Nanophase materials and nanocomposites, characterized by an ultra fine grain size (less than 100 nm) have attracted wide spread interest in recent years by virtue of their unusual mechanical, electrical, optical, magnetic, and energetic properties. Studies have shown that the thermal behavior of nano‐scaled materials is quite different from micron‐sized powders. Nanosized metallic and explosive powders have been used as solid propellant and explosive mixtures to increase efficiency. At the same time recent studies reveal that the presence of nanosized metals in propellants does not necessary translate into an increased burning rate and burning temperature. The reasons of this effect are far from being clear. This paper presents a new approach to the production of nanocomposites of some energetic materials – ammonium nitrite, cyclotrimethylene trinitramine (RDX), and aluminum – by the vacuum co‐deposition technique. The thermal behavior of the synthesized nanopowder and nanocomposites is investigated. A substantial difference in burning rate of RDX nanopowder has been found in comparison to micron‐sized material. Experimental results allow investigating the effects of nanosized materials on the combustion characteristics.
The modern “energetic‐on‐a‐chip” trend envisages reducing size and cost while increasing safety and maintaining the performance of energetic articles. However, the fabrication of reactive structures at micro‐ and nanoscales remains a challenge due to the spatial limitations of traditional tools and technologies. These mature techniques, such as melt casting or slurry curing, represent the formative approach to design as distinct from the emerging additive manufacturing (3D printing). The present review discusses various methods of additive manufacturing based on their governing principles, robustness, sample throughput, feasible compositions and available geometries. For chemical composition, nanothermites are among the most promising systems due to their high ignition fidelity and energetic performance. Applications of reactive microstructures are highlighted, including initiators, thrusters, gun propellants, caseless ammunition, joining and biocidal agents. A better understanding of the combustion and detonation phenomena at the micro‐ and nanoscale along with the advancement of deposition technologies will bring further developments in this field, particularly for the design of micro/nanoelectromechanical systems (MEMS/NEMS) and propellant grains with improved performance.
This study focused on kinetic modeling of a specific type of multistep heterogeneous reaction comprising exothermic and endothermic reaction steps, as exemplified by the practical kinetic analysis of the experimental kinetic curves for the thermal decomposition of molten ammonium dinitramide (ADN). It is known that the thermal decomposition of ADN occurs as a consecutive two step mass-loss process comprising the decomposition of ADN and subsequent evaporation/decomposition of in situ generated ammonium nitrate. These reaction steps provide exothermic and endothermic contributions, respectively, to the overall thermal effect. The overall reaction process was deconvoluted into two reaction steps using simultaneously recorded thermogravimetry and differential scanning calorimetry (TG-DSC) curves by considering the different physical meanings of the kinetic data derived from TG and DSC by P value analysis. The kinetic data thus separated into exothermic and endothermic reaction steps were kinetically characterized using kinetic computation methods including isoconversional method, combined kinetic analysis, and master plot method. The overall kinetic behavior was reproduced as the sum of the kinetic equations for each reaction step considering the contributions to the rate data derived from TG and DSC. During reproduction of the kinetic behavior, the kinetic parameters and contributions of each reaction step were optimized using kinetic deconvolution analysis. As a result, the thermal decomposition of ADN was successfully modeled as partially overlapping exothermic and endothermic reaction steps. The logic of the kinetic modeling was critically examined, and the practical usefulness of phenomenological modeling for the thermal decomposition of ADN was illustrated to demonstrate the validity of the methodology and its applicability to similar complex reaction processes.
Thermal decomposition of solids often includes simultaneous occurrence of the overlapping processes with unequal contributions in a specific physical quantity variation during the overall reaction (e.g., the opposite effects of decomposition and evaporation on the caloric signal). Kinetic analysis for such reactions is not a straightforward, while the applicability of common kinetic calculation methods to the particular complex processes has to be justified. This study focused on the critical analysis of the available kinetic calculation methods applied to the mathematically simulated thermogravimetry (TG) and differential scanning calorimetry (DSC) data. Comparing the calculated kinetic parameters with true kinetic parameters (used to simulate the thermoanalytical curves), some caveats in the application of the Kissinger, isoconversional Friedman, Vyazovkin and Flynn–Wall–Ozawa methods, mathematical and kinetic deconvolution approaches and formal kinetic description were highlighted. The model-fitting approach using simultaneously TG and DSC data was found to be the most useful for the complex processes assumed in the study.
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