Time-resolved synchrotron X-ray study of crystalline phase transition in poly(aryl ether ketone ketone) containing alternated terephthalic/isophthalic moieties

Unique crystallization and melting behavior in poly(aryl ether ketone ketone) containing alternated terephthalic and isophthalic moieties were studied by time-resolved synchrotron x-ray methods. Recently, this material has been shown to exhibit three polymorphs (forms I, II, and III). In this work, we further investigated their distinctive thermal properties and found that form I is the dominating and the most thermally stable phase while form II is favored by fast nucleation conditions and is the least stable phase. On the other hand, form III represents a minor intermediate phase that usually coexists with form I and can be transferred from form II and to form I. Structural and morphological changes in form I have been followed by simultaneous wide-angle x-ray diffraction (WAXD)/small-angle x-ray scattering (SAXS) measurements during cold- or melt-crystallization and subsequent melting. In all cases, a larger dimensional change was found in the crystallographic a-axis than the b-axis during heating and cooling. This may be due to the greater lateral stress variation with respect to temperature along the a direction of the primary lamellae which is induced by either the formation of secondary lamellae or the preferential chain-folding direction in poly(aryl ether ketone ketone)s. During the phase transitions of form II ← III in the cold-crystallized specimen and form III ← I in the melt-crystallized samples, lamellar variables (long period, lamellar thickness, and invariant) obtained from SAXS remain almost constant. This indicates that the density distribution in the long spacing is independent of the melting in form II or III. For melt-crystallization, the corresponding changes in unit-cell dimensions and lamellar morphology during the annealing-induced low endotherm are most consistent with the argument that these changes are due to the melting of thin lamellar population. © 1995 John Wiley & Sons, Inc.     

Vibrational control of crystal growth from liquid phase

Modeling and numerical simulations of the convective flows induced by the vibration of the monocrystal during crystal growth have been performed for two configurations simulating the Cz and FZ methods. This permitted to emphasize the role of different vibrational mechanisms in the formation of the average flows. It is shown that an appropriate combination of these mechanisms can be used to counteract the usual convective flows (buoyancy- and/or thermocapillary-driven) inherent to crystal growth processes from the liquid phase. While vibrational convection is rather complex due to these identified mechanisms, the new modeling used in the present paper opens up very promising perspectives to efficiently control heat and mass transfer during real industrial applications of crystal growth from the liquid phase.     

Pseudo-Strong Regularity Around a Set

A generalization of strong regularity around a vertex subset C of a graph Γ, which makes sense even if Γis non-regular, is studied. Such a structure appears, together with a kind of distance-regularity around C , when an spectral bound concerning the so-called predistance polynomial of C is attained. As a main consequence of these results, it is shown that a regular (connected) graph Γwith d + 1 distinct eigenvalues is distance-regular, and its distance- d graph Γ d is strongly regular with parameters a = c , if and only if the number of vertices at distance d from each vertex satisfies an expression which depends only on the order of Γand the different eigenvalues of Γ.     

Electron-transfer kinetics and activation barriers for the reductions of nitrosonium and nitronium ions in aprotic solvents

Using the cyclic voltammetry (CV), the electron-transfer kinetics for the reductions of NO⁺ and NO₂⁺ cations have been studied at the Pt electrode in nitromethane, sulfolane, and propylene carbonate. The heterogeneous rate constants have been determined by two independent procedures from the transfer coefficient α, the diffusion coefficient D, from a detailed examination of the CV-peak separations, and from an inspection of the values of the cathodic peak potentials at different scan rates. The results have been compared to those reported in the literature, and discussed. In the classical model, outer-sphere electron-transfer reactions are considered subject to an activation energy arising from solvent reorganization and bond reorganization processes. The solvent and molecular reorganizational barriers for these electroreductions have been assessed in aprotic media. The Marcus-Hush theory has been applied to the self-exchange reactions of the NO₂⁺/NO₂ and NO⁺/NO couples in an attempt to predict the rate of electron transfer. The findings indicate some improvement between theory and experiment. However, it should be noted that the experimental values of k_s found for the NO₂⁺ reduction in the solvents used are still too high in comparison with those determined theoretically. In view of the fairly strong coordination of the solvent molecule(s) as ligand(s) to NO₂⁺ and NO⁺ cations, we believe that such discrepancies should stem, to some extent, from the involvement of an inner-sphere pathway by generation of an activated complex on the surface of the Pt electrode. © 1993 John Wiley & Sons, Inc.     

AN ALTERNATIVE SPECIFICATION FOR MODELING GROUNDWATER DYNAMICS

This research extends previous work with dynamic models to manage groundwater quality by using the consumptive nitrate use rate instead of the nitrate application rate. The analysis indicates that misspecification results in overestimation of economic benefits, and supra-optimum nitrogen fertilizer application rates and groundwater nitrate stocks at a steady state.     

Chemical composition and reaction analysis of single aerosol particles

In situ measurements of gas-liquid surface reactions of single aerosol microdroplets are presented. By means of optical levitation in combination with elastic (Mie) and inelastic (Raman) light scattering it is possible to get information on the chemistry of e.g. acid/base reactions as well as the physical behavior of single microparticles.     

Selective saturation and inversion of multiple resonances in high-resolution solid-state 13C experiments using slow spinning CP/MAS and tailored DANTE pulse sequences.

Taking advantage of the long 13C T1 values generally encountered in solids, selective saturation and inversion of more than one resonance in 13C CP/MAS experiments can be achieved by sequentially applying several DANTE pulse sequences centered at different transmitter frequency offsets. A new selective saturation pulse sequence is introduced composed of a series of 90 degrees DANTE sequences separated by interrupted decoupling periods during which the selected resonance is destroyed. Applications of this method, including the simplification of the measurement of the principal values of the 13C chemical shift tensor under slow MAS conditions, are described. The determination of the aromaticity of coal using a relatively slow MAS rate is also described.