Solid state ion transport and phase behaviour in composites of N,N-methyl propylpyrrolidinium tetrafluoroborate and amorphous polyethylene oxide

The binary and ternary addition of 2 wt.% LiBF₄ and 2 wt.% amorphous polyethylene oxide (aPEO) respectively to the plastic crystal forming salt P₁₃BF₄ (where P₁₃⁺=methylpropyl pyrrolidinium cation) was investigated with specific focus on the phase behaviour and evaluation of transport characteristics. Differential scanning calorimetry (DSC), optical thermomicroscopy, solid state nuclear magnetic resonance (NMR), and AC impedance spectroscopy were used to develop an understanding of the conduction process in the pure and mixed systems. The morphology of the ternary compound appeared as hexagonal spherulites upon solidification. Multinuclear NMR Pulsed Field Gradient measurements (¹H,¹⁹F,⁷Li) to probe both cation and anion diffusion coefficients are reported. The anion is shown to be the most diffusive (at 320 K:¹⁹F=2.5×10⁻¹¹ m² s⁻¹; 1H: 1.8×10⁻¹¹ m² s⁻¹; ⁷Li: 1.1×10⁻¹¹ m² s⁻¹) in the ternary compound, with enhanced conductivity (2.7×10⁻⁵ S cm⁻¹ at 310 K) just below the melt.

Ion conductivity in amorphous polymer/salt mixtures

Amorphous polymer/salt mixtures based on polyvinyl alcohol and poly(hydroxyethylacrylate) and poly(hydroxyethylmethacrylate) are described. The polyvinylalcohol materials have been prepared by a solvent free hot pressing technique as well as the traditional solvent casting method. The hot pressing technique allows the production of samples which are genuinely free of solvents and thereby has allowed an assessment in this work of the effect of residual solvent on conductivity. The acrylate materials were prepared by direct polymerization of monomer/salt mixtures, thus avoiding the need for solvents. These materials have glass transitions around or well above room temperature, but nonetheless have conductivities as high as 10⁻⁷ S/cm at room temperature. The temperature and composition dependence of conductivity are also presented.

Thermal stability of the Al70Ni10Ti10Zr5Ta5 amorphous alloy powder fabricated by mechanical alloying

An Al₇₀Ni₁₀Ti₁₀Zr₅Ta₅ amorphous alloy powder was fabricated by mechanical alloying. The phase structure and characteristic temperatures of the alloy were determined by X-ray diffraction, transmission electron microscopy and differential scanning calorimetry. The glass transition behavior and crystallization kinetics were analyzed using Lasocka and Kissinger functions. The results show that the alloy has a higher crystallization temperature, a higher effective activation energy of crystallization and a wider supercooled liquid region than the previously reported values, suggesting a high thermal stability and promising applications.

Synthesis of high surface area amorphous tin-zinc oxides by a sol-gel method

A new method to synthesize conducting oxide nanoparticles with low photocatalytic activity was investigated. Initially, the preparation of amorphous ZnO-SnO2 solid solution nanoparticles was studied using a sol-gel technique. It was found that X-ray amorphous nanopowders with low photocatalytic activity were produced when the precipitates were heat treated below 500 °C. However, FT-IR data showed that the sample may not be an oxide semiconductor. A mixture of ZnO and SnO2 crystalline nanoparticles was also produced at 800 °C and found to have much reduced photoactivity than commercial ZnO nanoparticles having a similar specific surface area.

Trophic cul-de-sac, Pyrazus ebeninus, limits trophic transfer through an estuarine detritus-based food web

The importance to food-webs of trophic cul-de-sacs, species that channel energy flow away from higher trophic levels, is seldom considered outside of the pelagic systems in which they were first identified. On intertidal mudflats, inputs of detritus from saltmarshes, macroalgae or microphytobenthos are generally regarded as a major structuring force underpinning food-webs and there has been no consideration of trophic cul-de-sacs to date. A fully orthogonal three-factor experiment manipulating the density of the abundant gastropod, Pyrazus ebeninus, detritus and macrobenthic predators on a Sydney mudflat revealed large deleterious effects of the gastropod, irrespective of detrital loading or the presence of predators. Two months after experimental manipulation, the standing-stock of microphytobenthos in plots with high (44 per m²) densities of P. ebeninus was 20% less than in plots with low (4 per m²) densities. Increasing densities of P. ebeninus from low to high halved the abundance of macroinvertebrates and the average number of species. In contrast, the addition of detritus had differing effects on microphytobenthos (positively affected) and macroinvertebrates (negatively affected). Over the two-months of our experiment, no predatory mortality of P. ebeninus was observed and high densities of P. ebeninus decreased impacts of predators on macroinvertebrate abundances. Given that the dynamics of southeast Australian mudflats are driven more by disturbance than seasonality in predators and their interactions with prey, it is likely that Pyrazus would be similarly resistant to predation and have negative effects on benthic assemblages at other times of the year, outside of our study period. Thus, in reducing microphytobenthos and the abundance and species richness of macrofauna, high abundances of the detritivore P. ebeninus may severely limit the flow of energy up the food chain to commercially-important species. This study therefore suggests that trophic cul-de-sacs are not limited to the eutrophied pelagic systems in which they were first identified, but may exist in other systems as well.

Influences of agricultural landuse and seasonal changes in abiotic conditions on invertebrate colonisation of riparian leaf detritus in intermittent streams

The structure and function of agricultural stream reaches with sparse riparian and floodplain vegetation differ from those of forested reaches, but may be ‘reset’ as these streams flow through reaches with forested riparian zones. We investigated whether invertebrate colonisation of River Red Gum (Eucalyptus camaldulensis) leaf packs in lowland intermittent streams was influenced by the adjacent reach-scale landuse (cleared farmland or forested reserve) within an agricultural catchment in Victoria, Australia. Further, we examined the influence of seasonal changes in hydrology and associated changes in abiotic conditions on the colonisation of leaves by repeating experiments over two summers and one spring. Across these experiments, there were no consistent differences in the structure of communities that colonised leaves in farmland and reserve reaches. In both seasons, most leaf colonists were collectors and few were shredders in both farmland and reserve reaches. Relative abundances of gastropod grazers were much higher in summer than in spring. The structure of invertebrate communities colonising leaves in the different reaches converged over time when streams flowed in spring, but diverged over time as the streams dried and abiotic conditions within disconnected pools became increasingly harsh in summer. Thus, patterns of leaf pack colonisation were influenced by the regional climate causing large seasonal changes in hydrology, but not by reach-scale landuse. The large-scale disturbances of agricultural landuse across the catchment and a supra-seasonal drought probably contributed to low diversities of invertebrate communities in the streams.

Amorphous carbon nitrogenated films prepared by plasma immersion ion implantation and deposition

In this work, an investigation was conducted on amorphous hydrogenated-nitrogenated carbon films prepared by plasma immersion ion implantation and deposition. Glow discharge was excited by radiofrequency power (13.56 MHz, 40 W) whereas the substrate-holder was biased with 25 kV negative pulses. The films were deposited from benzene, nitrogen and argon mixtures. The proportion of nitrogen in the chamber feed (R-N) was varied against that of argon, while keeping the total pressure constant (1.3 Pa). From infrared reflectance-absorbance spectroscopy it was observed that the molecular structure of the benzene is not preserved in the film. Nitrogen was incorporated from the plasma while oxygen arose as a contaminant. X-ray photoelectron spectroscopy revealed that N/C and O/C atomic ratios change slightly with R-N. Water wettability decreased as the proportion of N in the gas phase increased while surface toughness underwent just small changes. Nanoindentation measurements showed that film deposition by means of ion bombardment was beneficial to the mechanical properties of the film-substrate interface. The intensity of the modifications correlates well with the degree of ion bombardment. (c) 2006 Elsevier B.V. All rights reserved.

Amorphous hydrogenated carbon films treated by SF(6) plasma

This work was performed to verify the chemical structure, mechanical and hydrophilic properties of amorphous hydrogenated carbon films prepared by plasma enhanced chemical vapor deposition, using acetylene/argon mixture as monomer. Films were prepared in a cylindrical quartz reactor, fed by 13.56 MHz radiofrequency. The films were grown during 5 min, for power varying from 25 to 125 W at a fixed pressure of 9.5 Pa. After deposition, all samples were treated by SF(6) plasma with the aim of changing their hydrophilic character. Film chemical structure investigated by Raman spectroscopy, revealed the increase of sp(3) hybridized carbon bonds as the plasma power increases. Hardness measurements performed by the nanoindentation technique showed an improvement from 5 GPa to 14 GPa following the increase discharge power. The untreated films presented a hydrophilic character, which slightly diminished after SF(6) plasma treatment.

Development of amorphous carbon protective coatings on poly(vinyl)chloride

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Properties of hydrogenated amorphous carbon films deposited by PECVD and modified by SF6 plasma

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

In situ evaluation of the remineralizing capacity of pit and fissure sealants containing amorphous calcium phosphate and/or fluoride

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)