michael r. zachariah - umd
TRANSCRIPT
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
Michael R. ZachariahProfessor
Probing the Reaction Dynamics of Nanoenergetic Materials
Department of Chemistry and Biochemistry
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
NanoEnergetic Materials
METAL/OXIDIZER
∆Hvolume (kcal/cc)
10 2 3
10 2 3 4 5 6 7
∆Hmass (kcal/g)
4
∆Hvolume
HIGH EXPLOSIVE
CL-20
TNT
PETN
HMX
Al/Ni2O3
Al/MoO3
Al/Teflon
Al/KClO4
∆Hmass
METAL/OXIDIZER
∆Hvolume (kcal/cc)
10 2 3
10 2 3 4 5 6 7
∆Hmass (kcal/g)
4
∆Hvolume
HIGH EXPLOSIVE
CL-20
TNT
PETN
HMX
Al/Ni2O3
Al/MoO3
Al/Teflon
Al/KClO4
∆Hmass
Fischer and Grubelich, 32nd AIAA/ASME/SAE/ASEE Joint Propulsion Conference, Lake Buena Vista, FL 1996. Thomas N. Hall and James R. Holden, Navy Explosives Handbook, NSWCMP 88-116, 1988.
2 32Al + 3MO Al O 3M H→ + ∆
Fuel Oxidizer
+
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
Energy release from Thermite > CHNO chemistry.
But, we know very little about mechanisms of ignition and propagation.
We are still groping to establish a conceptual mechanism, let alone advance to a mathematical model.
Thermodynamics
KineticsThermites are much slower than CHNO Systems;
- Smaller thermites are faster => Nano
Motivation
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
Metastable Interstitial Composites
MoO3, CuO, etc.Al
Al2O3
• How can we study the reactivity of nanocomposites ?
AlCuO??????
Al203
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
A New Approach: T-Jump Mass Spectrometry/Optical Emission
I or RI or RI or R
Mass-Spec Optical Emission
Fine wire coated and rapidly heated
Basic Approach:
Coat wire with:• Organics, • Organics+ binder• Thermites,• Thermites + organics• Sputtered thin films• Etc.
Photonsionse-
How to characterize the reactivity of powder of ultrafast nanocomposites ?
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
T-Jump Wire IgnitionExample of heating rate of 1.7 X 105 C/s
Wire temperature determined by resistance.
Tem
p (K
)
Norm
alized Intensity (a.u.)
Time (ms)
400
600
800
1000
1200
1400
1600
0
0.2
0.4
0.6
0.8
1
0 1 2 3 4 5 6 7 8
Temp 6 11:50:52 AM 10/24/2008
Ignition temperature ~ 1250 K
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
Positively charged ions accelerated by Electric field move up time-of-flight tube to the detector
Detector
V
Oscilloscope Computer
V
T-Jump Mass-Spectrometry
Electron Gun
Vp
Possibility to study the ignition kinetics of Nanocomposites using mass spectrometry.
CAN BE PULSED UP TO 20kHz,to obtain multi-mass spectra from each combustion event.
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
Ignition of NanoThermite in T-Jump Mass-Spec:
High speed video 33,000 fps
Al + CuO => Al2O3 + Cu
70 µ
m
High Speed X-Ray Movie, 135,000 fps (total time = 1.8 msec)
Obtained at Argonne National LabCollaboration with T. Hufnagel , JHU.
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
Time Resolved Thermite Mass-SpectrumStoichometric Al/CuO- one spectrum every 100 µs.
Al/CuO nanocomposite under heating rate 8.8 ×105 K/s
Al +CuO => Al2O3 + Cu
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
0
100 H2O+
N2
+
O2
+
(a). background
0
200
CO2
+
Al+
H2O+
O2
+
Cu+
Al2O+
(b). Al/CuO thermite
0
200
0 20 40 60 80 100
CO2
+Al+
H2O+
Al2O+
Fe+
(c). Al/Fe2O
3 thermite
M/z
Background:H2O mass 18N2 mass 28O2 mass 32
Al/CuO thermiteOxygen species mass 16, 32Al mass 27Cu mass 63,65Al2O mass 70
Al/Fe2O3 thermiteAl mass 27 Fe mass 56Al2O mass 70
All have:CO mass 28CO2 mass 44
Difference between two systems: Oxygen species
Al2O is reaction product
More Details in Thermite Spectra Al +CuO => Al2O3 + Cu
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
0
50
100
150
200
800
900
1000
1100
1200
1300
1400
1500
1 1.5 2 2.5 3 3.5 4 4.5 5
Oxygen release from CuO, Fe2O3, ZnO
Inte
nsity
(a.u
.)
Temperature (C
)
Time (ms)
Cuo TempZno TempFe2O3 Temp
O2 from CuO
O2 from Fe2O3
O2 from ZnO
Temp ofCuO O2 release
Temp ofFe2O3 O2 release
Reactivity From Pressure Cell:CuO >> Fe2O3 >> ZnO (doesn’t even burn)
Oxidizer Decomposition (Melting) Point:CuO < Fe2O3 < ZnO
Results suggest that oxidizer decomposition to release O2 is important for ignition and that the amount of O2 release correlates with the reactivity.
Comparison of O2 Release from CuO , Fe2O3, ZnO
Gas Release from CuOX-Ray 135,000 fpsTotal time = 3 msec.
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
800
1000
1200
1400
1600
800 1000 1200 1400 1600
O2 R
eleas
e Te
mp
(C)
Ignition Temp (C)
Al/SnO2
Al/WO3
Al/Fe2O
3
Al/CuO
O2 Release Temperature vs. Ignition Temperature
There is a strong correlation between O2 release and the ignition temperature.
Comparing thermite ignition with O2 release from the neat oxide powders:
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
0 10 20 30 40 50 60 70 80
m/z
Al2O
CuAl
O2
CO2O
Al2O
CO2AlOO
2
Al
CuO
Al/CuO(Fuel RichEq ratio=3)
Al/CuO(Stoichiometric)
Enhanced PeaksAl
AlO (new peak)Al2O
Diminished PeaksO, O2
CO2
Cu
-Shift from excess oxidizer (high O2 peak) to excess fuel (high Al peak)
Fuel Rich VS Stoichiometric
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
How does the Al get out, since it has an oxide shell ?
We have observed hollow particles observed in Oxidation of Nanoaluminum
Diffusion mechanism for nano-aluminum•Molten aluminum diffuses outward.•Aluminum reacts with oxygen.
Hollow Product
MDM was proposed to explain the high reactivity in MICs (Levitas et al. 2006, 2007)
Molten Al Spallation of alumina shell
Molten Al clusters
Aluminum particle with core shell structure
Melt Dispersion
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
What is Role of Oxide Thickness on Reaction Time
Al nanoparticles ( ~50 nm dia) usually have an oxide shell of ~ 2nm.
50 n
m Oxide shellAl core
Al particles are oxidized @ 400 C for different lengths of time :a) 6 mins - 3 nm shell (based on wt. gain)b) 12 mins - 4 nm shell
Prepare Al with different Oxide Shell thickness
50 n
m
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
Ignition Delay vs Oxide Shell Thickness
- Ignition delay increases with shell thickness- Suggests a transport limit
Tem
pera
ture
(K)
Norm
. Intensity (a.u.)
Time (ms)
2 nm
Pulse turned off
4 nm
400
600
800
1000
1200
0
0.2
0.4
0.6
0.8
1
0 1 2 3 4 5 6 7
3 nm
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
Effective diffusion coeff., Deff = L2/ t
2 nm
50 n
m
L (nm) t (us) Deff (cm2/s)2 80 5e-10
3 480 1.9e-10
4 1000 1.6e-10
Steady State Temperature = 730 K
Mass spectrometric data shows same trend in ignition delay
Effective Diffusion Coefficient in Oxide Shell from Ignition Delay
Del
ay ti
me
(us)
Shell thickness (nm)
0
500
1000
1500
2000
1 2 3 4
No Steady State
Tsteady = 730 K
Ignition Delay Time
0
500
1000
1500
2000
1 2 3 4
No Steady State
Tsteady = 730 K
MS_Cu Signal
Effective Diff. Coeff. are consistent.
Park et al., J. Phys. Chem. B, 2005D= 10E-8 – 10E-9 cm2/sec
Vashista and co-workers 10E-6 cm2/sec
Ignition Delay Time
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
NanoCrystals of Al
Hi-Res Image
FeOMn
Elemental Map
Core-Shell Reactive Oxidizers
KMnO4
Fe2O3
KClO4
CuO
Coating Al with Ni
Al coated with Perfluorohexadecanoic Acid
Center for Energetic Concepts Development
U N I V E R S I T Y O F M A R Y L A N D, C O L L E G E P A R K, M D 2 0 7 4 2, U S A
T E L. 3 0 1 – 4 0 5 – 5 2 0 5 ; F A X 3 0 1 – 3 1 4 – 9 4 7 7 ; w w w . c e c d . u m d . e d u
Conclusions• Development of new mass spectrometry tool enables us to probe reaction dynamics of ultra-fast condensed state systems at high heating rates.
• Metal oxides appear to release O2 and the ignition temperature would appear to correlate with O2 release. However, some other systems not discussed today show indications of heterogeneous reactions.
• Al from oxide coated particles seem to leak out by a diffusion mechanism.
• A very short transient ion generation pulse ( 20 us) occurs just at the ignition point ( not discussed today)
• New classes of nanocomposites offer opportunities to tune reaction profiles.
Publications may be downloaded from www.enme.umd.edu/~mrz