Amorphization induced by pressure: results for zeolites and general implications

We report an {\sl ab initio} study of pressure-induced amorphization (PIA) in zeolites, which are model systems for this phenomenon. We confirm the occurrence of low-density amorphous phases like the one reported by Greaves {\sl et al.} [Science {\bf 308}, 1299 (2005)], which preserves the crystalline topology and might constitute a new type of glass. The role of the zeolite composition regarding PIA is explained. Our results support the correctness of existing models for the basic PIA mechanim, but suggest that energetic, rather than kinetic, factors determine the irreversibility of the transition.Comment: 4 pages with 3 figures embedded. More information at http://www.icmab.es/dmmis/leem/jorg

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

High-Temperature Thermodynamic Properties Of Forsterite

The high-temperature thermodynamic properties of forsterite were reviewed in the light of a new determination of the isobaric heat capacity (C(p)), up to 1850 K, and Raman spectroscopic measurements, up to 1150 K and 10 GPa. The C(p) measurements and available data on thermal expansion (alpha) and bulk modulus (K) show that the isochoric specific heat (C-nu) exceeds the harmonic limit of Dulong and Petit above 1300 K. This intrinsic anharmonic behavior of C-nu) can be modeled by introducing anharmonic parameters a(i) = (partial-lnv(i)/partial-T)V which are calculated from the measured pressure and temperature shifts of the vibrational frequencies. These parameters are all negative, with absolute values lower for the stretching modes of the SiO4 tetrahedra (a(i) almost-equal-to - 1 x 10(-5) K-1) than for the lattice modes (a(i) almost-equal-to 2 x 10(-5) K-1). Through the relation C(p) = C-nu) + alpha-2K(T)VT, the calculated anharmonic C-nu) and the measured C(p) are then used to determine the temperature dependences of the thermal expansion and bulk modulus of forsterite, up to 2000 K, in agreement with recent experimental results. Finally, all these data point to an inconsistency for the Gruneisen parameter of forsterite, whereby the macroscopic parameter gamma = alpha-VK(T)/C-nu) cannot be evaluated simply at high temperature by summation of the individual isothermal mode Gruneisen parameters gamma-iT = K(T) (partial-lnv(i)/partial-P)

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

Post-operative Aspergillus mediastinitis in a man who was immunocompetent: a case report

<p>Abstract</p> <p>Introduction</p> <p><it>Aspergillus </it>spp. infections mainly affect patients who are immunocompromised, and are extremely rare in immunocompetent individuals.</p> <p>Case presentation</p> <p><it>Aspergillus </it>post-operative mediastinitis is considered to be a devastating infection, usually affecting patients undergoing cardiothoracic surgery with specific predisposing factors. We describe the case of an immunocompetent 68-year-old Caucasian man with severe chronic thromboembolic pulmonary hypertension, who underwent pulmonary thromboendarterectomy and developed post-operative mediastinitis due to <it>Aspergillus flavus</it>. The environmental control did not reveal the source of <it>A. flavus </it>infection and, despite combined antifungal therapy, our patient died as a result of septic shock and multiple organ failure.</p> <p>Conclusion</p> <p><it>Aspergillus </it>mediastinitis mainly affects patients after cardiosurgery operations with predisposing factors, and it is unusual in patients who are immunocompetent. The identification of the <it>Aspergillus </it>spp. source is often difficult, and there are no guidelines for the administration of pre-emptive therapy in this population of at-risk patients.</p

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