Influence of electrolyte cations on electron transport and electron transfer in dye-sensitized solar cells

The influence of different electrolyte cations ((Li+, Na+, Mg2+, tetrabutyl ammonium (TBA+)) on the TiO2 conduction band energy (Ec) the effective electron lifetime (τn), and the effective electron diffusion coefficient (Dn) in dye-sensitized solar cells (DSCs) was studied quantitatively. The separation between Ec and the redox Fermi level, EF,redox, was found to decrease as the charge/radius ratio of the cations increased. Ec in the Mg2+ electrolyte was found to be 170 meV lower than that in the Na+ electrolyte and 400 meV lower than that in the TBA+ electrolyte. Comparison of Dn and τn in the different electrolytes was carried out by using the trapped electron concentration as a measure of the energy difference between Ec and the quasi-Fermi level, nEF, under different illumination levels. Plots of Dn as a function of the trapped electron density, nt, were found to be relatively insensitive to the electrolyte cation, indicating that the density and energetic distribution of electron traps in TiO2 are similar in all of the electrolytes studied. By contrast, plots of τn versus nt for the different cations showed that the rate of electron back reaction is more than an order of magnitude faster in the TBA+ electrolyte compared with the Na+ and Li+ electrolytes. The electron diffusion lengths in the different electrolytes followed the sequence of Na+ > Li+ > Mg2+ > TBA+. The trends observed in the AM 1.5 current–voltage characteristics of the DSCs are rationalized on the basis of the conduction band shifts and changes in electron lifetime.

Assessing the Impact of Sensor Accuracy and Sensor Choice on Air Traffic Conflict Risk Estimation using Risk-Ratio Concepts

One of the primary desired capabilities of any future air traffic separation management system is the ability to provide early conflict detection and resolution effectively and efficiently. In this paper, we consider the risk of conflict as a primary measurement to be used for early conflict detection. This paper focuses on developing a novel approach to assess the impact of different measurement uncertainty models on the estimated risk of conflict. The measurement uncertainty model can be used to represent different sensor accuracy and sensor choices. Our study demonstrates the value of modelling measurement uncertainty in the conflict risk estimation problem and presents techniques providing a means of assessing sensor requirements to achieve desired conflict detection performance.

Normative and critical criteria for iliotibial band and iliopsoas muscle flexibility

Context: The Ober and Thomas tests are subjective and involve a "negative" or "positive" assessment, making them difficult to apply within the paradigm of evidence-based medicine. No authors have combined the subjective clinical assessment with an objective measurement for these special tests. Objective: To compare the subjective assessment of iliotibial band and iliopsoas flexibility with the objective measurement of a digital inclinometer, to establish normative values, and to provide an evidence-based critical criterion for determining tissue tightness. Design: Cross-sectional study. Setting: Clinical research laboratory. Patients or Other Participants: Three hundred recreational athletes (125 men, 175 women; 250 in injured group, 50 in control group). Main Outcome Measure(s): Iliotibial band and iliopsoas muscle flexibility were determined subjectively using the modified Ober and Thomas tests, respectively. Using a digital inclinometer, we objectively measured limb position. lnterrater reliability for the subjective assessment was compared between 2 clinicians for a random sample of 100 injured participants, who were classified subjectively as either negative or positive for iliotibial band and iliopsoas tightness. Percentage of agreement indicated interrater reliability for the subjective assessment. Results: For iliotibial band flexibility, the average inclinometer angle was -24.59 degrees +/- 7.27 degrees. A total of 432 limbs were subjectively assessed as negative (-27.13 degrees +/- 5.53 degrees) and 168 as positive (-16.29 degrees +/- 6.87 degrees). For iliopsoas flexibility, the average inclinometer angle was -10.60 degrees +/- 9.61 degrees. A total of 392 limbs were subjectively assessed as negative (-15.51 degrees +/- 5.82 degrees) and 208 as positive (0.34 degrees +/- 7.00 degrees). The critical criteria for iliotibial band and iliopsoas flexibility were determined to be -23.16 degrees and -9.69 degrees, respectively. Between-clinicians agreement was very good, ranging from 95.0% to 97.6% for the Thomas and Ober tests, respectively. Conclusions: Subjective assessments and instrumented measurements were combined to establish normative values and critical criterions for tissue flexibility for the modified Ober and Thomas tests.

Classifier selection using sequential error ratio criterion for multi-instance and multi-sample fusion

Classifier selection is a problem encountered by multi-biometric systems that aim to improve performance through fusion of decisions. A particular decision fusion architecture that combines multiple instances (n classifiers) and multiple samples (m attempts at each classifier) has been proposed in previous work to achieve controlled trade-off between false alarms and false rejects. Although analysis on text-dependent speaker verification has demonstrated better performance for fusion of decisions with favourable dependence compared to statistically independent decisions, the performance is not always optimal. Given a pool of instances, best performance with this architecture is obtained for certain combination of instances. Heuristic rules and diversity measures have been commonly used for classifier selection but it is shown that optimal performance is achieved for the `best combination performance' rule. As the search complexity for this rule increases exponentially with the addition of classifiers, a measure - the sequential error ratio (SER) - is proposed in this work that is specifically adapted to the characteristics of sequential fusion architecture. The proposed measure can be used to select a classifier that is most likely to produce a correct decision at each stage. Error rates for fusion of text-dependent HMM based speaker models using SER are compared with other classifier selection methodologies. SER is shown to achieve near optimal performance for sequential fusion of multiple instances with or without the use of multiple samples. The methodology applies to multiple speech utterances for telephone or internet based access control and to other systems such as multiple finger print and multiple handwriting sample based identity verification systems.

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.

Hybrid antibacterial fabrics with extremely high aspect ratio Ag/AgTCNQ nanowires

This study reports the synthesis of extremely high aspect ratios (>3000) organic semiconductor nanowires of Ag–tetracyanoquinodimethane (AgTCNQ) on the surface of a flexible Ag fabric for the first time. These one-dimensional (1D) hybrid Ag/AgTCNQ nanostructures are attained by a facile, solution-based spontaneous reaction involving immersion of Ag fabrics in an acetonitrile solution of TCNQ. Further, it is discovered that these AgTCNQ nanowires show outstanding antibacterial performance against both Gram negative and Gram positive bacteria, which outperforms that of pristine Ag. The outcomes of this study also reflect upon a fundamentally important aspect that the antimicrobial performance of Ag-based nanomaterials may not necessarily be solely due to the amount of Ag+ ions leached from these nanomaterials, but that the nanomaterial itself may also play a direct role in the antimicrobial action. Notably, the applications of metal-organic semiconducting charge transfer complexes of metal-7,7,8,8-tetracyanoquinodimethane (TCNQ) have been predominantly restricted to electronic applications, except from our recent reports on their (photo)catalytic potential and the current case on antimicrobial prospects. This report on growth of these metal-TCNQ complexes on a fabric not only widens the window of these interesting materials for new biological applications, it also opens the possibilities for developing large-area flexible electronic devices by growing a range of metal-organic semiconducting materials directly on a fabric surface.

The relationship between kurtosis- and envelope-based indexes for the diagnostic of rolling element bearings

The coupling of kurtosis based-indexes and envelope analysis represents one of the most successful and widespread procedures for the diagnostics of incipient faults on rolling element bearings. Kurtosis-based indexes are often used to select the proper demodulation band for the application of envelope-based techniques. Kurtosis itself, in slightly different formulations, is applied for the prognostic and condition monitoring of rolling element bearings, as a standalone tool for a fast indication of the development of faults. This paper shows for the first time the strong analytical connection which holds for these two families of indexes. In particular, analytical identities are shown for the squared envelope spectrum (SES) and the kurtosis of the corresponding band-pass filtered analytic signal. In particular, it is demonstrated how the sum of the peaks in the SES corresponds to the raw 4th order moment. The analytical results show as well a link with an another signal processing technique: the cepstrum pre-whitening, recently used in bearing diagnostics. The analytical results are the basis for the discussion on an optimal indicator for the choice of the demodulation band, the ratio of cyclic content (RCC), which endows the kurtosis with selectivity in the cyclic frequency domain and whose performance is compared with more traditional kurtosis-based indicators such as the protrugram. A benchmark, performed on numerical simulations and experimental data coming from two different test-rigs, proves the superior effectiveness of such an indicator. Finally a short introduction to the potential offered by the newly proposed index in the field of prognostics is given in an additional experimental example. In particular the RCC is tested on experimental data collected on an endurance bearing test-rig, showing its ability to follow the development of the damage with a single numerical index.

A school by any other name...is still a rock band?

How is your academic institution structured? If you work within a university, then no doubt you are familiar with the use of faculties or perhaps colleges. What about departments or schools? Whatever names or structures are employed, how would you describe the working relationship between academics and professional staff members? As a research scientist and academic over the last twenty years, my appointments have almost always been made through academic departments or schools. In each case, the academic unit has been led by a senior academic manager, such as a chair or head, supported by a dedicated team of professional staff. More recently, however, I have had the opportunity of leading an academic discipline and the experience has led me to reflect more broadly about leadership styles and academic structures within the Australian higher education sector. The written record of this reflection was published last year in the Australian Universities Review (Harkin and Healy, 2013), but I’m pleased to be able to provide a brief synopsis here for the readership of Insights.

Comparison of functionals for metal hexaboride band structure calculations

Density functional calculations of the electronic band structure for superconducting and semi-conducting metal hexaborides are compared using a consistent suite of assumptions and with emphasis on the physical implications of computed models. Spin polarization enhances mathematical accuracy of the functional approximations and adds significant physical meaning to model interpretation. For YB6 and LaB6, differences in alpha and beta projections occur near the Fermi energy. These differences are pronounced for superconducting hexaborides but do not occur for other metal hexaborides.

Ananyi (Going) by Tjupi Band

Research background: Ananyi (Going) is an intercultural music project with lyrics sung in Luritja and English, undertaken in collaboration with the Tjupi Band and producer Jeffrey McLaughlin. The project contributes to cultural maintenance for Australian First Nations peoples, and is informed by prior work in this area by scholars including Peter Dunbar-Hall, Chris Gibson and Karl Neuenfeldt. These existing studies have discussed the complexities of intercultural collaboration, and the types of cultural politics that are involved when Indigenous and non-Indigenous musicians and scholars work together on projects of cultural significance. Critical race theory has also informed the creative work, as a means of interpreting the implicit and explicit discourses of race that arise through intercultural creative practice. The project asked the research question, how can collaborative music making contribute to intercultural understanding and the maintenance of Australian First Nations languages and cultures? Research contribution: The project has identified that recorded popular music is important in the maintenance of Luritja language and culture, and that intercultural collaboration in the areas of digital sound production and distribution can assist with cultural maintenance in both local and national contexts. Research significance: The compact disc was released on the CAAMA Music label, and supported through competitive grants from the Australian Government’s Contemporary Music Touring Grant and the Arnhem Land Progress Association (ALPA). The research context of the work is detailed in Brydie-Leigh Bartleet and Gavin Carfoot 2013. "Desert harmony: Stories of collaboration between Indigenous musicians and university students." International Education Journal: Comparative Perspectives 12 (1): 180-196.

Ambiguity Acceptance Testing : A Comparison of the Ratio Test and Difference Test

Integer ambiguity resolution is an indispensable procedure for all high precision GNSS applications. The correctness of the estimated integer ambiguities is the key to achieving highly reliable positioning, but the solution cannot be validated with classical hypothesis testing methods. The integer aperture estimation theory unifies all existing ambiguity validation tests and provides a new prospective to review existing methods, which enables us to have a better understanding on the ambiguity validation problem. This contribution analyses two simple but efficient ambiguity validation test methods, ratio test and difference test, from three aspects: acceptance region, probability basis and numerical results. The major contribution of this paper can be summarized as: (1) The ratio test acceptance region is overlap of ellipsoids while the difference test acceptance region is overlap of half-spaces. (2) The probability basis of these two popular tests is firstly analyzed. The difference test is an approximation to optimal integer aperture, while the ratio test follows an exponential relationship in probability. (3) The limitations of the two tests are firstly identified. The two tests may under-evaluate the failure risk if the model is not strong enough or the float ambiguities fall in particular region. (4) Extensive numerical results are used to compare the performance of these two tests. The simulation results show the ratio test outperforms the difference test in some models while difference test performs better in other models. Particularly in the medium baseline kinematic model, the difference tests outperforms the ratio test, the superiority is independent on frequency number, observation noise, satellite geometry, while it depends on success rate and failure rate tolerance. Smaller failure rate leads to larger performance discrepancy.

Vibrational spectroscopic characterization of the sulphate–halide mineral sulphohalite – implications for evaporites

The mineral sulphohalite – Na6(SO4)2FCl is a rare sodium halogen sulphate and occurs associated with evaporitic deposits. Sulphohalite formation is important in saline evaporites and in pipe scales. Sulphohalite is an anhydrous sulphate–halide with an apparent variable anion ratio of formula Na6(SO4)2FCl. Such a formula with oxyanions lends itself to vibrational spectroscopy. The Raman band at 1003 cm−1 is assigned to the (SO4)2− ν1 symmetric stretching mode. Shoulders to this band are found at 997 and 1010 cm−1. The low intensity Raman bands at 1128, 1120 and even 1132 cm−1 are attributed to the (SO4)2− ν3 antisymmetric stretching vibrations. Two symmetric sulphate stretching modes are observed indicating at least at the molecular level the non-equivalence of the sulphate ions in the sulphohalite structure. The Raman bands at 635 and 624 cm−1 are assigned to the ν4 SO42− bending modes. The ν2 (SO4)2− bending modes are observed at 460 and 494 cm−1. The observation of multiple bands supports the concept of a reduction in symmetry of the sulphate anion from Td to C3v or even C2v. No evidence of bands attributable to the halide ions was found.

Self-organized vertically aligned single-crystal silicon nanostructures with controlled shape and aspect ratio by reactive plasma etching

The formation of vertically aligned single-crystalline silicon nanostructures via "self-organized" maskless etching in Ar+ H 2 plasmas is studied. The shape and aspect ratio can be effectively controlled by the reactive plasma composition. In the optimum parameter space, single-crystalline pyramid-like nanostructures are produced; otherwise, nanocones and nanodots are formed. This generic nanostructure formation approach does not involve any external material deposition. It is based on a concurrent sputtering, etching, hydrogen termination, and atom/radical redeposition and can be applied to other nanomaterials.

Thermodynamical and plasma-driven kinetic growth of high-aspect-ratio nanostructures : effect of hydrogen termination

The results of studies on the growth of high-aspect nanostructures in low-temperature non-equilibrium plasmas of reactive gas mixtures with or without hydrogen are presented. The results suggest that the hydrogen in the reactive plasma strongly affects the length of the nanostructures. This phenomenon is explained in terms of selective hydrogen passivation of the lateral and top surfaces of the surface-supported nanostructures. The theoretical model describes the effect of the atomic hydrogen passivation on the nanostructure shape and predicts the critical hydrogen coverage of the lateral surfaces necessary to achieve the nanostructure growth with the pre-determined shape. Our results demonstrate that the use of a strongly non-equilibrium plasma is very effective in significantly improving the shape control of quasi-one-dimensional single-crystalline nanostructures.

Multi-scale hybrid numerical simulation of the growth of high-aspect-ratio nanostructures

Recently, a variety high-aspect-ratio nanostructures have been grown and profiled for various applications ranging from field emission transistors to gene/drug delivery devices. However, fabricating and processing arrays of these structures and determining how changing certain physical parameters affects the final outcome is quite challenging. We have developed several modules that can be used to simulate the processes of various physical vapour deposition systems from precursor interaction in the gas phase to gas-surface interactions and surface processes. In this paper, multi-scale hybrid numerical simulations are used to study how low-temperature non-equilibrium plasmas can be employed in the processing of high-aspect-ratio structures such that the resulting nanostructures have properties suitable for their eventual device application. We show that whilst using plasma techniques is beneficial in many nanofabrication processes, it is especially useful in making dense arrays of high-aspect-ratio nanostructures.