Investigation of interfacial charging and discharging in double-layer pentacene-based metal-insulator-metal device with polyterpenol blocking layer using electric field induced second harmonic generation

Time-resolved electric field induced second harmonic generation technique was used to probe the carrier transients within double-layer pentacene-based MIM devices. Polyterpenol thin films fabricated from non-synthetic environmentally sustainable source were used as a blocking layer to assist in visualisation of single-species carrier transportation during charging and discharging under different bias conditions. Results demonstrated that carrier transients were comprised of charging on electrodes, followed by carrier injection and charging of the interface. Polyterpenol was demonstrated to be a sound blocking material and can therefore be effectively used for probing of double-layer devices using EFISHG.

Scheduling trains as a blocking parallel-machine job shop scheduling problem

In this paper, the train scheduling problem is modelled as a blocking parallel-machine job shop scheduling (BPMJSS) problem. In the model, trains, single-track sections and multiple-track sections, respectively, are synonymous with jobs, single machines and parallel machines, and an operation is regarded as the movement/traversal of a train across a section. Due to the lack of buffer space, the real-life case should consider blocking or hold-while-wait constraints, which means that a track section cannot release and must hold the train until next section on the routing becomes available. Based on literature review and our analysis, it is very hard to find a feasible complete schedule directly for BPMJSS problems. Firstly, a parallel-machine job-shop-scheduling (PMJSS) problem is solved by an improved shifting bottleneck procedure (SBP) algorithm without considering blocking conditions. Inspired by the proposed SBP algorithm, feasibility satisfaction procedure (FSP) algorithm is developed to solve and analyse the BPMJSS problem, by an alternative graph model that is an extension of the classical disjunctive graph models. The proposed algorithms have been implemented and validated using real-world data from Queensland Rail. Sensitivity analysis has been applied by considering train length, upgrading track sections, increasing train speed and changing bottleneck sections. The outcomes show that the proposed methodology would be a very useful tool for the real-life train scheduling problems

Predicting active material utilisation in LiFePO4 electrodes using a multi-scale mathematical model

A mathematical model is developed to simulate the discharge of a LiFePO4 cathode. This model contains 3 size scales, which match with experimental observations present in the literature on the multi-scale nature of LiFePO4 material. A shrinking-core is used on the smallest scale to represent the phase-transition of LiFePO4 during discharge. The model is then validated against existing experimental data and this validated model is then used to investigate parameters that influence active material utilisation. Specifically the size and composition of agglomerates of LiFePO4 crystals is discussed, and we investigate and quantify the relative effects that the ionic and electronic conductivities within the oxide have on oxide utilisation. We find that agglomerates of crystals can be tolerated under low discharge rates. The role of the electrolyte in limiting (cathodic) discharge is also discussed, and we show that electrolyte transport does limit performance at high discharge rates, confirming the conclusions of recent literature.

A multi-train movement simulator with moving blocking signalling

Abstract Being as a relatively new approach of signalling, moving-block scheme significantly increases line capacity, especially on congested railways. This paper describes a simulation system for multi-train operation under moving-block signalling scheme. The simulator can be used to calculate minimum headways and safety characteristics under pre-set timetables or headways and different geographic and traction conditions. Advanced software techniques are adopted to support the flexibility within the simulator so that it is a general-purpose computer-aided design tool to evaluate the performance of moving block signalling.

Scheduling Trains with Priorities : a no-wait blocking parallel-machine job-shop scheduling model

The paper investigates train scheduling problems when prioritised trains and non-prioritised trains are simultaneously traversed in a single-line rail network. In this case, no-wait conditions arise because the prioritised trains such as express passenger trains should traverse continuously without any interruption. In comparison, non-prioritised trains such as freight trains are allowed to enter the next section immediately if possible or to remain in a section until the next section on the routing becomes available, which is thought of as a relaxation of no-wait conditions. With thorough analysis of the structural properties of the No-Wait Blocking Parallel-Machine Job-Shop-Scheduling (NWBPMJSS) problem that is originated in this research, an innovative generic constructive algorithm (called NWBPMJSS_Liu-Kozan) is proposed to construct the feasible train timetable in terms of a given order of trains. In particular, the proposed NWBPMJSS_Liu-Kozan constructive algorithm comprises several recursively-used sub-algorithms (i.e. Best-Starting-Time-Determination Procedure, Blocking-Time-Determination Procedure, Conflict-Checking Procedure, Conflict-Eliminating Procedure, Tune-up Procedure and Fine-tune Procedure) to guarantee feasibility by satisfying the blocking, no-wait, deadlock-free and conflict-free constraints. A two-stage hybrid heuristic algorithm (NWBPMJSS_Liu-Kozan-BIH) is developed by combining the NWBPMJSS_Liu-Kozan constructive algorithm and the Best-Insertion-Heuristic (BIH) algorithm to find the preferable train schedule in an efficient and economical way. Extensive computational experiments show that the proposed methodology is promising because it can be applied as a standard and fundamental toolbox for identifying, analysing, modelling and solving real-world scheduling problems.

Low temperature synthesis of carbon nanotubes on indium tin oxide electrodes for organic solar cells

The electrical performance of indium tin oxide (ITO) coated glass was improved by including a controlled layer of carbon nanotubes directly on top of the ITO film. Multi-wall carbon nanotubes (MWCNTs) were synthesized by chemical vapor deposition, using ultra-thin Fe layers as catalyst. The process parameters (temperature, gas flow and duration) were carefully refined to obtain the appropriate size and density of MWCNTs with a minimum decrease of the light harvesting in the cell. When used as anodes for organic solar cells based on poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM), the MWCNT-enhanced electrodes are found to improve the charge carrier extraction from the photoactive blend, thanks to the additional percolation paths provided by the CNTs. The work function of as-modified ITO surfaces was measured by the Kelvin probe method to be 4.95 eV, resulting in an improved matching to the highest occupied molecular orbital level of the P3HT. This is in turn expected to increase the hole transport and collection at the anode, contributing to the significant increase of current density and open circuit voltage observed in test cells created with such MWCNT-enhanced electrodes.

Blocking layer optimisation of poly(3-hexylthiopene)based solid state dye sensitized solar cells

The optimisation study of the fabrication of a compact TiO2 blocking layer (via Spray Pyrolysis Deposition) for poly (3-hexylthiopene) (P3HT) for Solid State Dye Sensitized Solar Cells (SDSCs) is reported. We used a novel spray TiO2 precursor solution composition obtained by adding acetylacetone to a conventional formulation (Diisopropoxytitanium bis (acetylacetonate) in ethanol). By Scanning Electron Microscopy a TiO2 layer with compact morphology and thickness of around 100 nmis shown. Through a Tafel plot analysis an enhancement of the device diode-like behaviour induced by the acetylacetone blocking layer respect to the conventional one is observed. Significantly, the device fabricatedwith the acetylacetone blocking layer shows an overall increment of the cell performance with respect to the cellwith the conventional one (DJsc/Jsc = +13.8%, DFF/FF = +39.7%, DPCE/PCE = +55.6%). A conversion efficiency optimumis found for 15 successive spray cycles where the diode-like behaviour of the acetylacetone blocking layer is more effective. Over three batches of cells (fabricated with P3HT and dye D35) an average conversion efficiency value of 3.9% (under a class A sun simulator with 1 sun A.M. 1.5 illumination conditions) was measured. From the best cell we fabricated a conversion efficiency value of 4.5% was extracted. This represents a significant increment with respect to previously reported values for P3HT/dye D35 based SDSCs.

Who’s blocking the Chinese Internet? The rise of cybercultures and the generational conflicts in China

As a decentralised communication technology, the Internet has offered much autonomy and unprecedented communication freedom to the Chinese public. Yet the Chinese government has imposed different forms of censorship over cyberspace. However, the Hong Kong erotic photo scandal reshuffles the traditional understanding of censorship in China as it points to a different territory. The paper takes the Hong Kong erotic photo scandal in 2008 as a case study and aims to examine the social and generational conflicts hidden in China. When thousands of photos containing sexually explicit images of Hong Kong celebrities were released on the Internet, gossip, controversies and eroticism fuelled the public discussion and threatened traditional values in China. The Internet provides an alternative space for the young Chinese who have been excluded from mainstream social discourse to engage in public debates. This, however, creates concerns, fear and even anger among the older generations in China, because they can no longer control, monitor and educate their children in the way that their predecessors have done for centuries. The photo scandal illustrates the internal social conflicts and distrust between generations in China and the generational conflict has a far-reaching political ramification as it creates a new concept of censorship.

Study of the underlying electrochemistry of polycrystalline gold electrodes in aqueous solution and electrocatalysis by large amplitude Fourier transformed alternating current voltammetry

Polycrystalline gold electrodes of the kind that are routinely used in analysis and catalysis in aqueous media are often regarded as exhibiting relatively simple double-layer charging/discharging and monolayer oxide formation/ removal in the positive potential region. Application of the large amplitude Fourier transformed alternating current (FT-ac) voltammetric technique that allows the faradaic current contribution of fast electron-transfer processes to be emphasized in the higher harmonic components has revealed the presence of well-defined faradaic (premonolayer oxidation) processes at positive potentials in the double-layer region in acidic and basic media which are enhanced by electrochemical activation. These underlying quasi-reversible interfacial electron-transfer processes may mediate the course of electrocatalytic oxidation reactions of hydrazine, ethylene glycol, and glucose on gold electrodes in aqueous media. The observed responses support key assumptions associated with the incipient hydrous oxide adatom mediator (IHOAM) model of electrocatalysis.

Electrocrystallization of phase I, CuTCNQ (TCNQ= 7, 7, 8, 8-tetracyanoquinodimethane), on indium tin oxide and boron-doped diamond electrodes

The electrochemical reduction of TCNQ to TCNQ•- in acetonitrile in the presence of [Cu(MeCN)4]+ has been undertaken at boron-doped diamond (BDD) and indium tin oxide (ITO) electrodes. The nucleation and growth process at BDD is similar to that reported previously at metal electrodes. At an ITO electrode, the electrocrystallization of more strongly adhered, larger, branched, needle-shaped phase I CuTCNQ crystals is detected under potential step conditions and also when the potential is cycled over the potential range of 0.7 to −0.1 V versus Ag/AgCl (3 M KCl). Video imaging can be used at optically transparent ITO electrodes to monitor the growth stage of the very large branched crystals formed during the course of electrochemical experiments. Both in situ video imaging and ex situ X-ray diffraction and scanning electron microscopy (SEM) data are consistent with the nucleation of CuTCNQ taking place at a discrete number of preferred sites on the ITO surface. At BDD electrodes, ex situ optical images show that the preferential growth of CuTCNQ occurs at the more highly conducting boron-rich areas of the electrode, within which there are preferred sites for CuTCNQ formation.

Effect of the mediator in feedback mode-based SECM interrogation of indium tin-oxide and boron-doped diamond electrodes

Indium tin-oxide (ITO) and polycrystalline boron-doped diamond (BDD) have been examined in detail using the scanning electrochemical microscopy technique in feedback mode. For the interrogation of electrodes made from these materials, the choice of mediator has been varied. Using Ru(CN) 4− 6 (aq), ferrocene methanol (FcMeOH), Fe(CN) 3− 6 (aq) and Ru(NH 3) 3+ 6 (aq), approach curve experiments have been performed, and for purposes of comparison, calculations of the apparent heterogeneous electron transfer rates (k app) have been made using these data. In general, it would appear that values of k app are affected mainly by the position of the mediator reversible potential relative to the relevant semiconductor band edge (associated with majority carriers). For both the ITO (n type) and BDD (p type) electrodes, charge transfer is impeded and values are very low when using FcMeOH and Fe(CN) 3− 6 (aq) as mediators, and the use of Ru(NH 3) 3+ 6(aq) results in the largest value of k app. With ITO, the surface is chemically homogeneous and no variation is observed for any given mediator. Data is also presented where the potential of the ITO electrode is fixed using a ratio of the mediators Fe(CN) 3− 6(aq) and Fe(CN) 4− 6(aq). In stark contrast, the BDD electrode is quite the opposite and a range of k app values are observed for all mediators depending on the position on the surface. Both electrode surfaces are very flat and very smooth, and hence, for BDD, variations in feedback current imply a variation in the electrochemical activity. A comparison of the feedback current where the substrate is biased and unbiased shows a surprising degree of proportionality.

Electrochemical fabrication of metallic nanostructured electrodes for electroanalytical applications

The use of electrodeposited metal-based nanostructures for electroanalytical applications has recently received widespread attention. There are several approaches to creating nanostructured materials through electrochemical routes that include facile electrodeposition at either untreated or modified electrodes, or through the use of physical or chemical templating methods. This allows the shape, size and composition of the nanomaterial to be readily tuned for the application of interest. The use of such materials is particularly suited to electroanalytical applications. In this mini-review an overview of recently developed nanostructured materials developed through electrochemical routes is presented as well as their electroanalytical applications in areas of biological and environmental importance.