Nano-Voids in Ultrafine Explosive Particles: Characterization and Effects on Thermal Stability.

Ultrafine explosives show high safety and reliable initiation and have been widely used in aerospace, military, and industrial systems. The outstanding performance of ultrafine explosives is largely given by the unique void defects according to the simulation results. However, the structures and effects of internal nano-voids in ultrafine explosive particles have been rarely investigated experimentally. In this work, contrast-variation small angle X-ray scattering was verified to reliably measure the structures of internal nano-voids in ultrafine explosive 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105) and 2,2',4,4',6,6'-hexanitro diphenylethylene (HNS). The size of nano-voids is around 10 nm, and the estimated number of nano-voids in a single particle is considerable. Moreover, the thermal stability of ultrafine LLM-105 was improved via changing the structures of nano-voids. This work provides a methodology for the study of nano-void defects in ultrafine organic particles and may pave the path to enhance the performance of ultrafine explosives via defect engineering.

Rotational Cluster Anion Enabling Superionic Conductivity in Sodium-Rich Antiperovskite Na3OBH4.

Sodium superionic conductors are keys to develop high safety and low cost all-solid-state sodium batteries. Among developed sodium ionic conductors, antiperovskite-type ionic conductors have attracted vast interest due to their high structural tolerance and good formability. Herein, we successfully synthesize Na3OBH4 with cubic antiperovskite structure by solid-state reaction from Na2O and NaBH4. Na3OBH4 exhibits ionic conductivity of 4.4 × 10-3 S cm-1 at room temperature (1.1 × 10-2 S cm-1 at 328 K) and activation energy of 0.25 eV. The ionic conductivity is 4 orders of magnitude higher than the existing antiperovskite Na3OX (X = Cl, Br, I). It is shown that such enhancement is not only due to the specific cubic antiperovskite structure of Na3OBH4 but also because of the rotation of BH4 cluster anion. This work deepens the understanding of the antiperovskite structure and the role of cluster anions for superionic conduction.

Metastable tetragonal Cu2Se hyperbranched structures: large-scale preparation and tunable electrical and optical response regulated by phase conversion.

Despite the promising applications of copper selenide nanoparticles, an in-depth elucidation of the inherent properties of tetragonal Cu(2)Se (ß-Cu(2)Se) has not been performed because of the lack of a facile synthesis on the nanoscale and an energy-intensive strategy is usually employed. In this work, a facile wet-chemical strategy, employing HCOOH as reducing agent, has been developed to access single-crystalline metastable ß-Cu(2)Se hyperbranched architectures for the first time. The process avoids hazardous chemistry and high temperatures, and thus opens up a facile approach to the large-scale low-cost preparation of metastable ß-Cu(2)Se hyperbranched architectures. A possible growth mechanism to explain the formation of the ß-Cu(2)Se dendritic morphology has been proposed based on time-dependent shape evolution. Further investigations revealed that the metastable ß-Cu(2)Se can convert into the thermodynamically more stable cubic α-Cu(2-x)Se maintaining the dendritic morphology. An increase in electrical conductivity and a tunable optical response were observed under ambient conditions. This behavior can be explained by the oxidation of the surface of the ß-Cu(2)Se hyperbranched structures, ultimately leading to solid-state phase conversion from ß-Cu(2)Se into superionic conductor α-Cu(1.8)Se, which has potential applications in energy-related devices and sensors.

The influence of temperature and component proportion on stability, sensitivity, and mechanical properties of LLM-105/HMX co-crystals via molecular dynamics simulation.

Based on molecular dynamics (MD) simulation, the binding energy, cohesive energy density (CED), bond length, and mechanical parameters were calculated for 2,6-diamino-3,5-dinitropyrazine-l-oxide (LLM-105) crystal, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) crystal, and their co-crystals under different temperatures. Three LLM-105/HMX patterns were constructed to investigate the influence of component proportion on structures and properties of co-crystals, in which the mole ratios of LLM-105 and HMX are 1:1, 1:2, and 2:1. The effect of temperature and components on the stability and sensitivity were investigated as well. The results show that the binding energies, CED and mechanical parameters of all the co-crystals, decrease when the temperature increases from 248 to 398 K, while their maximum N-NO2 bond length (Lmax) increases with rising temperature, indicating that the sensitivities increase and stabilities decrease when temperature rises. At all temperatures, co-crystals exhibit larger CED and shorter bond length than that of single explosive, demonstrating that they are more stable and less sensitive than single crystal, where the stability of co-crystals was ordered as 2:1>1:1>1:2. Moreover, the bulk modulus (K) and shear modulus (G) of co-crystals are lower than that of HMX, conversely, the Cauchy pressure and K/G are higher than that of HMX, implying co-crystals have better ductility. Finally, the 2:1 ratio of LLM-105/HMX co-crystal was identified as the excellent one, owning to the highest binding energy, highest CED, shortest Lmax, and greatest ductility. Graphical Abstract Models of LLM-105/HMX and one of the properties.

Environmentally friendly gamma-MnO2 hexagon-based nanoarchitectures: structural understanding and their energy-saving applications.

Although about 200,000 metric tons of gamma-MnO(2) are used annually worldwide for industrial applications, the gamma-MnO(2) structure is still known to possess a highly ambiguous crystal lattice. To better understand the gamma-MnO(2) atomic structure, hexagon-based nanoarchitectures were successfully synthesized and used to elucidate its internal structure for the present work. The structural analysis results, obtained from the hexagon-based nanoarchitectures, clearly show the coexistence of akhtenskite (epsilon-MnO(2)), pyrolusite (beta-MnO(2)), and ramsdellite in the so-called gamma-MnO(2) phase and verified the heterogeneous phase assembly of the gamma-MnO(2) state, which violates the well-known "De Wolff" model and derivative models, but partially accords with Heuer's results. Furthermore, heterogeneous gamma-MnO(2) assembly was found to be a metastable structure under hydrothermal conditions, and the individual components of the heterogeneous gamma-MnO(2) system have structural similarities and a high lattice matches with pyrolusite (beta-MnO(2)). The as-obtained gamma-MnO(2) nanoarchitectures are nontoxic and environmentally friendly, and the application of such nanoarchitectures as support matrices successfully mitigates the common problems for phase-change materials of inorganic salts, such as phase separation and supercooling-effects, thereby showing prospect in energy-saving applications in future "smart-house" systems.

Contrast Variation Small Angle Neutron Scattering Investigation of Micro- and Nano-Sized TATB.

Small angle neutron scattering (SANS) with contrast variation was used to characterize the fractal behavior and embedded porosity of micro/nano-sized 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) crystallites, gauging the effects of particle sizes on the microstructural features. Scattering results reveal that the external surface of micro-sized TATB crystallites are continuous and smooth interfaces and their internal pores display a surface fractal structure (surface fractal dimension 2.15 < DS < 2.25), while the external surface of nano-sized TATB particles exhibit a surface fractal structure (surface fractal dimension 2.36 < DS < 2.55) and their internal pores show a two-level volume fractal structure (large voids consist of small voids). The voids volume fraction of nano-sized TATB particles are found increased distinctively when compared with micro-sized TATB particles on length scale between 1 nm and 100 nm. Specific surface areas are also estimated based on Porod law method, which are coincident with Brunauer-Emmett-Teller (BET) measurements. The contrast variation technique distinguishes the information of internal voids from external surface, suggesting SANS is a powerful tool for determining the microstructural features, which can be used to establish the relationship between microstructures and properties of micro/nano-energetic materials.

Theoretical calculation into the effect of molar ratio on the structures, stability, mechanical properties and detonation performance of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane/ 1,3,5-trinitro-1,3,5-triazacyco-hexane cocrystal.

Molecular dynamics (MD) simulation was conducted to research the effect of molar ratio on the thermal stability, mechanical properties, and detonation performance of HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane)/RDX (1,3,5-trinitro-1,3,5-triazacyco-hexane) cocrystal explosive at ambient condition. The binding energy, mechanical properties, and the detonation parameters of the pure ß-HMX, RDX crystal, and the cocrystal models were got and contrasted. The results demonstrate that molar ratio has a great influence on the properties of the cocrystal system. The binding energy of the cocrystals has the maximum values at the 1:1 molar ratio, indicating that the stability of HMX/RDX(1:1) cocrystal is the best and HMX and RDX may prefer to cocrystallizing at 1:1 molar ratio. What's more, the tensile modulus (E) and shear modulus (G) of the HMX/RDX(1:1) cocrystals have the minimum value, while the C12-C44 and K/G have the maximum value, implying that the cocrystal at 1:1 molar ratio has the best mechanical properties. Simultaneously, the E, K, and G of the cocrystals are all smaller than those of ß-HMX's and generally larger than those RDX's, while the Cauchy pressure (C12-C44) and K/G ratio were greater, demonstrating that cocrystallizing can improve the brittleness and enhance the ductility. The detonation velocity (D) and detonation pressure (P) decrease with the rising RDX content, while the properties are still superior to the pure RDX crystal; thus, the energy properties of the cocrystal are still excellent. In a word, HMX/RDX cocrystal at 1:1 molar ratio has the best thermal stability, mechanical properties, and the excellent energetic performance.

Theoretical investigation into the influence of molar ratio on mixture system: α, γ, δ-HMX molecules coexisting with ß-HMX crystal.

Molecular dynamics (MD) simulation was conducted to research the effect of molar ratios for α/ß-HMX, γ/ß-HMX, and δ/ß-HMX(octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) mixture systems on thermal stability, sensitivity, and mechanical properties of explosives, and the computing models were established by Materials Studio (MS). The binding energies, the maximum trigger bond length (LN-NO2), cohesive energy density as well as mechanical properties of the mixture systems and the pure ß-HMX crystal were obtained and contrasted. The results demonstrate that the molar ratios have great influence on the binding capacity of molecules between α, γ, δ-HMX, and ß-HMX in the mixture systems. The binding energies decrease with the increase of molecular molar ratio and have the maximum values at the 1:1 M ratio. The maximum trigger bond length does not change apparently after mixing, while the cohesive energy density (CED) increases as the molar ratio increases but are all smaller than the pure ß-HMX crystal, demonstrating that the sensitivity of the mixture systems increases. The mechanical properties decrease after mixture, which illustrates that the mechanical properties of the pure crystal are superior to the mixture systems.

Microstructure Changes in Polyester Polyurethane upon Thermal and Humid Aging.

The microstructure of compression molded Estane 5703 films exposed to 11%, 45%, and 80% relative humidity and 70 °C for 1 and 2 months has been studied by small-angle neutron scattering (SANS), Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). Scattering data indicated increase of the interdomain distance and domain size with a higher humidity and longer aging time. GPC data showed a progressive shortening of polyurethane chains with increasing humidity and aging time. The shortening of the polyurethane chains caused a drop of the glass transition temperature of soft segments, and promoted crystallization of the soft segments during long-time storage of the aged samples at room temperature. FTIR showed a substantial increase in the number of inter-urethane H-bonds in the aged samples. This correlates with the increase of the hard domain size and the degree of phase separation as measured by SANS. The data collected reveals that the reduced steric hindrance caused by hydrolysis of ester links in polybutylene adipate residues promotes the organization of hard segments into domains, leading to the increase of domain size and distance, as well as phase segregation in aged Estane. These findings provide insight into the effects of humidity and thermal aging on the microstructure of aged polyester urethane from molecular to nanoscale level.

Topochemical transformation route to atomically thick Co3O4 nanosheets realizing enhanced lithium storage performance.

We first demonstrate the rational design and fabrication of novel atomically thick Co3O4 nanosheets (ATCNs) with a specific facet exposed by topochemical transformation from layered intermediate precursors to optimize energy storage. The eminently enhanced lithium storage performance can be attributed not only to the synergistic advantages of inorganic graphene analogues but also the increase of Co(2+) atoms and charge redistribution for ATCNs, which were first revealed by means of synchrotron radiation X-ray absorption near-edge spectroscopy. This work opens the window for the preparation of non-layered atomically thick nanosheets, which will significantly enrich the species of inorganic graphene analogues and optimize energy storage by reasonable materials design and fabrication.