The Instabilisation of Dye-Fibre Bonds by Peroxide Treatments

The results are presented of an investigation into the instability induced in dye-fibre bonds by peroxide treatments. The nature of the reactions involved are discussed.     

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.     

Relative roles of chemical and mass transfer rate control in fluidized-bed combustion of coal chars

The relative roles of mass transfer and chemical reaction in controlling combustion rates in fluidized beds are examined in the light of measurements of char-particle combustion kinetics and correlated data on gas—particle mass transfer in fluidized beds. It is concluded that at 1200 K mass transfer is the main rate-control influence for materials having reactivities the same as, or higher than, a char from a swelling bituminous coal. Mass transfer has little effect on the combustion rate of materials whose reactivity to oxygen is one-tenth that of the bituminous coal char. At 800 K, chemical reaction control is dominant for all reactivities considered. The main uncertainty in the present calculations arises from the lack of a suitable analysis of mass-transfer rates in conditions appropriate to fluidized-bed combustion.     

Fully aliphatic polyimides from adamantane‐based diamines for enhanced thermal stability,solubility, transparency,and low dielectric constant

We have synthesized a series of fully aliphatic polyimides (APIs) from bicyclo[2,2,2]oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride (BOCA) and various aliphatic diamines, including linear aliphatic, flexible alicyclic, and rigid adamantyl diamines. We performed the polymerization reactions using one‐step syntheses in m‐cresol at elevated temperatures without the isolation of poly(amic) acid. The chemical composition and structure of the polymers were characterized by nuclear magnetic resonance (NMR) and infrared (IR) spectrometry. The characterization data are reported from analyses using gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimeter (DSC), and wide‐angle X‐ray diffraction (WXAD) measurements. The polyimides are also subjected to solubility, solution viscosity, tensile strength, transparency, and dielectric constant measurements. The resultant polyimides possess well‐controlled molecular weight, reasonable intrinsic viscosity, good transparency, enhanced solubility, low dielectric constants, and high glass transition temperature, together with marginal thermal and mechanical stability. These properties were enhanced in copolyimides containing equimolar amounts of rigid and flexible moieties. These rigid‐rod APIs derived from the alicyclic dianhydride and aliphatic diamines are promising candidates as advanced materials for future applications in micro‐ and photoelectronic devices. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3316–3326, 2006     

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.     

Azide Reactive Dyes

Reactive dyes containing a sulphonylazide group can undergo fixation on nylon substrates by two different mechanisms. Under aqueous dyeing conditions, at or below 120d? C, the free amino end-groups of the polymer attack the sulphonylazide group with displacement of azide ion, and results in attachment of the dye to the substrate by a sulphonamide linkage. In contrast, if the dyed substrate is subjected to dry heat fixation at 170d? C, the azide group decomposes to a sulphonylnitrene species which undergoes insertion into C-H bonds of the polymer. The dye is again attached by a sulphonamide bridge, but in this case the amount of dye that can be fixed is independent of the amino end-group content of the polymer.     

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.     

TEM Characterization of Single- and Multilayer Triol-Based Sol–Gel PZT (53/47) Thin Films

Integrated lead zirconate titanate thin films deposited on Pt/Ti/SiO₂/Si substrates using a novel triol-based route were characterized using X-ray diffraction and transmission electron microscopy. Crack-free single-layer PZT films of up to 200 nm thick were prepared by triol-based sol–gel processing onto Pt/Ti/SiO₂/Si substrates. Films ∼75 nm thick exhibited a microstructure free of pores and second phase. As film thickness increased, film texture changed from {100} to {111} perovskite. Essentially, single-phase multilayer films could be prepared by the deposition and pyrolysis of several 75 nm layers, followed by a single crystallization step. The influence of heat-treatment schedule on the microstructure and orientation of the multilayer films is discussed. Comparison has been made between multilayer films prepared using the triol-based sol and an inverted mixing order/acetic acid-based sol.     

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.