The mechanism of photoprotection of wool by UV absorbers of the 2-hydroxybenzophenone class

The mechanism by which sulfonated 2-hydroxybenzophenone ultraviolet (UV) absorbers protect wool fabric against photoyellowing has been studied. The absorption and luminescence properties of two 2-hydroxybenzophenone-5-sulfonates and four 2-hydroxybenzophenone-2′hyphen;sulfonates are compared. The 2-hydroxy-benzophenones are nonfluorescent in wool, but they all show phosphorescence at room temperature. The phosphorescence is attributed to the phenolate anion produced by ionization of the hydroxyl group. The nature of substituents in the 3-position and 4-position of the phenolic ring is important in controlling the formation of luminescent species which may initiate unwanted photochemical reactions in wool. The protective screening effect of each absorber in wool fabric has been determined theoretically, using a method of analysis based on diffuse reflectance spectroscopy; the results are compared with the values determined experimentally by measuring the changes in yellowness that result when treated and untreated fabrics are exposed to fluorescent sunlamps (maximum energy at 310 nm). In all cases, UV screening was shown to be the important mode of photostabilization. The levels of photoprotection were much higher than those reported previously for treated fabrics that were exposed for long periods to simulated sunlight, behind glass. Possible reasons for the poor long-term performance of the 2-hydroxybenzophenones in wool are discussed.     

Comments on the use of buckminsterfullerene encapsulated in zeolite Y as a potential catalyst

Buckminsterfullerene encapsulated within zeolite Y is found not to be a reactive radical initiator for the formation of dimethoxyethane from dimethyl ether below 200° C. Above this temperature the expected acid catalysed conversion of dimethyl ether to hydrocarbons is observed. Dimethoxyethane formation is observed when bibenzoyl peroxide is used as a radical initiator. These studies indicate that any radical formed by the encapsulated buckminsterfullerene is relatively unreactive.     

The Effect of Organic Diluent on the Extraction of Eu(III) by HEH[EHP]

ABSTRACT

Because there are fewer tools available to probe the interactions therein, the effect of the fundamental chemistry of the organic diluent on solvent extraction equilibria has been under-characterized relative to the aqueous. As a result, diluents for solvent extraction are often selected for an application not for their utility as a medium for reaction, but for other (often equally) important reasons (like low flammability). To begin to improve this imbalance in the science, twenty different diluents have been used in a study of the extraction of radiotracer ^152/154Eu³⁺ from dilute nitric acid solutions using the extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]). To increase the utility of the study and to honor the memory of Professor Jan Rydberg, this investigation was conducted by a cadre of comparatively inexperienced separation scientists (who are as a result no longer inexperienced separation scientists) as a radioanalytical chemistry and solvent extraction educational exercise. Slope analysis was used to determine the apparent stoichiometry of the extracted metal complex. The results discussed in the following indicate that, while the pH dependence exhibits the expected three H⁺ exchanged per metal ion extracted, the extractant dependence suggests that the number of protonated extractant molecules in the extracted complex changes with the organic diluent. The experimentally observed “extractant dependency” ranges from 2.5 to 3.0 dimer equivalent molecules per extracted metal ion. Ironically, in the diluents exhibiting the highest apparent M:(HA)₃ stoichiometry, HEH[EHP] extracts Eu³⁺ less efficiently. Europium luminescence spectroscopy was used to probe for changes in the first coordination sphere of the complex in different diluents. A model and conceptual framework for understanding these observations is described.     

Temperature and processing effects on lithium ion conductivity of solution-deposited lithium zirconium phosphate (LiZr2P3O12) thin films

Lithium zirconium phosphate (LiZr₂P₃O₁₂) thin films have been prepared on platinized silicon substrates via a chemical solution deposition approach with processing temperatures between 700°C and 775°C. Films that were subject to a single high-temperature anneal were found to crystallize at temperatures above 725°C. Crystallization was observed in films annealed after each deposited layer at 700°C and above. In both cases, grain size was found to increase with annealing temperature. Ion conductivity was found to increase with annealing temperature in singly annealed films. In per-layer annealed films ion conductivity was found to initially increase then decrease with increasing annealing temperature. A maximum ion conductivity of 1.6 × 10⁻⁶ S/cm was observed for the singly annealed 775°C condition, while a maximum ion conductivity of 5.8 × 10⁻⁷ S/cm was observed for the 725°C per-layer annealed condition. These results are consistent with an increasing influence of cross-plane, internal interface resistance and vapor phase carrier loss in the per-layer annealed samples. This work demonstrates that post-deposition processing methods can strongly affect the ion conducting properties of LiZr₂P₃O₁₂ thin films.     

Biobased flexible polyurethane foams manufactured from lactide-based polyester-ether polyols for automotive applications

In this study, biobased polyester-ether polyols derived from meso-lactide and dimer acids were evaluated for flexible polyurethane foams (PUF) applications. Initially, the catalyst concentration was optimized for the biobased PUF containing 30% of biobased polyol (70% petroleum-based polyol). Then, the same formulation was used for biobased PUF synthesis containing 10%–40% of biobased polyols. The performance of biobased PUF was compared with the performance of the control foam made with 100% petroleum-based polyol. The characteristic times (cream, top of the cup, string gel, rise, tack-free) of biobased PUF were determined. The biobased PUF were evaluated for the mechanical (tensile and compressive) and morphological properties. As the wet compression set is important for automotive applications, it was measured for all biobased PUF. The thermal degradation behavior of biobased PUF was also evaluated and compared with the control foam. The effect of different hydroxyl and acid values of polyols on the mechanical properties of biobased PUF is also discussed. The miscibility of all components of PUF formulations is crucial in order to produce a foam with uniform properties. Thus, the miscibility of biobased polyols with commercial petroleum-based polyol was studied.     

How to “alternatize” a clustering algorithm

Given a clustering algorithm, how can we adapt it to find multiple, nonredundant, high-quality clusterings? We focus on algorithms based on vector quantization and describe a framework for automatic ‘alternatization’ of such algorithms. Our framework works in both simultaneous and sequential learning formulations and can mine an arbitrary number of alternative clusterings. We demonstrate its applicability to various clustering algorithms—k-means, spectral clustering, constrained clustering, and co-clustering—and effectiveness in mining a variety of datasets.     

Cyclic voltammetry on electrode surfaces covered with porous layers: An analysis of electron transfer kinetics at single-walled carbon nanotube modified electrodes

Cyclic voltammetry is recorded of the oxidation of ferrocyanide on a glassy carbon electrode modified with multiple layers of single-walled carbon nanotubes. The current response is interpreted in terms of semi-infinite planar diffusion towards the macro-electrode surface and in terms of oxidation of the electroactive species trapped in pockets in between the nanotubes. A thin layer model is used to illustrate the effects of diffusion within a porous layer. It is found that a semi-infinite planar diffusion model alone is not appropriate for interpreting the kinetics of the electron transfer at this electrode surface. In particular, caution should be exercised in respect of comparing voltammetric peak-to-peak potential separations between naked electrodes and nanotube-modified electrodes for the inference of electrocatalysis via electron transfer via the nanotubes.     

Minimal ordering constraints for some families of variable symmetries

Variable symmetries in a constraint satisfaction problem can be broken by adding lexicographic ordering constraints. Existing general methods of generating such sets of ordering constraints can require a huge number of constraints. This adds an unacceptable overhead to the solving process. Methods exist by which this large set of ordering constraints can be reduced to a much smaller set automatically, but their application is also prohibitively costly. In contrast, this paper takes a bottom-up approach. It examines some commonly-occurring families of groups and derives a minimal set of ordering constraints sufficient to break the symmetry each group describes. These minimal sets are then used as building blocks to generate minimal sets of ordering constraints for groups constructed via direct and imprimitive wreath products. Experimental results confirm the value of minimal sets of ordering constraints, which can now be generated much more cheaply than with previous methods.     

Configuring and enhancing measurement systems for damage identification

Engineers often decide to measure structures upon signs of damage to determine its extent and its location. Measurement locations, sensor types and numbers of sensors are selected based on judgment and experience. Rational and systematic methods for evaluating structural performance can help make better decisions. This paper proposes strategies for supporting two measurement tasks related to structural health monitoring - (1) installing an initial measurement system and (2) enhancing measurement systems for subsequent measurements once data interpretation has occurred. The strategies are based on previous research into system identification using multiple models. A global optimization approach is used to design the initial measurement system. Then a greedy strategy is used to select measurement locations with maximum entropy among candidate model predictions. Two bridges are used to illustrate the proposed methodology. First, a railway truss bridge in Zangenberg, Germany, is examined. For illustration purposes, the model space is reduced by assuming only a few types of possible damage in the truss bridge. The approach is then applied to the Schwandbach bridge in Switzerland, where a broad set of damage scenarios is evaluated. For the truss bridge, the approach correctly identifies the damage that represents the behaviour of the structure. For the Schwandbach bridge, the approach is able to significantly reduce the number of candidate models. Values of candidate model parameters are also useful for planning inspection and eventual repair.