Temperature dependence of the electrical conductivity of imidazolium ionic liquids

The electrical conductivities of 1-alkyl-3-methylimidazolium tetrafluoroborate ionic liquids and of 1-hexyl-3-methylimidazolium ionic liquids with different anions were determined in the temperature range between 123 and 393 K on the basis of dielectric measurements in the frequency range from 1 to 10(7) Hz. Most of the ionic liquids form a glass and the conductivity values obey the Vogel-Fulcher-Tammann equation. The glass transition temperatures are increasing with increasing length of the alkyl chain. The fragility is weakly dependent on the alkyl chain length but is highly sensitive to the structure of the anion. (c) 2008 American Institute of Physics.

Influence of the anion on the electrical conductivity and glass formation of 1-butyl-3-methylimidazolium ionic liquids

Six ionic liquids based on the 1-butyl-3-methylimidazolium cation have been studied. As anions Cl-, Br-, I-, [NCS](-), [N(CN)(2)](-), and [BF4](-) were selected. The electrical conductivities were determined between 173 and 393 K based on impedance measurements in the frequency range from 0.1 to 10(7) Hz. The electrical conductivity increases, whereas the glass transition temperature, the fragility, and the low temperature activation energy decrease with increasing anion size. The results can be understood from the changing anion-cation interaction strength with changing anion size and from the energy landscape interpretation of the glass transition dynamics. (C) 2010 American Institute of Physics. [doi:10.1063/1.3455892]

Electrical conductivity and glass formation in nitrile-functionalized pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids: chain length and odd–even effects of the alkyl spacer between the pyrrolidinium ring and the nitrile group

The electrical conductivity of a series of pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids, functionalized with a nitrile (cyano) group at the end of an alkyl chain attached to the cation, was studied in the temperature range between 173 K and 393 K. The glass formation of the ionic liquids is influenced by the length of the alkyl spacer separating the nitrile function from the pyrrolidinium ring. The electrical conductivity and the viscosity do not show a monotonic dependence on the alkyl spacer length, but rather an odd-even effect. An explanation for this behavior is given, including the potential energy landscape picture for the glass transition.

Electrical and Rheological Percolation of PMMA/MWCNT Nanocomposites as a Function of CNT Geometry and Functionality

The ability of carbon nanotubes (CNTs) to reinforce and enhance the electrical conductivity of polymer matrices is a function of both the aspect ratio and surface chemistry of the CNTs. Hitherto, due to the variability in MWCNT synthesis methods it has not been possible to study the effect of MWCNT aspect ratio and functionality on polymer composite properties. This paper was the first to report the correlation between MWCNT aspect ratio and functionality on the formation of electrical and rheological percolated networks. Furthermore, the fundamental ballistic conductance of MWCNTs made using arc discharge and chemical vapour deposition techniques was reported.

Conductivity/activation energy relationships for cement-based materials undergoing cyclic thermal excursions

The electrical conductivity of a range of concrete mixes, with and without supplementary cementitious materials (SCM), is studied through multiple cycles of heating and cooling over the extended temperature range −30/+70 °C. When presented in an Arrhenius format, the experimental results display hysteresis effects at the low-temperature end of the thermal cycle and, in those concretes containing supplementary cementitious materials at higher water/binder ratios, hysteresis effects were evident over the entire temperature range becoming more discernible with increasing number of thermal cycles. The depression in both the freezing and thawing point could be clearly identified and was used to estimate pore-neck and pore-cavity radii. A simplified approach is presented to evaluate the volumetric ratio of frozen pore water in terms of conductivity measurements. The results also show that the conductivity and activation energy of the concrete specimens were related to the water/binder ratio, type of SCM, physical state of the pore water and the thermal cycling regime.

Can the scaling behavior of electric conductivity be used to probe the self-organizational changes in solution with respect to the ionic liquid structure? The case of [C8MIM][NTf2]

Electrical conductivity of the supercooled ionic liquid [C8MIM][NTf2], determined as a function of temperature and pressure, highlights strong differences in its ionic transport behavior between low and high temperature regions. To date, the crossover effect which is very well known for low molecular van der Waals liquids has been rarely described for classical ionic liquids. This finding highlights that the thermal fluctuations could be dominant mechanisms driving the dramatic slowing down of ion motions near Tg. An alternative way to analyze separately low and high temperature dc-conductivity data using a density scaling approach was then proposed. Based on which a common value of the scaling exponent [gamma] = 2.4 was obtained, indicating that the applied density scaling is insensitive to the crossover effect. By comparing the scaling exponent [gamma] reported herein along with literature data for other ionic liquids, it appears that [gamma] decreases by increasing the alkyl chain length on the 1-alkyl-3-methylimidazolium-based ionic liquids. This observation may be related to changes in the interaction between ions in solution driven by an increase in the van der Waals type interaction by increasing the alkyl chain length on the cation. This effect may be related to changes in the ionic liquid nanostructural organization with the alkyl chain length on the cation as previously reported in the literature based on molecular dynamic simulations. In other words, the calculated scaling exponent [gamma] may be then used as a key parameter to probe the interaction and/or self-organizational changes in solution with respect to the ionic liquid structure.

Broken symmetry and pseudogaps in ropes of carbon nanotubes

Since the discovery of carbon nanotubes, it has been speculated that these materials should behave like nanoscale wires with unusual electronic properties and exceptional strength. Recently, 'ropes' of close-packed single-wall nanotubes have been synthesized in high yield. The tubes in these ropes are mainly of the (10,10) type3, which is predicted to be metallic. Experiments on individual nanotubes and ropes indicate that these systems indeed have transport properties that qualify them to be viewed as nanoscale quantum wires at low temperature. It has been expected that the close-packing of individual nanotubes into ropes does not change their electronic properties significantly. Here, however, we present first-principles calculations which show that a broken symmetry of the (10,10) tube caused by interactions between tubes in a rope induces a pseudogap of about 0.1 eV at the Fermi level. This pseudogap strongly modifies many of the fundamental electronic properties: we predict a semimetal-like temperature dependence of the electrical conductivity and a finite gap in the infrared absorption spectrum. The existence of both electron and hole charge carriers will lead to qualitatively different thermopower and Hall-effect behaviours from those expected for a normal metal.

Composites of poly(ε-caprolactone) and Mo6S3I6 Nanowires

Composites of poly(e-caprolactone) (PCL) and molybdenum sulfur iodine (MoSI) nanowires were prepared using twin-screw extrusion. Extensive microscopic examination of the composites revealed the nanowires were well dispersed in the PCL matrix, although bundles of Mo6S3I6 ropes were evident at higher loadings. Secondary electron imaging (SEI) showed the nanowires had formed an extensive network throughout the PCL matrix, resulting in increased electrical conductivity of PCL, by eight orders of magnitude, and an electrical percolation threshold of 6.5T10S3vol%. Thermal analysis (DSC), WAXD, and hot stage polarized optical microscopy (HSPOM) experiments revealed Mo6S3I6 addition altered PCL crystallization kinetics, nucleation density, and crystalline content. A greater number of smaller spherulites were formed via heterogeneous nucleation. The onset of thermal decomposition (TGA) of PCL decreased by 70-C, a consequence of the thermal degradation of Mo6S3I6 to MoO3, which in turn accelerates the formation of volatile gases during the first stage of PCL decomposition.

Geophysical and geochemical survey of a large marine pockmark on the Malin Shelf, Ireland

Marine pockmarks are a specific type of seabed geological setting resembling craters or pits and are considered seabed surface expressions of fluid flow in the subsurface. A large composite pockmark on the Malin Shelf, off the northern coast of Ireland was surveyed and ground truthed to assess its activity and investigate fluid related processes in the subsurface. Geophysical (including acoustic and electromagnetic) data confirmed the subsurface presence of signatures typical of fluids within the sediment. Shallow seismic profiling revealed a large shallow gas pocket and typical gas related indicators such as acoustic blanking and enhanced reflectors present underneath and around the large pockmark. Sulphate profiles indicate that gas from the shallow reservoir has been migrating upwards, at least recently. However, there are no chimney structures observed in the sub-bottom data and the migration pathways are not apparent. Electromagnetic data show slightly elevated electrical conductivity on the edges of the pockmarks and a drop below regional levels within the confines of the pockmark, suggesting changes in physical properties of the sediment. Nuclear Magnetic Resonance (NMR) experiments were employed to characterize the organic component of sediments from selected depths. Very strong microbial signatures were evident in all NMR spectra but microbes outside the pockmark appear to be much more active than inside. These observations coincide with spikes in conductivity and the lateral gas bearing body suggesting that there is an increase in microbial activity and biomass when gas is present.

Recycled carbon fiber filled polyethylene composites

Composites of recycled carbon fiber (CF) with up to 30 wt % loading with polyethylene (PE) were prepared via melt compounding. The morphology of the composites and the degree of dispersion of the CF in the PE matrix was examined using scanning electron microscopy, and revealed the CF to be highly dispersed at all loadings and strong interfacial adhesion to exist between the CF and PE. Raman and FTIR spectroscopy were used to characterize the surface chemistry and potential bonding sites of recycled CF. Both the Young's modulus and ultimate tensile stress increased with increasing CF loading, but the percentage stress at break was unchanged up to 5 wt % loading, then decreased with further successive addition of CF. The effect of CF on the elastic modulus of PE was examined using the Halpin-Tsai and modified Cox models, the former giving a better fit with the values determined experimentally. The electrical conductivity of the PE matrix was enhanced by about 11 orders of magnitude on addition of recycled CF with a percolation threshold of 7 and 15 wt % for 500-mu m and 3-mm thick samples. (c) 2007 Wiley Periodicals, Inc.

Role of Predalors, Habitat Attributes, and Spatial Autocorrelation on the Distribution of Eggs in the Northern Spectacled Salamander (Salamandrina perspicillata)

We predicted that the probability of egg occurrence of salamander Salamandrina perspicillata depended on stream features and predation by native crayfish Austropotamobius fulcisianus and the introduced trout Salmo trutta. We assessed the presence of S. perspicillata at 54 sites within a natural reserve of southern Tuscany, Italy. Generalized linear models with binomial errors were constructed using egg presence/absence and altitude, stream mean size and slope, electrical conductivity, water pH and temperature, and a predation factor, defined according to the presence/absence of crayfish and trout. Some competing models also included an autocovariate term, which estimated how much the response variable at any one sampling point reflected response values at surrounding points. The resulting models were compared using Akaike's information criterion. Model selection led to a subset of 14 models with Delta AIC(c) <7 (i.e., models ranging from substantial support to considerably less support), and all but one of these included an effect of predation. Models with the autocovariate term had considerably more support than those without the term. According to multimodel inference, the presence of trout and crayfish reduced the probability of egg occurrence from a mean level of 0.90 (SE limits: 0.98-0.55) to 0.12 (SE limits: 0.34-0.04). The presence of crayfish alone had no detectable effects (SE limits: 0.86-0.39). The results suggest that introduced trout have a detrimental effect on the reproductive output of S. perspicillata and confirm the fundamental importance of distinguishing the roles of endogenous and exogenous forces that act on population distribution.

Photosynthetic pigments in soils from northern Victoria Land (continental Antarctica) as proxies for soil algal community structure and function

Although soil algae are among the main primary producers in most terrestrial ecosystems of continental Antarctica, there are very few quantitative studies on their relative proportion in the main algal groups and on how their distribution is affected by biotic and abiotic factors. Such knowledge is essential for understanding the functioning of Antarctic terrestrial ecosystems. We therefore analyzed biological soil crusts from northern Victoria Land to determine their pH, electrical conductivity (EC) water content (W), total and organic C (TC and TOC) and total N (TN) contents, and the presence and abundance of photosynthetic pigments. In particular, the latter were tested as proxies for biomass and coarse-resolution community structure. Soil samples were collected from five sites with known soil algal communities and the distribution of pigments was shown to reflect differences in the relative proportions of Chlorophyta, Cyanophyta and Bacillariophyta in these sites. Multivariate and univariate models strongly indicated that almost all soil variables (EC, W, TOC and TN) were important environmental correlates of pigment distribution. However, a significant amount of variation is independent of these soil variables and may be ascribed to local variability such as changes in microclimate at varying spatial and temporal scales. There are at least five possible sources of local variation: pigment preservation, temporal variations in water availability, temporal and spatial interactions among environmental and biological components, the local-scale patchiness of organism distribution, and biotic interactions. (C) 2009 Elsevier Ltd. All rights reserved.

Developments in performance-based testing of concrete

Implementation of both design for durability and performance-based standards and specifications are limited by the lack of rapid, simple, science-based test methods for characterizing the transport properties and deterioration resistance of concrete. To this end, this paper presents the background rationale and current developments in the application of electrical property measurements - conductivity in this instance - as a testing methodology to evaluate the relative performance of a range of concrete mixes. The technique can not only be used on standard specimens (e.g. cubes), but also lends itself to in-situ monitoring thereby allowing measurements to be obtained on the as-placed concrete. It is the latter which forms the focus of the current work. Conductivity measurements are presented for concretes with and without supplementary cementitious materials (SCM's) from demoulding up to 400-days. It is shown that electrical conductivity measurements display a continual decrease over the entire test period and attributed to the pore structure refinement due to hydration and pozzolanic reaction in those concretes containing blast furnace slag or fly ash. The term Formation Factor is introduced to rank concrete performance in terms of is resistance to chloride penetration.

A durability performance-index for concrete: developments in a novel test method

Implementation of both design for durability and performance-based standards and specifications are limited by the lack of rapid, simple, science based test methods for characterising the transport properties and deterioration resistance of concrete. This paper presents developments in the application of electrical property measurements as a testing methodology to evaluate the relative performance of a range of concrete mixes. The technique lends itself to in-situ monitoring thereby allowing measurements to be obtained on the as-placed concrete. Conductivity measurements are presented for concretes with and without supplementary cementitious materials (SCM’s) from demoulding up to 350 days. It is shown that electrical conductivity measurements display a continual decrease over the entire test period and attributed to pore structure refinement due to hydration and pozzolanic reaction. The term formation factor is introduced to rank concrete performance in terms of is resistance to chloride penetration.