Catalytic Membrane Reactor: Multilayer membranes elaboration

International audienceMethane conversion to syngas is very attractive for hydrogen or clean fuel production and provides an alternative to oil products. An efficient architecture for the membrane reactor is constituted of a porous support, a thin dense membrane and a catalyst layer. This work is focused on the elaboration process of such asymmetric membranes by co-sintering of at least the porous support and the dense membrane and specially the choice of well adapted materials. La0.8Sr0.2Fe0.7Ga0.3O3-δ perovskite material has been chosen as the dense membrane because it exhibits a good compromise between oxygen flux and stability. The choice of the material for the porous support is mainly oriented by the sintering behaviour of the membrane, the thermal expansion behaviour of both layers to avoid cracks formation under working conditions and the chemical inertness of both materials. Several formulations fulfilling these three requirements were synthesized by liquid phase reaction and tape-cast. A pore forming agent was added in the support tapecasting slurry in order to create a controlled porosity. Then, the porous support has been characterized in term of gas permeability and thermal expansion under working conditions. Keywords: Ceramic membrane, co-sintering, perovskite, syngas, mixed conducting materials

Oxygen permeation and dimensional stability under pO2 gradient of (La,Sr)(Fe, Ga)O3-delta perovskite membranes

International audienceNatural gas conversion into syngas, is very attractive for hydrogen or cleanfuel production and provides a new alternative to oil products ......

Pressure-induced amorphization, crystal-crystal transformations and the memory glass effect in interacting particles in two dimensions

We study a model of interacting particles in two dimensions to address the relation between crystal-crystal transformations and pressure-induced amorphization. On increasing pressure at very low temperature, our model undergoes a martensitic crystal-crystal transformation. The characteristics of the resulting polycrystalline structure depend on defect density, compression rate, and nucleation and growth barriers. We find two different limiting cases. In one of them the martensite crystals, once nucleated, grow easily perpendicularly to the invariant interface, and the final structure contains large crystals of the different martensite variants. Upon decompression almost every atom returns to its original position, and the original crystal is fully recovered. In the second limiting case, after nucleation the growth of martensite crystals is inhibited by energetic barriers. The final morphology in this case is that of a polycrystal with a very small crystal size. This may be taken to be amorphous if we have only access (as experimentally may be the case) to the angularly averaged structure factor. However, this `X-ray amorphous' material is anisotropic, and this shows up upon decompression, when it recovers the original crystalline structure with an orientation correlated with the one it had prior to compression. The memory effect of this X-ray amorphous material is a natural consequence of the memory effect associated to the underlying martensitic transformation. We suggest that this kind of mechanism is present in many of the experimental observations of the memory glass effect, in which a crystal with the original orientation is recovered from an apparently amorphous sample when pressure is released.Comment: 13 pages, 13 figures, to be published in Phys. Rev.

Melting and Pressure-Induced Amorphization of Quartz

It has recently been shown that amorphization and melting of ice were intimately linked. In this letter, we infer from molecular dynamics simulations on the SiO2 system that the extension of the quartz melting line in the metastable pressure-temperature domain is the pressure-induced amorphization line. It seems therefore likely that melting is the physical phenomenon responsible for pressure induced amorphization. Moreover, we show that the structure of a "pressure glass" is similar to that of a very rapidly (1e+13 to 1e+14 kelvins per second) quenched thermal glass.Comment: 9 pages, 4 figures, LaTeX2

Oxygen permeation, thermal and chemical expansion of (La, Sr)(Fe, Ga)O3−δ perovskite membranes

International audienceDense ceramic membranes made from mixed conductors are interesting because of their potential applications formethane conversion into syngas (H2 and CO mixture). Such membranes need to present a low differential dimensional variation between the opposite faces submitted to a large gradient of oxygen partial pressure, in order to minimize mechanical stresses generated through the membrane thickness. Besides, high oxygen permeability is required for high methane reforming rate. La(1−x)SrxFe(1−y)GayO3−δ materials fulfil these two main requirements and were retained as membranes in catalytic membrane reactors (CMR). The variations of expansion and oxygen permeation of La(1−x)SrxFe(1−y)GayO3−δ perovskite materials with the partial substitution of lanthanum and iron cations, temperature and oxygen partial pressure, were studied. For low temperatures (800 ◦C), TEC, then dimensional stability of the membrane, and oxygen permeation of La(1−x)SrxFe(1−y)GayO3−δ materials, are significantly affected by Sr content and oxygen partial pressure. Ga has a stabilisation effect on the TEC and has no influence on oxygen permeation flux. A good compromise between dimensional stability and oxygen permeation of materials was found to be La0.7Sr0.3Fe0.7Ga0.3O3−δ compositio

Temperature Evolution of Sodium Nitrite Structure in a Restricted Geometry

The NaNO$_{2}$ nanocomposite ferroelectric material in porous glass was studied by neutron diffraction. For the first time the details of the crystal structure including positions and anisotropic thermal parameters were determined for the solid material, embedded in a porous matrix, in ferro- and paraelectric phases. It is demonstrated that in the ferroelectric phase the structure is consistent with bulk data but above transition temperature the giant growth of amplitudes of thermal vibrations is observed, resulting in the formation of a "premelted state". Such a conclusion is in a good agreement with the results of dielectric measurements published earlier.Comment: 4 pages, 4 figure

Mechanical versus thermodynamical melting in pressure-induced amorphization: the role of defects

We study numerically an atomistic model which is shown to exhibit a one--step crystal--to--amorphous transition upon decompression. The amorphous phase cannot be distinguished from the one obtained by quenching from the melt. For a perfectly crystalline starting sample, the transition occurs at a pressure at which a shear phonon mode destabilizes, and triggers a cascade process leading to the amorphous state. When defects are present, the nucleation barrier is greatly reduced and the transformation occurs very close to the extrapolation of the melting line to low temperatures. In this last case, the transition is not anticipated by the softening of any phonon mode. Our observations reconcile different claims in the literature about the underlying mechanism of pressure amorphization.Comment: 7 pages, 7 figure

Search for Fingerprints of Tetrahedral Symmetry in 156Gd^{156}Gd

Theoretical predictions suggest the presence of tetrahedral symmetry as an explanation for the vanishing intra-band E2-transitions at the bottom of the odd-spin negative parity band in $^{156}Gd$. The present study reports on experiment performed to address this phenomenon. It allowed to determine the intra-band E2 transitions and branching ratios B(E2)/B(E1) of two of the negative-parity bands in $^{156}Gd$.Comment: presented by Q.T. Doan at XLII Zakopane School of Physics: Breaking Frontiers: Submicron Structures in Physics and Biology, May 2008. 5 pages, minor corrections. To be published in the proceeding

Frequency dependent specific heat of viscous silica

We apply the Mori-Zwanzig projection operator formalism to obtain an expression for the frequency dependent specific heat c(z) of a liquid. By using an exact transformation formula due to Lebowitz et al., we derive a relation between c(z) and K(t), the autocorrelation function of temperature fluctuations in the microcanonical ensemble. This connection thus allows to determine c(z) from computer simulations in equilibrium, i.e. without an external perturbation. By considering the generalization of K(t) to finite wave-vectors, we derive an expression to determine the thermal conductivity \lambda from such simulations. We present the results of extensive computer simulations in which we use the derived relations to determine c(z) over eight decades in frequency, as well as \lambda. The system investigated is a simple but realistic model for amorphous silica. We find that at high frequencies the real part of c(z) has the value of an ideal gas. c'(\omega) increases quickly at those frequencies which correspond to the vibrational excitations of the system. At low temperatures c'(\omega) shows a second step. The frequency at which this step is observed is comparable to the one at which the \alpha-relaxation peak is observed in the intermediate scattering function. Also the temperature dependence of the location of this second step is the same as the one of the $\alpha-$peak, thus showing that these quantities are intimately connected to each other. From c'(\omega) we estimate the temperature dependence of the vibrational and configurational part of the specific heat. We find that the static value of c(z) as well as \lambda are in good agreement with experimental data.Comment: 27 pages of Latex, 8 figure