Study of triplet kinetic of thermal decomposition reaction and sensitivity to impact and electrostatic discharge of HMX polymorphs

Journal of Thermal Analysis and Calorimetry - The polymorphs of HMX explosive show the different sensitivities to heat, friction, impact, shock, electrostatic charge, etc. Knowledge and...     

Assessment of Thermal Stability and Detonation Performance of 4-Amino-1,2,4-triazolium Nitrate as compared to 2,4,6-Trinitrotoluene for Melt-cast Explosives

4-Amino-1,2,4-triazolium nitrate (4-ATN) is an energetic and non-sensitive ionic liquid, which was introduced as a good candidate in previous works for the replacement of 2,4,6-trinitrotoluene (TNT) in melt-cast explosives. Since previous studies used pure nitric acid for nitration of 4-ATN, the effect of the use of low price industrial nitric acids (50 %, 70 % and 98 %) is investigated on the percent yields of 4-ATN. The thermogravimetric and differential scanning calorimetry (TGA/DSC) are done on the synthesized 4-ATN with impure nitric acid at a heating rate of 10 K · min^–1 by the vacuum system. The obtained TGA/DSC curves confirm decomposition of 4-ATN involving melting and dissociation. Derivative thermogravimetric (DTG) curves of 4-ATN at various heating rates are applied to obtain activation energy of thermolysis by several model-free techniques. The calculated activation energies are in the range 78.7–87.7 kJ · mol^–1, which are about 10 kJ · mol^–1 more than the reported activation energy of industrial TNT (purity 98.2 %), i.e. 66–70 kJ · mol^–1. Assessments of detonation performance of 4-ATN are also compared with TNT, which show higher detonation performance of 4-ATN. Thus, 4-ATN can be used with nitramine compounds as melt-cast explosives with higher thermal stability and detonation performance than corresponding nitramine compound/TNT explosives.     

Effect of solidification temperature of lead alloy grids on the electrochemical behavior of lead-acid battery

One of the main electrochemical characteristics of a lead-acid battery is amount of water consumption. The effect of solidification temperature on electrochemical behavior (mainly hydrogen overvoltage) of Pb–Ca–Sn–Al (0.09%, Ca; 0.9%, Sn; 0.02%, Al) and Pb–Sb–Sn (1.7%, Sb; 0.24%, Sn) alloys, which are used in making the grid of lead-acid batteries, has been studied by cyclic voltammetry (CV) and linear sweep voltammety for different concentrations of sulfuric acid (ranging from 0.5 mol L^–1 to 4.0 mol L^–1). The morphology of the grid at some solidification temperatures was studied by optical microscopy. After one sweep of CV the surface of the electrode was investigated by using scanning electron microscopy.The results show that the potential of hydrogen evolution depends on the solidification temperature of the grids during production (mold temperature of grid casting). Also, at different solidification temperatures, different passivation phenomena, electrode surface constituents, and structure were observed.     

Fabrication of a nanostructured TiO2/carbon nanotube composite electrode for voltammetric and impedimetric determination of NTO explosive in the water and soil samples

An electrochemical oxidation route was developed for sensitive and selective assay of nitrotriazolone (NTO) explosive in some environmental samples on a multi-walled carbon nanotube (MWCNTs)/TiO₂ nanocomposite paste electrode, for prevention of the analytical interference of conventional reducible energetic compounds. Detailed evaluations were made for the electrochemical behaviour of NTO on the modified electrode by adsorptive stripping voltammetry, electrochemical impedance spectroscopy (EIS) and chronoamperometry techniques in the pH range of 2.0–10.0. Parameters such as diffusion coefficient constant of NTO were calculated, and various experimental conditions were also optimised. Under optimal conditions the calibration curve had two linear dynamic ranges of 130.0–3251.5 μg L^?1 and 6.5–26.0 mg L^?1 with a detection limit of 26.0 μg L^?1 (0.2 μmol L^?1) and precision of <3%. This electrochemical sensor was further applied to determine NTO in real soil and water samples with satisfactory results.     

Application of surface electrochemical passivation of lead-antimony alloy for a simple and rapid electrochemical determination of antimony content

A simple, rapid and selective electrochemical method is proposed as a novel and powerful analytical technique for the solid phase determination of less than 4% antimony in lead-antimony alloys without any separation and chemical pretreatment. The proposed method is based on the surface antimony oxidation of Pb/Sb alloy to Sb(III) at the thin oxide layer of PbSO₄/PbO that is formed by oxidation of Pb and using linear sweep voltammetric (LSV) technique. Determination was carried out in concentrate H₂SO₄ solution. The influence of reagent concentration and variable parameters was studied. Antimony of Pb/Sb alloys can be determined in the range of 0.0056–4.00% with a detection limit of 0.0045% and maximum relative standard deviation of 4.26%. This method was applied for the determination of Sb in lead/acid battery grids satisfactory.     

Assessment of the effect of N-oxide group in a new high-performance energetic tetrazine derivative on its physicochemical and thermodynamic properties,sensitivity, and combustion and detonation performance

Chemistry of Heterocyclic Compounds - This work uses density functional theory and suitable predictive methods to assess the effect of N-oxide group in 1,2-bis(6-nitro-1,2,4,5-tetrazin-3-yl)diazene...     

Development of a voltammetric procedure for assay of thebaine at a multi-walled carbon nanotubes electrode: quantification and electrochemical studies

The study of electrochemical behavior and determination of thebaine (THEB), an opiate alkaloid, is described on a multi-walled carbon nanotube (MWCNT) modified glassy carbon electrode by adsorptive stripping voltammetry and electrochemical impedance spectroscopy. The results indicated that MWCNT electrodes remarkably enhance electrocatalytic activity toward the oxidation of THEB in a wide pH range of 2.0–10.0, and it shows two irreversible and diffusion-controlled anodic peaks. Then, a sensitive, simple, and time-saving cyclic voltammetric procedure was developed for the analysis of THEB in human urine samples. Under optimized conditions, the oxidation peak has two linear dynamic ranges of 1.0–80.0 and 100.0–600.0 μM, with detection limit of 0.23 μM and a precision of <4% (relative standard deviation for eight analysis).     

Electrodeposited silver nanodendrites electrode with strongly enhanced electrocatalytic activity

Highly uniform dendritic silver nanostructures as a new electrode material, have been synthesized by electrodeposition on the glassy carbon (GC) electrode with assistance of polyethylene glycol 400 (PEG-400) as a soft template, to achieve a superior electrocatalyst with enhanced detection sensitivity in electroanalysis compared to conventional bulk Ag electrodes. The effects of the growth conditions such as concentrations of the reagents and applied potentials on the morphology and structure of as-prepared tree-like nanostructures have also been investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD). In the silver nanodendrites (AgNDs), the diameter of the trunk is around 100-200 nm with length up to 10-40 μm, and the length of its branches can reach 10 μm. In addition, the electrocatalytic behavior of this modified electrode was exploited as a sensitive detection system for the reduction of RDX high explosive, hydrogen peroxide and hexacyanoferrate (HCF) by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. Also, the obtained results were compared to multiwalled carbon nanotubes (MWCNTs) and bulk silver electrodes. These studies show that the nanodendritic silvers significantly increase the electron-transfer rate of the electrochemical reactions by as much as 1-2 orders of magnitude.     

Electrochemistry and Adsorptive Stripping Voltammetric Determination of Amoxicillin on a Multiwalled Carbon Nanotubes Modified Glassy Carbon Electrode

The study of electrochemical behavior of amoxicillin (AMX), a β‐lactam antibiotic, is described on a multiwalled carbon nanotubes (MWCNTs) modified electrode by electrochemical impedance spectroscopy (EIS) and adsorptive stripping voltammetry for sensitive determination of AMX in pharmaceutical and human urine samples within a wide pH range from 2.0 to 10.0. Also, studies by Fe₂O₃ nanoparticles modified carbon paste electrode show that iron oxide impurities in the MWCNTs are not active sites for sensing of amoxicillin. Under optimized conditions, the oxidation peak has two linear dynamic ranges of 0.6–8.0 and 10.0–80.0 μM with a detection limit of 0.2 μM and a precision of <4%.     

A Simple Method for Reliable Estimation of the Bubble Energy in the Underwater Explosion

The bubble energy is the main part of the chemical energy of the explosive that is formed upon the propagation of a shock wave through the water for the underwater explosion. A simple method is introduced for reliable prediction of the bubble energy of composite explosives containing aluminum (Al) and/or ammonium perchlorate (AP). It is shown that the bubble energy of composite Al/AP explosives depends on the number of moles of chlorine, carbon, and Al atoms. Experimental data of 56 composite Al/AP explosives are used to construct and test the novel model of the bubble energy. Statistical parameters of the new model, in external validation containing 35 composite Al/AP explosives as the training set, have the values 0.43 and 1.15 MJ · kg^–1 for the root mean squared error (RMSE) and maximum of errors (Max Error) of the new model, respectively. The values of RMSE and Max Error for 21 composite Al/AP explosives as test set are also 0.60 and 2.22 MJ · kg^–1, respectively. Cross validations of the new method corresponding to the coefficients of determination for leave‐one‐out (Q²_LOO) and the fivefold cross validation (Q²_5CV) are 0.8573 and 0.8403, respectively, which confirms goodness‐of‐fit, goodness‐of‐prediction, accuracy and precision of the novel model. It is shown that the novel correlation can be applied for pure and composite explosives, which do not contain Al/AP.