Elaboration, Characterization and Thermal Decomposition Kinetics of New Nanoenergetic Composite Based on Hydrazine 3-Nitro-1,2,4-triazol-5-one and Nanostructured Cellulose Nitrate.

This research aims to develop new high-energy dense ordinary- and nano-energetic composites based on hydrazine 3-nitro-1,2,4-triazol-5-one (HNTO) and nitrated cellulose and nanostructured nitrocellulose (NC and NMCC). The elaborated energetic formulations (HNTO/NC and HNTO/NMCC) were fully characterized in terms of their chemical compatibility, morphology, thermal stability, and energetic performance. The experimental findings implied that the designed HNTO/NC and HNTO/NMCC formulations have good compatibilities with attractive characteristics such as density greater than 1.780 g/cm3 and impact sensitivity around 6 J. Furthermore, theoretical performance calculations (EXPLO5 V6.04) displayed that the optimal composition of the as-prepared energetic composites yielded excellent specific impulses and detonation velocities, which increased from 205.7 s and 7908 m/s for HNTO/NC to 209.6 s and 8064 m/s for HNTO/NMCC. Moreover, deep insight on the multi-step kinetic behaviors of the as-prepared formulations was provided based on the measured DSC data combined with isoconversional kinetic methods. It is revealed that both energetic composites undergo three consecutive exothermic events with satisfactory activation energies in the range of 139-166 kJ/mol for HNTO/NC and 119-134 kJ/mol for HNTO/NMCC. Overall, this research displayed that the new developed nanoenergetic composite based on nitrated cellulose nanostructure could serve as a promising candidate for practical applications in solid rocket propellants and composite explosives.

Unravelling the thermal behavior and kinetics of unsaturated polyester resin supplemented with organo-nanoclay.

The integration of nanoclays within polymeric systems to develop high-performance materials is an emerging research field that has garnered significant attention. In this context, an organically modified montmorillonite (OMMT) is utilized as a reinforcing agent for unsaturated polyester resin (UPR) with loads of 1%, 3%, and 5 wt%. The modification of montmorillonite nanoclay (MMT) using a quaternary ammonium compound is performed through an effective repetitive modification process under reflux conditions. The curing behavior of the unsaturated polyester resin containing organically modified clay catalyzed with methyl ethyl ketone peroxide (MEKP) initiator and promoted by cobalt naphthenate accelerator is investigated using dynamic differential scanning calorimetry (DSC) followed by kinetic analysis using isoconversional methods. The dynamic DSC curing curves showed a bimodal exothermic peak, where two independent reactions, namely, redox and thermal decomposition of the initiator occurred. In this study, novel insights into the curing reaction of the studied UPR and UPR/OMMT systems have been revealed through the application of the Trache-Abdelaziz-Siwani (TAS) and Sbirrazzuoli (VYA/CE) isoconversional methods. These methods have enabled the elucidation of the intricate mechanisms and phenomena that impact the curing reaction, including the dilution effect in the redox reaction and the diffusion phenomenon at the end of the thermal decomposition reaction. The incorporation of nanoclay into unsaturated polyester resin (UPR) resulted in a reduction in the activation energy for both the redox and thermal reactions. Specifically, the energetic barrier decreased from 93.85 and 101.58 kJ mol-1 for pristine UPR to 60.71 and 72.93 kJ mol-1 for UPR/OMMT-5 in the redox and thermal reactions, respectively. The addition of OMMT caused a significant decrease in the pre-exponential factor. The values of UPR/OMMT-5 were 2.75 × 105 and 5.50 × 106 for the redox and thermal decomposition reactions, respectively, compared to 1.41 × 1012 and 5.13 × 1013 for UPR. The thermogravimetric analysis demonstrated that UPR/OMMT systems were more stable than UPR.

A comprehensive review on processing, characteristics, and applications of cellulose nanofibrils/graphene hybrid-based nanocomposites: Toward a synergy between two-star nanomaterials.

Nanostructured materials are fascinating since they are promising for intensely enhancing materials' performance, and they can offer multifunctional features. Creating such high-performance nanocomposites via effective and mild approaches is an inevitable requirement for sustainable materials engineering. Nanocomposites, which combine two-star nanomaterials, namely, cellulose nanofibrils (CNFs) and graphene derivatives (GNMs), have recently revealed interesting physicochemical properties and excellent performance. Despite numerous studies on the production and application of such systems, there is still a lack of concise information on their practical uses. In this review, recent progress in the production, modification, properties, and emerging uses of CNFs/GNMs hybrid-based nanocomposites in various fields such as flexible energy harvesting and storage, sensors, adsorbents, packaging, and thermal management, among others, are comprehensively examined and described based on recent investigations. Nevertheless, numerous challenges and gaps need to be addressed to successfully introduce such nanomaterials in large-scale industrial applications. This review will certainly help readers understand the design approaches and potential applications of CNFs/GNMs hybrid-based nanocomposites for which new research directions in this emerging topic are discussed.

Development and Characterization of New Energetic Composites Based on HNTO/AN Co-Crystal and Nitro-Cellulosic Materials.

To develop advanced cellulose-based energetic composites, new types of high-energy-density formulations containing hydrazine 3-nitro-1,2,4-triazol-5-one (HNTO)/ammonium nitrate (AN) cocrystals combined with nitrocellulose or nanostructured cellulose nitrate (NC and NMCC) were experimentally characterized. The prepared energetic formulations were analyzed in terms of their physicochemical properties, mechanical sensitivities, structural features, and thermal behavior. Their heats of combustion and theoretical energetic performance were assessed as well. Experimental results exhibited the inherent characteristics of the designed NC@HNTO/AN and NMCC@HNTO/AN, including improved density, specific impulse, and impact sensitivity compared to their raw compounds. Besides that, thermo-kinetic findings revealed that the as-prepared insensitive and high-energy-density composites undergo two exothermic decomposition processes, and that NC@HNTO/AN has higher thermal activity. The present study demonstrated the outstanding characteristics of the new composites and could serve as a reference for developing more advanced cellulose-based energetic formulations.

Towards Investigating the Effect of Ammonium Nitrate on the Characteristics and Thermal Decomposition Behavior of Energetic Double Base NC/DEGDN Composite.

This research work aimed to elaborate on a new modified double-base propellant containing nitrocellulose (NC), ammonium nitrate (AN), and diethylene glycol dinitrate (DEGDN). The developed AN/NC-DEGDN formulation was successfully obtained through a casting process and fully characterized in terms of its chemical structure, morphological features, and thermal behavior. Beforehand, theoretical calculation by the CEA-NASA program was applied to select the optimal composition of the formulation. Experimental findings demonstrated the homogenous dispersion of AN oxidizer in the NC-DEGDN matrix without alteration of their molecular structures. The catalytic influence of AN on the thermal decomposition behavior of NC-DEGDN film was also elucidated by thermal analyses. When AN was incorporated into the formulation, the decomposition peak temperatures for the different decomposition processes were shifted toward lower temperatures, while the total enthalpy of decomposition increased by around 1272.24 J/g. In addition, the kinetics of the thermal decomposition of the developed modified double base propellant were investigated using DSC results coupled with model kinetic approaches. It was found that the addition of AN decreases the activation energy of nitrate esters from 134.5 kJ/mol to 118.84 kJ/mol, providing evidence for its excellent catalytic effect. Overall, this investigation could serve as a reference for developing future generation of modified double-base propellants.

Cellulose nanofibrils-graphene hybrids: recent advances in fabrication, properties, and applications.

With the fast-developing social economy and the acceleration of industrialization, seeking effective renewable, sustainable, and environmentally friendly resources that show promising properties is an urgent task and a crucial means to achieve sustainable progress in the face of the growing depletion of non-renewable resources and the deterioration of environmental issues. Cellulose nanofibrils (CNFs) are natural polymeric nanomaterials with excellent biocompatibility, biodegradability, good mechanical features, high strength, low density, high specific surface area, and tunable chemistry. Their combination with other nanomaterials, such as graphene derivatives (GNMs), has been demonstrated to be effective since they produce hybrids with outstanding physicochemical properties, tailorable functionality, and high performance. In this review, recent advances in the preparation, modification, and emerging application of CNFs/GNMs hybrids are described and discussed using the latest studies. First, the concise background of nanocellulose and graphene derivatives is provided, followed by the interfacial interactions between CNFs and GNMs. The different hybrids exhibit great promise in separation, adsorption, optics, flexible electronics, energy storage, thermal management, barrier and packaging, and electromagnetic shielding. The main challenges that inhibit the applicability of these hybrids are finally highlighted, and some perspectives for future research directions are provided.

Optimized energetic HNTO/AN co-crystal and its thermal decomposition kinetics in the presence of energetic coordination nanomaterials based on functionalized graphene oxide and cobalt.

The present research aims to select the optimal molar ratio of hydrazine 3-nitro-1,2,4-triazol-5-one (HNTO) and ammonium nitrate (AN) to produce an energetic co-crystal. For a comparison purpose, the heat release, cost, density and hygroscopicity of the different co-crystals were evaluated. The obtained results indicated that HNTO/AN at the 1 : 3 ratio exhibited a higher heat release, better thermal stability, low water content and a reasonable cost, compared to other co-crystals. This new co-crystal was fully characterized through powder X-ray diffraction (XRD), infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC), confirming that this latter displayed similar characteristics to those of the co-crystal with a 1 : 1 ratio, which was recently developed. On the other hand, the catalytic activity of two energetic coordination polymers of triaminoguanidine-cobalt (T-Co) complexes, with or without graphene oxide (GO-T-Co-T), on the thermolysis of the developed co-crystal has been also assessed by DSC under non-isothermal conditions. It is revealed that these catalysts have greatly decreased the decomposition temperature of the HNTO/AN cocrystal. Moreover, because of the complete decomposition in the case of the (HNTO/AN)/GO-T-Co-T composite, the heat release has been increased as well. Isoconversional integral kinetic methods were exploited to determine the kinetic parameters of the different systems. According to the obtained results, these catalysts have a strong catalytic action on the decomposition of the co-crystal AN/HNTO for which the activation energy and the pre-exponential factor are considerably lowered. Consequently, the developed co-crystal and the energetic catalysts could be considered as potential ingredients for the next generation of composite solid propellant formulations.