Tunable Multiresponsive Methacrylic Acid Based Inverse Opal Hydrogels Prepared by Controlling the Synthesis Conditions

Methacrylic acid based inverse opal hydrogels (MIOHs) have been prepared by controlling the synthesis conditions, including cross-linker content, solvent content, and water content in solvent mixtures to explore the effect of the synthesis conditions (especially solvent content and mixture) on the response performance. Various response events (pH, solvent, ionic strength, 1,4-phenylenediamine dihydrochloride (PDA) response) have been investigated. For pH, solvent response, the same response behaviors have been observed: both the increased solvent (only ethanol) content and the enhanced water content in solvent will lead to the reduced response level of MIOHs compared to that of the increased cross-linker content. However, two different kinds of response behaviors for ionic strength response have been found by adjusting the synthesis conditions. The kinetics of pH response shows characteristics of a diffusion-limited process, and the equilibrium response time is about 20 min, which cannot be reduced by changing the synthesis conditions.

Highly efficient inverted top-emitting organic light-emitting diodes using a lead monoxide electron injection layer

By introducing an effective electron injection layer (EIL) material, i.e., lead monoxide (PbO), combined with the optical design in device structure, a high efficiency inverted top-emitting organic light-emitting diode (ITOLED) with saturated and quite stable colors for different viewing angles is demonstrated. The green ITOLED based on 10-(2-benzothiazolyl)-1, 1, 7, 7-tetramethyl-2, 3, 6, 7-tetrahydro-1H, 5H, 11H-[1] benzopyrano [6, 7, 8-ij] quinolizin-11-one exhibits a maximum current efficiency of 33.8 cd/A and a maximum power efficiency of 16.6 lm/W, accompanied by a nearly Lambertian distribution as well as hardly detectable color variation in the 140 forward viewing cone. A detailed analysis on the role mechanism of PbO in electron injection demonstrates that the insertion of the PbO EIL significantly reduces operational voltage, thus greatly improving the device efficiency.

Lead(IV) dioxide: an effective electron injection material to realize high-efficiency inverted top-emitting organic light-emitting diodes

Lead(IV) dioxide (PbO2) has been used as the electron injection layer (EIL) to realize high-efficiency inverted top-emitting organic light-emitting diodes (I-TOLEDs). It can be seen that the inserting of the PbO2 EIL significantly reduces operational voltage, thus greatly improving the current efficiency and power efficiency of fabricated I-TOLEDs. The 10-(2-benzothiazolyl)-1, 1, 7, 7-tetramethyl-2, 3, 6, 7-tetrahydro-1H, 5H, 11H-[1] benzopyrano [6, 7, 8-ij] quinolizin-11-one (C545T)-based I-TOLEDs with the PbO2 EIL exhibit a maximum current efficiency of 31.6 cd A(-1) and a maximum power efficiency of 14.3 lm W-1, which are both higher than 22.5 cd A(-1) and 5.4 lm W-1 of the I-TOLEDs with LiF as the EIL respectively. A detailed analysis with respect to the role mechanism of PbO2 in electron injection has been presented. The improvement in EL performance is attributed to the formation of the interfacial dipoles at the electrode interface due to charge transfer between PbO2 and Alq(3).

Novel PPV-based light-emitting polymers containing siloxane moiety

Two PPV-based copolymers consisting siloxane linkage have been synthesized by melt condensation of bisphenol and dianilinodimethylsilane. The rigid PPV segments act as chromosphere and allow fine turning of band gap for blue-light emission, while the flexible siloxane units lead to the effective interruption of conjugation and the enhancement of solubility. The UV-vis absorption, photoluminescent and eletroluminescent properties have been studied.

Monitoring knowledge: a text-based approach

Schierz, A. (2007). Monitoring knowledge: a text-based approach. Terminology, 13 (2), 125-154. Sponsorship: EPSRC DTG Project IQ, EU IST-FET FP6-516169

A Customizable Camera-based Human Computer Interaction System Allowing People With Disabilities Autonomous Hands Free Navigation of Multiple Computing Task

Many people suffer from conditions that lead to deterioration of motor control and makes access to the computer using traditional input devices difficult. In particular, they may loose control of hand movement to the extent that the standard mouse cannot be used as a pointing device. Most current alternatives use markers or specialized hardware to track and translate a user's movement to pointer movement. These approaches may be perceived as intrusive, for example, wearable devices. Camera-based assistive systems that use visual tracking of features on the user's body often require cumbersome manual adjustment. This paper introduces an enhanced computer vision based strategy where features, for example on a user's face, viewed through an inexpensive USB camera, are tracked and translated to pointer movement. The main contributions of this paper are (1) enhancing a video based interface with a mechanism for mapping feature movement to pointer movement, which allows users to navigate to all areas of the screen even with very limited physical movement, and (2) providing a customizable, hierarchical navigation framework for human computer interaction (HCI). This framework provides effective use of the vision-based interface system for accessing multiple applications in an autonomous setting. Experiments with several users show the effectiveness of the mapping strategy and its usage within the application framework as a practical tool for desktop users with disabilities.

Vector Associative Maps: Unsupervised Real-time Error-based Learning and Control of Movement Trajectories

This article describes neural network models for adaptive control of arm movement trajectories during visually guided reaching and, more generally, a framework for unsupervised real-time error-based learning. The models clarify how a child, or untrained robot, can learn to reach for objects that it sees. Piaget has provided basic insights with his concept of a circular reaction: As an infant makes internally generated movements of its hand, the eyes automatically follow this motion. A transformation is learned between the visual representation of hand position and the motor representation of hand position. Learning of this transformation eventually enables the child to accurately reach for visually detected targets. Grossberg and Kuperstein have shown how the eye movement system can use visual error signals to correct movement parameters via cerebellar learning. Here it is shown how endogenously generated arm movements lead to adaptive tuning of arm control parameters. These movements also activate the target position representations that are used to learn the visuo-motor transformation that controls visually guided reaching. The AVITE model presented here is an adaptive neural circuit based on the Vector Integration to Endpoint (VITE) model for arm and speech trajectory generation of Bullock and Grossberg. In the VITE model, a Target Position Command (TPC) represents the location of the desired target. The Present Position Command (PPC) encodes the present hand-arm configuration. The Difference Vector (DV) population continuously.computes the difference between the PPC and the TPC. A speed-controlling GO signal multiplies DV output. The PPC integrates the (DV)·(GO) product and generates an outflow command to the arm. Integration at the PPC continues at a rate dependent on GO signal size until the DV reaches zero, at which time the PPC equals the TPC. The AVITE model explains how self-consistent TPC and PPC coordinates are autonomously generated and learned. Learning of AVITE parameters is regulated by activation of a self-regulating Endogenous Random Generator (ERG) of training vectors. Each vector is integrated at the PPC, giving rise to a movement command. The generation of each vector induces a complementary postural phase during which ERG output stops and learning occurs. Then a new vector is generated and the cycle is repeated. This cyclic, biphasic behavior is controlled by a specialized gated dipole circuit. ERG output autonomously stops in such a way that, across trials, a broad sample of workspace target positions is generated. When the ERG shuts off, a modulator gate opens, copying the PPC into the TPC. Learning of a transformation from TPC to PPC occurs using the DV as an error signal that is zeroed due to learning. This learning scheme is called a Vector Associative Map, or VAM. The VAM model is a general-purpose device for autonomous real-time error-based learning and performance of associative maps. The DV stage serves the dual function of reading out new TPCs during performance and reading in new adaptive weights during learning, without a disruption of real-time operation. YAMs thus provide an on-line unsupervised alternative to the off-line properties of supervised error-correction learning algorithms. YAMs and VAM cascades for learning motor-to-motor and spatial-to-motor maps are described. YAM models and Adaptive Resonance Theory (ART) models exhibit complementary matching, learning, and performance properties that together provide a foundation for designing a total sensory-cognitive and cognitive-motor autonomous system.

Finding optimal alternatives based on efficient comparative preference inference

Choosing the right or the best option is often a demanding and challenging task for the user (e.g., a customer in an online retailer) when there are many available alternatives. In fact, the user rarely knows which offering will provide the highest value. To reduce the complexity of the choice process, automated recommender systems generate personalized recommendations. These recommendations take into account the preferences collected from the user in an explicit (e.g., letting users express their opinion about items) or implicit (e.g., studying some behavioral features) way. Such systems are widespread; research indicates that they increase the customers' satisfaction and lead to higher sales. Preference handling is one of the core issues in the design of every recommender system. This kind of system often aims at guiding users in a personalized way to interesting or useful options in a large space of possible options. Therefore, it is important for them to catch and model the user's preferences as accurately as possible. In this thesis, we develop a comparative preference-based user model to represent the user's preferences in conversational recommender systems. This type of user model allows the recommender system to capture several preference nuances from the user's feedback. We show that, when applied to conversational recommender systems, the comparative preference-based model is able to guide the user towards the best option while the system is interacting with her. We empirically test and validate the suitability and the practical computational aspects of the comparative preference-based user model and the related preference relations by comparing them to a sum of weights-based user model and the related preference relations. Product configuration, scheduling a meeting and the construction of autonomous agents are among several artificial intelligence tasks that involve a process of constrained optimization, that is, optimization of behavior or options subject to given constraints with regards to a set of preferences. When solving a constrained optimization problem, pruning techniques, such as the branch and bound technique, point at directing the search towards the best assignments, thus allowing the bounding functions to prune more branches in the search tree. Several constrained optimization problems may exhibit dominance relations. These dominance relations can be particularly useful in constrained optimization problems as they can instigate new ways (rules) of pruning non optimal solutions. Such pruning methods can achieve dramatic reductions in the search space while looking for optimal solutions. A number of constrained optimization problems can model the user's preferences using the comparative preferences. In this thesis, we develop a set of pruning rules used in the branch and bound technique to efficiently solve this kind of optimization problem. More specifically, we show how to generate newly defined pruning rules from a dominance algorithm that refers to a set of comparative preferences. These rules include pruning approaches (and combinations of them) which can drastically prune the search space. They mainly reduce the number of (expensive) pairwise comparisons performed during the search while guiding constrained optimization algorithms to find optimal solutions. Our experimental results show that the pruning rules that we have developed and their different combinations have varying impact on the performance of the branch and bound technique.

Leveraging lessons learned in organizations through implementing practice-based organizational learning and performance improvement - An opportunity for context-based intelligent assistant support (CIAS)

Organizations that leverage lessons learned from their experience in the practice of complex real-world activities are faced with five difficult problems. First, how to represent the learning situation in a recognizable way. Second, how to represent what was actually done in terms of repeatable actions. Third, how to assess performance taking account of the particular circumstances. Fourth, how to abstract lessons learned that are re-usable on future occasions. Fifth, how to determine whether to pursue practice maturity or strategic relevance of activities. Here, organizational learning and performance improvement are investigated in a field study using the Context-based Intelligent Assistant Support (CIAS) approach. A new conceptual framework for practice-based organizational learning and performance improvement is presented that supports researchers and practitioners address the problems evoked and contributes to a practice-based approach to activity management. The novelty of the research lies in the simultaneous study of the different levels involved in the activity. Route selection in light rail infrastructure projects involves practices at both the strategic and operational levels; it is part managerial/political and part engineering. Aspectual comparison of practices represented in Contextual Graphs constitutes a new approach to the selection of Key Performance Indicators (KPIs). This approach is free from causality assumptions and forms the basis of a new approach to practice-based organizational learning and performance improvement. The evolution of practices in contextual graphs is shown to be an objective and measurable expression of organizational learning. This diachronic representation is interpreted using a practice-based organizational learning novelty typology. This dissertation shows how lessons learned when effectively leveraged by an organization lead to practice maturity. The practice maturity level of an activity in combination with an assessment of an activity’s strategic relevance can be used by management to prioritize improvement effort.

Caesarean section and subsequent pregnancy outcome: a Danish register-based cohort study

Background and Aims: Caesarean section rates have increased in recent decades and the effects on subsequent pregnancy outcome are largely unknown. Prior research has hypothesised that Caesarean section delivery may lead to an increased risk of subsequent stillbirth, miscarriage, ectopic pregnancy and sub-fertility. Structure and Methods: Papers 1-3 are systematic reviews with meta-analyses. Papers 4-6 are findings from this thesis on the rate of subsequent stillbirth, miscarriage, ectopic pregnancy and live birth by mode of delivery. Results Systematic reviews and meta-analyses: A 23% increased odds of subsequent stillbirth; no increase in odds of subsequent ectopic pregnancy and a 10% reduction in the odds of subsequent live birth among women with a previous Caesarean section were found in the various meta-analyses. Danish cohorts: Results from the Danish Civil Registration System (CRS) cohort revealed a small increased rate of subsequent stillbirth and ectopic pregnancy among women with a primary Caesarean section, which remained in the analyses by type of Caesarean. No increased rate of miscarriage was found among women with a primary Caesarean section. In the CRS data, women with a primary Caesarean section had a significantly reduced rate of subsequent live birth particularly among women with primary elective and maternal-requested Caesarean sections. In the Aarhus Birth Cohort, overall the effect of mode of delivery on the rate and time to next live birth was minimal. Conclusions: Primary Caesarean section was associated with a small increased rate of stillbirth and ectopic pregnancy, which may be in part due to underlying medical conditions. No increased rate of miscarriage was found. A reduced rate of subsequent live birth was found among Caesarean section in the CRS data. In the smaller ABC cohort, a small reduction in rate of subsequent live birth was found among women with a primary Caesarean section and is most likely due to maternal choice rather than any ill effects of the Caesarean. The findings of this study, the largest and most comprehensive to date will be of significant interest to health care providers and women globally.

Synthesis and characterisation of novel superficially porous silica based stationary phases for use in liquid chromatography

The concept of pellicular particles was suggested by Horváth and Lipsky over fifty years ago. The reasoning behind the idea of these particles was to improve column efficiency by shortening the pathways analyte molecules can travel, therefore reducing the effect of the A and C terms. Several types of shell particles were successfully marketed around this time, however with the introduction of high quality fully porous silica under 10 μm, shell particles faded into the background. In recent years a new generation of core shell particles have become popular within the separation science community. These particles allow fast and efficient separations that can be carried out on conventional HPLC systems. Chapter 1 of this thesis introduces the chemistry of chromatographic stationary phases, with an emphasis on silica bonded phases, particularly focusing on the current state of technology in this area. The main focus is on superficially porous silica particles as a support material for liquid chromatography. A summary of the history and development of these particles over the past few decades is explored, along with current methods of synthesis of shell particles. While commercial shell particles have a rough outer surface, Chapter 2 focuses on the novel approach to growth of smooth surface superficially porous particles in a step-by-step manner. From the Stöber methodology to the seeded growth technique, and finally to the layer-bylayer growth of the porous shell. The superficially porous particles generated in this work have an overall diameter of 2.6 μm with a 350 nm porous shell; these silica particles were characterised using SEM, TEM and BET analysis. The uniform spherical nature of the particles along with their surface area, pore size and particle size distribution are examined in this chapter. I discovered that these smooth surface shell particles can be synthesised to give comparable surface area and pore size in comparison to commercial brands. Chapter 3 deals with the bonding of the particles prepared in Chapter 2 with C18 functionality; one with a narrow and one with a wide particle size distribution. This chapter examines the chromatographic and kinetic performance of these silica stationary phases, and compares them to a commercial superficially porous silica phase with a rough outer surface. I found that the particle size distribution does not seem to be the major contributor to the improvement in efficiency. The surface morphology of the particles appears to play an important role in the packing process of these particles and influences the Van Deemter effects. Chapter 4 focuses on the functionalisation of 2.6 μm smooth surface superficially porous particles with a variety of fluorinated and phenyl silanes. The same processes were carried out on 3.0 μm fully porous silica particles to provide a comparison. All phases were accessed using elemental analysis, thermogravimetric analysis, nitrogen sorption analysis and chromatographically evaluated using the Neue test. I observed comparable results for the 2.6 μm shell pentaflurophenyl propyl silica when compared to 3.0 μm fully porous silica. Chapter 5 moves towards nano-particles, with the synthesis of sub-1 μm superficially porous particles, their characterisation and use in chromatography. The particles prepared are 750 nm in total with a 100 nm shell. All reactions and testing carried out on these 750 nm core shell particles are also carried out on 1.5 μm fully porous particles in order to give a comparative result. The 750 nm core shell particles can be synthesised quickly and are very uniform. The main drawback in their use for HPLC is the system itself due to the backpressure experienced using sub – 1 μm particles. The synthesis of modified Stöber particles is also examined in this chapter with a range of non-porous silica and shell silica from 70 nm – 750 nm being tested for use on a Langmuir – Blodgett system. These smooth surface shell particles have only been in existence since 2009. The results displayed in this thesis demonstrate how much potential smooth surface shell particles have provided more in-depth optimisation is carried out. The results on packing studies reported in this thesis aims to be a starting point for a more sophisticated methodology, which in turn can lead to greater chromatographic improvements.

Contrasting the efficiency of radiation belt losses caused by ducted and nonducted whistler-mode waves from ground-based transmitters

It has long been recognized that whistler-mode waves can be trapped in plasmaspheric whistler ducts which guide the waves. For nonguided cases these waves are said to be "nonducted", which is dominant for L < 1.6. Wave-particle interactions are affected by the wave being ducted or nonducted. In the field-aligned ducted case, first-order cyclotron resonance is dominant, whereas nonducted interactions open up a much wider range of energies through equatorial and off-equatorial resonance. There is conflicting information as to whether the most significant particle loss processes are driven by ducted or nonducted waves. In this study we use loss cone observations from the DEMETER and POES low-altitude satellites to focus on electron losses driven by powerful VLF communications transmitters. Both satellites confirm that there are well-defined enhancements in the flux of electrons in the drift loss cone due to ducted transmissions from the powerful transmitter with call sign NWC. Typically, ∼80% of DEMETER nighttime orbits to the east of NWC show electron flux enhancements in the drift loss cone, spanning a L range consistent with first-order cyclotron theory, and inconsistent with nonducted resonances. In contrast, ∼1% or less of nonducted transmissions originate from NPM-generated electron flux enhancements. While the waves originating from these two transmitters have been predicted to lead to similar levels of pitch angle scattering, we find that the enhancements from NPM are at least 50 times smaller than those from NWC. This suggests that lower-latitude, nonducted VLF waves are much less effective in driving radiation belt pitch angle scattering. Copyright 2010 by the American Geophysical Union.

Combined vertex-based - cell-centred finite volume method for flows in complex geometries

CFD modelling of 'real-life' processes often requires solutions in complex three dimensional geometries, which can often result in meshes where aspects of it are badly distorted. Cell-centred finite volume methods, typical of most commercial CFD tools, are computationally efficient, but can lead to convergence problems on meshes which feature cells with high non-orthogonal shapes. The vertex-based finite volume method handles distorted meshes with relative ease, but is computationally expensive. A combined vertex-based - cell-centred (VB-CC) technique, detailed in this paper, allows solutions on distorted meshes that defeat purely cell-centred physical models to be employed in the solution of other transported quantities. The VB-CC method is validated with benchmark solutions for thermally driven flow and turbulent flow. An early application of this hybrid technique is to three-dimensional flow over an aircraft wing, although it is planned to use it in a wide variety of processing applications in the future.

Numerical simulation of vacuum dezincing of lead alloy

Removing zinc by distillation can leave the lead bullion virtually free of zinc and also produces pure zinc crystals. Batch distillation is considered in a hemispherical kettle with water-cooled lid, under high vacuum (50 Pa or less). Sufficient zinc concentration at the evaporating surface is achieved by means of a mechanical stirrer. The numerical model is based on the multiphysics simulation package PHYSICA. The fluid flow module of the code is used to simulate the action of the stirring impeller and to determine the temperature and concentration fields throughout the liquid volume including the evaporating surface. The rate of zinc evaporation and condensation is then modelled using Langmuir’s equations. Diffusion of the zinc vapour through the residual air in the vacuum gap is also taken into account. Computed results show that the mixing is sufficient and the rate-limiting step of the process is the surface evaporation driven by the difference of the equilibrium vapour pressure and the actual partial pressure of zinc vapour. However, at higher zinc concentrations, the heat transfer through the growing zinc crystal crust towards the cold steel lid may become the limiting factor because the crystallization front may reach the melting point. The computational model can be very useful in optimising the process within its safe limits.

Intermetallic phase detection in lead-free solders using synchrotron X-ray diffraction

The high-intensity, high-resolution x-ray source at the European Synchrotron Radiation Facility (ESRF) has been used in x-ray diffraction (XRD) experiments to detect intermetallic compounds (IMCs) in lead-free solder bumps. The IMCs found in 95.5Sn3.8Ag0.7Cu solder bumps on Cu pads with electroplated-nickel immersion-gold (ENIG) surface finish are consistent with results based on traditional destructive methods. Moreover, after positive identification of the IMCs from the diffraction data, spatial distribution plots over the entire bump were obtained. These spatial distributions for selected intermetallic phases display the layer thickness and confirm the locations of the IMCs. For isothermally aged solder samples, results have shown that much thicker layers of IMCs have grown from the pad interface into the bulk of the solder. Additionally, the XRD technique has also been used in a temperature-resolved mode to observe the formation of IMCs, in situ, during the solidification of the solder joint. The results demonstrate that the XRD technique is very attractive as it allows for nondestructive investigations to be performed on expensive state-of-the-art electronic components, thereby allowing new, lead-free materials to be fully characterized.