Infrared spectroscopy investigation of various plasma-deposited polymer films irradiated with 170 keV He+ ions

This work illustrates the advantages of using p-polarized radiation at an incidence angle of 70 degrees in contrast to the conventional unpolarized beam at normal (or near-normal) incidence for the infrared spectroscopic study of polycarbosilane, polysilazane and polysiloxane thin films synthesized by plasma enhanced chemical vapor deposition (PECVD) and subsequently irradiated with 170 keV He+ ions at fluences from 1 x 10(14) to 1 x 10(16) cm(-2). Several bands not seen using the conventional mode could be observed in the polarized mode. (c) 2006 Elsevier B.V. All rights reserved.

Fabrication of novel light-emitting devices based on green-phosphor/conductive-polymer composites

We report on light-emitting devices based on a green-phosphor compound (Mn-doped zinc silicate, Zn2SiO4: Mn) dispersed in a conductive polymeric blend (poly-o-methoxyaniline/polyvinylene fluoride, POMA/PVDF-TrFE). The devices exhibited high luminance in the green, good stability and homogeneous brilliance over effective areas up to 5 cm(2). The electroluminescence (EL) spectrum presented essentially the same characteristics as the photoluminescence (PL) and cathodoluminescence spectra, indicating that the light emission originates from decay of the same excited species, regardless of the excitation source. Operating characteristics were analyzed with current density - voltage (J - V) and luminance voltage ( L - V) curves to investigate the nature of the electroluminescence of the active material, which is still not completely understood.

Determination of site-site distance and site concentration within polymer beads: A combined swelling-electron paramagnetic resonance study

[GRAPHICS]This work proposes a combined swelling-electron paramagnetic resonance (EPR) approach aiming at determining some unusual polymer solvation parameters relevant for chemical processes occurring inside beads. Batches of benzhydrylamine-resin (BHAR), a copolymer of styrene-1% divinylbenzene containing phenylmethylamine groups were, labeled with the paramagnetic amino acid 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amine-4-carboxylic acid (TOAC), and their swelling properties and EPR spectra were examined in DCM and DMF. By taking into account the BHARs labeling degrees, the corresponding swelling values, and some polymer structural characteristics, it was possible to calculate polymer swelling parameters, among them, the volume and the number of sites per bead, site-site distances and site concentration. The latter values ranged from 17 to 170 angstrom and from 0.4 to 550 mM, respectively. EPR spectroscopy was applied to validate the multistep calculation strategy of these swelling parameters. Spin-spin interaction was detected in the labeled resins at site-site distances less than approximately 60 A or probe concentrations higher than approximately 1 x 10(-2) M, in close agreement with the values obtained for the spin probe free in solution. Complementarily, the yield of coupling reactions in different resins indicated that the greater the inter-site distance or the lower the site concentration, the faster the reaction. The results suggested that the model and the experimental measurements developed for the determination of solvation parameters represent a relevant step forward for the deeper understanding and improvement of polymer-related processes.

Interaction between poly(ethylene glycol) and C12E8 investigated by dynamic light scattering, time-resolved fluorescence quenching, and calorimetry

Dynamic light scattering (DLS), time-resolved fluorescence quenching (TRFQ), and isothermal titration microcalorimetry have been used to show that, in dilute solution, low molecular weight poly(ethylene glycol) (PEG, M-w = 12 kDa) interacts with the nonionic surfactant octaethylene glycol n-dodecyl monoether, C12E8, to form a complex. Whereas the relaxation time distributions for the binary C12E8/water and PEG/water systems are unimodal, in the ternary mixtures they may be either uni- or bimodal depending on the relative concentrations of the components. At low concentrations of PEG or surfactant, the components of the relaxation time distribution are unresolvable, but the distribution becomes bimodal at higher concentrations of either polymer or surfactant. For the ternary system in excess surfactant, we ascribe, on the basis of the changes in apparent hydrodynamic radii and the scattered intensities, the fast mode to a single micelle, the surface of which is associated with the polymer and the slow mode to a similar complex but containing two or three micelles per PEG chain. Titration microcalorimetry results show that the interaction between C12E8, and PEG is exothermic and about 1 kJ mol(-1) at concentrations higher than the CMC of C12E8. The aggregation number, obtained by TRFQ, is roughly constant when either the PEG or the C12E8 concentration is increased at a given concentration of the second component, owing to the increasing amount of surfactant micelles inside the complex.

Helium ion irradiation of polymer films deposited from TMS-Ar plasmas

Polymer films synthesized from plasmas of a tetramethylsilane - Ar mixture were modified by irradiation with 170 keV He ions at fluences ranging from 1 x 10(14) to 1 x 10(16) cm(-2). As revealed by infrared spectroscopy, the ion beam produced intense bond rearrangements, such as the depletion of bonding groups (C-H and Si-H), and induced the formation of new ones, such as O-H and Si-O. From the nanoindentation measurements, a remarkable increase in the surface hardness of the films was observed as the ion fluence was increased. The increases in hardness were accompanied by an increase in the film compaction as shown by using a combination of RBS and film thickness measurements. From both hardness and infrared measurements A was concluded that, under the He ion bombardment, the polymer structure is transformed into a silicon oxycarbide network.

A new method for extending the range of conductive polymer sensors for contact force

This paper describes a technique for extending the force range of thin conductive polymer force sensors used for measuring contact force. These sensors are conventionally used for measuring force by changing electrical resistance when they are compressed. The new method involves measuring change in electrical resistance when the flexible sensor, which is sensitive to both compression and bending, is sandwiched between two layers of spring steel, and the structure is supported on a thin metal ring. When external force is applied, the stiffened sensor inside the spring steel is deformed within the annular center of the ring, causing the sensor to bend in proportion to the applied force. This method effectively increases the usable force range, while adding little in the way of thickness and weight. Average error for loads between 10 N and 100 N was 2.2 N (SD = 1.7) for a conventional conductive polymer sensor, and 0.9 N (SD = 0.4) using the new approach. Although this method permits measurement of greater loads with an error less than 1 N, it is limited since the modified sensor is insensitive to loads less than 5 N. These modified sensors are nevertheless useful for directly measuring normal force applied against handles and tools and other situations involving forceful manual work activities, such as grasp, push, pull, or press that could not otherwise be measured in actual work situations.

Immobilization and electrochemical properties of anionic complexes on a V2O5/surfactant nanocomposite

in this work, we report a new way of modifying an electrode by combining the intrinsic conductivity property of vanadium pentoxide xerogel with its water insolubility in the presence of the cationic surfactant N-cetyl-N,N,N,trimethyl-ammonium bromide (CTA(+)Br(-)). The obtained hybrid compound enables the immobilization of electroactive anions such as hexacyanoferrate (III) ([Fe(CN)(6)](3-)) and its analogue pentacyanonitrosylferrate (II) ([Fe(CN)(5)NO](2-)), rather than cations. (C) 2002 Elsevier B.V. B.V. All rights reserved.

FLUORINATED POLYMER-FILMS FROM RF PLASMAS CONTAINING BENZENE AND SULFUR HEXAFLUORINE

Mixtures of C6H6 and SF6 were polymerized in an r.f. discharge. Actinometry (quantitative optical emission spectroscopy) was used to determine trends in the plasma concentrations of the species F, H and CH as a function of the proportion of SF6 in the feed. Infrared spectroscopy and electron spectroscopy for chemical analysis were employed to characterize the deposited material. Increasing proportions of SF, in the feed produced increased fragmentation of the benzene molecules and greater fluorination of the deposited material. The deposition rate, as determined by optical interferometry, was found to be enhanced about 4 times by the presence of 10-20% SF6 in the feed. At 50% SF6 in the feed, deposition rates were greater than in pure C6H6 plasmas despite the (probably large) etching effect of atomic fluorine from the discharge. Relationships between the plasma composition, electron density and temperature, film composition and growth rate are discussed.

Formation and characterization of soy bean oil/surfactant/water microemulsions

Pseudoternary phase diagrams, at 25 degrees C, were constructed for the systems soy bean oil (SBO)/surfactant/water, with single anionic sodium bis(2-ethylhexyl)sulfosuccinate (AOT), nonionic monoolein (MO) and mixtures of these surfactants, showing the isotropic phase of W/O microemulsions (MEs). The area of ME formation in the phase diagrams was shown to be dependent of the relative amount of surfactants, being larger for MO:AOT equals to 2:1. Rheological and dynamic light scattering (DLS) studies indicated that the viscosity of the isotropic ME phase exhibited two different behaviors depending on composition. The viscosity of dry MEs initially decreased with increasing amount of water following a dilution line in the phase diagram, i.e., a constant surfactant:SBO percentage ratio. As the water content increased the relative viscosity attained a minimum and then increased. This minimum could be related to the transition between two ME regions, L-2 and L'(2), having different characteristics. DLS measurements confirm the existence of ordinary W/O ME droplets in the L-2 region and suggest the existence of another structure in the L'(2) region. The size of the MEs droplets in L-2 phase ranges from 3.6 to 16.5 nm, depending on composition of SBO, surfactant and water. Small angle X-ray scattering (SAXS) also indicates the existence of structures with different characteristics, for the SAXS curves exhibit a typical micelle asymmetrical peak at low scattering vector q for MEs in L-2 but a symmetrical correlation peak at higher q vector in L'(2). (c) 2006 Elsevier B.V. All rights reserved.

Kinetic parameters of polymer degradation by SAPO-37

High density poly(ethylene) has been submitted to thermal degradation alone, and in the presence of silicoaluminophosphate SAPO-37. The processes were carried out in a reactor connected on line to a gas chromatograph/mass spectrometer in order to analyze the evolved products. Polymer degradation was also evaluated by thermogravimetry, from room temperature until 800 degreesC, under nitrogen dynamic atmosphere, with multiple heating rates. From TG curves, the activation energy related to degradation process was calculated using the Flynn and Wall multiple heating rate kinetic model for pure polymer (PE) and for polymer in the presence of catalyst (PE/S37). SAPO-37 showed good selectivity for low molecular mass hydrocarbons in PE catalytic degradation.