High‐resolution 13C–nuclear magnetic resonance study of heterogeneous amorphous polymers

The combination of solid‐state nuclear magnetic resonance (NMR) techniques is very helpful for examining the behavior of heterogeneous amorphous polymers. With the magic‐angle spinning (MAS) technique, employing special conditions, only the mobile fraction of the molecule can be assigned. Cross‐polarization magic‐angle spinning (CPMAS) permits the evaluation of changes in the NMR line shapes and chemical shifts. The employment of proton spin‐lattice relaxation times (T₁ and T₁ρ) gives useful information on the molecular dynamic in heterogeneous polymers. From these parameters the response of the molecular mobility behavior of the polymer chains can be obtained. The results of the present work are discussed in this article in terms of molecular mobility and domain formations of heterogeneous amorphous polymers in order to understand the relations in the structure–mobility property. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 473–476, 2003     

Imidazolium-substituted ionic (co)polythiophenes: Compositional influence on solution behavior and thermal properties

A series of ionic polythiophenes, in homopolymer and random copolymer configurations, is prepared via the Grignard metathesis (GRIM) polymerization protocol and subsequent substitution on the bromohexyl side chains with N-methylimidazole. The introduced structural variations – comonomer ratio, side chain composition, counter ions – allow tuning of the thermal properties and solution behavior of the resulting conjugated polymers. As expected, the solubility depends majorly on the number of ionic groups and the counter ions. The most peculiar behavior is observed for the P3HT-P3(MIM)HT-Br 50/50 random copolymer, which shows organization of the polymer chains in solution and thin film dependent on the preparation conditions. Dynamic light scattering studies confirm that the ordered solid-state structure is somewhat maintained when the copolymer is dissolved in a bad solvent mixture. The ionic (co)polythiophenes are generally more resistant to thermal degradation than their precursors. The precursor polymers all show a clear semi-crystalline behavior, with a decrease in crystallinity upon decreasing the number of regular 3-hexylthiophene units. On the other hand, the studied ionic (co)polythiophenes are fully amorphous. Changes in the counter ions have dramatic effects on the thermal properties. Bromine counter ions render the polymers strongly hygroscopic. The novel materials are of particular appeal in the field of organic photovoltaics, in which the imidazolium-substituted (co)polythiophenes can be beneficially applied as constituents of either active layers or electron transport layers. Their processability from green solvents is also of major importance for the field.     

Influence of Phase Modifiers on the Degradation of Tri-n-octylamine/dodecane Extracting Mixture by an Acidic Solution of Vanadium (V)

The kinetics of degradation of a mixture of tri-n-octylamine (extractant) and various alcoholic phase modifiers in n-dodecane in contact with acidic aqueous sulfate solutions containing vanadium (V) has been investigated. The nature of the modifier influences the kinetics of degradation and an improvement of the resistance against the chemical degradation is obtained when secondary alcohol (2-nonanol) or tertiary alcohols such as 9-octyl-9-heptadecanol are used as phase modifiers instead of 1-tridecanol. For instance, the kinetic constant of degradation is divided by one half when 9-octyl-9-heptadecanol is used as phase modifier instead of 1-tridecanol. On the contrary, the alcohols containing aromatic substituents or fluorine atoms are responsible for an increase of the chemical degradation of the extraction solvent.     

Compatibility of silorane composite repaired with methacrylate-based restorative systems

The aim of this study was to evaluate the repair bond strength of silorane composites using either the silorane or methacrylate-based restorative systems. Expired silorane composite was used as the substrate material in all experimental groups. Silorane blocks (5?×?5?×?4?mm) were fabricated and stored at 37?°C for 24?h. Six experimental groups were developed according to the repair: I-silorane composite (no intermediary); II-P90 Bond/Silorane; III-P90 Adhesive System (primer/bond)/silorane; IV-P90 bond/Scotchbond Universal/methacrylate composite (Filtek P60); V-Scotchbond Universal/methacrylate; and VI-silane/Adper Single Bond 2/methacrylate. The repaired blocks were stored for 24?h at 37?°C, and then sectioned, yielding stick-shaped specimens (0.5?mm²) that were tested in tensile (0.5?mm/min). The results were analyzed using ANOVA/Tukey test (α?=?0.05). The interfacial micromorphology and nanoleakage were also analyzed under SEM. Scotchbond Universal/methacrylate composite, either associated with the P90 bond or not, exhibited similar bond strength to that of P90 Adhesive System/silorane composite. Scotchbond Universal either associated with the P90 Bond or not to repair the silorane allowed no pre-testing failures. The worst scenarios were repairing the silorane with no intermediary (G-I) or combination silane/Adper Single Bond 2/methacrylate composite (G-VI) that presented significantly lower bond strengths and higher incidences of pre-failure testing. The importance of the silane was not confirmed. Characteristic micromorphology and no signs of nanoleakage were identified in all experimental groups. The silane-containing, phosphorylated methacrylate-based adhesive associated with a methacrylate composite was proven to reliably repair the expired composite in a similar way to that of the application of dedicated silorane adhesive.     

Oxidative and carbonaceous patterning of Si surface in an organic media by scanning probe lithography

A simple top-down fabrication technique that involves scanning probe lithography on Si is presented. The writing procedure consists of a chemically selective patterning in mesitylene. Operating in an organic media is possible to perform local oxidation or solvent decomposition during the same pass by tuning the applied bias. The layer deposited with a positively biased tip with sub-100-nm lateral resolution consists of nanocrystalline graphite, as verified by Raman spectroscopy. The oxide pattern obtained in opposite polarization is later used as a mask for dry etching, showing a remarkable selectivity in SF₆ plasma, to produce Si nanofeatured molds.     

Variations in diffusion coefficient of disperse dyes in single PET fibres: monitored and interpreted by confocal laser scanning microscopy

A novel method is proposed for determining the diffusion coefficient (D) of disperse dyes in PET fibres. Concentration-distance profiles are recorded on optical sections of single fibres by confocal laser scanning microscopy. This allows for an accurate value of the true diffusion coefficient in the fibres as well as for a founded insight in the dye diffusion process and its interrelation with the glass transition, which is not possible by the commonly used methods. At 130 °C, the common industrial dyeing temperature, the diffusion coefficient showed to be constant for the dyes tested, with D being about five times larger for the anthraquinone dye than for the benzodifuranone dye. At 100-110 °C, near to the start of the glass transition region of the fibres, D could no longer be regarded as a constant for the anthraquinone dye but was concentration dependent. This was explained by the plasticising effect of the anthraquinone dye.     

Composition and thermal properties of Rhea oil and its fractions

The rhea (Rhea americana) is a large running bird of the ratite family, native to South America. Oil extracted from rhea fat tissue is used in cosmetic manufacture. Here, the thermal behaviour and the fatty acid and triacylglycerol composition of Uruguayan rhea oil are studied. The results are compared with those obtained from two commercial samples of emu oil. The fatty acid profiles of emu and rhea oils are similar. Small variations are reflected in the non‐identical thermal behaviour of the oils. The solid content of both oils is fairly similar at room temperature. Thus, emu oil and rhea oil may replace one another in certain formulations, without resulting in important changes in physicochemical behaviour. The semisolid rhea oil was fractionated in two successive stages: an olein was obtained at 15 °C, which was refractionated at 10 °C. The thermogram of the olein obtained by cooling at 15 °C does not have the peak found at 34 °C in the thermogram of the original oil and is a softer product than the original oil. A further stage of fractionation of this olein produced a new liquid phase of slightly different thermal behaviour from that of the original olein. This product has a solid fat index around 7% at 15 °C and has melted completely at 20 °C. This second olein has more appropriate physical characteristics than those of the olein obtained from the first fractionation when used in liquid cosmetic formulations.