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And Nano-Scale Energetic Materials for Advanced Gun Propulsion, Their Material Properties, and Their Effects on Ballistic Performance

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And Nano-Scale Energetic Materials for Advanced Gun Propulsion, Their Material Properties, and Their Effects on Ballistic Performance Cprht Wrnn & trtn h prht l f th Untd Stt (tl , Untd Stt Cd vrn th n f phtp r thr rprdtn f prhtd trl. Undr rtn ndtn pfd n th l, lbrr nd rhv r thrzd t frnh phtp r thr rprdtn. On f th pfd ndtn tht th phtp r rprdtn nt t b “d fr n prp thr thn prvt td, hlrhp, r rrh. If , r rt fr, r ltr , phtp r rprdtn fr prp n x f “fr tht r b lbl fr prht nfrnnt, h ntttn rrv th rht t rf t pt pn rdr f, n t jdnt, flfllnt f th rdr ld nvlv vltn f prht l. l t: h thr rtn th prht hl th r Inttt f hnl rrv th rht t dtrbt th th r drttn rntn nt: If d nt h t prnt th p, thn lt “ fr: frt p t: lt p n th prnt dl rn h n tn lbrr h rvd f th prnl nfrtn nd ll ntr fr th pprvl p nd brphl th f th nd drttn n rdr t prtt th dntt f I rdt nd flt. ABSTRACT NOVEL MICRON- AND NANO-SCALE ENERGETIC MATERIALS FOR ADVANCED GUN PROPULSION, THEIR MATERIAL PROPERTIES, AND THEIR EFFECTS ON BALLISTIC PERFORMANCE by Thelma Gatuz Manning This dissertation focused on the investigation of novel materials that are both energetic and inert in their micron- and nano-scale crystalline form. The characterization of the materials properties and its effects on the ballistic performance when incorporated into a composite material were evaluated as a gun propellant for application in a future weapon system for the US Army. Some of these materials may find dual use in civilian applications. Applications in small and medium arms, artillery, tank, aircraft, and shipboard gun systems will all benefit from these advancements. Not only will gun system performance be improved for greater stand-off range and accuracy, but the ability to perform consistently across a broad temperature range. Additionally, an improved performance and longer gun barrel life achievable by tailoring the combustion products, lowering the propellant flame temperature, minimum sensitivity of burning velocity to pressure, temperature and gas velocity (erosive burning) and with munitions that are insensitive to outside stimulus attack will give such systems a significant advantage during military use. In addition, "green" chemistry and lower lifecycle cost were taken into consideration during this research. The approach to be taken was to incorporate these novel materials into a gun propellant formulation by using nitramine-based micron scale cyclotrimethylene trinitramine (RDX) explosives in combination with synthesized novel ingredients in nanoscale crystalline form, characterize the material properties and predict the ballistic performance across the ballistic temperature range. The nano-scale crystalline materials evaluated consisted of polymeric nitrogen stabilized in single wall carbon nanotubes (SWNTs), nitrogenated boron nanotubes / nanofibers (BNNTs/BNNFs), nano-aluminum, and titanium dioxide. The polymeric nitrogen and the nitrogenated boron nanotubes / nanofibers (BNNTs/BNNFs), should provide an enhancement in the propellant burn rate by achieving the burn rate differential goal of 3:1 between the fast and the slow burning propellant and at the same time improve the gun propellant performance by lowering the CO/CO2 ratio and raising the / CO ratio for mitigating gun bore wear and erosion, respectively. For the synthesis approaches of polymeric nitrogen stabilized in carbon nanotubes, the following synthesis method were performed, optimized and compared: Electrochemical Reactions, Microwave Induced Electrochemical Chemical Reactions and Plasma Enhanced Chemical Vapor Deposition (PE-CVD). The Electrochemical Reaction process has proven to be the most efficient synthesis approach for the polymeric nitrogen based on analytical results obtained through Raman Spectroscopy, Laser Ablation Mass Spectroscopy, Scanning Electron Microscope, Fourier Transform Infrared-Attenuated Total Reflectance (FTIR-ATR) and Differential Scanning Calorimeter/Thermal Gravimetric Analysis (DSC/TGA). The PE-CVD is the second recommended synthesis approach to synthesize the polymeric nitrogen although a cost benefit economic analysis has to be performed which is beyond the objectives of this research work. r th nth f th ntrntd brn nntb th f th n brhdrd t ntt th rtn h prvn t b th t ptzd pr d t h lr rtn tprtr hh pprxtl 5 °C hn prd th th rtn tprtr f 95 °C hn n Mn rd (M n th thrll ndd C pr h ll l nth f brn nntb /nnfbr rrd t n M pdr l rd ( pdr tlt nd trtrd hxnl frr zlt pdr fll hvd t 95C h lt f th nntb prdd hd b n ptrp nd trnn ltrn rp nl h EM dt h th prdtn f 1- n brn nntb n th M nd Mbl Crtlln Mtrl (MCM-1 n th nth pr NOVEL MICRON- AND NANO-SCALE ENERGETIC MATERIALS FOR ADVANCED GUN PROPULSION, THEIR MATERIAL PROPERTIES, AND THEIR EFFECTS ON BALLISTIC PERFORMANCE by Thelma Gatuz Manning A Dissertation Submitted to the Faculty of New Jersey Institute of Technology in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Materials Science and Engineering Interdisciplinary Program in Materials Science and Engineering May 2010 Copyright 0 2010 by Thelma G Manning ALL RIGHTS RESERVED APPROVAL PAGE NOVEL MICRON- AND NANO-SCALE ENERGETIC MATERIALS FOR ADVANCED GUN PROPULSION, THEIR MATERIAL PROPERTIES, AND THEIR EFFECTS ON BALLISTIC PERFORMANCE Thelma Gatuz Manning 'Dr. Boris Khusid, Dissertation Co-Advisor Date Professor, Department of Chemical, Biological and Pharmaceutical Engineering, NJIT Dr. Zafar Iqbar, Dissertation Co-Advisor Date Research Professor, Department of Chemistry and Environmental Science, NJIT Dr. Nuggehalli M. Ravindra, Dissertation Committee Member Date Department Chair and Professor, Department of Physics, NJIT Marek Sosnowski, Dissertation Committee Member Date Professor, Department of Electrical and Computer Engineering, NJIT Dr. Rao Surapaneni, Dissertation Committee Member Date Energetics Lead Technical Expert US Army Armament Research, Development and Engineering Center, Picatinny, NJ IOGAICA SKEC Athr: Thelma G. Manning r: Doctor of Philosophy t f rth May 21, 1949 Undrrdt nd Grdt Edtn: • Doctor of Philosophy in Materials Science and Engineering, New Jersey Institute of Technology, Newark, NJ, 2010 • Master of Science in Mechanical Engineering, City College of New York, 1981 • Master of Science in Chemical Engineering, Polytechnic University of New York, 1977 • Master of Engineering in Chemical Engineering, University of the Philippines, Diliman, Metro Manila, Philippines 1973 • Bachelor of Science in Chemical Engineering, University of Santo Thomas, Manila, Philippines 1971 Mjr: Materials Science and Engineering rnttn nd bltn: Thelma G. Manning and Zafar Iqbal, "Polymeric Nitrogen Stabilized on Carbon Nanotubes: A Highly Energetic, Green Explosive", Chemical Physics Letters, Manuscript Number CPLETT-10-596 for Peer Review, March 26, 2010. Thelma G. Manning and Zafar Iqbal, "Polymeric Nitrogen Stabilized on Carbon Nanotubes: A Highly Energetic, Green Explosive", US Patent Provisional Application Serial Number 61/321,584 (UNCLASSIFIED), Picatinny Arsenal, NJ, April 7, 2010. v Thelma G. Manning and Zafar Iqbal, "Synthesis of Polymeric Nitrogen Stabilized on Carbon Nanotubes: A Highly Energetic, Green Explosive", 2010 Insensitive Munitions and Energetic Materials Technology Symposium, IMEMTS 2010, 11 - 14th October 2010, Munich, Germany. Thelma G. Manning and Zafar Iqbal, "Polymeric Nitrogen Stabilized on Carbon Nanotubes: A Highly Energetic, Green Explosive", Proceedings of the 41 t International ICT-Conference, FRAUNHOFER-INSTITUT FOR CHEMISCHE ECOOGIE rnhfr IC ph-vn-rnhfr-Strβ 7 737 fnztl (rhn Krlrh Grn ptd n 9 — l 1 Thelma G. Manning and Zafar Iqbal, "Polymeric Nitrogen Stabilized on Carbon Nanotubes: A Highly Energetic, Green Explosive", Proceedings of the 57th Joint Army-Navy-NASA-Air Force (JANNAF) Propulsion Meeting / 7th Modeling and Simulation Subcommittee (MSS) / 5th Liquid Propulsion Subcommittee (LPS) / 4th Spacecraft Propulsion Subcommittee (SPS) Joint Meeting, Cheyenne, Colorado Springs, Colorado, accepted May 3-7, 2010. Thelma G. Manning and Dr. Zafar Iqbal," Polymeric Nitrogen Stabilized on Carbon Nanotubes: A Highly Energetic, Green Explosive", National Capital Region Energetics Symposium, College of Southern Maryland, La Plata Campus, MD, April 27-29, 2009. Thelma Manning, Eugene Rozumov, Duncan Park Sam Moy, and Donald Chiu, ARMY Advanced Gun Propellant Formulations, Proceedings of the 55th JANNAF Propulsion Meeting / 42nd Combustion Subcommittee / 30th Airbreathing Propulsion Subcommittee / 30th Exhaust Plume Technology Subcommittee / 24th Propulsion Systems Hazards Subcommittee / 12th Spectral and In-band Radiometric Imaging of Targets and Scenes User Group Joint Meeting, U.S. Army RDECOM-ARDEC, Boston, MA, May 12-16, 2008. Thelma G. Manning, D. Chiu and D. Park," Characterization and Ballistic Properties of High Energy High Performance ETPE Gun Propellant for Future Large Caliber Applications", Proceedings of the 2005 JANNAF 40 th Combustion Sub- Committee/28th APS/22nd PSHS/ 4th MSS Joint Meeting at Charleston Convention Center & Charleston AFB, Charleston, S. Carolina, 13-17 Jun 2005. Dedicated to my beloved father and mother for their love and support throughout all these years. v ACKNOWLEDGMENT My sincerest thanks go to Professor Zafar Iqbal for his commitment, encouragement, and selfless contribution toward my academic development. I am fortunate to have him as my mentor and co-advisor. I would like to express my deepest appreciation to Professor Boris Khusid as my co-advisor and for his guidance in the characterization instrument in his class. I am very thankful to Professor Marek Sosnowski for his helpful advice on the design of experiments and operation of the plasma enhanced chemical vapor deposition equipment in his laboratory. I would also like to thank Dr Rao Surapaneni from the US Army RDECOM ARDEC for his advice, suggestions and encouragement during the experimental design of the synthesis experiments. I greatly appreciate Professor Nuggehalli Ravindra for his kind help, understanding, considerations and time for serving on my dissertation committee. I would like to thank Anitha Patlolla for showing me how to make the nanopapers and other routine laboratory work, for example, running the galvanostat—potentiometer.
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