2004 ARMY ENERGETIC MATERIALS MURI AND DURINT REVIEW MEETING Picatinny Arsenal Officers Club 27-28 October

2004

NANO ENGINEERED ENERGETIC MATERIALS (NEEM) MURI Overview

Richard A. Yetter The Pennsylvania State University and the NEEM MURI Team

Issues and Motivation

Potential benefits of nano energetic materials:
More powerful. More reliable. More reproducible. Reduced vulnerability. Safer to handle. Controlled rate of energy release. Higher density. Reduced sensitivity. Increased storage lifetime. Multi-functionality.

Modest gains to date:

While some performance improvement has been demonstrated, the full extent of the anticipated gains from nanoscale energetic materials has not been realized in large part due to the incompatibility of length scales.

Objectives
Develop new methodologies to assemble nano-energetic materials that provide concurrent increases in performance and managed energy release rate while reducing sensitivity. Obtain fundamental understanding of the relationship between the design of nanoengineered energetic materials and their reactive and mechanical behaviors.

Critical Technology Issues

Self-assembly and supramolecular chemistry of the fuel and oxidizer elements of energetic materials have lagged far behind chemistries in other disciplines (e.g., microelectronics, biological systems, and pharmaceuticals). There is no fundamental understanding of what type of supramolecular structures provide desirable performance in combustion, mechanical, and hazard characteristics.

Design Possibilities
conventionally assembled energetic material with micron-to-millimeter scale energetic structures

self-assembled micron-to-millimeter scale energetic structure

micron-crystalline oxidizer nano-energetic materials nano Al & B nano RDX, HMX, & ADN carbon nanotubes nano-metallic particle

polymer binder

nano-crystalline oxidizer

self-assembled energetic material with gradient in chemical composition

Program Philosophy
Bring together leaders in nanotechnology and propellants and explosives Couple multiscale modeling and multiscale diagnostics Research and develop new concepts for assembling and understanding the dynamics of nano engineered energetic materials

Participating MURI Team Members

David Allara, PSU: chemistry, nanotechnology, self-assembly Ralph Nuzzo, UIUC: chemistry, nanotechnology, self-assembly Dana Dlott, UIUC: chemistry, energetic materials, ultrafast laser spectroscopy Priya Vashishta, USC: physics, materials, atomistic modeling Rajiv Kalia, USC: physics, materials, multiscale modeling Aiichiro Nakano, USC: physics, materials, multiscale modeling Vigor Yang, PSU: engineering, energetic materials, combustion modeling Richard Yetter, PSU: engineering, energetic materials, combustion diagnostics Kenneth Kuo, PSU: engineering, energetic materials, combustion and ballistics

Program Elements
Synthesis and Assembly Theoretical Analysis and Design Experimental Characterization

Program Structure and Interactions

PSU UIUC
-m ac ro

Synthesis & Assembly

na no

Theoretical Modeling & Simulation

ma c

NEEM

Experimental Characterization & Diagnostics

UIUC PSU
ro ac

USC PSU

ro -

na no

no na

-m

Synthesis, Self-Assembly, and Supramolecular Chemistry of NanoStructured Energetic Materials

Significant Research Experience on Al Synthesis, Fabrication, and Surface Chemistry Nuzzo UIUC, Allara - PSU

SAMs on Al(native oxide)/Al Al(metal)-SAM Structures & Interactions Al Vapor Deposition Processes Al Surface Chemistry Materials Characterization

Nano Scale Energetic Materials Synthesis and Passivation: Nuzzo-UIUC & Allara-PSU
Develop new synthetic methodologies for affecting the low temperature synthesis of highly reactive nanoclusters
High surface area aluminum nanoparticles would be ideal high-energy materials Stabilized nano-clusters via A few examples of small aluminum clusters have metal ligand interactions recently been described (reductive syntheses), but there are no investigations of their use as high H Si H energy materials 3/2 H2 H The Al nanoparticles consist of metallic aluminum cores surrounded by a monolayer of a protective Si shell 10 and 100 aluminum atoms and particle diameters between 0.5 and 1.3 nm Generalize and Expand Synthetic Approaches AlH -TMA
3

TMA + 3/2 H2

Potential route to capped Al nanocluster

Nano Scale Energetic Materials Synthesis and Passivation: Nuzzo-UIUC & Allara-PSU

AlI + LiN(SiMe3)2 Al77[N(SiMe3)2]202-

Aluminum cluster (far right) consists of nested shells containing (from left to right) 13, 44, and 20 aluminum atoms
A. Ecker, E. Weckert, and H. Schnckel Nature 1997, 387, 379.

Generalize and Expand Synthetic Approaches to Aluminum Clusters with Sizes Ranging to 100 nm
New SAMs for Cluster Passivation and Size Control Thermal Cluster Growth Ligand-Directed Association Directed Synthesis Full Characterization/Understanding of Structure and Properties at all Length Scales

High Energy Content Nanocomposites: Nuzzo-UIUC Novel Growth Chemistries

Sub mm Teflon particles swollen in solvent, Al nanoparticles grown & passivated in pores, Spherical particles packed to form lattice of passivated nanoparticles

Teflon telomer particles

Swollen particles

Al growth via infusion

Encapsulation by vitrification

Composites from Aerosol and Particle Spray Deposition Processes, e.g., Nanoparticle Metal/Fluorocarbon Composites Dispersible to
~0.2 m Particles PFK/PFE Zonyl MP 1100 Thermal Spray Deposition (e.g. TMAA / TiCl4 / MP 1100)

Nano Structured Energetic Materials-Model Systems Nuzzo-UIUC

Develop strategies for manipulating the larger mesoscopic organization of high energy nanoscale materials by directed design Fabrication of Energetic Structures Using a Soft Lithographic Patterning Technique
Master Spin-Cast PFSOx UVO
Weld Two Aluminum Films

Sputter Deposit Aluminumx2

Adhesive Contact
Laminate Decal

Decal Transfer
Decal Release for 3D Integration

10m

Bottom layer strong oxidant such as HMX, which is readily deposited in thin film form from the vapor phase

Nano Structured Energetic Materials-Model Systems Nuzzo-UIUC

Fabrication of Energetic Structures Using Decal Transfer Lithography
Photoresist pixel post array 5-250 mm (dia); 5-150 mm (ht) Si Si Remove PDMS membrane stencil mask. 3-100 mm (thick) Si Place PDMS membrane on substrate. - Stacked disks of oxidizer, e.g., RDX - Al with 5 mm pitch - Si is a silicon wafer - PDMS is a conformal silicone polymer membrane -capable of achieving submicron resolution in large pattern area Master Spin coat and cure thin PDMS film.

Evaporate layer through membrane.

Effect depositions for sequential levels. Cap or align second mask for 3D structures Lift-off membrane to reveal pixel array. Cap or align second mask for 3D structures

Nano Structured Energetic Materials-Model Systems Allara-PSU

Thin film nanostacks [ fuel-(oxidizer-fuel)N- ] (~1-3 nm thick)
oxidizer layer (SAM) fuel (Al, etc.)

passivation layer template layer

Interface/Surface characterization static Capabilities:

in-situ (UHV): IR, XPS, ToF-SIMS, AFM ultrasensitive BET for planar-scale surface/pore areas Model structure characterizations: structures, chemical interactions at interfaces T dependence of structures (stability, chem degradation)

Shock Precipitation and Supercritical Fluid (SCF) Processing of Nano-sized Oxidizers: Kuo-PSU
Two solvent-based methods will be examined in this study
Shock precipitation (SP) technique; Supercritical fluid (SCF) technique. A combined SP/SCF processing technique will also be considered.

Oxidizer crystals to be considered include: RDX, ADN (ammonium dinitramide), HNF and FOX-7 (1,1-diamino-2,2-dinitroethylene). Two SCF methods will be investigated for application to energetic materials (w/ Victor Stepanov of ARDEC):
Rapid Expansion of Supercritical Solutions (RESS). Supercritical Anti-Solvent precipitation (SAS). Rapid mixing via opposed-jet impinging flows will be applied to increase the rate of nucleation and thus reduce the particle size while increasing yield.

Theoretical Modeling of Nano-Structured Energetic Materials from the Atomistic/Molecular Scale to the Macroscale

Coupled FE/MD/QM Simulations Vashishta, Kalia, Nakano - USC

Approach: Finite element (FE) Atomistic molecular dynamics (MD) Quantum-mechanical (QM) calculation based on density functional theory (DFT) Challenge: Seamlessly couple QM scheme & MD approach based on effective interatomic potentials Collaboratory for Advanced Computing & Simulations (CACS)
1,512 processor Intel Xeon Linux cluster at USC 2.4 million processor-hours of computing on IBM SP4 & Compaq AlphaServer at DoD Major Shared Resources Centers
Multiscale QM/MD/FE simulation (top) implemented on a Grid (bottom) of supercomputers, data archive, and virtual environment

Nano Aluminum Particle Oxidation Vashishta, Kalia, Nakano - USC

Number of Atoms: ~ 250,000 Al, ~ 550,000 O; Initial Al cluster 100 radius Metal Oxide Core-Shell Structure Oxidative Percolation Oxidation Under Closed Conditions

Oxide thickness saturates at 40 after 0.5 ns good agreement with experiment (Nieh et al., Acta mater. 44, 3781 (1996)

OAl4 clusters percolate to form a neutral shield around Al nanoparticle, which impedes oxidation

No heat dissipation allows rapid T increase in surface and core. Larger spheres correspond to oxygen and smaller spheres to aluminum; color represents the T.

RDX Molecule on Al (111) Surface Vashishta, Kalia, Nakano - USC

Quantum mechanical MD simulation in the framework of the density functional theory (DFT)

NEEM Behavior in Two-Phase Flow Environments at Meso & Macro Scales : Yang - PSU
Couple Relevant Processes at Micro and Meso Length Scales to Macroscale Phenomena Investigate the transport and combustion of nanosized particles in reactive flow environments Establish general analysis accommodating particle & thermo-fluid dynamics for two-phase flow interactions Identify key mechanisms and parameters for maximizing energy release 10
1

Aerosol Al - Air Flame

~ 1 cm

1.9 cm

10

Flame Speed (m/s)

Combustion-Wave Structure of HMXGAP PseudoSecondary Rapid Consumption of Propellant Flame Zone HCN and NO
Tsf = ~ 2000 K Major Species in Dark Zone: N2 , H2O, NO, CO, HCN, H 2CO, N2O, H2, CO2 Tdark zone= ~ 1250 K Decomposition, Evaporation, and Gas-Phase Reactions (Bubble) Ts = ~ 700 K Tmelt = 558 K GAP Polymer Residue Primary Flame Zone (HMX Vapor /Liquid Interface) Foam Layer (HMX Melt Front) Heterogeneous Solid Phase HMX GAP Dark Zone

f = 0.8
100 100

10

-1

10

-1

10

-2

10

-2

Analytical prediction Numerical prediction Experimental data

10

-6

10

-5

10

-4

Al Particle Diameter (m)

Optimization of NEEM Fabrication Techniques based on Supercritical (SCF) Processing: Yang - PSU
Numerical Modeling and Optimization of SCF Fabrication Techniques: Rapid expansion of supercritical solution (RESS) Supercritical anti-solvent precipitation (SAS) Modeling will include: Important near- and super- critical fluid phenomena, including transcritical thermodynamic and transport anomalies Parametric studies will examine effects of flow parameters and hardware design attributes on production of nano-sized materials Outcome will be improvements to existing techniques and new innovative concepts
Density gradient field
Shadowgraph images for injection of supercritical methane/ethylene fluid into subcritical environments at various conditions xCH4=0.1 and d=1.0 mm.

Pinj/Pc Tinj /Tc Pinj/Pchm g (Cp/Cv)

1.15 1.23 35.7 1.56

1.16 1.03 36.7 5.51

The Tinj/Tc=1.03 jet has a large jet expansion angle and opaque appearance due to condensation Jet expansion angle differences may come from differences in specific heat ratios and the pressure rise due to the release of latent heat during condensation

Experimental Characterization of Reactive and Mechanical Behaviors of Nano-Structured Energetic Materials

Time and space resolved spectroscopy of nanoenergetic materials: Dlott - UIUC

Approach Picosecond laser flash-heating of nanoenergetic materials (Picosecond CARS, time-resolved emission, streakscope for long distance and directional propagation) Ultrafast (sub ns) microscopy of laser-initiated materials Femtosecond IR laser, time resolved IR spectroscopy (CH, C-C, Al-O, Al-F, C-F, O-H, etc.) Femtosecond laser-driven shock compression and shock spectroscopy of nanoenergetic materials (pressure 5-10 GPa, material velocity ~0.8 km/s, shock velocity ~4 km/s (40/ps), compression factor DV = 0.2, rise time 2-3 ps, fall time 15 ps)

High repetition rate laser flash-heating (100/s) Dlott - UIUC

transparent polymer oxidizer 10 cm 40 mg sample (3 mm thick). Each shot 50 ng (150 mm diam). 105 shots per sample

100 ps oxidizer 100 nm pulse

100 ps heating pulse is matched to metal particle thermal conduction. Particle is uniformly heated, surroundings cold

1 mm

Fast Spectroscopy of Laser Initiated Nanoenergetic Materials: Dlott - UIUC

Nitrate group consumption in Alex/NC
1.0 0.8 0.6 0.4 0.2 0.0 -1
wh abr en upt rea tra n cti on sitio sc n oa ~300 ps lse ce conc.

J = 5.9 J/cm2

ONO2 survival fraction

indep 0 1 2 3 delay time (ns) 4 5

intensity (arb)

0.2% 0.5% 1.0% 2.0%

Energy release via time-resolved emission

1% in NC 5.6 J/cm2 3.9 J/cm2 1.8 J/cm2 0.4 J/cm2 2ns several ns 0 10 20 time (ns) 30

Energy release ~2 ns at low concentration Slows down at higher fluence as reaction propagates over greater distances

Surface and Subsurface Analysis of Nano Engineered Energetic Materials: Yetter - PSU
In-situ reacting energetic material studies using upright and inverted optical microscopes with high speed photography, micro particle image velocimetry, micro laser induced fluorescence and micro Raman spectrometry In-situ studies of reacting energetic materials using environmental scanning electron microscope at surface and subsurface temperatures of bulk material
Heating Stage

Examples of Diagnostics Implementation

CO2 Laser Irradiation / Ignition Source/ / Flame Propagation Energetic Material Beam Expander Microscope Objective Epi-Fluorecent Prism/Filter Cube CCD Camera

Nd:YAG Laser Microscope

CO2 Laser Irradiation / Ignition Source / Flame Propagation Spectrometer Energetic Material Microscope Objective Epi-Fluorecent Prism/Filter Cube Microscope

Sample Crucible Heated Cell of FEI Quanta 200 SEM for simulating surface processes during reaction

CCD Camera

ICCD

ESEM

Micro Burner for Combustion Analysis of Nano Composites and Nano Metallic - Metallic Oxidizer Systems: Yetter - PSU
Igniter High-Speed Camera Optical Combustion Chamber Thermite Mixture Pyrometer

Formulate and study the reaction dynamics of nano-composite thermite systems Investigate systems that produce significant gas at high-energy release rates Determine the effect of composition and physical characteristics of the trapped gas, initial temperature, and pressure on regression rates of mixtures

Molten Product Container

Optical Combustion Chamber Ignite thermite mixture or pressed pellet to study effect of pressure, initial temperature, trapped gas effect High-speed video records to determine regression rate Pyrometer to measure the surface temperature of the condensed phase products LIF to measure presence of AlO

Formulation and Combustion Analysis of New and Advanced Nano-Energetic Materials and Propellants Kuo - PSU
Burning Rate Measurements of Newly Processed Propellants Burning Surface Observation of Propellants with Nano-Particles Laser Ignition Characteristics of New propellants with Nanosized Energetic Particles
Solid Propellant Strand Burner: capabilities/features Optically accessible Up to 9,500 psi capability Temperature control 60oC < T < 80o
100 AHE/AME AHE/Nano-RDX 3.2

2.8

10 Burn Rate

2.4

Burning Rate Ratio

1 AME - RDX/BBA/Alex Nano-RDX/BBA/Alex AHE - HNF/RDX/BBA/AL 0.1 1000 10 Pressure [psig]

4

1.6

1 mm Time [ms]:0 140 270 450 630

1.2

10

0.8

Propellant burning at 8,000 psi

Interactions External to MURI TEAM

Center for NanoEnergetic Materials ARO DURINT

Synthesis & Assembly

DoD and DoE Laboratories

Theoretical Simulation & Modeling

NEEM

Experimental Characterization & Diagnostics

Energetic Materials Design ARO MURI

Industry

Emails of Team Member

David Allara, PSU: dla3@psu.edu Ralph Nuzzo, UIUC: r-nuzzo@uiuc.edu Dana Dlott, UIUC: dlott@scs.uiuc.edu Priya Vashishta, USC: priyav@usc.edu Rajiv Kalia, USC: rkalia@usc.edu Aiichiro Nakano, USC: anakano@usc.edu Vigor Yang, PSU: vigor@psu.edu Richard Yetter, PSU: rayetter@psu.edu Kenneth Kuo, PSU: kenkuo@psu.edu