Glass transition,crystallization, and morphology relationships in miscible poly(aryl ether ketones) and poly(ether imide) blends

The relationships among glass transition, crystallization, melting, and crystal morphology of poly(aryl ether ketone) (PAEK)/poly(other imide) (PEI) blends was studied by thermal, optical and small-angle x-ray scattering (SAXS) methods. Two types of PAEK were chosen for this work: poly(aryl ether ether ketone), PEEK, and poly(aryl ether ketone ketone), PEKK, which have distinctly different crystallization rates. Both PAEKs show complete miscibility with PEI in the amorphous phase. As PAEK crystallizes, the noncrystallizable PEI component is rejected from the crystalline region, resulting in a broad amorphous population, which was indicated by the broadening and the increase of T_g over that of the purely amorphous mixture. The presence of the PEI component significantly decreases the bulk crystallization and crystal growth rate of PAEK, but the equilibrium melting temperature and crystal surface free energies are not affected. The morphology of the PEI segregation was investigated by SAXS measurements. The results indicated that the inter(lamellar-bundle) PEI trapping morphology was dominant in the PEEK/PEI blends under rapid crystallization conditions, whereas the interspherulitic morphology was dominant in the slow crystallizing PEKK/PEI blends. These morphologies were qualitatively explained by the expression δ=D/G, where G was the crystal growth rate and D was the mutual diffusion coefficient. © 1993 John Wiley & Sons, Inc.     

A Classification of Fully Residually Free Groups of Rank Three or Less

A groupGisfully residually freeprovided to every finite setS ⊂ G\{1} of non-trivial elements ofGthere is a free groupF_Sand an epimorphismh_S:G → F_Ssuch thath_S(g) ≠ 1 for allg ∈ S. Ifnis a positive integer, then a groupGisn-freeprovided every subgroup ofGgenerated bynor fewer distinct elements is free. Our main result shows that a fully residually free group of rank at most 3 is either abelian, free, or a free rank one extension of centralizers of a rank two free group. To prove this we prove that every 2-free, fully residually free group is actually 3-free. There are fully residually free groups which are not 2-free and there are 3-free, fully residually free groups which are not 4-free.     

Equivalence of Two Approaches to Integrable Hierarchies of KdV type

The equivalence between the approaches of Drinfeld-Sokolov and Feigin-Frenkel to the mKdV and KdV hierarchies is established. A new derivation of the mKdV equations in the zero curvature form is given. Connection with the Baker-Akhiezer function and the tau-function is also discussed. Received: Received: 1 July 1996 / Accepted: 21 October 1996     

Solvent dynamics following charge transfer at the liquid-liquid interface

The dynamics of solvent reorganization following charge transfer at the interface between two immiscible liquids, one polar and the other non-polar are investigated by molecular dynamics. Both charge separation and charge recombination processes in two different orientations at the surface are considered and are compared with the same processes in the bulk polar solvent. The relaxation at the surface is significantly slower than in the bulk, in contrast to predictions of continuum models. The linear response approximation works reasonably well in the bulk but fails at the interface. The Langevin model is in poor agreement with the exact equilibrium correlations, especially at short time, but can qualitatively account for the overall rate.     

A nonlinear bilevel model for analysis of electric utility demand-side planning issues

An application of bilevel programming in the electric utility industry is presented. The model is nonlinear and is used to analyze various economic issues that affect electric utility planning. The electric utility at the upper level of the model seeks to minimize costs or maximize benefits while controlling electric rates and subsidizing energy conservation programs. Customers at the lower level attempt to maximize their net benefit by consuming electricity and investing in conservation. This model considers factors such as free riders and the rebound effect which affect the net benefits of utility resource plans but are ignored by most planning models. The model's solutions shed light on utility issues including whether there can be a practical difference between various objectives, including minimizing cost (least cost planning) and maximizing net social welfare (value based planning).     

Rational forms for twistings of enveloping algebras of simple Lie algebras

We give rational forms for twistings of classical enveloping algebras. We also remark a link with the generalized formalism of Gurevich, Manin, and Cartier.     

A STUDY OF STRUCTURE AND PROPERTY CHANGES OF BIODEGRADABLE POLYGLYCOLIDE AND POLY(GLYCOLIDE-co-LACTIDE)FIBERS DURING PROCESSING AND IN VITRO DEGRADATION*

Structure and properties of bioabsorbable polyglycolide (PGA) and poly(glycolide-co-lactide) (PGA-co-PLA)fibers were investigated during several industrial processing stages and in vitro degradation by means of wide-angle X-raydiffraction (WAXD), dynamic mechanical analysis (DMA) and mechanical property tests. In the orientation stage, the PGAfibers were found to have higher degrees of crystallinity than corresponding PGA-co-PLA samples produced under similarconditions. In the hot-stretching and post-annealing stages, after fibers were braided, PGA samples were found to gain morecrystallinity and higher T_g than PGA-co-PLA samples. The higher crystallinity in PGA fibers resulted in a slower rate ofdegradation. DMA results showed that a great deal of internal stress that was built during orientation and hot-stretchingstages was released in the post-annealing stage for a1l PGA and PGA-co-PLA samples. During earlier stages of in vitrodegradation, both PGA and PGA-co-PLA samples exhibited the typical cleavage-induced crystallization mechanism. Theheat shrinkage in the glass transition area was found to disappear after 6-8 days of degradation for all PGA and PGA-co-PLAsamples, indicating the amorphous portions of the polymers lost orientation after a short period in the buffer solution, mostlikely due to relaxation of the cleaved chains.     

Continuous,on-demand generation and separation of diphenylphosphoryl azide

Diphenylphosphorylazide (DPPA) has been synthesized in microfluidics with near-100% yield in sub-3 minute residence time, affordably, and with a process design that minimizes hazards associated with hydrazoic acid (HN₃) production. A pilot-plant scale continuous process for the on-demand synthesis of diphenylphosphoryl azide (DPPA) that can readily be integrated with subsequent transformations was designed, built, and validated. Using Corning's Low Flow reactor system coupled to a membrane separator and in-line Fourier Transform Infrared (FTIR), DPPA was safely produced at a rate of 1?mol/hr as a 2.0?M anhydrous toluene stream. Continuous FTIR was able to reliably monitor product quality, purity and concentration, showcasing the ease and utility of this continuous flow process for manufacturing common, safe pharmaceutical precursors.