Chemical Fingerprinting of Polymers Using Electron Energy-Loss Spectroscopy.

Electron energy-loss spectroscopy (EELS) is becoming an important tool in the characterization of polymeric materials. The sensitivity of EELS to changes in the chemical structure of polymeric materials dictates its applicability. In particular, it is important for compositional analysis to have reference spectra of pure components. Here, we report the spectra of the carbon K-edge of six polymers (polyethylene, polypropylene, polybutylene terephthalate, and polylactic acid) including copolymers (styrene acrylonitrile and acrylonitrile butadiene styrene), to be used as reference spectra for future EELS studies of polymers. We have successfully decomposed the carbon K-edge of each of the polymers and assigned the observed peaks to bonding transitions. The spectra have been acquired in standard experimental conditions, and electron beam damage has been taken into account during establishment of spectral-structural relationships. We found that the more commonly available low-energy resolution spectrometers are adequate to chemically fingerprint linear saturated hydrocarbons such as PE, PP, and PLA. We have thus moved a step closer toward creating an atlas of polymer EELS spectra, which can be subsequently used for chemical bond mapping of polymeric materials with nanoscale spatial resolution.

Molecular dynamics simulations to calculate glass transition temperature and elastic constants of novel polyethers.

Molecular dynamics simulations studies are carried out on hydroxyl terminated polyethers that are useful in energetic polymeric binder applications. Energetic polymers derived from oxetanes with heterocyclic side chains with different energetic substituents are designed and simulated under the ensembles of constant particle number, pressure, temperature (NPT) and constant particle number, volume, temperature (NVT). Specific volume of different amorphous polymeric models is predicted using NPT-MD simulations as a function of temperature. Plots of specific volume versus temperature exhibited a characteristic change in slope when amorphous systems change from glassy to rubbery state. Several material properties such as Young's, shear, and bulk modulus, Poisson's ratio, etc. are predicted from equilibrated structures and established the structure-property relations among designed polymers. Energetic performance parameters of these polymers are calculated and results reveal that the performance of the designed polymers is comparable to the benchmark energetic polymers like polyNIMMO, polyAMMO and polyBAMO. Overall, it is worthy remark that this molecular simulations study on novel energetic polyethers provides a good guidance on mastering the design principles and allows us to design novel polymers of tailored properties.

Computational screening of oxetane monomers for novel hydroxy terminated polyethers.

Energetic hydroxy terminated polyether prepolymers find paramount importance in search of energetic binders for propellant applications. In the present study, density functional theory (DFT) has been employed to screen the various novel energetic oxetane derivatives, which usually construct the backbone for these energetic polymers. Molecular structures were investigated at the B3LYP/6-31G* level, and isodesmic reactions were designed for calculating the gas phase heats of formation. The condensed phase heats of formation for designed compounds were calculated by the Politzer approach using heats of sublimation. Among the designed oxetane derivatives, T4 and T5 possess condensed phase heat of formation above 210 kJ mol(-1). The crystal packing density of the designed oxetane derivatives varied from 1.2 to 1.6 g/cm(3). The detonation velocities and pressures were evaluated using the Kamlet-Jacobs equations, utilizing the predicted densities and HOFCond. It was found that most of the designed oxetane derivatives have detonation performance comparable to the monomers of benchmark energetic polymers viz., NIMMO, AMMO, and BAMO. The strain energy (SE) for the oxetane derivatives were calculated using homodesmotic reactions, while intramolecular group interactions were predicted through the disproportionation energies. The concept of chemical hardness is used to analyze the susceptibility of designed compounds to reactivity and chemical transformations. The heats of formation, density, and predicted performance imply that the designed molecules are expected to be candidates for polymer synthesis and potential molecules for energetic binders.

A DFT study of aminonitroimidazoles.

Density functional theory (DFT) calculations at the B3LYP/aug-cc-pVDZ level were performed to explore the geometric and electronic structures, band gaps, thermodynamic properties, densities and performances of aminonitroimidazoles. The calculated performance properties, stabilities and sensitivities of the model compounds appear to be promising compared with those of the known explosives 2,4-dinitro-1H-imidazole (2,4-DNI), 1-methyl-2,4,5-trinitroimidazole (MTNI), hexahydro-1,3,5-trinitro-1,3,5-triazinane (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetraazocane (HMX). The position of the NH(2) or the number of NO(2) groups on the diazole presumably determines the structure, heat of formation, stability, sensitivity, density and performance of the compound.

Synthesis, characterisation, thermal and explosive properties of 4,6-dinitrobenzofuroxan salts.

Two new initiatory molecules, e.g. rubidium and cesium salts of 4,6-dinitrobenzofuroxan (DNBF) have been prepared by reacting sodium salt of 4,6-dinitrobenzofuroxan (DNBF) with rubidium nitrate and cesium nitrate, respectively, at 60 degrees C in aqueous medium. The characterisation of compounds by IR, (1)H-NMR, elemental analysis and metal content is described along with some of the evaluated thermal and explosive properties. The results indicate that cesium salt of DNBF (Cs-DNBF) appears promising initiatory and may suitably replace potassium salt of DNBF (K-DNBF), being used currently in initiatory compositions.