Thermogravimetric kinetics of crude glycerol.

The pyrolysis of the crude glycerol from a biodiesel production plant was investigated by thermogravimetry coupled with Fourier transform infrared spectroscopy. The main gaseous products are discussed, and the thermogravimetric kinetics derived. There were four distinct phases in the pyrolysis process of the crude glycerol. The presence of water and methanol in the crude glycerol and responsible for the first decomposition phase, were shown to catalyse glycerol decomposition (second phase). Unlike the pure compound, crude glycerol decomposition below 500 K leaves behind a large mass fraction of pyrolysis residues (ca. 15%), which eventually partially eliminate in two phases upon reaching significantly higher temperatures (700 and 970 K, respectively). An improved iterative Coats-Redfern method was used to evaluate non-isothermal kinetic parameters in each phase. The latter were then utilised to model the decomposition behaviour in non-isothermal conditions. The power law model (first order) predicted accurately the main (second) and third phases in the pyrolysis of the crude glycerol. Differences of 10-30 kJ/mol in activation energies between crude and pure glycerol in their main decomposition phase corroborated the catalytic effect of water and methanol in the crude pyrolysis. The 3-D diffusion model more accurately reproduced the fourth (last) phase, whereas the short initial decomposition phase was poorly simulated despite correlation coefficients ca. 0.95-0.96. The kinetics of the 3rd and 4th decomposition phases, attributed to fatty acid methyl esters cracking and pyrolysis tarry residues, were sensitive to the heating rate

Importance of electronic self-consistency in the TDDFT based treatment of nonadiabatic molecular dynamics

A mixed quantum-classical approach to simulate the coupled dynamics of electrons and nuclei in nanoscale molecular systems is presented. The method relies on a second order expansion of the Lagrangian in time-dependent density functional theory (TDDFT) around a suitable reference density. We show that the inclusion of the second order term renders the method a self-consistent scheme and improves the calculated optical spectra of molecules by a proper treatment of the coupled response. In the application to ion-fullerene collisions, the inclusion of self-consistency is found to be crucial for a correct description of the charge transfer between projectile and target. For a model of the photoreceptor in retinal proteins, nonadiabatic molecular dynamics simulations are performed and reveal problems of TDDFT in the prediction of intra-molecular charge transfer excitations.Comment: 9 pages, 8 figures. Minor changes in content wrt older versio

Transport critical current of Solenoidal MgB2/Cu Coils Fabricated Using a Wind-Reaction In-situ Technique

In this letter, we report the results of transport Jc of solenoid coils upto 100 turns fabricated with Cu-sheathed MgB2 wires using a wind-reaction in-situ technique. Despite the low density of single core and some reaction between Mg and Cu-sheath, our results demonstrate the decrease in transport Jc with increasing length of MgB2 wires is insignificant. Solenoid coils with diameter as small as 10 mm can be readily fabricated using a wind-reaction in-situ technique. The Jc of coils is essentially the same as in the form of straight wires. A Jc of 133,000 A/cm2 and 125,000 A/cm2 at 4 K and self field has been achieved for a small coil wound using Cu-sheathed tape and Cu-sheathed wire respectively. These results indicate that the MgB2 wires have a great potential for lage scale applicationsComment: 6 pages, 4 figures, 1 tabl

Temperature dependence of electron-spin relaxation in a single InAs quantum dot at zero applied magnetic field

The temperature-dependent electron spin relaxation of positively charged excitons in a single InAs quantum dot (QD) was measured by time-resolved photoluminescence spectroscopy at zero applied magnetic fields. The experimental results show that the electron-spin relaxation is clearly divided into two different temperature regimes: (i) T < 50 K, spin relaxation depends on the dynamical nuclear spin polarization (DNSP) and is approximately temperature-independent, as predicted by Merkulov et al. (ii) T > about 50 K, spin relaxation speeds up with increasing temperature. A model of two LO phonon scattering process coupled with hyperfine interaction is proposed to account for the accelerated electron spin relaxation at higher temperatures.Comment: 10 pages, 4 figure

Hydrogen production by sorption-enhanced steam reforming of glycerol

Catalytic steam reforming of glycerol for H(2) production has been evaluated experimentally in a continuous flow fixed-bed reactor. The experiments were carried out under atmospheric pressure within a temperature range of 400-700 degrees C. A commercial Ni-based catalyst and a dolomite sorbent were used for the steam reforming reactions and in situ CO(2) removal. The product gases were measured by on-line gas analysers. The results show that H(2) productivity is greatly increased with increasing temperature and the formation of methane by-product becomes negligible above 500 degrees C. The results suggest an optimal temperature of approximately 500 degrees C for the glycerol steam reforming with in situ CO(2) removal using calcined dolomite as the sorbent, at which the CO(2) breakthrough time is longest and the H(2) purity is highest. The shrinking core model and the 1D-diffusion model describe well the CO(2) removal under the conditions of this work