Date of Award

Fall 2014

Document Type


Degree Name

Doctor of Philosophy in Materials Science and Engineering - (Ph.D.)


Committee for the Interdisciplinary Program in Materials Science and Engineering

First Advisor

N. M. Ravindra

Second Advisor

Zafar Iqbal

Third Advisor

Xianqin Wang

Fourth Advisor

Frank J. Owens

Fifth Advisor

Cristiano L. Dias


With the urgent need for new environmentally-friendly energetic materials, the field of polymeric nitrogen, predicted to be a high energy density energetic, is now at a critical stage in its development. In spite of extensive first principles calculations regarding the existence and stability of different polymeric nitrogen structures, their successful syntheses have been rare. This dissertation describes the first detailed study of a plasma-enhanced chemical vapor deposition (PECVD) approach to the synthesis of polymeric nitrogen. PECVD provides non-equilibrium conditions known to produce high pressure-temperature phases. Molecular nitrogen mixed with hydrogen and argon is used as the gas phase precursor to provide nitrogen and passivating hydrogen species. In addition, either solid sodium and lithium azide or azide solution infiltrated sheets of carbon nanotube substrates have been used to initiate plasma polymerization to a polymeric nitrogen phase. Characterization of the samples produced were conducted using micro-Raman spectroscopy, attenuated total reflectance-Fourier transform infrared spectroscopy, powder X-ray diffraction, and temperature programmed desorption. Sample morphologies and compositions have also been performed using scanning electron microscopy combined with energy- dispersive X-ray analysis. The results show that a mixture of polymeric nitrogen phases is formed that is stable under ambient conditions and decompose near 400°C. The long-sought-after cubic-gauche polymeric nitrogen (cg-PN) phase, produced only in a diamond anvil cell at high pressure high temperature conditions and not recoverable under ambient conditions, is shown by the powder diffraction data to be one of the polymeric nitrogen phases synthesized by the plasma process. Density Functional Theory (DFT) calculations were also used to investigate the metastability of cg-PN and that of related nitrogen clusters at ambient conditions in order to understand some of the results. Although these phases were obtained with and without carbon nanotube substrates, the spectroscopic results suggest that carbon nanotubes play a significant role in faster and more efficient plasma synthesis possibly due to stabilization of a PN phase inside the walls of carbon nanotubes. The effect of carbon nanotubes on polymeric nitrogen growth will be investigated by transmission electron microscopy in future studies.