Solid–liquid phase equilibria for binary mixtures of propellant’s stabilizers

Solid–liquid equilibria for three binary mixtures of N-(2-acetoxyethyl)-p-nitroaniline (1) + 2-nitrodiphenylamine (2), N-(2-acetoxyethyl)-p-nitroaniline (1) + ethyl centralite (2) and N-(2-acetoxyethyl)-p-nitroaniline (1) + methyl centralite (2) have been determined experimentally using differential scanning calorimeter (DSC). Simple eutectic behaviours for these systems have been observed. The experimental results have been correlated by means of NRTL and UNIQUAC equations. The root-mean-square deviations of the solubility temperatures for all measured data vary from 0.61 to 3.32 K and depend on the particular model used. The best solubility correlation has been obtained with the UNIQUAC model.     

Experimental determination and prediction of (solid + liquid) phase equilibria for binary mixtures of heavy alkanes and fatty acids methyl esters

Solid–liquid equilibria for three binary mixtures of {n-eicosane (1) + methyl palmitate (2)}, {n-tetracosane (1) + methyl stearate (2)} and {n-octacosane (1) + methyl stearate (2)} were measured using differential scanning calorimeter. Simple eutectic behaviours for these systems were observed. The experimental results were correlated by means of the modified UNIFAC (Larsen and Gmehling versions), UNIQUAC and ideal models. The root-mean-square deviations of the solubility temperatures for all measured data vary from 0.21 K (for UNIQUAC model) to 1.07 K (for Ideal model) and depend on the particular model used. The best solubility correlation was obtained with UNIQUAC model.     

Weighted product Hardy space associated with operators

Assuming that the operators L₁, L₂ are self-adjoint and {\mathrm{e}}^{-{{\displaystyle tL}}_i}(i=\mathrm{1},\mathrm{2}) satisfy the generalized Davies-Gaffney estimates, we shall prove that the weighted Hardy space {{\displaystyle H}}_{{{\displaystyle L}}_{\mathrm{1}},{{\displaystyle L}}_{\mathrm{2}},\omega }^{\mathrm{1}}({ℝ}^{{{\displaystyle n}}_{\mathrm{1}}}\times {ℝ}^{{{\displaystyle n}}_{\mathrm{2}}}) associated to operators L₁, L₂ on product domain, which is defined in terms of area function, has an atomic decomposition for some weight \omega.     

Experimental determination and prediction of (solid + liquid) phase equilibria for binary mixtures of aromatic and fatty acids methyl esters

Solid–liquid equilibria for binary mixtures of {methyl stearate (1) + biphenyl (2)}, {methyl stearate (1) + naphthalene (2)}, {methyl palmitate (1) + biphenyl (2)} and {methyl palmitate (1) + naphthalene (2)} were measured using differential scanning calorimeter. Simple eutectic behaviours for these systems were observed. The experimental results were correlated by means of the NRTL, Wilson, UNIQUAC and ideal models. The root-mean-square deviations of the solubility temperatures for all measured data vary from 0.5477 K (for UNIQUAC model) to 7.79 K; the deviations depend on the binary system studied and particular model used. The best solubility correlation was obtained with UNIQUAC model and this observation confirms previous results.     

Thermal behavior and decomposition kinetics of composite solid propellants in the presence of amide burning rate suppressants

The employment of burning rate suppressants in the solid rocket propellant formulation is long known. Different research activities have been conducted to well understand the mechanism of suppression, but literature about the action of oxamide (OXA) and azodicarbonamide (ADA) on the thermal decomposition of composite propellant is still scarce. The focus of this study is on investigating the effect of burning rate suppressants on the thermal behavior and decomposition kinetics of composite solid propellants. Thermogravimetric analysis (TG) and differential thermal analysis have been used to identify the changes in the thermal and kinetic behaviors of coolant-based propellants. Two main decomposition stages were observed. It was found that OXA played an inhibition effect on both stages, whereas the ADA acts as a catalyst in the first stage and as coolant in the second one. The activation energy dependent on the conversion rate was estimated by two model-free integral methods: Kissinger–Akahira–Sunose (KAS) and Flynn–Wall–Ozawa (FWO) based on the TG data obtained at different heating rates. The mechanism of action of coolants on the decomposition of solid propellants was confirmed by the kinetic investigation as well.     

Design and characterization of new advanced energetic biopolymers based on surface functionalized cellulosic materials

A new class of energetic biopolymers, which contain nitrate ester (O-NO₂) and nitramine (N-NO₂) as explosophoric groups, was successfully synthesized by surface modification of renewable pristine cellulose (PC) and microcrystalline cellulose (MCC) via epichlorohydrin-mediated amination followed by nitration process to produce new promising energetic aminated and nitrated cellulose and microcrystalline cellulose (APCN and AMCCN). Their structural, thermal, crystallinity and morphological features were examined and compared to those of the common cellulose nitrate. Furthermore, their energetic performances were evaluated by EXPLO5 V6.04 software. Experimental results confirm the successful chemical functionalization process to develop insensitive APCN and AMCCN with outstanding features such as nitrogen content of 15.01% and 15.39%, density of 1.692 g/cm³ and 1.708 g/cm³, and detonation velocity of 7526 m/s and 7752 m/s, respectively, which are significantly higher than those of the nitrated unmodified cellulosic biopolymers. The present investigation provides a suitable pathway to design new insensitive and energy-rich dense cellulosic biopolymers for potential application in high-performance solid propellants and composite explosives.

     

Comments on “An experimental investigation on heating rate effect in the thermal behavior of perhydrous bituminous coal during pyrolysis”

This paper has the intension of discussing about the published paper by Wu et al. (J Therm Anal Calorim 119:2195–2203, 2015). The original paper has shown some errors in quoting and using the Coats–Redfern integral kinetic equation. This discussion is focused on the employment of this model, and some arguments and clarifications are also given.     

Study on the influence of ageing on chemical and mechanical properties of N,N′-dimethyl-N,N′-diphenylcarbamide stabilized propellants

Double-base propellants undergo chemical, physical and mechanical changes upon ageing, leading to changes in ballistic performance and presenting explosive hazards. This report studies the variation of chemical and mechanical properties of aged N,N′-dimethyl-N,N′-diphenylcarbamide (methyl centralite) stabilized propellants in order to simulate and evaluate the natural ageing throughout the artificial one. Therefore, a comparative study of stabilizer depletion, plasticizers content, heat of combustion and mechanical properties such as storage modulus, loss modulus and damping of naturally and artificially aged propellants has been carried out by the following techniques: high-performance liquid chromatography (HPLC), thermogravimetric analyzer (TG), calorimeter of combustion and dynamic mechanical analyzer (DMA), respectively. The results obtained show that all properties are closely connected. In addition, the determination of stabilizer depletion, plasticizers evaporation, decrease of heat of combustion and mechanical properties are very useful for a better understanding of the decomposition and ageing behaviour of propellants. The HPLC investigation of stabilizer has shown good stability of the propellants. The results obtained for DMA have shown that some considerable changes of the mechanical and viscoelastic properties of the propellants occurred during ageing. These results confirm the results obtained by TG for the reduction of the nitroglycerine amount and the decrease of the heat of combustion.