Monitoring the polyamide 11 degradation by thermal properties and X‐ray fluorescence spectrometry allied to chemometric methods

The influence of temperature (110 and 120 °C) on the ageing of piping made from polyamide 11 (PA‐11) containing 10–12% of plasticizer was studied using deionized water (pH ≈ 7.0). A clean analytical methodology has been employed for quality control of polymeric materials: energy‐dispersive X‐ray fluorescence spectrometry (ED‐XRF). It provides a fast and suitable technique to characterize chemical elements because of its multielemental capability, good sensitivity, high precision, short analytical time, and nondestructive nature. Herein, the content of additive in PA‐11 was monitored from ED‐XRF measurements where the abundance of the S line is directly related to the ageing time, agreeing with the thermogravimetric analysis. The XRF data were allied to chemometric treatment to classify PA‐11 samples according to the amount of additive and weight average molar mass change, predicting the ageing time, and viscosity values of PA‐11. Therefore, the XRF can be used as a clean analytical methodology to monitor the PA‐11 degradation, thus eliminating the use of toxic organic solvents (necessary to viscosity measurements) and reducing the working time. Also, the effect of hydrolysis on the structure over time and the material morphology were monitored through measurements of dynamic mechanical analysis and differential scanning calorimetry. Copyright © 2012 John Wiley & Sons, Ltd.     

Anderson-like Transition for a Class of Random Sparse Models in <Emphasis Type=Italic>d</Emphasis>≥2 Dimensions

We show that the Kronecker sum of d≥2 copies of a random one-dimensional sparse model displays a spectral transition of the type predicted by Anderson, from absolutely continuous around the center of the band to pure point around the boundaries. Possible applications to physics and open problems are discussed briefly.     

General decay rate estimates for viscoelastic dissipative systems

The linear viscoelastic equation is considered. We prove uniform decay rates of the energy by assuming a nonlinear feedback acting on the boundary, without imposing any restrictive growth assumption on the damping term and strongly weakening the usual assumptions on the relaxation function. Our estimate depends both on the behavior of the damping term near zero and on the behavior of the relaxation function at infinity.     

Phase diagrams of lyotropic cholesteric fluids

Experimental investigations of lyotropic cholesterics fluids are presented which show that changes in the shape anisotropy and chirality of the micellar population determine the topology of the temperature-concentration phase diagrams. For given amounts of the substances which induce the chirality and modify the shape anisotropy of the micelles, two distinct biaxial cholesteric phases are disclosed in the phase diagrams. This is interpreted in the framework of the catastrophe theory of phase transitions.     

Note on the applicability of the Peierls-Yoccoz method

A simple criterion for the approximate validity of the single projection Peierls-Yoccoz method is discussed. A procedure for chosing the generator coordinate is proposed.     

Existence and uniform decay for a non‐linear viscoelastic equation with strong damping

This paper is concerned with the non‐linear viscoelastic equation We prove global existence of weak solutions. Furthermore, uniform decay rates of the energy are obtained assuming a strong damping Δu_t acting in the domain and provided the relaxation function decays exponentially. Copyright © 2001 John Wiley & Sons, Ltd.     

Mechanisms of nucleophilic substitution reactions of methylated hydroxylamines with bis(2,4-dinitrophenyl)phosphate. Mass spectrometric identification of key intermediates

Mono- and dimethylation of hydroxylamine on nitrogen does not significantly affect rates of initial attack of NHMeOH and NMe(2)OH on bis(2,4-dinitrophenyl)phosphate (BDNPP), which is largely by oxygen phosphorylation. O-Methylation, however, blocks this reaction and NH(2)OMe then slowly reacts with BDNPP via N-attack at phosphorus and at the aryl group. With NHMeOH, the initial product of O-attack at phosphorus reacts further, either by reaction with a second NHMeOH or by a spontaneous shift of NHMe to the aryl group via a transient cyclic intermediate. There is a minor N-attack of NHMeOH on BDNPP in an S(N)2(Ar) reaction. Reactions occurring via N-attack are blocked by N-dimethylation, and reaction of NMe(2)OH with BDNPP occurs via O-attack, generating a long-lived product. Reaction mechanisms have been probed, and intermediates identified, by using both NMR and MS spectroscopy, with the novel interception of key reaction intermediates in the course of reaction by electrospray ionization mass and tandem mass spectrometry.     

Unified Approach to Stabilization of Waves on Compact Surfaces by Simultaneous Interior and Boundary Feedbacks of Unrestricted Growth

Let $\mathcal{M}\subset\mathbb{R}^{3}$ be an oriented compact surface on which we consider the system: $$\left \{ \begin{array}{l@{\quad}l} u_{tt} - \Delta_{\mathcal{M}} u + a(x)g_{0}(u_{t})=0 & \text{in } \mathcal{M}\times\mathopen{]} 0,\infty[ ,\\ \partial_{\nu_{co}}u +u + b(x)g(u_t)=0 & \text{on } \partial \mathcal {M}\times\mathopen{]}0,+\infty[. \end{array} \right . $$ If $\mathcal{M}$ along with the localizers a, b and the nonlinear feedbacks g,g ₀ satisfy certain conditions then uniform (but not necessarily exponential) decay rates of the finite energy of solutions can be established. We present a unified approach that bridges and extends a number of earlier results on stabilization of 2nd-order hyperbolic equations on manifolds. The methodology captures geometric requirements for damping acting simultaneously on subsets of the interior and of the boundary, and shows how placements of these feedbacks can complement each other depending on the underlying surface. In addition, the results conveniently incorporate the existing theory that allows elimination of geometric conditions from the controlled boundary (in absence of nearby interior damping), and elimination of damping entirely from certain boundary neighborhoods. The model also admits feedbacks that grow sub- or super-linearly not only at the origin, but also at infinity and demonstrates an interplay between the regularity of solutions and asymptotic energy decay rates.     

Preparative treatment with NaOH to selectively concentrate iron oxides of a Chilean volcanic soil?material to produce effective heterogeneous Fenton catalyst

A Chilean volcanic Ultisol material was first size-fractionated so as to obtain the fraction with mean particle sizes ??<?53 ??m. This sample was then sequentially treated three or five times with 5 mol L^???1 NaOH, in an attempt to evaluate the effectiveness of the selective chemical dissolution to concentrate iron oxides, as a preparation procedure before using the materials as heterogeneous Fenton catalysts. The effects of those treatments on the iron oxides mineralogy were monitored with Mössbauer spectroscopy. The NaOH-treated samples were tested as catalysts towards the H₂O₂ decomposition. Three or five sequential NaOH treatments were found to be comparably effective, by concentrating nearly the same proportion of iron oxides in the remaining solid phase (25.1 ± 0.4 and 23.3 ± 0.2 mass%, respectively). 298 K-Mössbauer patterns were similar for both samples, with a central (super)paramagnetic Fe^3?+? doublet and a broad sextet, assignable to several closely coexisting magnetically ordered forms of iron oxides. Despite of this nearly similar effect of the two treatments, the Ultisol material treated three times with NaOH presents higher heterogeneous catalytic efficiency and is more suitable to decompose H₂O₂ than that with five treatments.