Theory of “Cohesive” vs “Adhesive” Separation in an Adhering System

It is shown that there is limited validitity to the doctrine that true interfacial separation, in an adhering system, is highly improbable. An analysis employing the Griffith-Irwin crack theory yields these results: The important parameters are, difference in elastic moduli, ΔE; differences in g, the energy dissipation per unit crack extension; thickness, Δ₁ or δ₂, of the region where dissipation occurs; and the presence or absence of strong interfacial bonds. If the forces across the interface are appreciably weaker than the cohesive forces in either phase, there is a strong minimum in g at the interface. For flaws of equal size, an interfacial flaw will be the site of initiation of failure. If strong interfacial bonds are present, then if Δg and ΔE have the same sign, failure is most probable, deep within one phase. If Δg and ΔE have opposite signs, failure may be initiated, and may propagate, at a distance δ from the interface, in the phase with lower g. This may be mistaken for weak-boundary layer failure.     

Interrogation of “surface,” “skin,” and “core” orientation in thermotropic liquid‐crystalline copolyester moldings by near‐edge X‐ray absorption fine structure and wide‐angle X‐ray scattering

Injection molding thermotropic liquid‐crystalline polymers (TLCPs) usually results in the fabrication of molded articles that possess complex states of orientation that vary greatly as a function of thickness. “Skin‐core” morphologies are often observed in TLCP moldings. Given that both “core” and “skin” orientation states may often differ both in magnitude and direction, deconvolution of these complex orientation states requires a method to separately characterize molecular orientation in the surface region. A combination of two‐dimensional wide‐angle X‐ray scattering (WAXS) in transmission and near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy is used to probe the molecular orientation in injection molded plaques fabricated from a 4,4′‐dihydroxy‐α‐methylstilbene (DHαMS)‐based thermotropic liquid crystalline copolyester. Partial electron yield (PEY) mode NEXAFS is a noninvasive ex situ characterization tool with exquisite surface sensitivity that samples to a depth of 2 nm. The effects of plaque geometry and injection molding processing conditions on surface orientation in the regions on‐ and off‐ axis to the centerline of injection molded plaques are presented and discussed. Quantitative comparisons are made between orientation parameters obtained by NEXAFS and those from 2D WAXS in transmission, which are dominated by the microstructure in the skin and core regions. Some qualitative comparisons are also made with 2D WAXS results from the literature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Fatty acids characterization in “Alicante” and “Jijona” nougat bars,two Spanish sweets

In this work the fatty acids in two typical Spanish sweets have been characterized: Alicante and Jijona nougat bars, using gas chromatography with a flame-ionization detector. The majority of the fatty acids in these two sweets are unsaturated, and only a low proportion is saturated, which turns them into a type of food with low influence on cholesterol resulting in low atherogenic power, due to the low amount of saturated fatty acids, which is far from constituting 1/3 of the total sum of fatty acids granted by a diet, a limit that has been advised by a great number of International Scientific Committees.     

Salt‐Controlled Selectivity in “on Water” and “in Water” Passerini‐Type Multicomponent Reactions

We have demonstrated that simple sodium salts can completely reverse the product ratios of the Passerini reaction in aqueous media. Furthermore, the use of the “salting‐in” salt and a small excess of the nucleophile gives significantly higher yields than the use of the saturated solution of the nucleophile alone.     

Comparison study of a chiral stationary phase based on cellulose derivatives prepared by “grafting from” and “grafting to” methods

Chiral stationary phase (CSP) with cellulose derivatives was synthesized using the “grafting from” and “grafting to” methods. The “grafting to” method involves the bonding of a preformed end‐functionalized polymer to reactive surface amine groups on the silica gel. The “grafting from” involves the immobilization of initiator onto the aminated silica gel followed by atom transfer radical polymerization (ATRP) to generate the chiral polymer chains. The successful preparation of the CSP with cellulose derivatives prepared by ATRP was confirmed by FE‐SEM, XPS, EA, and thermal analysis. The chiral resolution of the CSP with cellulose derivatives was evaluated by high‐performance liquid chromatography using 10 racemates with various mobile phases that consisted of hexane/alcohol, hexane/THF, and hexane/chloroform. Furthermore, the CSP with cellulose derivatives prepared by “grafting from” and “grafting to” were compared and discussed. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The role of pore structure in the catalytic behavior of “unaged” and “aged” silica-alumina catalysts

This is a review of research concerning the role played by the porous structure of silica-alumina catalysts on the evolution of organic catalytic processes. A strong effect of the geometrical shape of the pores on catalytic activity and selectivity has been evidenced. The experimental results have also been interpreted by means of a simplified mathematical model, able to relate selectivity for a reaction of the type A → B → C to the geometrical features of macro-microporous catalyst pellets, or granules. The theoretical results are in qualitatively satisfactory agreement with the experimental data.     

The “alexandrite effect” in gemstones

The term “alexandrite effect” is used in gemology to describe a distinct change of color appearance when a gemstone is switched from daylight to incandescent light. Gemstones that exhibit the alexandrite effect can actually be divided into four categories based upon the value of the calculated absolute hue-angle change of the material under different pairs of illuminants. the alexandrite effect is a non-color-constancy phenomenon. It can be explained by a combination of both chromaticity adaptations to the different light sources, and vision system responses to the spectral distribution of the light emitted by alexandrite effect gemstones when they are illuminated alternatively by the different light sources.     

Flow of polymer melts in a disc-type extruder and in rotational devices of the “cone-plate” and “plate-plate” type

The flow pattern of a polyethylene melt in the working gap of a disc-type extruder has been visualized. It is shown that there is complex circulating flow in the working gap of the extruder. The flow lines are spirals of Archimedes. An investigation into the qualitative picture of the flow of a polyethylene melt in rotational devices of the “plate-plate” and “cone-plate” type showed that in such devices a complex circulating flow is also realized and the flow lines are spirals of Archimedes.     

Molecular weight distribution control in a semibatch “living” anionic polymerization. I. Theoretical study

A method to produce homopolymers of preestablished molecular weight distribution (MWD), through “living” anionic polymerizations carried out in homogeneous semibatch reactors is proposed and theoretically justified. In the direct form of the technique, very fast reactions are assumed, and the monomer and “killing” agent feed flows are obtained from the knowledge of the desired MWD, the system spreading function, the total reaction time, the initial reaction volume, and the reagent concentrations. Alternatively, by controlling a reactor outlet flow instead of the “killing” agent feed, an external deactivation of the “living” ends can be implemented. The method can be extended to slow reactions, to more elaborated mechanisms, and to take into account the unwanted deactivation of “living” ends by impurities in the monomer solution feed.     

Inorganic Quantum Dot Materials and their Applications in “Organic” Hybrid Solar Cells

Semiconductor quantum dots (QDs) are promising materials for polymer‐nanocrystal hybrid solar cells (HSCs). The aim of this review article is to present a comprehensive and current overview of inorganic QDs and their applications in HSCs. Fundamental properties of QDs are first illustrated. And then recent studies that have been done to elucidate charge dynamics of QDs and improve hybrid device performance are summarised and discussed in detail. Finally, an outlook is presented considering current existing challenges in HSCs.     

Antioxidative Effect of “Herbalox” on Edible Oils

Antioxidative effect of BHA (Butylated hydroxyanisole) and rosemary extract (Herbalox Type 0) in soybean and sunflower seed oil were investigated. Stability to oxidation was determined by measurement of induction time with the Rancimat 679 at 100°C. Changes in control (no antioxidant added) and experimental oil samples were monitored. The addition of antioxidants reduce oxidation thus increasing product stability. Presence of synthetic antioxidant BHA in sunflower seed oil at the concentration of 0.02% (w/w) increases induction time from 6.0 to 8.09 hours. The results obtained indicated higher synthetic antioxidant efficacy compared with natural Herbalox Type 0 antioxidant, as the induction time for the later one, used at the same concentration, increased from originally 6.0 to 6.67 hours.