Formulation development and characterization of cellulose acetate nitrate based propellants for improved insensitive munitions properties

AbstractCellulose acetate nitrate (CAN) was used as an insensitive energetic binder to improve the insensitive munitions (IM) properties of gun propellants to replace the M1 propellant used in 105 mm artillery charges. CAN contains the energetic nitro groups found in nitrocellulose (NC), but also acetyl functionalities, which lowered the polymer's sensitivity to heat and shock, and therefore improved its IM properties relative to NC. The formulation, development and small-scale characterization testing of several CAN-based propellants were done. The formulations, using insensitive energetic solid fillers and high-nitrogen modifiers in place of nitramine were completed. The small scale characterization testing, such as closed bomb testing, small scale sensitivity, thermal stability, and chemical compatibility were done. The mechanical response of the propellants under high-rate uni-axial compression at, hot, cold, and ambient temperatures were also completed. Critical diameter testing, hot fragment conductive ignition (HFCI) tests were done to evaluate the propellants' responses to thermal and shock stimuli. Utilizing the propellant chemical composition, theoretical predictions of erosivity were completed. All the small scale test results were utilized to down-select the promising CAN based formulations for large scale demonstration testing such as the ballistic performance and fragment impact testing in the 105 mm M67 artillery charge configurations. The test results completed in the small and large scale testing are discussed

Approaches to Open Fullerenes: Synthesis and Kinetic Stability of Diels-Alder Adducts of Substituted Isobenzofurans and C60

International audienceWe have examined the reactions of 1,3-disubstituted isobenzofurans with the fullerene C60 in the context of an approach to open a large orifice on the fullerene framework. A variety of substituted isobenzofurans (6a-h), generated from the reaction of 1,4-substituted 1,4-epoxynaphthalenes 3a-h with 3,6-bis(2- pyridyl)-1,2,4,5-tetrazine (4a) or 1,2,4,5-tetrazine (4b), were added to C60 to afford the Diels-Alder adducts 7a-h. The thermal stability of these adducts toward retro-Diels-Alder fragmentation differs greatly in solution from that in the solid state. In solution, the relatively facile retro-Diels-Alder fragmentation of monoadducts 7a and 7c, to give C60 and the free isobenzofurans 6a and 6c, have rate constants (and activation barriers) of k ) 9.29 10-5 s-1 at 70 °C (Ea ) 32.6 kcal mol-1) and k ) 1.36 10-4 s-1 at 40 °C (Ea ) 33.7 kcal mol-1), respectively, indicating that the addition of isobenzofurans to C60 is readily reversible at those temperatures. In the solid state, thermogravimetric analysis of adduct 7a indicates that its decomposition occurs only within the temperature range of 220-300 °C. As a result, these compounds can be stored at room temperature in the solid state for several weeks without significant decomposition but have to be handled within several hours in solution

Enhanced Propellant Performance via Environmentally Friendly Curable Surface Coating

Surface coating of granular propellants is widely used in a multiplicity of propellants for small, medium and large caliber ammunition. All small caliber ball propellants exhibit burning progressivity due to application of effective deterrent coatings. Large perforated propellant grains have also begun utilizing plasticizing and impregnated deterrent coatings with the purpose of increasing charge weights for greater energy and velocity for the projectile. The deterrent coating and impregnation process utilizes volatile organic compounds (VOCs) and hazardous air pollutants (HAPs) which results in propellants that need to be forced air dried which impacts air quality. Propellants undergo temperature fluctuations during their life. Diffusion coefficients vary exponentially with variations in temperature. A small temperature increase can induce a faster migration, even over a short period of time, which can lead to large deviations in the concentration. This large concentration change in the ammunition becomes a safety or performance liability. The presence of both polymeric deterrents and nitroglycerin(NG) in the nitrocellulose matrix and organic solvents leads to higher diffusion rates. This results in continued emissions of VOCs and HAPs. Conventional polymers tend to partition within the propellant matrix. In other words, localized mixing can occur between the polymer and underlying propellant. This is due to solvent induced softening of the polymer vehicle over the propellant grain. In effect this creates a path where migration can occur. Since nitrate esters, like NG, are relatively small, it can exude to the surface and create a highly unstable and dangerous situation for the warfighter. Curable polymers do not suffer from this partitioning due to “melting” because no VOC solvents are present. They remain surface coated. The small scale characterization testing, such as closed bomb testing, small scale sensitivity, thermal stability, and chemical compatibility, will be presented. The 30 mm gun demonstration firing data at hot, cold, and ambient temperatures will also be presented

Innovative boron nitride-doped propellants

The U.S. military has a need for more powerful propellants with balanced/stoichiometric amounts of fuel and oxidants. However, balanced and more powerful propellants lead to accelerated gun barrel erosion and markedly shortened useful barrel life. Boron nitride (BN) is an interesting potential additive for propellants that could reduce gun wear effects in advanced propellants (US patent pending 2015-026P). Hexagonal boron nitride is a good lubricant that can provide wear resistance and lower flame temperatures for gun barrels. Further, boron can dope steel, which drastically improves its strength and wear resistance, and can block the formation of softer carbides. A scalable synthesis method for producing boron nitride nano-particles that can be readily dispersed into propellants has been developed. Even dispersion of the nano-particles in a double-base propellant has been demonstrated using a solvent-based processing approach. Stability of a composite propellant with the BN additive was verified. In this paper, results from propellant testing of boron nitride nano-composite propellants are presented, including closed bomb and wear and erosion testing. Detailed characterization of the erosion tester substrates before and after firing was obtained by electron microscopy, inductively coupled plasma and x-ray photoelectron spectroscopy. This promising boron nitride additive shows the ability to improve gun wear and erosion resistance without any destabilizing effects to the propellant. Potential applications could include less erosive propellants in propellant ammunition for large, medium and small diameter fire arms