Environmental sustainability of urban road transport : an integrated analysis for life cycle emission impact

Despite of significant contributions of urban road transport to global economy and society, it is one of the largest sources of local and global emission impact. In order to address the environmental concerns of urban road transport it is imperative to achieve a holistic understanding of contributory factors causing emissions which requires a complete look onto its whole life cycle. Previous studies were mainly based on segmental views which mostly studied environmental impacts of individual transport modes and very few considered impacts other than operational phase. This study develops an integrated life cycle inventory model for urban road transport emissions from a holistic modal perspective. Singapore case was used to demonstrate the model. Results show that total life cycle greenhouse gas emission from Singapore’s road transport sector is 7.8 million tons per year. The total amount of criteria air pollutants are also estimated in this study.

Electropolishing of polycrystalline YBa2Cu3O7-δ to meet the need for sharp needle geometry

An electropolishing method has been developed for preparing sharp needles from polycrystalline YBa2Cu3O7-δ by modifying a recipe for TEM specimen preparation. The method is characterized by a polishing temperature of below 0°C, a non-acidic electrolyt and an even removal of the constituent phases. An approach was employed of combining I-V measurements for polishing process and microscopical observation of surface morphology in finding optimum polishing conditions. TEM evidenced that no preferential attack appeared to grain boundaries. X-ray diffractometry and electron diffraction implied that no change in oxygen content occurred during electropolishing. The sharpness of the tip was examined by field-ion microscopy.

Improved catalyst, particularly for emission control

A catalyst comprising a catalytic material supported on a support, characterized in that the support comprises particles predominantly having a max. particle size of less than 1000 nm and an aspect ratio of greater than, and the. catalytic material is mainly present in the form of discrete islands of catalytic material supported on the support, with a substantial proportion of the islands of catalytic material being sep. and isolated from other islands of catalytic material. The islands of catalytic material are sep. and isolated from other islands of catalytic material such that diffusion and growth of the islands of catalytic material at elevated temp. is minimized or avoided. The disclosure and examples pertain to emission control catalysts. [on SciFinder(R)]

Investigation of mediated oxidation of ascorbic acid by ferrocenemethanol using large-amplitude fourier transformed ac voltammetry under quasi-reversible electron-transfer conditions at an indium tin oxide electrode

The ability of the technique of large-amplitude Fourier transformed (FT) ac voltammetry to facilitate the quantitative evaluation of electrode processes involving electron transfer and catalytically coupled chemical reactions has been evaluated. Predictions derived on the basis of detailed simulations imply that the rate of electron transfer is crucial, as confirmed by studies on the ferrocenemethanol (FcMeOH)-mediated electrocatalytic oxidation of ascorbic acid. Thus, at glassy carbon, gold, and boron-doped diamond electrodes, the introduction of the coupled electrocatalytic reaction, while producing significantly enhanced dc currents, does not affect the ac harmonics. This outcome is as expected if the FcMeOH (0/+) process remains fully reversible in the presence of ascorbic acid. In contrast, the ac harmonic components available from FT-ac voltammetry are predicted to be highly sensitive to the homogeneous kinetics when an electrocatalytic reaction is coupled to a quasi-reversible electron-transfer process. The required quasi-reversible scenario is available at an indium tin oxide electrode. Consequently, reversible potential, heterogeneous charge-transfer rate constant, and charge-transfer coefficient values of 0.19 V vs Ag/AgCl, 0.006 cm s (-1) and 0.55, respectively, along with a second-order homogeneous chemical rate constant of 2500 M (-1) s (-1) for the rate-determining step in the catalytic reaction were determined by comparison of simulated responses and experimental voltammograms derived from the dc and first to fourth ac harmonic components generated at an indium tin oxide electrode. The theoretical concepts derived for large-amplitude FT ac voltammetry are believed to be applicable to a wide range of important solution-based mediated electrocatalytic reactions.

Voltammetric monitoring of gold nanoparticle formation facilitated by glycyl-L-tyrosine : relation to electronic spectra and transmission electron microscopy images

Voltammetric techniques have been introduced to monitor the formation of gold nanoparticles produced via the reaction of the amino acid glycyl-L-tyrosine with Au(III) (bromoaurate) in 0.05 M KOH conditions. The alkaline conditions facilitate amino acid binding to Au(III), inhibit the rate of reduction to Au(0), and provide an excellent supporting electrolyte for voltammetric studies. Data obtained revealed that a range of time-dependent gold solution species are involved in gold nanoparticle formation and that the order in which reagents are mixed is critical to the outcome. Concomitantly with voltammetric measurements, the properties of gold nanoparticles formed are probed by examination of electronic spectra in order to understand how the solution environment present during nanoparticle growth affects the final distribution of the nanoparticles. Images obtained by the ex situ transmission electron microscopy (TEM) technique enable the physical properties of the nanoparticles isolated in the solid state to be assessed. Use of this combination of in situ and ex situ techniques provides a versatile framework for elucidating the details of nanoparticle formation.

A combined scanning electron micrograph and electrochemical study of the effect of chemical interaction on the cyclability of lithium electrodes in an ionic liquid electrolyte

The effect of storage time on the cyclability of lithium electrodes in an ionic liquid electrolyte, namely 0.5 m LiBF4 in N-methyl-N-propyl pyrrolidinium bis(fluorosulfonyl)imide, [C3mpyr+][FSI–], was investigated. A chemical interaction was observed which is time dependent and results in a morphology change of the Li surface due to build up of passivation products over a 12-day period. The formation of this layer significantly impacts on the Li electrode resistance before cycling and the charging/discharging process for symmetrical Li|0.5 m LiBF4 in [C3mpyr+][FSI–]|Li coin cells. Indeed it was found that introducing a rest period between cycling, and thereby allowing the chemical interaction between the Li electrode and electrolyte to take place, also impacted on the charging/discharging process. For all Li surface treatments the electrode resistance decreased after cycling and was due to significant structural rearrangement of the surface layer. These results suggest that careful electrode pretreatment in a real battery system will be required before operation.

Reusable surface confined semi-conducting metal-TCNQ and metal-TCNQF4 catalysts for electron transfer reactions

The synthesis of organic semiconducting materials based on silver and copper-TCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) and their fluorinated analogues has received a significant amount of attention due to their potential use in organic electronic applications. However, there is a scarcity in the identification of different applications for which these interesting materials may be suitable candidates. In this work, we address this by investigating the catalytic properties of such materials for the electron transfer reaction between ferricyanide and thiosulphate ions in aqueous solution, which to date has been almost solely limited to metallic nanomaterials. Significantly it was found that all the materials investigated, namely CuTCNQ, AgTCNQ, CuTCNQF4 and AgTCNQF4, were catalytically active and, interestingly, the fluorinated analogues were superior. AgTCNQF4 demonstrated the highest activity and was tested for its stability and re-usability for up to 50 cycles without degradation in performance. The catalytic reaction was monitored via UV-vis spectroscopy and open circuit potential versus time measurements, as well as an investigation of the transport properties of the films via electrochemical impedance spectroscopy. It is suggested that morphology and bulk conductivity are not the limiting factors, but rather the balance between the accumulated surface charge from electron injection via thiosulphate ions on the catalyst surface and transfer to the ferricyanide ions which controls the reaction rate. The facile fabrication of re-usable surface confined organic materials that are catalytically active may have important uses for many more electron transfer reactions.

Lateral charge propagation effects during the galvanic replacement of electrodeposited MTCNQ (M= Cu, Ag) microstructures with gold and its influence on catalysed electron transfer reactions

The galvanic replacement of isolated electrodeposited semiconducting CuTCNQ microstructures on a glassy carbon (GC) substrate with gold is investigated. It is found that anisotropic metal nanoparticles are formed which are not solely confined to the redox active sites on the semiconducting materials but are also observed on the GC substrate which occurs via a lateral charge propagation mechanism. We also demonstrate that this galvanic replacement approach can be used for the formation of isolated AgTCNQ/Au microwire composites which occurs via an analogous mechanism. The resultant MTCNQ/Au (M = Cu, Ag) composite materials are characterized by Raman, spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and investigated for their catalytic properties for the reduction of ferricyanide ions with thiosulphate ions in aqueous solution. Significantly it is demonstrated that gold loading, nanoparticle shape and in particular the MTCNQ–Au interface are important factors that influence the reaction rate. It is shown that there is a synergistic effect at the CuTCNQ/Au composite when compared to AgTCNQ/Au at similar gold loadings.

Method for making a material, particularly for emission control catalyst

A method for forming a material comprising a metal oxide supported on a support particle comprising the steps of: (a) providing a precursor mixt. comprising a soln. contg. one or more metal cations and (i) a surfactant; or (ii) a hydrophilic polymer; said precursor mixt. further including support particles; and (b) treating the precursor mixt. from (a) above by heating to remove the surfactant or hydrophilic polymer and form metal oxide having nanosized grains, wherein at least some of the metal oxide formed in step (b) is deposited on or supported by the support particles and the metal oxide has an oxide matrix that includes metal atoms derived solely from sources other than the support particles. The disclosure and examples pertain to emission control catalysts. [on SciFinder(R)]

The detection of incipient faults in small multi-cylinder diesel engines using multiple acoustic emission sensors

This thesis investigates condition monitoring (CM) of diesel engines using acoustic emission (AE) techniques. The AE signals recorded from a small size diesel engine are mixtures of multiple sources from multiple cylinders. Thus, it is difficult to interpret the information conveyed in the signals for CM purposes. This thesis develops a series of practical signal processing techniques to overcome this problem. Various experimental studies conducted to assess the CM capabilities of AE analysis for diesel engines. A series of modified signal processing techniques were proposed. These techniques showed promising results of capability for CM of multiple cylinders diesel engine using multiple AE sensors.

Glycerol carbonate as green solvent for pretreatment of sugarcane bagasse

Background Pretreatment of lignocellulosic biomass is a prerequisite for effective saccharification to produce fermentable sugars. We have previously reported an effective low temperature (90 °C) process at atmospheric pressure for pretreatment of sugarcane bagasse with acidified mixtures of ethylene carbonate (EC) and ethylene glycol (EG). In this study, “greener” solvent systems based on acidified mixtures of glycerol carbonate (GC) and glycerol were used to treat sugarcane bagasse and the roles of each solvent in deconstructing biomass were determined. Results Pretreatment of sugarcane bagasse at 90 °C for only 30 min with acidified GC produced a solid residue having a glucan digestibility of 90% and a glucose yield of 80%, which were significantly higher than a glucan digestibility of 16% and a glucose yield of 15% obtained for bagasse pretreated with acidified EC. Biomass compositional analyses showed that GC pretreatment removed more lignin than EC pretreatment (84% vs 54%). Scanning electron microscopy (SEM) showed that fluffy and size-reduced fibres were produced from GC pretreatment whereas EC pretreatment produced compact particles of reduced size. The maximal glucan digestibility and glucose yield of GC/glycerol systems were about 7% lower than those of EC/ethylene glycol (EG) systems. Replacing up to 50 wt% of GC with glycerol did not negatively affect glucan digestibility and glucose yield. The results from pretreatment of microcrystalline cellulose (MCC) showed that (1) pretreatment with acidified alkylene glycol (AG) alone increased enzymatic digestibility compared to pretreatments with acidified alkylene carbonate (AC) alone and acidified mixtures of AC and AG, (2) pretreatment with acidified GC alone slightly increased, but with acidified EC alone significantly decreased, enzymatic digestibility compared to untreated MCC, and (3) there was a good positive linear correlation of enzymatic digestibility of treated and untreated MCC samples with congo red (CR) adsorption capacity. Conclusions Acidified GC alone was a more effective solvent for pretreatment of sugarcane bagasse than acidified EC alone. The higher glucose yield obtained with GC-pretreated bagasse is possibly due to the presence of one hydroxyl group in the GC molecular structure, resulting in more significant biomass delignification and defibrillation, though both solvent pretreatments reduced bagasse particles to a similar extent. The maximum glucan digestibility of GC/glycerol systems was less than that of EC/EG systems, which is likely attributed to glycerol being less effective than EG in biomass delignification and defibrillation. Acidified AC/AG solvent systems were more effective for pretreatment of lignin-containing biomass than MCC.

Scanning electron microscopic study of microstructure of Gala apples during hot air drying

Microscopic changes occur in plant food materials during drying significantly influence the macroscopic properties and quality factors of the dried food materials. It is very critical to study microstructure to understand the underlying cellular mechanisms to improve performance of the food drying techniques. However, there is very limited research conducted on such microstructural changes of plant food material during drying. In this work, Gala apple parenchyma tissue samples were studied using a scanning electron microscope for gradual microstructural changes as affected by temperature, time and moisture content during hot air drying at two drying temperatures: 57 ℃ and 70 ℃. For fresh samples, the average cellular parameter values were; cell area: 20000 μm2, ferret diameter: 160 μm, perimeter: 600 μm, roundness: 0.76, elongation: 1.45 and compactness: 0.84. During drying, a higher degree of cell shrinkage was observed with cell wall warping and increase in intercellular space. However, no significant cell wall breakage was observed. The overall reduction of cell area, ferret diameter and perimeter were about 60%, 40% and 30%. The cell roundness and elongation showed overall increments of about 5% and the compactness remained unchanged. Throughout the drying cycle, cellular deformations were mainly influenced by the moisture content. During the initial and intermediate stages of drying, cellular deformations were also positively influenced by the drying temperature and the effect was reversed at the final stages of drying which provides clues for case hardening of the material.

Synthesis, photophysical and electrochemical properties of aza-boron-diquinomethene complexes

A series of aza-boron-diquinomethene (aza-BODIQU) complexes with different aryl-substituents (B1–B6) were synthesized and characterized. Their photophysical properties were investigated systematically via spectroscopic and theoretical methods. All complexes exhibit strong 1π–π* absorption bands and intense fluorescent emission bands in the visible spectral region at room temperature. The fluorescence spectra in solution show the mirror image features of the S0→S1 absorption bands, which can be assigned to the 1π–π*/1ICT (intramolecular charge transfer) emitting states. Except for B6, all complexes exhibit high photoluminescence quantum yields (ΦPL = 0.47–0.93). The spectroscopic studies and theoretical calculations indicate that the photophysical properties of these aza-BODIQUs can be tuned by the appended aryl-substituents, which would be useful for rational design of boron–fluorine complexes with high emission quantum yield for organic light-emitting applications.

Comparing skin biopsy with confocal microscopy : diagnostic yield of nerve fiber density

Background and aims: The assessment of intra-epidermal nerve fiber density (IENFD) in skin biopsies and corneal nerve fiber density (CNFD) using corneal confocal microscopy (CCM) provides promising techniques to detect small nerve fiber damage in patients with peripheral neuropathy. To help define the clinical utility of each of these techniques in patients with diabetic neuropathy we have assessed sensitivity and specificity of IENFD and CNFD in predicting the following: 1) diabetic polyneuropathy (DPN); 2) risk of foot ulceration (RFU); 3) initial small fiber neuropathy (iSFN); 4) severe small fiber neuropathy (sSFN)...