A new kinetic model for predicting polyamide 6-6 hydrolysis and its mechanical embrittlement

PA 6-6 hydrolysis at 60, 70, 80 and 90 °C in distilled water has been studied by Fourier transform infrared spectroscopy, viscometry in molten state, differential scanning calorimetry and uniaxial tensile testing. The molar mass decreases sharply from the early periods of exposure to reach an equilibrium value of about MnE ≈ 10−11 kg mol−1 almost temperature independent. Hydrolytic chain scissions destroy the entanglement network in the amorphous phase and liberate small macromolecular segments which rearrange locally and initiate a chemicrystallisation. As expected, the embrittlement occurs at a very low conversion of the hydrolysis, in particular when the number average molar mass becomes lower than a critical value of about MnF ≈ 17 kg mol−1, i.e. very close to its initial value. A new kinetic model has been derived from the classical mechanistic scheme of reversible hydrolysis. This model describes satisfyingly all the kinetic characteristics of the reversible hydrolysis of PA 6-6 not controlled by water diffusion: decrease in molar mass, increase in crystallinity ratio and decrease in ultimate elongation, but also of other types of polyamides previously studied, such as PA 11. Moreover, when it is used as an inverse method, this model gives access to the rate constants of hydrolysis and condensation reactions. It is thus an interesting tool for elucidating structure/rate constant relationships in common families of hydrolysable polymers

Characterisation of the influence function non-additivities for a 1024-actuator MEMS deformable mirror

In order to evaluate the potential of MEMS deformable mirrors for open-loop applications, a complete calibration process was performed on a 1024-actuator mirror. The mirror must be perfectly calibrated to obtain deterministic membrane deflection. The actuator's stroke-voltage relationship and the effect of the non- additivity of the influence functions are studied and finally integrated in an open-loop control process. This experiment aimed at minimizing the residual error obtained in open-loop control.Comment: 6 pages, 9 figures, Proceedings of the 1st AO for ELT conference, June 2009, Pari

Spatio-angular Minimum-variance Tomographic Controller for Multi-Object Adaptive Optics systems

Multi-object astronomical adaptive-optics (MOAO) is now a mature wide-field observation mode to enlarge the adaptive-optics-corrected field in a few specific locations over tens of arc-minutes. The work-scope provided by open-loop tomography and pupil conjugation is amenable to a spatio-angular Linear-Quadratic Gaussian (SA-LQG) formulation aiming to provide enhanced correction across the field with improved performance over static reconstruction methods and less stringent computational complexity scaling laws. Starting from our previous work [1], we use stochastic time-progression models coupled to approximate sparse measurement operators to outline a suitable SA-LQG formulation capable of delivering near optimal correction. Under the spatio-angular framework the wave-fronts are never explicitly estimated in the volume,providing considerable computational savings on 10m-class telescopes and beyond. We find that for Raven, a 10m-class MOAO system with two science channels, the SA-LQG improves the limiting magnitude by two stellar magnitudes when both Strehl-ratio and Ensquared-energy are used as figures of merit. The sky-coverage is therefore improved by a factor of 5.Comment: 30 pages, 7 figures, submitted to Applied Optic

A new kinetic model for predicting polyamide 6-6 hydrolysis and its mechanical embrittlement

PA 6-6 hydrolysis at 60, 70, 80 and 90 °C in distilled water has been studied by Fourier transform infrared spectroscopy, viscometry in molten state, differential scanning calorimetry and uniaxial tensile testing. The molar mass decreases sharply from the early periods of exposure to reach an equilibrium value of about MnE ≈ 10−11 kg mol−1 almost temperature independent. Hydrolytic chain scissions destroy the entanglement network in the amorphous phase and liberate small macromolecular segments which rearrange locally and initiate a chemicrystallisation. As expected, the embrittlement occurs at a very low conversion of the hydrolysis, in particular when the number average molar mass becomes lower than a critical value of about MnF ≈ 17 kg mol−1, i.e. very close to its initial value. A new kinetic model has been derived from the classical mechanistic scheme of reversible hydrolysis. This model describes satisfyingly all the kinetic characteristics of the reversible hydrolysis of PA 6-6 not controlled by water diffusion: decrease in molar mass, increase in crystallinity ratio and decrease in ultimate elongation, but also of other types of polyamides previously studied, such as PA 11. Moreover, when it is used as an inverse method, this model gives access to the rate constants of hydrolysis and condensation reactions. It is thus an interesting tool for elucidating structure/rate constant relationships in common families of hydrolysable polymers

Foam drainage study during plateau border mineralisation

International audienceWe investigate the drainage of a foaming solution during inorganic polycondensation by macroscopic measurements and local observations. We reveal an original mineralisation mechanism starting from Plateau border interfaces. This slow process is not able to counteract the destabilizing effects of foam drainage and we therefore propose a new strategy in which mineralisation is assisted by a biopolymer

On the movements of the North Atlantic Subpolar Front in the preinstrumental past

Author Posting. © American Meteorological Society, 2016. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Climate 29 (2016): 1545-1571, doi:10.1175/JCLI-D-15-0509.1.Three sediment records of sea surface temperature (SST) are analyzed that originate from distant locations in the North Atlantic, have centennial-to-multicentennial resolution, are based on the same reconstruction method and chronological assumptions, and span the past 15 000 yr. Using recursive least squares techniques, an estimate of the time-dependent North Atlantic SST field over the last 15 kyr is sought that is consistent with both the SST records and a surface ocean circulation model, given estimates of their respective error (co)variances. Under the authors’ assumptions about data and model errors, it is found that the 10°C mixed layer isotherm, which approximately traces the modern Subpolar Front, would have moved by ~15° of latitude southward (northward) in the eastern North Atlantic at the onset (termination) of the Younger Dryas cold interval (YD), a result significant at the level of two standard deviations in the isotherm position. In contrast, meridional movements of the isotherm in the Newfoundland basin are estimated to be small and not significant. Thus, the isotherm would have pivoted twice around a region southeast of the Grand Banks, with a southwest–northeast orientation during the warm intervals of the Bølling–Allerød and the Holocene and a more zonal orientation and southerly position during the cold interval of the YD. This study provides an assessment of the significance of similar previous inferences and illustrates the potential of recursive least squares in paleoceanography.OM acknowledges support from the U.S. National Science Foundation. CW acknowledges support from the European Research Council ERC Grant ACCLIMATE 339108.2016-08-1