Predicting physical properties of ionic liquids

A simple method to predict the densities of a range of ionic liquids from their surface tensions, and vice versa, using a surface-tension-weighted molar volume, the parachor, is reported. The parachors of ionic liquids containing 1-alkyl-3-methylimidazolium cations were determined experimentally, but were also calculated directly from their structural compositions using existing parachor contribution data for neutral compounds. The calculated and experimentally determined parachors were remarkably similar, and the latter data were subsequently employed to predict the densities and surface tensions of the investigated ionic liquids. Using a similar approach, the molar refractions of ionic liquids were determined experimentally, as well as calculated using existing molar refraction contribution data for uncharged compounds. The calculated molar refraction data were employed to predict the refractive indices of the ionic liquids from their surface tensions. The errors involved in the refractive index predictions were much higher than the analogous predictions employing the parachor, but nevertheless demonstrated the potential for developing parachor and molar refraction contribution data for ions as tools to predict ionic liquid physical properties.

Determination of the Physical Properties of Room Temperature Ionic Liquids Using a Love Wave Device

In this work, we have shown that a 100 MHz Love wave device can be used to determine whether room temperature ionic liquids (RTILs) are Newtonian fluids and have developed a technique that allows the determination of the density-viscosity product, rho eta of a Newtonian RTIL. In addition, a test for a Newtonian response was established by relating the phase change to insertion loss change. Five concentrations of a water-miscible RTIL and seven pure RTILs were measured. The changes in phase and insertion loss were found to vary linearly with the square root of the density-viscosity product for values up to (rho eta)(1/2) similar to 10 kg m(-2) s(-1/2). The square root of the density-viscosity product was deduced from the changes in either phase or insertion loss using glycerol as a calibration liquid. In both cases, the deduced values of rho eta agree well with those measured using viscosity and density meters. Miniaturization of the device, beyond that achievable with the lower-frequency quartz crystal microbalance approach, to measure smaller volumes is possible. The ability to fabricate Love wave and other surface acoustic wave sensors using planar metallization technologies gives potential for future integration into lab-on-a-chip analytical systems for characterizing ionic liquids.

EFFECTS OF 3 DURABILITY ENHANCING PRODUCTS ON SOME PHYSICAL-PROPERTIES OF NEAR-SURFACE CONCRETE

This paper investigates the influence of three fundamentally different durability enhancing products, viz. microsilica, controlled permeability formwork and silane, on some of the physical proper ties of near surface concrete. Microsilica (silica fume) is a pozzolan, controlled permeability formwork (CPF) is used to provide a free draining surface to a concrete form, while silane is a surface treatment applied to hardened concrete to reduce the ingress of water. Comparisons are made between the products when used individually and used in conjunction with each other, with a view to assessing whether the use of combinations of products may be desirable to improve the durability of concrete in certain circumstances. The effect of these materials on various durability parameters, such as freeze-thaw deterioration, carbonation resistance and chloride ingress, is considered in terms of their effect on permeation properties and surface strength. The results indicated that a combination of silane and CPF produces concrete with very low air permeability and sorptivity values. The influence of microsilica was more pronounced in increasing the surface strength of concrete.

Physical properties of a new Deep Eutectic Solvent based on lithium bis[(trifluoromethyl)sulfonyl]imide and N-methylacetamide as superionic suitable electrolyte for lithium ion batteries and electric double layer capacitors

Herein we present a study on the physical/chemical properties of a new Deep Eutectic Solvent (DES) based on N-methylacetamide (MAc) and lithium bis[(trifluoromethyl)sulfonyl]imide (LiTFSI). Due to its interesting properties, such as wide liquid-phase range from -60°C to 280°C, low vapor pressure, and high ionic conductivity up to 28.4mScm at 150°C and at x=1/4, this solution can be practically used as electrolyte for electrochemical storage systems such as electric double-layer capacitors (EDLCs) and/or lithium ion batteries (LiBs). Firstly, relationships between its transport properties (conductivity and viscosity) as a function of composition and temperature were discussed through Arrhenius' Law and Vogel-Tamman-Fulcher (VTF) equations, as well as by using the Walden classification. From this investigation, it appears that this complex electrolyte possesses a number of excellent transport properties, like a superionic character for example. Based on which, we then evaluated its electrochemical performances as electrolyte for EDLCs and LiBs applications by using activated carbon (AC) and lithium iron phosphate (LiFePO) electrodes, respectively. These results demonstrate that this electrolyte has a good compatibility with both electrodes (AC and LiFePO) in each testing cell driven also by excellent electrochemical properties in specific capacitance, rate and cycling performances, indicating that the LiTFSI/MAc DES can be a promising electrolyte for EDLCs and LiBs applications especially for those requiring high safety and stability. © 2013 Elsevier Ltd.

Influence of chloride, water, and organic solvents on the physical properties of ionic liquids

We report here the first systematic study of the effect of impurities and additives (e.g., water, chloride, and cosolvents) on the physical properties of room-temperature ionic liquids. Remarkably, it was discovered that the viscosity of mixtures was dependent mainly on the mole fraction of added molecular solvents and only to a lesser extent upon their identity, allowing viscosity changes during the course of a reaction to be entirely predictable. While the addition of such molecular solvents decreases the viscosity and density, chloride impurities, arising from the preparation of the ionic liquids, increase viscosity dramatically. The commonly used methods of preparation were validated with respect to chloride impurity.

A Hundred Comets: The Visual-Wavelength Observations of the Survey of Ensemble Physical Properties of Cometary Nuclei (SEPPCoN)

We present new results from SEPPCoN, a Survey of Ensemble Physical Properties of Cometary Nuclei. This project is currently surveying 100 Jupiter-family comets (JFCs) to measure the mid-infrared thermal emission and visible reflected sunlight of the nuclei. The scientific goal is to determine the distributions of radius, geometric albedo, thermal inertia, axial ratio, and color among the JFC nuclei. In the past we have presented results from the completed mid-IR observations of our sample [1]; here we present preliminary results from ongoing, broadband visible-wavelength observations of nuclei obtained from a variety of ground-based facilities (Mauna Kea, Cerro Pachon, La Silla, La Palma, Apache Point, Table Mtn., and Palomar Mtn.), including contributions from the Near Earth Asteroid Telescope project (NEAT) archive. The nuclei were observed at high heliocentric distance (usually over 4 AU) and so many comets show either no or little contamination from dust coma. While several nuclei have been observed as snapshots, we have multiepoch photometry for many of our targets. With our datasets we are building a large database of photometry, and such a database is essential to the derivation of albedo and shape of a large number of nuclei, and to the understanding of biases in the survey. Support for this work was provided by NSF and the NASA Planetary Astronomy program. Reference: [1] Fernandez, Y.R., et al. 2007, BAAS 39, 827.

Constraining the physical properties of Type II-Plateau supernovae using nebular phase spectra

We present a study of the nebular phase spectra of a sample of Type II-Plateau supernovae with identified progenitors or restrictive limits. The evolution of line fluxes, shapes and velocities is compared within the sample, and interpreted by the use of a spectral synthesis code. The small diversity within the data set can be explained by strong mixing occurring during the explosion, and by recognizing that most lines have significant contributions from primordial metals in the H envelope, which dominates the total ejecta mass in these types of objects. In particular, when using the [O I] 6300, 6364 Å doublet for estimating the core mass of the star, care has to be taken to account for emission from primordial O in the envelope. Finally, a correlation between the Hα line width and the mass of 56Ni is presented, suggesting that higher energy explosions are associated with higher 56Ni production.

The Influence of Cation Structure on the Chemical-Physical Properties of Protic Ionic Liquids

In this study we investigated the influence of five different cations on the physical-chemical properties of protic ionic liquids (PILs) based on bis(trifluoromethanesulfonyl)imide (TFSI-). We showed that the viscosities, ionic conductivities, densities and thermal properties of these PIL are strongly affected by the structure of the protic cation. Furthermore, the influence of the cation structure on the lithium coordination was investigated by Raman spectroscopy for all investigated PIL-based electrolytes for lithium-ion batteries (LIBs). This investigation clearly demonstrates, that the lithium average coordination number in PIL-based electrolytes is strongly affected by (ring) size and the number of protons on the cations structure and, more importantly, it might be significantly lower (more than 60 of that of electrolytes containing aprotic ionic liquids (AILs). Electrochemical performances of these PILs-based electrolytes were then also investigated to dress some conclusion on their applicability for LIB.

Niobium oxides and niobates physical properties

Niobium oxides have been pointed as an alternative to tantalum in the production of solid electrolytic capacitors, with advantages regarding the dielectric constant, density and price. In this work, it is intended to create a new family of niobium oxides based capacitors, adapting the technology and production line currently used with tantalum. Despite the known potentialities of niobium oxides, and many types of niobates, in several technological applications, the understanding of these oxide systems is still noticeably insufficient. Hence, a careful bibliographic review is shown, which evidences the complexity of these materials, the difficulty in identifying of their different phases and polymorphs, as well as in the interpretation of their properties. In this context, several fundamental studies on niobium oxides are presented, namely structural, microstructural, optical and electrical characterizations, which allow not only to contribute in an important way for the general knowledge of the physical properties of these materials, but also to advance to a sustained development of the niobium oxides based solid electrolytic capacitors. Several processing parameters were studied, clearing the way towards the creation of a prototype. It was also decided to perform a preliminary study on the synthesis and characterization of other oxide systems based in niobium, namely rare-earth orthoniobates (RENbO4), which interest has been related to their optical properties and protonic conductivity. Hence, single and polycrystalline samples of RENbO4 were synthesized and characterized structural, optical and electrically, leaving open an interesting future work.

Fuzzy modelling of prescribed burning effects on soil physical properties

This paper presents the preliminary work of an approach where Fuzzy Boolean Nets (FBN) are being used to extract qualitative knowledge regarding the effect of prescribed fire burning on soil chemical physical properties. FBN were chosen due to the scarcity on available quantitative data.

POCN-type Pincer Complexes of NiII and NiIII : synthesis, reactivities, catalytic activities and physical properties

Cette thèse décrit la synthèse, la caractérisation, les réactivités, et les propriétés physiques de complexes divalents et trivalents de Ni formés à partir de nouveaux ligands «pincer» de type POCN. Les ligands POCN de type amine sont préparés d’une façon simple et efficace via l’amination réductrice de 3-hydroxybenzaldéhyde avec NaBH4 et plusieurs amines, suivie par la phosphination de l’amino alcool résultant pour installer la fonction phosphinite (OPR2); le ligand POCN de type imine 1,3-(i-Pr)2PC6H4C(H)=N(CH2Ph) est préparé de façon similaire en faisant usage de PhCH2NH2 en l’absence de NaBH4. La réaction de ces ligands «pincer» de type POCN avec NiBr2(CH3CN)x en présence d’une base résulte en un bon rendement de la cyclométalation du lien C-H situé en ortho aux fonctions amine et phosphinite. Il fut découvert que la base est essentielle pour la propreté et le haut rendement de la formation des complexes «pincer» désirés. Nous avons préparé des complexes «pincer» plan- carrés de type POCN, (POCNRR΄)NiBr, possédant des fonctions amines secondaires et tertiaires qui démontrent des réactivités différentes selon les substituants R et R΄. Par exemple, les complexes possédant des fonctions amines tertiaires ArCH2NR2 (NR2= NMe2, NEt2, and morpholinyl) démontrent des propriétés rédox intéressantes et pourraient être convertis en leurs analogues trivalents (POCNR2)NiBr2 lorsque réagis avec Br2 ou N-bromosuccinimide (NBS). Les complexes trivalents paramagnétiques à 17 électrons adoptent une géométrie de type plan-carré déformée, les atomes de Br occupant les positions axiale et équatoriale. Les analyses «DSC» et «TGA» des ces composés ont démontré qu’ils sont thermiquement stables jusqu’à ~170 °C; tandis que la spectroscopie d’absorption en solution a démontré qu’ils se décomposent thermiquement à beaucoup plus basse température pour regénérer les complexes divalents ne possédant qu’un seul Br; l’encombrement stérique des substitutants amines accélère cette route de décomposition de façon significative. Les analogues NMe2 et N(morpholinyl) de ces espèces de NiIII sont actifs pour catalyser la réaction d’addition de Kharasch, de CX4 à des oléfines telles que le styrène, tandis qu’il fut découvert que l’analogue le moins thermiquement stable (POCNEt2)Ni est complètement inerte pour catalyser cette réaction. Les complexes (POCNRH)NiBr possédant des fonctions amines secondaires permettent l’accès à des fonctions amines substituées de façon non symétrique via leur réaction avec des halogénures d’alkyle. Un autre avantage important de ces complexes réside dans la possibilité de déprotonation pour préparer des complexes POCN de type amide. De telles tentatives pour déprotoner les fonctions NRH nous ont permis de préparer des espèces dimériques possédant des ligands amides pontants. La nature dimérique des ces complexes [P,C,N,N-(2,6-(i-Pr)2PC6H3CH2NR)Ni]2 (R= PhCH2 et Ph) fut établie par des études de diffraction des rayons-X qui ont démontré différentes géométries pour les cœurs Ni2N2 selon le substituant N : l’analogue (PhCH2)N possède une orientation syn des substitutants benzyles et un arrangement ressemblant à celui du cyclobutane du Ni et des atomes d’azote, tandis que l’analogue PhN adopte un arrangement de type diamant quasi-planaire des atomes du Ni et des atomes d’azote et une orientation anti des substituants phényles. Les espèces dimériques ne se dissocient pas en présence d’alcools, mais elles promouvoient l’alcoolyse catalytique de l’acrylonitrile. De façon intéressante, les rendements de ces réactions sont plus élevés avec les alcools possédant des fonctions O-H plus acides, avec un nombre de «turnover» catalytique pouvant atteindre 2000 dans le cas de m-cresol. Nous croyons que ces réactions d’alcoolyse procèdent par activation hétérolytique de l’alcool par l’espèce dimérique via des liaisons hydrogènes avec une ou deux des fonctions amides du dimère. Les espèces dimériques de Ni (II) s’oxydent facilement électrochimiquement et par reaction avec NBS ou Br2. De façon surprenante, l’oxydation chimique mène à l’isolation de nouveaux produits monomériques dans lesquels le centre métallique et le ligand sont oxydés. Le mécanisme d’oxydation fut aussi investigué par RMN, «UV-vis-NIR», «DFT» et spectroélectrochimie.

Effect of the Vulcanization Time and Storage on the Stability and Physical Properties of Sulfur-Prevulcanized Natural Rubber Latex

Prevulcanized natural rubber latex was prepared by the heating of the latex compound at 55°C for different periods of time (2, 4, 6, 8, and 10 h). The changes in the colloidal stability and physical properties were evaluated during the course of prevulcanization. The prevulcanized latex compounds were stored for 300 days, and the properties were monitored at different storage intervals (0, 20, 40, 60, 120, 180, 240, and 300 days). During prevulcanization, the mechanical stability time increased, and the viscosity remained almost constant. The tensile strength increased during storage for a period of 20 days. The degree of crosslinking, modulus, elongation at break, and chloroform number were varied with the time of storage.