Investigating the impact and reaction pathway of toluene on a SOFC running on syngas

The integration of solid oxide fuel cells (SOFCs) with gasification systems have theoretically been shown to have a great potential to provide highly efficient distributed generation energy systems that can be fuelled by biomass including municipal solid waste. The syngas produced from the gasification of carbonaceous material is rich in hydrogen, carbon monoxide and methane that can fuel SOFCs. However, other constituents such as tar can cause catalyst deactivation, and blockage of the diffusion pathways. This work examines the impact of increasing concentrations of toluene as a model tar in a typical syngas composition fed to a NiO-GDC/TZ3Y/8YSZ/LSM-LSM SOFC membrane electrode assembly operating at 850°C and atmospheric pressure. Results suggest that up to 20 g/Nm3 of toluene and a low fuel utilisation factor (c.a. 17%) does not negatively impact cell performance and rather acts to increase the available hydrogen by undergoing reformation. At these conditions carbon deposition does occur, detected through EDS analysis, but serves to decrease the ASR rather than degrade the cell. Alternatively, the cell operating with 32 g/Nm3 toluene and with a fuel utilisation of 66.7% is dramatically affected through increased ASR which is assumed to be caused by increased carbon deposition. In order to test for the presence of tar products at the anode exhaust samples have been captured using an absorbing filter with results from HS-GC/MS analysis showing the presence of toluene only. © 2014 Hydrogen Energy Publications, LLC

Dynamical Structure Factor for the Alternating Heisenberg Chain: A Linked Cluster Calculation

We develop a linked cluster method to calculate the spectral weights of many-particle excitations at zero temperature. The dynamical structure factor is expressed as a sum of exclusive structure factors, each representing contributions from a given set of excited states. A linked cluster technique to obtain high order series expansions for these quantities is discussed. We apply these methods to the alternating Heisenberg chain around the dimerized limit ($\lambda=0$), where complete wavevector and frequency dependent spectral weights for one and two-particle excitations (continuum and bound-states) are obtained. For small to moderate values of the inter-dimer coupling parameter $\lambda$, these lead to extremely accurate calculations of the dynamical structure factors. We also examine the variation of the relative spectral weights of one and two-particle states with bond alternation all the way up to the limit of the uniform chain ($\lambda=1$). In agreement with Schmidt and Uhrig, we find that the spectral weight is dominated by 2-triplet states even at $\lambda=1$, which implies that a description in terms of triplet-pair excitations remains a good quantitative description of the system even for the uniform chain.Comment: 26 pages, 17 figure

Decoherence of Friedmann-Robertson-Walker Geometries in the Presence of Massive Vector Fields with U(1) or SO(3) Global Symmetries

Retrieval of classical behaviour in quantum cosmology is usually discussed in the framework of {\em midi}superspace models in the presence of scalar fields and the inhomogeneous modes corresponding either to gravitational or scalar fields. In this work, we propose an alternative model to study the decoherence of homogeneous and isotropic geometries where the scalar field is replaced by a massive vector field with a global internal symmetry. We study here the cases with $U(1)$ and $SO(3)$ global internal symmetries. The presence of a mass term breaks the conformal invariance and allows for the longitudinal modes of the spin-1 field to be present in the Wheeler-DeWitt equation. In the case of the U(1) global internal symmetry, we have only one single ``classical'' degree of freedom while in the case of the SO(3) global symmetry, we are led to consider a simple two-dimensional minisuperspace model. These minisuperspaces are shown to be equivalent to a set of coupled harmonic oscillators where the kinetic term of the longitudinal modes has a coefficient proportional to the inverse of the scale factor. The conditions for a suitable decoherence process and correlations between coordinate and momenta are established. The validity of the semi-classical Einstein equations when massive vector fields (Abelian and non-Abelian) are present is also discussed.Comment: 26 pages, CERN-TH.7241/94 DAMTP R-94/2

CE21: Total Cross Section for pd → pdπ^0 Close to Threshold

This research was sponsored by the National Science Foundation Grant NSF PHY-931478

Criticality in coupled quantum spin-chains with competing ladder-like and two-dimensional couplings

Motivated by the geometry of spins in the material CaCu$_2$O$_3$, we study a two-layer, spin-half Heisenberg model, with nearest-neighbor exchange couplings J and \alpha*J along the two axes in the plane and a coupling J_\perp perpendicular to the planes. We study these class of models using the Stochastic Series Expansion (SSE) Quantum Monte Carlo simulations at finite temperatures and series expansion methods at T=0. The critical value of the interlayer coupling, J_\perp^c, separating the N{\'e}el ordered and disordered ground states, is found to follow very closely a square root dependence on $\alpha$. Both T=0 and finite-temperature properties of the model are presented.Comment: 9 pages, 11 figs., 1 tabl

Critical Dynamics of Singlet Excitations in a Frustrated Spin System

We construct and analyze a two-dimensional frustrated quantum spin model with plaquette order, in which the low-energy dynamics is controlled by spin singlets. At a critical value of frustration the singlet spectrum becomes gapless, indicating a quantum transition to a phase with dimer order. This T=0 transition belongs to the 3D Ising universality class, while at finite temperature a 2D Ising critical line separates the plaquette and dimerized phases. The magnetic susceptibility has an activated form throughout the phase diagram, whereas the specific heat exhibits a rich structure and a power law dependence on temperature at the quantum critical point. We argue that the novel quantum critical behavior associated with singlet criticality discussed in this work can be relevant to a wide class of quantum spin systems, such as antiferromagnets on Kagome and pyrochlore lattices, where the low-energy excitations are known to be spin singlets, as well as to the CAVO lattice and several recently discovered strongly frustrated square-lattice antiferromagnets.Comment: 5 pages, 5 figures, additional discussion and figure added, to appear in Phys. Rev.

Structure optimization effects on the electronic properties of Bi2_2Sr2_2CaCu2_2O8_8

We present detailed first-principles calculations for the normal state electronic properties of the high T$_C$ superconductor Bi$_2$Sr$_2$CaCu$_2$O$_8$, by means of the linearized augmented plane wave (LAPW) method within the framework of density functional theory (DFT). As a first step, the body centered tetragonal (BCT) cell has been adopted, and optimized regarding its volume, $c/a$ ratio and internal atomic positions by total energy and force minimizations. The full optimization of the BCT cell leads to small but visible changes in the topology of the Fermi surface, rounding the shape of CuO$_2$ barrels, and causing both the BiO bands, responsible for the pockets near the \textit{\=M} 2D symmetry point, to dip below the Fermi level. We have then studied the influence of the distortions in the BiO plane observed in nature by means of a $\sqrt{2}\times\sqrt{2}$ orthorhombic cell (AD-ORTH) with $Bbmb$ space group. Contrary to what has been observed for the Bi-2201 compound, we find that for Bi-2212 the distortion does not sensibly shift the BiO bands which retain their metallic character. As a severe test for the considered structures we present Raman-active phonon frequencies ($q = 0$) and eigenvectors calculated within the frozen-phonon approximation. Focussing on the totally symmetric A$_{g}$ modes, we observe that for a reliable attribution of the peaks observed in Raman experiments, both $c$- and a-axis vibrations must be taken into account, the latter being activated by the in-plane orthorhombic distortion.Comment: 22 pages, 4 figure