Effects of residual solvent dimethyl formamide on the solid phase ripening of ultrafine explosive 2,2′,4,4′,6,6′-hexanitrostilbene

Abstract

Nowadays, ultrafine explosives are widely used in military fields. Ultrafine 2,2′,4,4′,6,6′-hexanitrostilbene (HNS) has emerged as an optimal primer for explosion foil initiators due to its excellent thermal stability and high-voltage short-pulse initiation performance. However, the solid phase ripening of ultrafine HNS leads to a degradation in its impact detonation performance. Previous studies have indicated that residual dimethyl formamide (DMF), which is present in ultrafine HNS prepared using the recrystallization method, affects ultrafine HNS ripening. The mechanism of residual solvent effects on solid phase ripening of ultrafine HNS is unclear. In this work, the specific surface area (SSA) derived from small angle X-ray scattering (SAXS) was utilized for kinetic fitting analysis to explore the mechanism by which residual solvents enhance the solid phase ripening of ultrafine HNS. The results of the SSA measured by in-situ SAXS under conditions of 150 °C for 40 h revealed that the sample with 0.2% residual DMF exhibited a 21.51% decrease in SSA, whereas the sample with only 0.04% residual DMF showed a decrease of 15.66%. Furthermore, the higher amounts of residual DMF accelerated the reduction in SSA with time. Kinetic fitting analysis demonstrated that reducing residual DMF would lower both the activation energy and the pre-exponential factor, consequently decreasing the rate constant of solid phase ripening. The mechanism was speculated that it primarily facilitated the Ostwald ripening (OR). Additionally, contrast variation small angle X-ray scattering (CV-SAXS) confirmed that coating of ultrafine HNS particles is an effective method for inhibiting ripening, significantly reducing both the rate and extent of ripening of ultrafine HNS. This study predicts how residual solvents impact the solid phase ripening process of ultrafine HNS and proposes strategies for enhancing the long-term stability of ultrafine explosives.