POLYANILINE-DISPERSED MERCURY-ELECTRODE FOR THE DETECTION OF MONOCHLORAMINE AND DICHLORAMINE

A novel type of electrochemical detector based on a polyaniline-dispersed mercury-coated glassy carbon chemically modified electrode was investigated for the detection of monochloramine and dichloramine. A polyaniline dispersed-mercury modified electrode, which was prepared by coating polyaniline on a thin mercury film electrode using fast-sweep voltammetry, was developed. The selectivity could be altered using various counter ions incorporated into the polymer. The results indicated that the use of a conducting polymer-based electrochemical sensor for the selective determination of chloramine is a feasible approach.

ELECTROCHEMICAL STUDY OF ISOPOLY-OXOMETALLATES AND HETEROPOLY-OXOMETALLATES FILM MODIFIED MICROELECTRODES .3. FURTHER STUDY OF ELECTRODE PROCESS OF ISOPOLYMOLYBDIC ANION DOPED IN POLYANILINE FILM

The isopolymolybdic anion-polyaniline film modified carbon fiber (CF) microelectrode with high stability and electroactivity in aqueous acid solution has been successfully prepared by cycling the potential between -0.15 V and +0.85 V vs. sce at 100 mV s-1 or applying constant potential (+0.85 V) for electropolymerization in a 0.5 M H2SO4 solution containing 5.0 x 10(-2) M aniline and 5.0 x 10(-3) M H4Mo8O26. The electrochemical behaviour of the isopolymolybdic anion entrapped in the polyaniline film is strongly influenced by the sweep-potential range besides the acidity of electrolyte solution. In some acidic electrolyte solution (eg 0.5 M H2SO4), the change of the sweep-potential range causes the structure alternation of the isopolymolybdic anion and resulting in a new electrode process. The cyclic voltammogram of Mo8O264- in 0.5 M H2SO4 solution exhibits three two-electron reversible waves between +0.70 and -0.20 V. However, when the potential sweeps to the lower-limit of -0.3 V, where the fourth four-electron cathodic wave appears, the redoxidation process of the reduction product of Mo8O264- becomes relatively complicated. The 10-electron reduction product seems to change into other isopolyanion (this unknown structure isopolyanions are simply called [Mo-O]), which can be reoxidized to Mo8O264- by five successive two-electron oxidation steps from -0.30 to +0.70 V. However, when the lower-limit of the cycling potential is maintained at -0.30 V and the upper-limit reduces to +0.40 V from +0.70 V, the [Mo-O] in the film exhibits four two-electron reversible waves. We have presented a novel explanation about its electrode reaction mechanism on the basis of our experimental results.

CATALYTIC REDUCTION OF HEMOGLOBIN AT THIONINE CHEMICALLY MODIFIED ELECTRODE AND FIA APPLICATIONS

Thionine-containing chemically modified electrode (cme) was constructed with glassy carbon substrate by potential sweep oxidation, electrodeposition and adsorption procedures, and electrocatalytic reduction of hemoglobin was carried out and characterized at the cme under batch and flow conditions. Comparison of the catalytic response toward hemoglobir obtained at the cme was made mainly in terms of the potential dependence, the detectability and long-term stability. When used in flow injection analysis (FIA) experiments with the detector monitored at a constant potential applied at -0.35 V vs sce, detection limit of 0.15-1.5 pmol level of hemoglobin injected was achieved at the cme, with linear response range over 2 orders of magnitude. All the cme s retained more than 70% of their initial hemoglobin response level over 8 h of continuous service in the flow-through system.

DIRECT ELECTRON-TRANSFER REACTION OF HEMEPROTEINS PROMOTED BY METHYLENE-BLUE MODIFIED ELECTRODE

The heterogeneous electron transfer reaction of hemeproteins including hemoglobin, myoglobin and cytochrome C at Pt mesh electrode adsorbed methylene blue has been investigated. Thin-layer spectroelectrochemical technique was used for observing the electron transfer processes of three kinds of proteins, and the corresponding electrode rate constants were measured.

Theory of Handwriting

Handwriting production is viewed as a constrained modulation of an underlying oscillatory process. Coupled oscillations in horizontal and vertical directions produce letter forms, and when superimposed on a rightward constant velocity horizontal sweep result in spatially separated letters. Modulation of the vertical oscillation is responsible for control of letter height, either through altering the frequency or altering the acceleration amplitude. Modulation of the horizontal oscillation is responsible for control of corner shape through altering phase or amplitude. The vertical velocity zero crossing in the velocity space diagram is important from the standpoint of control. Changing the horizontal velocity value at this zero crossing controls corner shape, and such changes can be effected through modifying the horizontal oscillation amplitude and phase. Changing the slope at this zero crossing controls writing slant; this slope depends on the horizontal and vertical velocity zero amplitudes and on the relative phase difference. Letter height modulation is also best applied at the vertical velocity zero crossing to preserve an even baseline. The corner shape and slant constraints completely determine the amplitude and phase relations between the two oscillations. Under these constraints interletter separation is not an independent parameter. This theory applies generally to a number of acceleration oscillation patterns such as sinusoidal, rectangular and trapezoidal oscillations. The oscillation theory also provides an explanation for how handwriting might degenerate with speed. An implementation of the theory in the context of the spring muscle model is developed. Here sinusoidal oscillations arise from a purely mechanical sources; orthogonal antagonistic spring pairs generate particular cycloids depending on the initial conditions. Modulating between cycloids can be achieved by changing the spring zero settings at the appropriate times. Frequency can be modulated either by shifting between coactivation and alternating activation of the antagonistic springs or by presuming variable spring constant springs. An acceleration and position measuring apparatus was developed for measurements of human handwriting. Measurements of human writing are consistent with the oscillation theory. It is shown that the minimum energy movement for the spring muscle is bang-coast-bang. For certain parameter values a singular arc solution can be shown to be minimizing. Experimental measurements however indicate that handwriting is not a minimum energy movement.

Sparsely Faceted Arrays: A Mechanism Supporting Parallel Allocation, Communication, and Garbage Collection

Conventional parallel computer architectures do not provide support for non-uniformly distributed objects. In this thesis, I introduce sparsely faceted arrays (SFAs), a new low-level mechanism for naming regions of memory, or facets, on different processors in a distributed, shared memory parallel processing system. Sparsely faceted arrays address the disconnect between the global distributed arrays provided by conventional architectures (e.g. the Cray T3 series), and the requirements of high-level parallel programming methods that wish to use objects that are distributed over only a subset of processing elements. A sparsely faceted array names a virtual globally-distributed array, but actual facets are lazily allocated. By providing simple semantics and making efficient use of memory, SFAs enable efficient implementation of a variety of non-uniformly distributed data structures and related algorithms. I present example applications which use SFAs, and describe and evaluate simple hardware mechanisms for implementing SFAs. Keeping track of which nodes have allocated facets for a particular SFA is an important task that suggests the need for automatic memory management, including garbage collection. To address this need, I first argue that conventional tracing techniques such as mark/sweep and copying GC are inherently unscalable in parallel systems. I then present a parallel memory-management strategy, based on reference-counting, that is capable of garbage collecting sparsely faceted arrays. I also discuss opportunities for hardware support of this garbage collection strategy. I have implemented a high-level hardware/OS simulator featuring hardware support for sparsely faceted arrays and automatic garbage collection. I describe the simulator and outline a few of the numerous details associated with a "real" implementation of SFAs and SFA-aware garbage collection. Simulation results are used throughout this thesis in the evaluation of hardware support mechanisms.

A simulation-based design method to transfer surface mount RF system to flip-chip die implementation

The flip-chip technology is a high chip density solution to meet the demand for very large scale integration design. For wireless sensor node or some similar RF applications, due to the growing requirements for the wearable and implantable implementations, flip-chip appears to be a leading technology to realize the integration and miniaturization. In this paper, flip-chip is considered as part of the whole system to affect the RF performance. A simulation based design is presented to transfer the surface mount PCB board to the flip-chip die package for the RF applications. Models are built by Q3D Extractor to extract the equivalent circuit based on the parasitic parameters of the interconnections, for both bare die and wire-bonding technologies. All the parameters and the PCB layout and stack-up are then modeled in the essential parts' design of the flip-chip RF circuit. By implementing simulation and optimization, a flip-chip package is re-designed by the parameters given by simulation sweep. Experimental results fit the simulation well for the comparison between pre-optimization and post-optimization of the bare die package's return loss performance. This design method could generally be used to transfer any surface mount PCB to flip-chip package for the RF systems or to predict the RF specifications of a RF system using the flip-chip technology.

Involvement of incipient hydrous oxide species in electrocatalysis at some metal electrode surfaces

In this thesis a novel theory of electrocatalysis at metal (especially noble metal)/solution interfaces was developed based on the assumption of metal adatom/incipient hydrous oxide cyclic redox transitions. Adatoms are considered as metastable, low coverage species that oxidise in-situ at potentials of often significantly cathodic to the regular metal/metal oxide transition. Because the adatom coverage is so low the electrochemical or spectroscopic response for oxidation is frequently overlooked; however, the product of such oxidation, referred to here as incipient hydrous oxide seems to be the important mediator in a wide variety of electrocatalytically demanding oxidation processes. Conversely, electrocatalytically demanding reductions apparently occur only at adatom sites at the metal/solution interface - such reactions generally occur only at potentials below, i.e. more cathodic than, the adatom/hydrous oxide transition. It was established that while silver in base oxidises in a regular manner (forming initially OHads species) at potentials above 1.0 V (RHE), there is a minor redox transition at much lower potentials, ca. o.35 v (RHE). The latter process is assumed to an adatom/hydrous oxide transition and the low coverage Ag(l) hydrous oxide (or hydroxide) species was shown to trigger or mediate the oxidation of aldehydes, e. g. HCHO. The results of a study of this system were shown to be in good agreement with a kinetic model based on the above assumptions; the similarity between this type of behaviour and enzyme-catalysed processes - both systems involve interfacial active sites - was pointed out. Similar behaviour was established for gold where both Au(l) and Au(lll) hydrous oxide mediators were shown to be the effective oxidants for different organic species. One of the most active electrocatalytic materials known at the present time is platinum. While the classical view of this high activity is based on the concept of activated chemisorption (and the important role of the latter is not discounted here) a vital role is attributed to the adatom/hydrous oxide transition. It was suggested that the well known intermediate (or anomalous) peak in the hydrogen region of the cyclic voltanmogram for platinum region is in fact due to an adatom/hydrous oxide transition. Using potential stepping procedures to minimise the effect of deactivating (COads) species, it was shown that the onset (anodic sweep) and termination (cathodic sweep) potential for the oxidation of a wide variety of organics coincided with the potential for the intermediate peak. The converse was also shown to apply; sluggish reduction reactions, that involve interaction with metal adatoms, occur at significant rates only in the region below the hydrous oxide/adatom transition.

A study of the oxygen electrochemistry of ruthenium and iridium

This thesis is concerned with an investigation of the anodic behaviour of ruthenium and iridium in aqueous solution and particularly of oxygen evolution on these metals. The latter process is of major interest in the large-scale production of hydrogen gas by the electrolysis of water. The presence of low levels of ruthenium trichloride ca. 10-4 mol dm-3 in acid solution give a considerable increase in the rate of oxygen evolution from platinum and gold, but not graphite, anodes. The mechanism of this catalytic effect was investigated using potential step and a.c. impedance technique. Earlier suggestions that the effect is due to catalysis by metal ions in solution were proved to be incorrect and it was shown that ruthenium species were incorporated into the surface oxide film. Changes in the oxidation state of these ruthenium species is probably responsible for the lowering of the oxygen overvoltage. Both the theoretical and practical aspects of the reaction were complicated by the fact that at constant potential the rates of both the catalysed and the uncatalysed oxygen evolution processes exhibit an appreciable, continuous decrease with either time or degree of oxidation of the substrate. The anodic behaviour of iridium in the oxide layer region has been investigated using conventional electrochemical techniques such as cyclic voltammetry. Applying a triangular voltage sweep at 10 Hz, 0.01 to 1.50V increases the amount of electric charge which the surface can store in the oxide region. This activation effect and the mechanism of charge storage is discussed in terms of both an expanded lattice theory for oxide growth on noble metals and a more recent theory of irreversible oxide formation with subsequent stoichiometry changes. The lack of hysteresis between the anodic and cathodic peaks at ca. 0.9 V suggests that the process involved here is proton migration in a relatively thick surface layer, i.e. that the reaction involved is some type of oxide-hydroxide transition. Lack of chloride ion inhibition in the anodic region also supports the irreversible oxide formation theory; however, to account for the hydrogen region of the potential sweep a compromise theory involving partial reduction of the outer regions of iridium oxide film is proposed. The loss of charge storage capacity when the activated iridium surface is anodized for a short time above ca. 1.60 V is attributed to loss by corrosion of the outer active layer from the metal surface. The behaviour of iridium at higher anodic potentials in acid solution was investigated. Current-time curves at constant potential and Tafel plots suggested that a change in the mechanism of the oxygen evolution reaction occurs at ca. 1.8 V. Above this potential, corrosion of the metal occurred, giving rise to an absorbance in the visible spectrum of the electrolyte (λ max = 455 nm). It is suggested that the species involved was Ir(O2)2+. A similar investigation in the case of alkaline electrolyte gave no evidence for a change in mechanism at 1.8 V and corrosion of the iridium was not observed. Oxygen evolution overpotentials were much lower for iridium than for platinum in both acidic and alkaline solutions.

Slow light with a swept-frequency source.

ct: We introduce a new concept for stimulated-Brillouin-scattering-based slow light in optical fibers that is applicable for broadly-tunable frequency-swept sources. It allows slow light to be achieved, in principle, over the entire transparency window of the optical fiber. We demonstrate a slow light delay of 10 ns at 1.55 μm using a 10-m-long photonic crystal fiber with a source sweep rate of 400 MHz/μs and a pump power of 200 mW. We also show that there exists a maximal delay obtainable by this method, which is set by the SBS threshold, independent of sweep rate. For our fiber with optimum length, this maximum delay is ~38 ns, obtained for a pump power of 760 mW.

Lament for String Quartet

This piece explores the changing nature of emotion focusing especially on the feeling of sorrow. The opening and ending parts of the first movement represent the overall motive of sorrow. The first movement opens with an augmented chord G-C#-F-B and from this chord the first violin expands upwards while the cello moves downwards towards the C chord (p.2). As the melody alternates between each part, there is a subtle change in harmony which creates tension and release and changes the sound color. In addition, ornamentation in each part reinforces the movement towards the C chord. This progression represents the inner emotion of lament. Sostenuto e largamente section (p.2) uses heterophony in order to express a feeling of chaos. Section Scherzando (p.4) uses the interval relationship M7 and m2, and is a respite from the overwhelming feeling of sorrow. The ending of the first movement (p.12) returns to create a second tension by every instrument ascending slowly, and the viola produces a distinctive melody derived from the previous chaotic section that ends on an Ab. The second movement contrasts with the first movement in order to express a concealed, not explicit, sorrow, and differs in both tempo and texture. The tempo is a waltz that is faster than the first movement. This produces a light, playful figure and a simple melody without much ornamentation. Imitation and canonic structure emphasize the individuality of the strings. The third movement merges material from the first movement rhythmic figure and the second movement pizzicato (p.17). It shows timbral change through con sordino, pizzicato arpeggio, and sul ponticello to display string techniques. An Allegro section (p.19) especially contrasts with Misterioso in rhythm and dynamics. In the Grazioso (p.22), random beats are accentuated by pizzicato arpeggio to de-emphasize the meter. Finally, there is a return to the ending figure of the first movement with con sordino (p.23) and sul ponticello in viola that articulates the internal tension and the timbral change to return to a voice of sorrow.

The collection and analysis of pre-evacuation times derived from evacuation trials and their application to evacuation modelling

This paper presents data relating to occupant pre-evacuation times from university and hospital outpatient facilities. Although the two occupancies are entirely different, they do employ relatively similar procedures: members of staff sweep areas to encourage individuals to evacuate.However the manner in which the dependent population reacts to these procedures is quite different. In the hospital case, the patients only evacuated once a member of the nursing staff had instructed them to do so, while in the university evacuation, the students were less dependent upon the actions of the staff, with over 50% of them evacuating with no prior prompting. In addition, the student pre-evacuation time was found to be dependent on their level of engagement in various activities.

Rheological characterisation and printing performance of Sn/Ag/Cu solder pastes

Lead-free solder paste printing process accounts for majority of the assembly defects in the electronic manufacturing industry. The study investigates rheological behaviour and stencil printing performance of the lead-free solder pastes (Sn/Ag/Cu). Oscillatory stress sweep test was carried out to study the visco-elastic behaviour of the lead-free solder pastes. The visco-elastic behaviour of the paste encompasses solid and liquid characteristic of the paste, which could be used to study the flow behaviour experienced by the pastes during the stencil printing process. From this study, it was found that the solid characteristics (G0) is higher than the liquid characteristic (G0 0) for the pastes material. In addition, the results from the study showed that the solder paste with a large G0 = G0 0 has a higher cohesiveness resulting in poor withdrawal of the paste during the stencil printing process. The phase angles (d) was used to correlate the quality of the dense suspensions to the formulation of solder paste materials. This study has revealed the value of having a rheological measurement for explaining and characterising solder pastes for stencil printing. As the demand for lead free pastes increases rheological measurements can assist with the formulation or development of new pastes.

Rheological characterisation of solder pastes and isotropic conductive adhesives used for flip-chip assembly

Solder pastes and isotropic conductive adhesives (ICAs) are widely used as a principal bonding medium in the electronic industry. This study investigates the rheological behaviour of the pastes (solder paste and isotropic conductive adhesives) used for flip-chip assembly. Oscillatory stress sweep test are performed to evaluate solid characteristic and cohesiveness of the lead-free solder pastes and isotropic conductive adhesive paste materials. The results show that the G' (storage modulus) is higher than G '' (loss modulus) for the pastes material indicating a solid like behaviour. It result shows that the linear visco-elastic region for the pastes lies in a very small stress range, below 10 Pa. in addition, the stress at which the value of storage modulus is equal to that of loss modulus can be used as an indicator of the paste cohesiveness. The measured cross-over stress at G'=G '' shows that the solder paste has higher stress at G'=G '' compared to conductive adhesives. Creep-recovery test method is used to study the slump behaviour in the paste materials. The conductive adhesive paste shows a good recovery when compared to the solder pastes. (C) 2008 Elsevier B.V. All rights reserved.

A methodology for characterising new lead-free solder paste formulations used for flip-chip assembly applications

The paper reports on the investigation of the rheological behaviour new lead-free solder pastes formulations for use in flip-chip assembly applications. The study is made up of three parts; namely the evaluation of the effect of plate geometry, the effect of temperature and processing environment and the effect of torsional frequencies on the rheological measurements. Different plate geometries and rheological tests were used to evaluate new formulations in terms of wall slip characteristics, linear viscoelastic region and shear thinning behaviour. A technique which combines the use of the creep-recovery and dynamic frequency sweep tests was used to further characterise the paste structure, rheological behaviour and the processing performance of the new paste formulations. The technique demonstrated in this study has wide utility for R & D personnel involved in new paste formulation, for implementing quality control procedures used in paste manufacture and packaging and for qualifying new flip-chip assembly lines