Synthesis, Characterization and Energetic Properties of Hydroxymethyl-Bishomocubanone Derivatives.

The present work reports synthesis, characterization and theoretical insights on novel hydroxymethyl-bishomocubanone derivatives. Twelve new bishomocubanes (BHCs) were synthesized and fully characterized by various spectroscopic techniques and single crystal X-ray analysis. The densities of the title compounds were found in the range of 1.34-1.59 g/cm3. Density-functional theory (DFT) based calculations at B3LYP/6-311++G(d,p) level of theory were performed on  ten selected BHC based cage compounds. Propulsive and ballistic properties of newly synthesized hydroxymethyl-bishomocubanone derivatives in solid and liquid propulsion systems were calculated, and the results suggested that these compounds are superior to conventional fuel RP1 and binder HTPB. The detonation parameters revealed that these compounds are not explosive in nature and safe to use as solid propellants. Furthermore, kinetic and thermal stabilities of the title compounds were determined by HOMO-LUMO energy gap, ESP maps, impact sensitivity (h50) and bond dissociation energies (BDEs) followed by thermogravimetric analysis (TGA) and differential thermogravimetry analysis (DTA). Three compounds, a dinitroazide (Isp,vac= 310.98s), a dinitrate (Isp,vac = 309.51s), and a dinitronitrate (Isp,vac= 309.20s) were found to be excellent candidates for volume limited applications.

Approaches to 1,4-Disubstituted Cubane Derivatives as Energetic Materials: Design, Theoretical Studies and Synthesis.

Novel 1,4-disubstituted cubane derivatives have been designed and selected ones have been successfully synthesized and characterized by various analytical and spectroscopic techniques, including single-crystal X-ray analysis. A detailed computational study at B3LYP/6-311++G(d,p) level of theory revealed that all newly designed 1,4-disubstituted cubane derivatives possess higher densities, higher density-specific impulse and superior ballistic properties when compared to conventional fuels, for example, RP-1. These compounds also exhibit acceptable kinetic and thermodynamic stabilities which were evaluated in terms of their HOMO-LUMO energy gap and bond dissociation energies, respectively, and are superior to TEX and many other compounds containing explosophoric groups. These results provide novel insights into the possible application of cubane-based energetic materials.

Investigation of sooting flames by color-ratio pyrometry with a consumer-grade DSLR camera.

The accurate measurement of temperature in sooty flames remains a challenging task. In this study, the procedure for calibration and use of a consumer-grade digital single-lens reflex (DSLR) camera for the measurement of temperature in sooty flames using color-ratio pyrometry (CRP) is elucidated. Owing to the necessity of acquiring RAW images for CRP, investigations conducted thus far have been limited to stable flames. In this work, the potential of a CANON EOS 550D DSLR camera for measuring temperature during a transient process such as a droplet combustion event at frame rates up to 50 fps is demonstrated. The spectral response curves of the camera-lens system were obtained with the help of a tunable laser source and a laser power meter, which were subsequently used to generate lookup tables for blackbody as well as soot radiation. Soot radiation was assumed to vary with wavelength (λ) as λ-α, where α is the soot dispersion exponent. The blackbody lookup table was validated against blackbody calibration data from 1023 to 1773 K. Experiments were conducted on a candle flame as well as a McKenna flat flame burner with ethylene-air mixtures of equivalence ratios 2.1 and 2.3. For estimating temperatures using CRP, soot particles were classified as nascent and mature soot with soot dispersion exponent (α) values of 4 and 1.38, respectively. The CRP results were found to yield a decent match with thermocouple measurements as well as data reported in the literature.

Liquid-phase decomposition mechanism for bis(triaminoguanidinium) azotetrazolate (TAGzT).

This work provides new insights for the liquid-phase decomposition of bis(triaminoguanidinium) azotetrazolate (TAGzT). The liquid-phase decomposition process was investigated using a combined experimental and computational approach. Sub-milligram samples of TAGzT were heated at rates of about 2000 K s-1 to a set temperature (230 to 260 °C) where liquid-phase decomposition occurred under isothermal conditions. Fourier transform infrared (FTIR) spectroscopy and time-of-flight mass spectrometry (ToFMS) were used to acquire transmittance spectra and mass spectra of the evolved gas-phase species from the rapid thermolysis, respectively. FTIR spectroscopy was also used to acquire the transmittance spectra of the condensate and residue formed from the decomposition. N2, NH3, HCN, N2H4, triaminoguanidine and 3-azido-1,2,4-triazol-4-ide anion were identified as products of liquid-phase decomposition. Quantum chemical calculations were used for confirming the identity of the species observed in experiments and for identifying elementary chemical reactions that formed these species. Based on the calculated free energy barriers of these elementary reactions, important reaction pathways were identified for the formation of each of the product species.

Pyrolysis characteristics and kinetics of acid tar waste from crude benzol refining: A thermogravimetry-mass spectrometry analysis.

Pyrolysis is an attractive thermochemical conversion technology that may be utilised as a safe disposal option for acid tar waste. The kinetics of acid tar pyrolysis were investigated using thermogravimetry coupled with mass spectrometry under a nitrogen atmosphere at different heating rates of 10, 15 and 20 K min-1 The thermogravimetric analysis shows three major reaction peaks centred around 178 °C, 258 °C, and 336 °C corresponding to the successive degradation of water soluble lower molecular mass sulphonic acids, sulphonated high molecular mass hydrocarbons, and high molecular mass hydrocarbons. The kinetic parameters were evaluated using the iso-conversional Kissinger-Akahira-Sunose method. A variation in the activation energy with conversion revealed that the pyrolysis of the acid tar waste progresses through complex multi-step kinetics. Mass spectrometry results revealed a predominance of gases such as hydrogen, methane and carbon monoxide, implying that the pyrolysis of acid tar waste is potentially an energy source. Thus the pyrolysis of acid tar waste may present a viable option for its environmental treatment. There are however, some limitations imposed by the co-evolution of corrosive gaseous components for which appropriate considerations must be provided in both pyrolysis reactor design and selection of construction materials.

Nitro-substituted bishomocubanes: synthesis, characterization, and application as energetic materials.

Several high-energy-density strained polycyclic compounds nitromethyl-l,3-bishomocubane (NMBHC), nitromethylene-1,3-bishomocubane (NMyBHC), and bis(nitromethyl)-1,3-bishomocubane (DNTMBHC), which were synthesized for the first time from bishomocubanone, hold potential for application as standalone fuels in liquid bipropellant systems or as additives in liquid and solid propellant formulations. DFT analysis at the B3LYP/6-31G(d) level of theory was employed to optimize the geometries of the compounds and to determine their densities, heats of formation, and various thermodynamic properties. The density specific impulse, determined by using equilibrium thermodynamics, demonstrated an improvement of 75 s for NMBHC and NMyBHC over standard hydrocarbons. The specific impulse with ammonium perchlorate showed an improvement of 25-30 s over hydroxy-terminated polybutadiene. Thermogravimetric analysis revealed that NMBHC, NMyBHC, and DNTMBHC evaporated readily with activation energies of 58.8, 69.2, and 74.5 kJ mol(-1), respectively.

Apparatus for probing preignition behavior of hypergolic materials.

The determination of the condensed-phase preignition chemistry of hypergolic bipropellant pairs has been considerably challenging due to toxicity and reactivity of the used materials. In this work, we describe a new experimental technique for characterizing preignition behavior of hypergolic materials. Small quantities of the bipropellant pair are brought in contact under isothermal conditions, and spectral transmission measurements on the evolved products are performed using Fourier transform infrared spectroscopy. The gaseous products are subsequently quantified to yield species concentration profiles at various temperatures, hence facilitating the elucidation of the detailed condensed-phase chemical kinetics responsible for the ignition in the gas phase.