Polymeric Nitrogen Stabilized on Carbon Nanotubes: A Highly Energetic, Green Explosive

Presented to the National Capital Region ENERGETICS SYMPOSIUM

April 27-29, 2009, College of Southern Maryland, La Plata Campus

Thelma G. Manning, RDAR-MEE-W, Energetics & Warheads Division, Propulsion Technology & Direct Fire Branch, ARDEC, Picatinny Arsenal Zafar Iqbal, New Jersey Institute of Technology, Newark, New Jersey
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Outline of talk

Introduction and Background: Structure and Energetics of Polymeric Nitrogen Planned Approach Early Results Summary and conclusions, go-forward and relevance to DoD

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Polymeric Nitrogen
Kuhl et al (Lawrence Livermore National Laboratory - 39th ICT Conference on Energetic Materials,2008) has theoretically determined the detonation properties of N4/N8 clusters with a face-centered- cubic (FCC) structure using numerical simulations Polymeric forms of N8 promise a factor of 10 theoretical increase in several performance metrics Has single-bonded polymeric phase (cubic gauche) of nitrogen with diamond like structure Nitrogen is uniquely stable because the diatomic molecule is bound by a triple bond (954 kJ/mole) Therefore decomposition of single-bonded (160 kJ/mole) polymeric nitrogen into N2 is highly exothermic FCC cubic polymeric nitrogen has been prepared by Eremets et al in minute quantities [Nature Materials 3 558, 2004] in a high pressure cell under 110 GPa pressure at 2000K

TNT

N8(fcc) 6673 3.1 19.74 3.14

Hd

1100 cal/g 1.63 g/cc 6.93 km/s 0.210 Mbar

0
DCJ

PCJ

Single-bonded polymeric phase (cubic gauche) of nitrogen with diamond-like structure

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Simulated Average Pressure in Bunker, TNT vs Polymeric N8

TNT

N8

Tens of Bars

Tens of Bars

Lower Room

Lower Room Upper

Upper

After: Ulrich et al, SAIC

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Polymeric Nitrogen Stabilized on Carbon Nanotubes

N4/N8 species deposited on into carbon nanotubes studied theoretically by Abou-Rachid et al using first principles molecular simulations Predicted that doped N4 and encapsulated N8 in CNT should be stable. Possible stable structures in CNTs predicted Preliminary synthesis of nitrogen doped multiwall carbon nanotubes by CVD indicated N-doping
Abou-Rachid et al, Phys. Rev. Lett. 100, 198401 (2008); Proc. ISICP, 2007.

Encapsulated N8 in CNT.

SEM

TEM

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Approach Synthesize polymeric nitrogen stabilized on sidewalls of carbon nanotubes using following steps
Single wall carbon nanotubes formed into self-assembled nanopaper membranes and then nitrogen doped Multiwall carbon nanotubes doped with nitrogen in-situ during thermal or plasma-enhanced CVD synthesis and then formed into nanopaper membranes Nanopaper electrodes used to perform electrochemical oxidation [Iqbal et al, Chem. Phys. Lett. 407, 68 (2005)] of nitrogen-doped nanotubes in sodium azide solution under uvirradiation to form polymeric nitrogen via N2 and N4 radicals

Process scale-up routes: microwave- and plasmaenhanced reaction techniques [Iqbal et al, Carbon 43, 1015 (2005); Jour. Amer. Chem. Soc. 128, 95 (2006); Synthetic Metals 158, 425 (2008)]

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Carbon Nanotube Synthesis

Thermal Chemical Vapor Deposition

Flow Controller Catalyst

N-CNTs
Vacuum Sensor

Gas C sources

H2 Ar
Furnace

melamine
Alcohol

To Vacuum Pump

Water bubbler

Plasma-Enhanced Chemical Vapor Deposition

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Electrochemical Reactions

Electrochemical oxidation reactions on N-doped carbon nanotube (CNT) electrode using cyclic voltammetry in 0.6 M NaN3 solution
oxidation Cyclic Voltammogram reduction
Electrochemical oxidation/reduction reactions at working CNT electrode: 2N3- 2N3o (radicals) +2e oxidation N4o + N2o
NaN3 in H2O

N:CNT working electrode

UV irradiation to create N2 and N4 radical species in solution through quartz window

Reduction would involve conversion of radicals back to ions, but if active sites present in N-doped CNTs, N4 radicals forming N8 clusters will be encapsulated on CNTs and oxidation reactions would predominate. In early experiments Raman spectroscopy will check for N4 and N8 clusters and polymeric networks on CNT sidewalls

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Results: Cyclic Voltammetry in NaN3 with carbon nanotube working electrode; Raman, DSC and TGA results

Raman oxidation Polymeric N

Eremets et al [Nature Materials 3, 558-563, 2004]

oxidation o

DSC & TGA

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More TGA and DSC results

Pure NaN3 powder 2 step exothermic decomp TGA

DSC O2/surfactant N4/N8

Nanopaper electrochemically oxidized in NaN3

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Summary, Conclusions and Go-forward

Results consistent with formation of polymeric nitrogen N4,N8 clusters on nanotube walls but further enhancement of the reaction and more detailed characterization needed one challenge is interference in Raman from intrinsic higher order line from CNTs in the 800 cm-1 range Evidence of two step decomposition at higher temperature in NaN3 reacted nanopaper from DSC and TGA. More work, e.g. DTA, needed for clearer understanding On-going work for higher yields Dope nanotube walls with N and then perform electrochemical reaction; also use high intensity uv source immersed in electrolyte Use direct CVD-synthesized N-doped multiwall nanotubes as template Perform nanotube reaction in solution with NaN3 under microwaves React NaN3 with nanotubes in plasma in PE-CVD reactor
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Relevance to the DoD Performance Parameters

Polynitrogen systems containing N8 and N4 promise a factor of 10 theoretically increased performance when compared to TNT see table on right. The synthesized nanotube - N8 and N4 will be compared with TNT performance characteristics listed in table On successful synthesis the nanotube- N4/N8 energetic material will be evaluated by incorporation into composite gun propellant in nitrocellulose binder system using JA2 as the baseline and explosives formulation as replacement for TNT

TNT

CNT-N4/N8
(FCC)

Hd ( cal/g) 0 (g/ cc) DCJ (km/s) PCJ (Mbar)

1100 1.63 6.93 0.210

6673 3.1 19.74 3.14

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Acknowledgement Project funded by US ARMY RDECOM ARDEC, RDAR-MEE-W, ACKNOWLEDGEMENT ENERGETICS & WARHEADS DIVISION, PICATINNY ARSENAL, NJ 07806 Contract DAAE30-01-9-0800 TOSA 0109 MOD 2

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