Theoretical and experimental correlations of gas dissolution, diffusion, and thermodynamic properties in determination of gas permeability and selectivity in supported ionic liquid membranes

Supported ionic liquid membranes (SILMs) has the potential to be a new technological platform for gas/organic vapour separation because of the unique non-volatile nature and discriminating gas dissolution properties of room temperature ionic liquids (ILs). This work starts with an examination of gas dissolution and transport properties in bulk imidazulium cation based ionic liquids [C_nmim][NTf2] (n = 2.4, 6, 8.10) from simple gas H₂, N₂, to polar CO₂, and C₂H₆, leading to a further analysis of how gas dissolution and diffusion are influenced by molecular specific gas-SILMs interactions, reflected by differences in gas dissolution enthalpy and entropy. These effects were elucidated again during gas permeation studies by examining how changes in these properties and molecular specific interactions work together to cause deviations from conventional solution–diffusion theory and their impact on some remarkably contrasting gas perm-selectivity performance. The experimental perm-selectivity for all tested gases showed varied and contrasting deviation from the solution–diffusion, depending on specific gas-IL combinations. It transpires permeation for simpler non-polar gases (H₂, N₂) is diffusion controlled, but strong molecular specific gas-ILs interactions led to a different permeation and selectivity performance for C₂H₆ and CO₂. With exothermic dissolution enthalpy and large order disruptive entropy, C₂H₆ displayed the fastest permeation rate at increased gas phase pressure in spite of its smallest diffusivity among the tested gases. The C₂H₆ gas molecules “peg” on the side alkyl chain on the imidazulium cation at low concentration, and are well dispersed in the ionic liquids phase at high concentration. On the other hand strong CO₂-ILs affinity resulted in a more prolonged “residence time” for the gas molecule, typified by reversed CO₂/N₂ selectivity and slowest CO₂ transport despite CO₂ possess the highest solubility and comparable diffusivity in the ionic liquids. The unique transport and dissolution behaviour of CO₂ are further exploited by examining the residing state of CO₂ molecules in the ionic liquid phase, which leads to a hypothesis of a condensing and holding capacity of ILs towards CO₂, which provide an explanation to slower CO₂ transport through the SILMs. The pressure related exponential increase in permeations rate is also analysed which suggests a typical concentration dependent diffusion rate at high gas concentration under increased gas feed pressure. Finally the strong influence of discriminating and molecular specific gas-ILs interactions on gas perm-selectivity performance points to future specific design of ionic liquids for targeted gas separations.

Double cyclometalation via carbon-silicon bond cleavage by palladium(II) acetate. X-ray structure of a cationic 1,4-dipalladated benzene ring and selective synthesis of heterobimetallic 1,4-phenylene-bridged platinum(II)-palladium(II) complexes

The disilylated compound 1,4-bis(trimethylsilyl)-2,3,5,6-tetrakis((dimethylamino)methyl)benzene, (Me(3)Si)(2)C2N4, 4, can be electrophilically palladated selectively at the C-Si bonds to afford the neutral 1,4-bis(palladium) complex [(AcOPd)(2)(C2N4)], from which the dicationic [(LPd)(2)(C2N4)](2+) (L = MeCN) organometallic species are accessible. The monosilylated species (Me(3)Si)(H)C2N4, 5, can be used for the preparation of the dicationic heterodinuclear platinum(II)-palladium(II) species [(LPd)(LPt)(C2N4)](2+) (L = MeCN) via a sequence of transmetalation of the organolithium derivative of 5 with [PtCl2(SEt(2))(2)], followed by a C-Si bond palladation reaction.

Emotional intelligence, personality and decoding non-verbal expressions of emotion

Previous research has highlighted theoretical and empirical links between measures of both personality and trait emotional intelligence (EI), and the ability to decode facial expressions of emotion. Research has also found that the posed, static characteristics of the photographic stimuli used to explore these links affects the decoding process and differentiates them from the natural expressions they represent. This undermines the ecological validity of established trait-emotion decoding relationships. This study addresses these methodological shortcomings by testing relationships between the reliability of participant ratings of dynamic, spontaneously elicited expressions of emotion with personality and trait EI. Fifty participants completed personality and self-report EI questionnaires, and used a computer-logging program to continuously rate change in emotional intensity expressed in video clips. Each clip was rated twice to obtain an intra-rater reliability score. The results provide limited support for links between both trait EI and personality variables and how reliably we decode natural expressions of emotion. Limitations and future directions are discussed.

Interaction strength, food web topology and the relative importance of species in food webs

P>1. We established complex marine communities, consisting of over 100 species, in large subtidal experimental mesocosms. We measured the strength of direct interactions and the net strength of direct and indirect interactions between the species in those communities, using a combination of theoretical and empirical approaches.

A Theoretical and Experimental Study of Resonance in a High Performance Engine Intake System: Part 1

The unsteady gas dynamic phenomena in engine intake systems of the type found in racecars have been examined. In particular, the resonant tuning effects, including cylinder-to-cylinder power variations, which can occur as a result of the interaction between an engine and its airbox have been considered. Frequency analysis of the output from a Virtual 4-Stroke 1D engine simulation was used to characterise the forcing function applied by an engine to an airbox. A separate computational frequency sweeping technique, which employed the CFD package FLUENT, was used to determine the natural frequencies of virtual airboxes in isolation from an engine. Using this technique, an airbox with a natural frequency at 75 Hz was designed for a Yamaha R6 4-cylinder motorcycle engine. The existence of an airbox natural frequency at 75 Hz was subsequently confirmed by an experimental frequency sweeping technique carried out on the engine test bed. A coupled 1D/3D analysis which employed the engine simulation package Virtual 4-Stroke and the CFD package FLUENT, was used to model the combined engine and airbox system. The coupled 1D/3D analysis predicted a 75 Hz resonance of the airbox at an engine speed of 9000 rpm. This frequency was the induction frequency for a single cylinder. An airbox was fabricated and tested on the engine. Static pressure was recorded at a grid of points in the airbox as the engine was swept through a speed range of 3000 to 10000 rpm. The measured engine speed corresponding to resonance in the airbox agreed well with the predicted values. There was also good correlation between the amplitude and phase of the pressure traces recorded within the airbox and the 1D/3D predictions.

Detecting the effects of diversity on measures of ecosystem function: experimental design, null models and empirical observations

Here we present a novel experimental approach to examine the relationship between diversity and ecosystem Function. We develop four null predictive models, with which to differentiate between the 'sampling effect' - the chance inclusion of a highly productive species, and 'species complementarity' - the complementary use of resources by species that differ in their niche or resource use. We investigate the effects of manipulating species and functional richness on ecosystem function in marine benthic system and using empirical data from our own experiments we illustrate the application of these models.

‘What Adult Worker Model? A Critical Look at Recent Social Policy Reform in Europe from a Gender and Family Perspective

Analyses regularly feature claims that European welfare states are in the process of creating an adult worker model. The theoretical and empirical basis of this argument is examined here by looking first at the conceptual foundations of the adult worker model formulation and then at the extent to which social policy reform in western Europe fits with the argument. It is suggested that the adult worker formulation is under-specified. A framework incorporating four dimensions—the treatment of individuals vis-à-vis their family role and status for the purposes of social rights, the treatment of care, the treatment of the family as a social institution, and the extent to which gender inequality is problematized—is developed and then applied. The empirical analysis reveals a strong move towards individualization as social policy promotes and valorizes individual agency and self-sufficiency and shifts some childcare from the family. Yet evidence is also found of continued (albeit changed) familism. Rather than an unequivocal move to an individualized worker model then, a dual earner, gender-specialized, family arrangement is being promoted. The latter is the middle way between the old dependencies and the new “independence.” This makes for complexity and even ambiguity in policy, a manifestation of which is that reform within countries involves concurrent moves in several directions.

Kinematic Analysis and Dimensional Synthesis of Exechon Parallel Kinematic Machine for Large Volume Machining

A parallel kinematic machine (PKM) topology can only give its best performance when its geometrical parameters are optimized. In this paper, dimensional synthesis of a newly developed PKM is presented for the first time. An optimization method is developed with the objective to maximize both workspace volume and global dexterity of the PKM. Results show that the method can effectively identify design parameter changes under different weighted objectives. The PKM with optimized dimensions has a large workspace to footprint ratio and a large well-conditioned workspace, hence justifies its suitability for large volume machining.

A Theoretical and Experimental Study of Resonance in a High Performance Engine Intake System: Part 2

The unsteady gas dynamic phenomena in a racecar airbox have been examined, and resonant tuning effects have been considered. A coupled 1D/3D analysis, using the engine simulation package Virtual 4-Stroke and the CFD package FLUENT, was used to model the engine and airbox. The models were experimentally validated. An airbox was designed with a natural frequency in the region of 75 Hz. A coupled 1D/3D analysis of the airbox and a Yamaha R6 4 cylinder engine predicted resonance at the single-cylinder induction frequency; 75 Hz at an engine speed of 9000 rpm.

Theoretical and FE analysis of ultrasonic welding of aluminum alloy 3003

Ultrasonic welding (consolidation) process is a rapid manufacturing process that is used to join thin layers of metal at low temperature and low energy consumption. Experimental results have shown that ultrasonic welding is a combination of both surface (friction) and volume (plasticity) softening effects. In the presented work, an attempt has been made to simulate the ultrasonic welding of metals by taking into account these effects (surface and volume). A phenomenological material model has been proposed, which incorporates these two effects (i.e., surface and volume). The thermal softening due to friction and ultrasonic (acoustic) softening has been included in the proposed material model. For surface effects, a friction law with variable coefficient of friction that is dependent on contact pressure, slip, temperature, and number of cycles has been derived from experimental friction tests. The results of the thermomechanical analyses of ultrasonic welding of aluminum alloy have been presented. The goal of this work is to study the effects of ultrasonic welding process parameters, such as applied load, amplitude of ultrasonic oscillation, and velocity of welding sonotrode on the friction work at the weld interface. The change in the friction work at the weld interface has been explained on the basis of softening (thermal and acoustic) of the specimen during the ultrasonic welding process. In the end, a comparison between experimental and simulated results has been presented, showing a good agreement. Copyright © 2009 by ASME.