Pyrolysis of 3-carene: Experiment, Theory and Modeling

Thermal decomposition studies of 3-carene, a bio-fuel, have been carried out behind the reflected shock wave in a single pulse shock tube for temperature ranging from 920 K to 1220 K. The observed products in thermal decomposition of 3-carene are acetylene, allene, butadiene, isoprene, cyclopentadiene, hexatriene, benzene, toluene and p-xylene. The overall rate constant for 3-carene decomposition was found to be k/s(-1) = 10((9.95 +/- 0.54)) exp(-40.88 +/- 2.71 kcal mol(-1) /RT). Ab-initio theoretical calculations were carried out to find the minimum energy pathway that could explain the formation of the observed products in the thermal decomposition experiments. These calculations were carried out at B3LYP/6-311 + G(d,p) and G3 level of theories. A kinetic mechanism explaining the observed products in the thermal decomposition experiments has been derived. It is concluded that the linear hydrocarbons are the primary products in the pyrolysis of 3-carene.

Pattern formation in thin films of polymer solutions: Theory and simulations

Self-assembly has been recognized as an efficient tool for generating a wide range of functional, chemically, or physically textured surfaces for applications in small scale devices. In this work, we investigate the stability of thin films of polymer solutions. For low concentrations of polymer in the solution, long length scale dewetting patterns are obtained with wavelength approximately few microns. Whereas, for concentrations above a critical value, bimodal dispersion curves are obtained with the dominant wavelength being up to two orders smaller than the usual dewetting length scale. We further show that the short wavelength corresponds to the phase separation in the film resulting in uniformly distributed high and low concentration regions. Interestingly, due to the solvent entropy, at very high concentration values of polymer, a re-entrant behaviour is observed with the dominant length scale now again corresponding to the dewetting wavelength. Thus, we show that the binary films of polymer solutions provide additional control parameters that can be utilized for generating functional textured surfaces for various applications. (C) 2016 AIP Publishing LLC.