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.

Ionic conductivity of polymer gels deriving from alkali metal ionic liquids and negatively charged polyelectrolytes

We have prepared polymer gel electrolytes with alkali metal ionic liquids (AMILs) that inherently contain alkali metal ions. The AMIL consisted of sulfate anion, imidazolium cation, and alkali metal cation. AMILs were mixed directly with poly(3-sulfopropyl acrylate) lithium salt or poly(2-acrylamido-2-methylpropanesulfonic acid) lithium salt to form polymer gels. The ionic conductivity of these gels decreased with increasing polymer fraction, as in general ionic liquid/polymer mixed systems. At low polymer concentrations, these gels displayed excellent ionic conductivity of 10⁻⁴ to 10⁻³ S cm⁻¹ at room temperature. Gelation was found to cause little change in the ⁷Li diffusion coefficient of the ionic liquid, as measured by pulse-field-gradient NMR. These data strongly suggest that the lithium cation migrates in successive pathways provided by the ionic liquids.

Nonadditivity of Faradaic currents and modification of capacitance currents in the voltammetry of mixtures of ferrocene and the cobaltocenium cation in protic and aprotic ionic liquids

Unexpected nonadditivity of currents encountered in the electrochemistry of mixtures of ferrocene (Fc) and cobaltocenium cation (Cc+) as the PF6 - salt has been investigated by direct current (dc) and Fourier-transformed alternating current (ac) cyclic voltammetry in two aprotic (1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium hexafluorophosphate) and three protic (triethylammonium formate, bis(2-hydroxyethyl)ammonium acetate, and triethylammonium acetate) ionic liquids (ILs). The voltammetry of the individual Fc0/+ and Cc+/0 couples always exhibits near-Nernstian behavior at glassy carbon and gold electrodes. As expected for an ideal process, the reversible formal potentials and diffusion coefficients at 23 ( 1 °C in each IL determined from measurement on individual Fc and Cc+ solutions were found to be independent of electrode material, concentration, and technique used for the measurement. However, when Fc and Cc+ were simultaneously present, the dc and ac peak currents per unit concentration for the Fc0/+ and Cc+/0 processes were found to be significantly enhanced in both aprotic and protic ILs. Thus, the apparent diffusion coefficient values calculated for Fc and Cc+ were respectively found to be about 25 and 35% larger than those determined individually in the aprotic ILs. A similar change in the Fc0/+ mass transport characteristics was observed upon addition of tetrabutylammonium hexafluorophosphate (Bu4NPF6), and the double layer capacitance also varied in distinctly different ways when Fc and Cc+ were present individually or in mixtures. Importantly, the nonadditivity of Faradaic current is not associated with a change in viscosity or from electron exchange as found when some solutes are added to ILs. The observation that the 1H NMR T1 relaxation times for the proton resonance in Cc+ also are modified in mixed systems implies that specific interaction with aggregates of the constituent IL ionic species giving rise to subtle structural changes plays an important role in modifying the mass transport, double layer characteristics, and dynamics when solutes of interest in this study are added to ILs. Analogous voltammetric changes were not observed in studies in organic solvent media containing 0.1 M added supporting electrolyte. Implications of the nonadditivity of Faradaic and capacitance terms in ILs are considered.

Influence of praseodymium - synergistic corrosion inhibition in mixed rare-earth diphenyl phosphate systems

Mixed rare-earth organophosphates have been investigated as potential corrosion inhibitors for AA2024-T3, and previously have shown synergistic inhibition behavior; however, the mechanism was not identified. In this paper, a key factor contributing to corrosion inhibition of AA2024-T3 with mischmetal diphenyl phosphate [Mm(dpp)3] is the unique stability of Pr(dpp)3 compared to other key rare earths in mischmetal. Although increasing pH causes precipitation of other components, the Pr compound is stable at higher pH. Electrochemically, a synergy is evident when Ce(dpp)3 and Pr(dpp)3 are combined. Raman mapping indicates the Pr(dpp)3 inhibitor leads to a more uniform coverage of the alloy.

A potential-controlled switch on/off mechanism for selective excitation in mixed electrochemiluminescent systems

We demonstrate the complete, rapid, and reversible switching between the emissions from two electrogenerated chemiluminescence (ECL) systems contained within the same solution, controlled by simple modification of the applied potential. The fundamental bases of the approach are the ability to selectively 'switch on' luminophores at distinct oxidation potentials, and an intriguing observation that the emission from the well-known electrochemiluminescent complex, fac-Ir(ppy)3, (where ppy is 2-phenylpyridinato), can be selectively 'switched-off' at high overpotentials. The dependence of this phenomenon on high concentrations of the co-reactant implicates quenching of the excited [Ir(ppy)3]* state by electron transfer. Rapid spectral scanning during modulation of the applied potential reveals well resolved maxima for mixtures comprising either green and red or green and blue luminophores, illustrating the vast potential of this approach for multiplexed ECL detection.

New H∞ control design for polytopic systems with mixed time-varying delays in state and input

This paper concerns with the problem of state-feedback H∞ control design for a class of linear systems with polytopic uncertainties and mixed time-varying delays in state and input. Our approach can be described as follows. We first construct a state-feedback controller based on the idea of parameter-dependent controller design. By constructing a new parameter-dependent Lyapunov-Krasovskii functional (LKF), we then derive new delay-dependent conditions in terms of linear matrix inequalities ensuring the exponential stability of the corresponding closed-loop system with a H∞ disturbance attenuation level. The effectiveness and applicability of the obtained results are demonstrated by practical examples.

Benchmark generation algorithm for stochastic mixed model assembly shop simulation and optimization

The Operations Research (OR) community have defined many deterministic manufacturing control problems mainly focused on scheduling. Well-defined benchmark problems provide a mechanism for communication of the effectiveness of different optimization algorithms. Manufacturing problems within industry are stochastic and complex. Common features of these problems include: variable demand, machine part specific breakdown patterns, part machine specific process durations, continuous production, Finished Goods Inventory (FGI) buffers, bottleneck machines and limited production capacity. Discrete Event Simulation (DES) is a commonly used tool for studying manufacturing systems of realistic complexity. There are few reports of detail-rich benchmark problems for use within the simulation optimization community that are as complex as those faced by production managers. This work details an algorithm that can be used to create single and multistage production control problems. The reported software implementation of the algorithm generates text files in eXtensible Markup Language (XML) format that are easily edited and understood as well as being cross-platform compatible. The distribution and acceptance of benchmark problems generated with the algorithm would enable researchers working on simulation and optimization of manufacturing problems to effectively communicate results to benefit the field in general.

Managing design knowledge with mixed-initiative dialogue

This paper is based on ongoing work in developing interactive interfaces to formal methods for encoding design knowledge. It reports on the development of a shared graphical notation to support user interaction with design knowledge based on mixed-initiative. Mixed-initiative provides a model of interaction where both the designer and the knowledge formalism may share responsibility over decisions. The paper discusses how a formal visual notation can support the mixed-initiative mode for developing and managing formal design knowledge. The notation addresses on the dialogue problem between the user and a knowledge based formalism and illustrates a model of interaction in which the user and the formalism can share and input data through a common shared resource, on a common shared task. The paper demonstrates the use of this notation in common decision tasks and the implications for seamless interaction with design support systems.

Mixed transfer function neural networks for generalization and knowledge extraction

This thesis develops a novel framework of nonlinear modelling to adaptively fit the complexity of the model to the problem domain resulting in a better modelling capability and a straightforward knowledge acquisition. The developed framework also permits increased comprehensibility and user acceptability of modelling results.

Mixed transfer function neural networks for knowledge acquistition

Modeling helps to understand and predict the outcome of complex systems. Inductive modeling methodologies are beneficial for modeling the systems where the uncertainties involved in the system do not permit to obtain an accurate physical model. However inductive models, like artificial neural networks (ANNs), may suffer from a few drawbacks involving over-fitting and the difficulty to easily understand the model itself. This can result in user reluctance to accept the model or even complete rejection of the modeling results. Thus, it becomes highly desirable to make such inductive models more comprehensible and to automatically determine the model complexity to avoid over-fitting. In this paper, we propose a novel type of ANN, a mixed transfer function artificial neural network (MTFANN), which aims to improve the complexity fitting and comprehensibility of the most popular type of ANN (MLP - a Multilayer Perceptron).

A formal model of mixed-initiative interaction in design exploration

Computer-based environments for supporting design are complex software artifacts. These tools need to use sound computational formalisms as well as address issues of human usability. The development of interactive and usable generative systems is a significant research area in design computation. Though classical search techniques play a central role in the generative kernels of these "closed-world" systems, the open-ended exploration of design spaces is the desirable goal. In this paper, we present a formal model of exploration that combines search with user driven exploration. We describe the role of interaction and agency in an experimental mixed-initiative design support system.

Energy efficiency rating systems for housing : an Australian perspective

Purpose – The purpose of this paper is to examine current trends in energy efficiency ratings and consider their likely impact on the Australian housing market.

Design/methodology/approach – The research is yet to be conducted; however a mixed method is proposed which is grounded on the theoretical model of consumer behaviour within housing markets. This model has been tested and demonstrated to be useful in predicting buyer behaviour.

Findings – Established theories of buyer perception indicate the introduction of energy efficiency rating systems will have an effect on the level of house prices.

Research limitations/implications – This research is focussed on housing in Australia but also has implications for other global housing markets which are addressing sustainability.

Practical implications – Outputs of this research have implications for policy makers, real estate agents and valuers.

Social implications – Increasing energy costs is likely to restructure the way housing markets operate with regard to sustainability and energy efficiency rating systems and also how they are understood.

Originality/value – This research will be in the Australian context utilising international modeling. As mandatory energy efficiency ratings have not been introduced, this research will be original.

Surface structure of SnOxNy thin films deposited using a filtered cathodic arc for novel energy storage systems

Tin oxide/nitride (SnOxNy) thin films were synthesised using a filtered cathodic vacuum arc deposition system. These films were deposited at room temperature with increasing amounts of reactive nitrogen gas to alter the nanostructure. To understand the surface structure of the coatings several techniques were used including scanning electron microscopy (SEM), atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD) and x-ray absorption spectroscopy (XAS). Preliminary results have shown that a cathodic arc can be used to deposit smooth films which exhibit a mixed tin oxide/nitride structure.