Les amers du choix pertinent des signes à la manipulation de l'espace

El mar no ofereix referències, l'única alternativa per descriure l'espai és la terra. Així neixen els senyals de pescadors i mariners. Un invent que va ser el resultat d'una cerca a l'atzar portat a terme a cop d'intuïció, d'assaig i error i coronat finalment pel descobriment de la geografia del fons marí. L'article se centra en els origens i la pràctica dels senyals relacionats amb la navegació i la pesca a la costa del departament francès dels Pirineus Orientals

Correlation between floppy to rigid transitions and non-Arrhenius conductivity in glasses

Non-Arrhenius behaviour and fast increase of the ionic conductivity is observed for a number of potassium silicate glasses $(1-x)SiO_2-xK_2O$ with potassium oxide concentration larger than a certain value $x=x_c=0.14$. Recovering of Arrhenius behaviour is provided by the annealing that enhances densification. Conductivity furthermore obeys a percolation law with the same critical concentration $x_c$. These various results are the manifestation of the floppy or rigid nature of the network and can be analyzed with constraint theory. They underscore the key role played by network rigidity for the understanding of conduction and saturation effects in glassy electrolytes.Comment: 4 pages, 4 EPS figure

Onset of rigidty in glasses: from random to self-organized networks

We review in this paper the signatures of a new elastic phase that is found in glasses with selected compositions. It is shown that in contrast with random networks, where rigidity percolates at a single threshold, networks that are able to self-organize to avoid stress will remain in an almost stress- free state during a compositional interval, an intermediate phase, that is bounded by a flexible phase and a stressed rigid phase. We report the experimental signatures and describe the theoretical efforts that have been accomplished to characterize the intermediate phase. We illustrate one of the methods used in more detail with the example of Group III chalcogenides and finally suggest further possible experimental signatures of self-organization.Comment: 27 pages, 6 figures, Proceedings of the Conference on Non-Crystalline Materials 10, to appear in Journal of Non-Crystalline Solid

Percolative conductivity in alkaline earth silicate melts and glasses

Ion conducting $(CaO)_x(SiO_2)_{1-x}$ glasses and melts show a threshold behaviour in dc conductivity near $x=x_t=0.50$, with conductivities increasing linearly at $x>x_t$. We show that the behaviour can be traced to a rigid ($x0.50$) elastic phase transition near $x=x_t$. In the floppy phase, conductivity enhancement is traced to increased mobility or diffusion of $Ca^{2+}$ carriers as the modified network elastically softens.Comment: 15 pages, 5 figures. Europhysics Letters (2003), in pres

Abrupt boundaries of intermediate phases and space filling in oxide glasses

Modulated DSC measurements on bulk (Na2O)x(GeO2)1-x glasses show a sharp reversibility window in the 14% < x < 19% soda range, which correlates well with a broad global minimum in molar volumes. Raman and IR reflectance TO and LO mode frequencies exhibit anomalies between xc(1) = 14% (stress transition) and xc(2) = 19% (rigidity transition), with optical elasticity power-laws confirming the nature of the transitions . Birefringence measurements dramatize the macroscopically stress-free nature of the Intermediate Phase in the reversibility window

Intermediate Phases, structural variance and network demixing in chalcogenides: the unusual case of group V sulfides

We review Intermediate Phases (IPs) in chalcogenide glasses and provide a structural interpretation of these phases. In binary group IV selenides, IPs reside in the 2.40 < r < 2.54 range, and in binary group V selenides they shift to a lower r, in the 2.29< r < 2.40 range. Here r represents the mean coordination number of glasses. In ternary alloys containing equal proportions of group IV and V selenides, IPs are wider and encompass ranges of respective binary glasses. These data suggest that the local structural variance contributing to IP widths largely derives from four isostatic local structures of varying connectivity r; two include group V based quasi-tetrahedral (r = 2.29) and pyramidal (r = 2.40) units, and the other two are group IV based corner-sharing (r = 2.40) and edge-sharing (r = 2.67) tetrahedral units. Remarkably, binary group V (P, As) sulfides exhibit IPs that are shifted to even a lower r than their selenide counterparts; a result that we trace to excess Sn chains either partially (As-S) or completely (P-S) demixing from network backbone, in contrast to excess Sen chains forming part of the backbone in corresponding selenide glasses. In ternary chalcogenides of Ge with the group V elements (As, P), IPs of the sulfides are similar to their selenide counterparts, suggesting that presence of Ge serves to reign in the excess Sn chain fragments back in the backbone as in their selenide counterparts

Microscopic Aspects of Stretched Exponential Relaxation (SER) in Homogeneous Molecular and Network Glasses and Polymers

Because the theory of SER is still a work in progress, the phenomenon itself can be said to be the oldest unsolved problem in science, as it started with Kohlrausch in 1847. Many electrical and optical phenomena exhibit SER with probe relaxation I(t) ~ exp[-(t/{\tau}){\beta}], with 0 < {\beta} < 1. Here {\tau} is a material-sensitive parameter, useful for discussing chemical trends. The "shape" parameter {\beta} is dimensionless and plays the role of a non-equilibrium scaling exponent; its value, especially in glasses, is both practically useful and theoretically significant. The mathematical complexity of SER is such that rigorous derivations of this peculiar function were not achieved until the 1970's. The focus of much of the 1970's pioneering work was spatial relaxation of electronic charge, but SER is a universal phenomenon, and today atomic and molecular relaxation of glasses and deeply supercooled liquids provide the most reliable data. As the data base grew, the need for a quantitative theory increased; this need was finally met by the diffusion-to-traps topological model, which yields a remarkably simple expression for the shape parameter {\beta}, given by d*/(d* + 2). At first sight this expression appears to be identical to d/(d + 2), where d is the actual spatial dimensionality, as originally derived. The original model, however, failed to explain much of the data base. Here the theme of earlier reviews, based on the observation that in the presence of short-range forces only d* = d = 3 is the actual spatial dimensionality, while for mixed short- and long-range forces, d* = fd = d/2, is applied to four new spectacular examples, where it turns out that SER is useful not only for purposes of quality control, but also for defining what is meant by a glass in novel contexts. (Please see full abstract in main text

Rings and rigidity transitions in network glasses

Three elastic phases of covalent networks, (I) floppy, (II) isostatically rigid and (III) stressed-rigid have now been identified in glasses at specific degrees of cross-linking (or chemical composition) both in theory and experiments. Here we use size-increasing cluster combinatorics and constraint counting algorithms to study analytically possible consequences of self-organization. In the presence of small rings that can be locally I, II or III, we obtain two transitions instead of the previously reported single percolative transition at the mean coordination number $\bar r=2.4$, one from a floppy to an isostatic rigid phase, and a second one from an isostatic to a stressed rigid phase. The width of the intermediate phase $~ \bar r$ and the order of the phase transitions depend on the nature of medium range order (relative ring fractions). We compare the results to the Group IV chalcogenides, such as Ge-Se and Si-Se, for which evidence of an intermediate phase has been obtained, and for which estimates of ring fractions can be made from structures of high T crystalline phases.Comment: 29 pages, revtex, 7 eps figure

Contribution a l'etude des transitions de phase structurales des perovskites CsCaCl3 et CsPbCl3 par resonance paramagnetique electronique de l'ion Gd3+

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