Kenneth E. Lee

Effects of Very Small Particle Size on Processing and Safety Properties of Energetic Formulations

Described in this paper are ongoing research efforts at ATK Thiokol on new formulations of gun propellants and explosives containing nano-sized materials. Funding for this work was provided both internally and by ARDEC. The nano-material properties as well as selected properties of intermediate compositions are reported. The explosives section of this paper focuses on the theoretical evaluation of nano-aluminum in explosives. The theoretical cylinder expansion energy of two common aluminized explosives, PAX-3 and PAX-28, are examined. The comparison examines the effect of aluminum content in small aluminum particles on metal pushing performance at V/V 0 = 6.5. ATK Thiokol and TACOM-ARDEC have teamed together to study the effect of nano-sized materials on advanced ETPE gun propellants. The gun propellant section of this paper focuses on the impact of nano-sized additives, specifically TiO 2 and aluminum, on selected ETPE propellants. The safety properties of the nano-aluminum and nano-TiO 2 analogs of two previously developed gun propellants, TGD-031 and TGD-035, are presented.

Synthesis and reactivity of functionalized rhenium germyl complexes (η5-C5H5)Re(NO)(PPh3)(GePh2X); dynamic equilibria with germylene complex [(η5-C5H5)Re(NO)(PPh3)(=GePh2)]+X−

Abstract Reaction of Li+[(η5-C5H5)Re(NO)(PPh3)]− with Ph3GeCl and Ph2GeCl2 (THF, −75°C) gives germyl complexes (η5-C5H5)Re(NO)(PPh3)(GePh3) (84%) and (η5-C5H5) Re(NO)(PPh3)(GePh2Cl) (3, 82%), respectively. Reaction of 3 and (CH3)3SiOTf gives (η5-C5H5)Re(NO)(PPh3)(GePh2OTf) (4, 82%). Several properties show the triflate substituent in 4 to be extremely labile. First, reaction of 4 and pyridine to give [(η5- C5H5)Re(NO)(PPh3)(GePh2NC5H5)]+TfO− (5) is complete in

Synthesis and Reactivity of Functionalized Dimethylgermyl Complexes of the Formula (η5-C5H5)Re(NO)(PPh3)(GeMe2X); Equilibria Involving the Dimethylgermylene Complex [(η5-C5H5)Re(NO)(PPh3)(=GeMe2)]• TfO−

Abstract Addition of Me2GeCl2 to Li+ [(η5-C5H5)Re(NO)(PPh3)] gives the chiral rhenium dimethylchlorogermyl complex (η5-C5H5)Re(NO)(PPh3)(GeMe2Cl) (92%), which reacts with LiAlH, and Me3SiOTf to yield (n5-C5H5)Re(NO)-(PPh3)(GeMe2H) (74%) and (η5-C5H5)Re(NO)(PPh3)(GeMe2OTf) (3; 94%), respectively. Reactions of 3 and halide salts give (η5-C5H5)Re(NO)-(PPh3)(GeMe2X) (X=F, Br, I; 81–83%). All compounds exhibit two 1H/ 13C NMR signals for the diastereotopic GeMe 2 groups at ambient temperature, except 3 for which coalescence occurs at 211 K (Δ≠=9.6 ± 0.2 kcal/mol). This is interpreted as indicating a rapid equilibrium with the dimethylgermylene complex [(n5-C5H5)Re(NO)(PPh3)(=GeMe2)]+ TfO−.