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

Thermal oxidation kinetics of additive free polyamide 6-6

Thermal aging of an additive free PA 6-6 has been elucidated at 90, 100, 120, 140, 150 and 160 C in airventiled ovens by Fourier transform infrared spectrophotometry, viscosimetry in molten state and uniaxial tensile testing. Oxidation of methylene groups starts after a considerably shorter induction period but reaches a lower maximal rate than in additive free PE. Cleavage of CeN bonds constitutes the main source of chain scissions. It leads to the formation of aldehyde chain-ends and a catastrophic decrease in molar mass. Embrittlement occurs at a very low conversion ratio of the oxidation process, in particular when the concentration of aldehyde chain-ends reaches a critical value of [PH¼O]F z 5.6 10 3 mol l 1, corresponding to a critical value of the number average molar mass ofMnFz17 kg mol 1. At this stage, the entanglement network in the amorphous phase is deeply damaged. A non-empirical kinetic model has been derived from the oxidation mechanistic scheme previously established for PE, but improved by adding elementary reactions specific to polyamides such as the rapid decomposition of unstable hydroxylated amide groups. This model describes satisfyingly the main features of the thermal oxidation kinetics of PA 6-6, but also of other types of aliphatic polyamides studied previously in the literature such as: PA 6, PA 12 and PA 4-6, as long as it is not controlled by oxygen diffusion. At the same time, it confirms the existence of an universal character for the thermal oxidation kinetics of aliphatic polyamides whatever their origin, i.e. their initial molar mass, crystallinity ratio, concentration of impurities, structural irregularities, etc

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

Attention please!

We study the impact of manipulating the attention of a decision-maker who learns sequentially about a number of items before making a choice. Under natural assumptions on the decision-maker’s strategy, directing attention toward one item increases its likelihood of being chosen regardless of its value. This result applies when the decisionmaker can reject all items in favor of an outside option with known value; if no outside option is available, the direction of the effect of manipulation depends on the value of the item. A similar result applies to manipulation of choices in bandit problems

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

LES study of deflagration to detonation mechanisms in a downsized spark ignition engine

Using 15 LES cycles of a high load/low speed spark ignition engine operating point, two different fresh gases autoignition regimes called knock and super-knock are analyzed. A direct “a posteriori” analysis of pressure waves and autoignition heat release observed in LES is proposed. It reveals that low to moderate knock intensity, corresponding to late spark timings (ST) is characterized by one or several random autoignition (AI) spots which consume the surrounding fresh gases without coupling with the AI heat release. On the contrary, the highest knock intensities correspond to what is usually called super-knock, a very intense knock observed under pre-ignition conditions or for very early ST, as done in this study. LES shows that the pressure waves generated by one or a couple of AI spots are strong enough to induce locally a strong fresh gases temperature increase leading itself to a substantial decrease of the AI delay. This allows to generate a coupling between the pressure wave and the AI reaction rate which reinforce each other, leading to maximum pressures and propagation speeds close to those of a detonation. These results therefore strongly support the hypothesis proposed in the literature that super-knock is characterized by a deflagration to detonation transition (DDT). An “a priori” analysis is also performed thanks to the use of a local detonation indicator based on Bradley’s DDT diagram. It is shown that this tool not only predicts the change of combustion regime as a function of the ST, but it also roughly succeeds in predicting the location and time of appearance of the DDT in the chamber. Unfortunately, the first AI spot is not always responsible for the DDT, implying that using cold flow LES to calculate the detonation indicator instead of a reacting LES as proposed here, would lead to a failure of the indicator in many cases