. A. Risha, Journal of Propulsion and Power, accepted for publication, 2006.“The Effect of Al2O3 Nano-Particles on an Al-CuO Nano-scale Thermite,” Malchi, J.Y., Foley, T.J., Yetter,
R.A., and Son, S. F., Combustion Science and Technology, in preparation, 2006.
NEEM MURI
• Extra slides
NEEM MURI
gravimetric H2 density (%mass)0 5 10 15 20 25
volu
met
ric H
2 den
sity
(kg
H2 m
-3)
0
20
40
60
80
100
120
140
160 5 g cm-3 2 g cm-3 1 g cm-3 0.7 g cm-3
MgH2
Mg2FeH6
Mg2NiH4
NaBH4
LiH
LiAlH4
KBH4NaAlH4
LiBH4
Al(BH4)3
C8H18liq
CH4liq
C4H10liq
H2liq (20.3K)
H2 physisorbed on carbon
pressurized H2gas
(composite material)P(MPa)
pressurized H2gas
(steel)P (MPa)
H2 chemisorbed on carbon
BaReH9
LaNi5H6
FeTiH1.7
nAl/H2O
NH3BH3
1320
5080
120200500
1320
5080
Solid Hydrogen Storage
Ref: A. Züttel, “Materials for Hydrogen Storage,” Materials Today, Sept.2003
NEEM MURI
RDX → 3CO+3H2O+3N2 −5 kJ/g
H2+0.5O2 → H2O −121 kJ/g
Al(s)+1.5H2O(l) → 0.5 Al2O3(s)+1.5H2(g) −18 kJ/gAl(s)+0.75O2→ 0.5 Al2O3(s) −31 kJ/g
Reaction Heat of Reaction per unit mass reactant
Overall Reaction Energetics
Al(s)+1.5H2O(l) → 0.5 Al2O3(s)+1.5H2(g) − 9 kJ/g
H2 + 0.5O2 → H2OPressurized storage @ 200MPa with composite material
Al(s)+1.5H2O(l)+0.75O2 → 0.5Al2O3(s)+1.5H2O(g) − 16 kJ/g
− 7 kJ/g
NEEM MURI
−5.5 kJ/cm3
Reaction Heat of Reaction per unit volume reactant
Overall Reaction Energetics
H2 + 0.5O2 → H2OPressurized storage @ 200MPa with composite material
Al(s)+1.5H2O(l)+0.75O2 → 0.5Al2O3(s)+1.5H2O(g) −24 kJ/cm3
NEEM MURI Present Work-Changing Oxidizer
•Was able to burn in 100% N2, but needed 1% O2 to ignite
NEEM MURI Fingering Combustion with Nano-Aluminum: Below Pecrit
No fingering
NEEM MURI Effect of Oxygen Content5% O2 (same O2 flow rate as when fingering occurred at 20%) –Yields products of the same color as the reactants; rough surface
100% O2 has an extremely fast first wave, distinct second wave front and coagulated alumina balls that adhere to the surface of the bottom plate as the products
NEEM MURI
• Early modeling (DeRis) and experiments (Fernandez-Pello)
• Low oxidizer velocities: spread rate becomes constant • Microgravity (Olsen et al.): flame front separates into fingers, spread
rate remains dependant on oxidizer velocity• Same occurs in gravity with a top plate (Zik et al.): the Peclet number
(voxh/DO2) determines when fingering occurs• Similar phenomenon happens with nAl as a fuel
Flame Spread
oxthickf vv ∝,