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.

Supersymmetric variational energies for the confined Coulomb system

The methodology based on the association of the variational method with supersymmetric quantum mechanics is used to evaluate the energy states of the confined hydrogen atom. (C) 2002 Elsevier B.V. B.V. All rights reserved.

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.

Nucleation and growth of mullite whiskers from lanthanum-doped aluminosilicate melts

Nucleation and growth of mullite whiskers in the La2O3-Al2O3-SiO2 system were investigated in the 1500degrees-1700degreesC temperature range. A differential thermal analysis (DTA) showed that the mullitization temperature decreases from 1350degreesC to 1240degreesC as a result of lanthania doping. In the temperature range of 1250-1500degreesC, most of the mullite grains have an Al2O3/SiO2 = 1.5 composition throughout the ceramic body; however, from 1400degreesC upward, the number of anisotropic grains with the Al2O3/SiO2 = 1.3 composition begins to increase. The concentration of alumina in the composition of the grain-boundary phase decreases as firing temperatures increase. At temperatures > 1500degreesC, alumina grains and whiskers grow on the internal and external surfaces of the ceramic body with the characteristic Al2O3/SiO2 = 1.3 composition. Removal of the mullite whisker layer by acid attack revealed an alumina-rich, rosace-like patterned microstructure correlated with the process of whisker nucleation and growth. In the early stages, whisker growth rates were found to be near 60 mum/h. Experimental evidence pointed to nucleation inside the thin glass layer on the external surface.

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.

Photoluminescence in quantum-confined SnO2 nanocrystals: Evidence of free exciton decay

Nanocrystalline SnO2 quantum dots were synthesized at room temperature by hydrolysis reaction of SnCl2. The addition of tetrabutyl ammonium hydroxide and the use of hydrothermal treatment enabled one to obtain tin dioxide colloidal suspensions with mean particle radii ranging from 1.5 to 4.3 nm. The photoluminescent properties of the suspensions were studied. The particle size distribution was estimated by transmission electron microscopy. Assuming that the maximum intensity photon energy of the photoluminescence spectra is related to the band gap energy of the system, the size dependence of the band gap energies of the quantum-confined SnO2 particles was studied. This dependence was observed to agree very well with the weak confinement regime predicted by the effective mass model. This might be an indication that photoluminescence occurs as a result of a free exciton decay process. (C) 2004 American Institute of Physics.

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.