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 ∝,