Comparative study of the microstructures and mechanical properties of direct laser fabricated and arc-melted AlxCoCrFeNi high entropy alloys

High entropy alloys (HEA) are a relatively new metal alloy system that have promising potential in high temperature applications. These multi-component alloys are typically produced by arc-melting, requiring several remelts to achieve chemical homogeneity. Direct laser fabrication (DLF) is a rapid prototyping technique, which produces complex components from alloy powder by selectively melting micron-sized powder in successive layers. However, studies of the fabrication of complex alloys from simple elemental powder blends are sparse. In this study, DLF was employed to fabricate bulk samples of three alloys based on the AlxCoCrFeNi HEA system, where x was 0.3, 0.6 and 0.85M fraction of Al. This produced FCC, FCC/BCC and BCC crystal structures, respectively. Corresponding alloys were also produced by arc-melting, and all microstructures were characterised and compared longitudinal and transverse to the build/solidification direction by x-ray diffraction, glow discharge optical emission spectroscopy and scanning electron microscopy (EDX and EBSD). Strong similarities were observed between the single phase FCC and BCC alloys produced by both techniques, however the FCC/BCC structures differed significantly. This has been attributed to a difference in the solidification rate and thermal gradient in the melt pool between the two different techniques. Room temperature compression testing showed very similar mechanical behaviour and properties for the two different processing routes. DLF was concluded to be a successful technique to manufacture bulk HEA[U+05F3]s.

Performance of suspended and attached growth MBR systems in treating high strength synthetic wastewater

The performance of laboratory-scale attached growth (AG) and suspended growth (SG) membrane bioreactors (MBRs) was evaluated in treating synthetic wastewater simulating high strength domestic wastewater. This study investigated the influence of sponge suspended carriers in AG-MBR system, occupying 15% reactor volume, on the removal of chemical oxygen demand (COD), total nitrogen (TN) and total phosphorus (TP), and compared it to that of SG-MBR. Results showed that the removal efficiencies of COD, TN and TP in AG-MBR were 98%, 89% and 58%, respectively as compared to 98%, 74% and 38%, respectively in SG-MBR. Improved TN removal in AG-MBR systems was primarily based on simultaneous nitrification and denitrification (SND) process. These results infer that the presence of small bio-particles having higher microbial activity and the growth of complex biomass captured within the suspended sponge carriers resulted in improved TN and TP removal in AG-MBR.

The impact of textile wet colouration on the environment in 2011

Wet textile colouration has the highest environmental impact of all textile processing steps. It consumes water, chemicals and energy and produces liquid, heat and gas waste streams. Liquid effluent streams are often quite toxic to the environment. There are a number of different dyeing processes, normally fibre type specific, and each has a different impact on the environment. This research investigated the energy, chemical and water requirements for the exhaust colouration of cotton, wool, polyester and nylon. The research investigated the liquid waste biological and chemical oxygen demand, salinity, pH and colour along with the energy required for drying after colouration. Polyester fibres had the lowest impact on the environment with lowest water and energy consumption in dyeing, good dye bath exhaustion, the lowest salinity levels in their effluent, relatively neutral pH effluent and low energy in drying. The wool and nylon had similar dye bath requirements and outputs however the nylon could be dyed at far lower liquor ratios and hence provided better energy and water use figures. The cotton and wool required high energy consumption in drying after colouration. Cotton performed poorly in all of the measured parameters.

Fouling in reverse osmosis (RO) membrane in water recovery from secondary effluent : a review

Reverse osmosis (RO) is the most preferable process for water recovery from secondary effluent (SE) because of its higher rejection of impurities with lower associated cost and higher quality of product. Fouling still is a major challenge during the water recovery due to higher contaminant loadings in SE and high rejection capability of this membrane. The presence of suspended solids, colloidal and organic matters, and high level of biological activities in SE further elevate fouling potentiality. This review was performed to identify major foulants causing hindrance in sustainable application of reverse osmosis and to present available pre-treatment options for these foulants. There are four fouling types present in RO namely; bio-fouling, inorganic/scaling, organic, and particulate fouling. Among them; bio-fouling is less understood but dominant since the pre-treatment options are not well developed. Other fouling mechanisms have been overcome by well developed pre-treatments. The major foulants for RO are dissolved and macromolecular organic substances, sparingly soluble inorganic compounds, colloidal and suspended particles, and micro-organisms. Some of these potential fouling water quality parameters (PFWQPs) are interrelated with each others such as electrical conductivity is a surrogate measure of total dissolved solids with established stable relationship. Most of these PFWQPs such as total suspended solids, turbidity, chemical oxygen demand can be removed by conventional pre-treatment; some such as colloidal particles and micro-organisms by modern options and even others such as endocrine disrupting compounds, pharmaceutical and personal care products are still challenging for current pre-treatments. These foulants need to be identified properly to integrate appropriate pre-treatments for minimizing fouling potentiality to increase water recovery at minimal costs.

Novel dithiolene complexes incorporating conjugated electroactive ligands

A series of new metal (M) dithiolene complexes bearing terthiophene (3, 12, M = Ni; 4, M = Pd; 5, 6, M = Au) and 2,5-bis(para-methoxyphenyl)thiophene units (14, M = Ni; 15, 16, M = Au; 17, M = Pd) have been synthesised in 38–99% yield. The electrochemical properties of the materials have been characterised by cyclic voltammetry and UV-vis spectroelectrochemistry. The nickel complexes possess low oxidation potentials (−0.12 to −0.25 V vs Ag/AgCl) due to the electron-rich dithiolene centres and all complexes display ligand-based redox activity. The terthiophene derivatives have been polymerised by electrochemical oxidation to give stable films with, in the case of poly(3), broad absorption characteristics. Charge transfer materials have been isolated from 14 and 16 with conductivities in the range 9 × 10⁻⁶ to 7 × 10⁻⁸ S cm⁻¹.

Comparison of the performance of ceramic microfiltration and ultrafiltration membranes in the reclamation and reuse of secondary wastewater

Advanced treatment of secondary wastewater generally has been achieved using polymeric microfiltration and ultrafiltration membranes. Newly developed ceramic membranes offer distinctive advantages over the currently employed membranes and were recently introduced for the purpose. This paper presents results of a pilot study designed to investigate the application of ceramic microfiltration (MF) and ultrafiltration (UF) membranes in the recovery of water from secondary wastewater. Synthetic wastewater similar to the quality of secondary treated wastewater was fed to ceramic MF and UF system in a cross-flow mode. The filtration experiments revealed that the flux recovery through tubular ceramic MF membrane was more sensitive to the variation in TMP compared with the tubular ceramic UF membrane over the range of TMP studied. The resistance in series model was used for the evaluation of the resistance to the permeate flux. The results revealed that for ceramic UF membrane, the contribution to the total resistance of fouling was higher than the inherent of the clean membrane resistance. However, both the clean membrane resistance and the fouling resistance contribute equally in the case of MF membrane. Various wastewater indices were measured to evaluate the effectiveness of the filtration treatment. The ceramic UF membrane consistently met water quality in the permeate in terms of colour, turbidity, chemical oxygen demand and absorbance, suggesting that the permeate water could be made to be reused or recycled for suitable purposes. However, MF membrane appeared to be incompetent with respect to the removal of colour. The unified membrane fouling index (UMFI) was used to measure the fouling potential of both the membranes. The result showed that for UF membrane, the value of UMFI is one order of magnitude higher than MF membrane. The overall results suggest that there were significant differences in the performance of both the ceramic UF and MF membranes that are likely to impact on the operation and maintenance of the membrane system.

Enhancement of aerobic granulation by zero-valent iron in sequencing batch airlift reactor

This study elucidates the enhancement of aerobic granulation by zero-valent iron (ZVI). A reactor augmented with ZVI had a start-up time of aerobic granulation (43 days) that was notably less than that for a reactor without augmentation (64 days). The former reactor also had better removal efficiencies for chemical oxygen demand and ammonium. Moreover, the mature granules augmented with ZVI had better physical characteristics and produced more extracellular polymeric substances (especially of protein). Three-dimensional-excitation emission matrix fluorescence showed that ZVI enhanced organic material diversity. Additionally, ZVI enhanced the diversity of the microbial community. Fe(2+) dissolution from ZVI helped reduce the start-up time of aerobic granulation and increased the extracellular polymeric substance content. Conclusively, the use of ZVI effectively enhanced aerobic granulation.

Characterization of the extracellular polymeric substances and microbial community of aerobic granulation sludge exposed to cefalexin

This study characterizes the extracellular polymeric substances and bacterial community composition of aerobic granules exposed to cefalexin (CLX). The presence of CLX potentially decreases granular stabilities, resulting in a lowered granule diameter. Chemical oxygen demand and NH4+-N removal efficiencies were slightly decreased and the denitrification process was inhibited with CLX addition. Extracellular polymeric substance contents were significantly increased in aerobic granules exposed to CLX. The shifts of fluorescence intensities and peak locations in 3D-EEM fluorescence spectra indicated changes of EPS components. High-throughput sequencing analysis showed aerobic granules with CLX addition in synthetic wastewater had superior diversity of microbial species, and this was the reason that the level and components of EPS changed. The species richness for bacteria was increased from 341 to 352, which was revealed by Chao1. The Shannon index of diversity rose slightly from 3.59 to 3.73 with CLX addition. The abundance of Proteobacteria significantly decreased, while the abundance of Bacteroidetes and Chloroflexi underwent a highly significant increase in aerobic granules exposed to CLX.

Enhanced photocatalytic activities of TiO2-SiO2 nanohybrids immobilized on cement-based materials for dye degradation

Using cement-based material as a matrix for photocatalytic hybrids is an important development for the large-scale application of photocatalytic technologies. In this work, photocatalytic activity of nanosized hybrids of TiO2/SiO2 (nano-TiO2-SiO2) for degradation of some organic dyes on cementitious materials was highlighted. For this purpose, an optimal inorganic sol-gel precursor was firstly applied to prepare the composites of nano-TiO2-SiO2 which was characterized by XRD, SEM and UV-Vis. Then, a thin layer was successfully coated on white Portland cement (WPC) blocks using a dipping process in a nano-TiO2-SiO2 solution. The effect of nano-TiO2-SiO2-coated WPC blocks on photocatalytic decomposition of three dyes, including Malachite green oxalate (MG), Methylene blue (MB) and Methyl orange (MO) were studied under UV irradiation and monitored by chemical oxygen demand tests. The results showed an increase in photocatalytic effects which depends on the structure and pH of the applied cement.

Confocal laser scanning microscopy elucidation of the micromorphology of the leaf cuticle and analysis of its chemical composition

Electron microscopy techniques such as transmission electron microscopy (TEM) and scanning electron microscopy (SEM) have been invaluable tools for the study of the micromorphology of plant cuticles. However, for electron microscopy, the preparation techniques required may invariably introduce artefacts in cuticle preservation. Further, there are a limited number of methods available for quantifying the image data obtained through electron microscopy. Therefore, in this study, optical microscopy techniques were coupled with staining procedures and, along with SEM were used to qualitatively and quantitatively assess the ultrastructure of plant leaf cuticles. Leaf cryosections of Triticum aestivum (wheat), Zea mays (maize), and Lupinus angustifolius (lupin) were stained with either fat-soluble azo stain Sudan IV or fluorescent, diarylmethane Auramine O and were observed under confocal laser scanning microscope (CLSM). For all the plant species tested, the cuticle on the leaf surfaces could be clearly resolved in many cases into cuticular proper (CP), external cuticular layer (ECL), and internal cuticular layer (ICL). Novel image data analysis procedures for quantifying the epicuticular wax micromorphology were developed, and epicuticular waxes of L. angustifolius were described here for the first time. Together, application of a multifaceted approach involving the use of a range of techniques to study the plant cuticle has led to a better understanding of cuticular structure and provides new insights into leaf surface architecture.

The reduction of oxygen on iron(II) oxide/poly(3,4-ethylenedioxythiophene) composite thin film electrodes

© 2014 Elsevier Ltd. All rights reserved. Conducting polymers (CPs) are currently being investigated for use in many applications owing to their abilities to catalyze a wide range of electrochemical reactions and act as an effective electrode support for various inorganic and organic electrocatalyst materials. Here, we have found that the deposition of poly(3,4-ethylenedioxythiophene) (PEDOT) through the use of an established base-inhibited chemical vapor-phase polymerization (VPP) procedure using an iron(III) tosylate oxidant results in the co-deposition of electrocatalytic iron(II) oxide species within the film. The presence of these species accounts for the 2-electron reduction of hydrogen peroxide that occurs on these electrodes during the series 4-electron oxygen reduction reaction. Furthermore, this realization leads to the possibility of fabricating thin film inorganic/CP composites of various compositions through careful choice of oxidant in a facile, one-step process. A combination of in situ Raman (487.77 nm laser) and in situ UV-Vis spectroscopy was used to probe the oxidation state of PEDOT in the thin film composite electrodes while reducing oxygen in alkaline conditions. These measurements show that the 2-electron electroreduction of hydrogen peroxide (or HO2 -) occurs only on the iron(II) oxide species in a reaction that is facilitated by an effective electron transfer from the delocalized electron orbitals of the PEDOT matrix. This approach could potentially be used in situ to monitor the electrocatalyst/electrode interface quality of conducting polymer-supported electrocatalysts.

'Laser chemistry' synthesis, physicochemical properties, and chemical processing of nanostructured carbon foams

Laser ablation of selected coordination complexes can lead to the production of metal-carbon hybrid materials, whose composition and structure can be tailored by suitably choosing the chemical composition of the irradiated targets. This 'laser chemistry' approach, initially applied by our group to the synthesis of P-containing nanostructured carbon foams (NCFs) from triphenylphosphine-based Au and Cu compounds, is broadened in this study to the production of other metal-NCFs and P-free NCFs. Thus, our results show that P-free coordination compounds and commercial organic precursors can act as efficient carbon source for the growth of NCFs. Physicochemical characterization reveals that NCFs are low-density mesoporous materials with relatively low specific surface areas and thermally stable in air up to around 600°C. Moreover, NCFs disperse well in a variety of solvents and can be successfully chemically processed to enable their handling and provide NCF-containing biocomposite fibers by a wet-chemical spinning process. These promising results may open new and interesting avenues toward the use of NCFs for technological applications.

The characterization and chemical reactivity of powdered wool

Wool powders with various particle sizes have been produced using different milling techniques. Scanning electron microscopy (SEM) showed gradual breakdown of the fibre as it was progressively converted into powder form. Chlorination enhanced the effectiveness of subsequent air-jet milling. X-ray photoelectron spectroscopy (XPS) revealed an increase in the surface concentrations of oxygen and nitrogen, and a decrease in carbon and sulphur on conversion of the fibres into powders, as the cortex became exposed on the powder surface. An increased surface concentration of cysteic acid was observed for the chlorinated powder. Rapid uptake of dye by wool powders was observed in situations where there was virtually no uptake by the original fibre. Hydrophobic dyes were more readily sorbed than were hydrophilic dyes. The chlorination treatment led to a decrease in the sorption of acid dyes. Confocal microscopy, used in conjunction with a fluorescent stain, showed that chemicals were able to penetrate wool particles, even at room temperature. The rate and extent of uptake of dye by the finer powders were comparable to that obtained with activated charcoal, even though the surface area of the charcoal was 100 times greater.

Deactivation and regeneration of oxygen reduction reactivity on double perovskite Ba2Bi0.1Sc0.2Co1.7O6−x cathode for intermediate-temperature solid oxide fuel cells

in situ high-temperature X-ray diffraction and thermal gravimetric- differential thermal analysis on room-temperature powder, as well as X-ray diffraction, Raman spectroscopy, and transmission electron microscopy on quenched powder, were applied to study crystal structure and phase transformations in Ba₂Bi_0.1Sc_0.2Co _1.7O_6-x (BBSC). Heating BBSC in air to over 800 °C produces a pure cubic phase with space group Fm3m (no. 225), and cooling down below 800 °C leads to a mixture of three noncubic phases including an unknown phase between 200 and 650 °C, a 2H hexagonal BaCoO3 with space group P63/mmc (no. 194) between 600 and 800 °C, and an intermediate phase at 800 °C. These three phases exist concurrently with the major cubic phase. The weight gain and loss between 300 and 900 °C suggest the occurrence of cobalt reduction, oxidation, and disproportion reactions with dominant reduction reaction at above 600 °C. The thermal expansion of BBSC was also examined by dilatometry. BBSC has a highly temperature-dependent thermal expansion coefficient which relates well with its structure evolution. Furthermore, the oxygen reduction reaction (ORR) of BBSC was probed by symmetrical cell and three-electrode configurations. The presence of hexagonal phase at 700 °C rarely affects the ORR performance of BBSC as evidenced by a slight increase of its area-specific resistance (ASR) value following 48 h of testing in this three-electrode configuration. This observation is in contrast to the commonly held point of view that noncubic phase deteriorates performance of perovskite compounds (especially in oxygen transport applications). Moreover, cathodic polarization treatment, for example, current discharge from BBSC (tested in three-electrode configuration), can be utilized to recover the original ORR performance. The cubic structure seems to be retained on the cathodic polarization - the normal cathode operating mode in fuel cells. Stable 72-h performance of BBSC in cathodic polarization mode further confirms that despite the presence of phase impurities, BBSC still demonstrates good performance between 500 and 700 °C, the desired intermediate operating temperature in solid oxide fuel cells.

Oxygen reduction reaction activity of La-based perovskite oxides in alkaline medium : a thin-film rotating ring-disk electrode study

In this work, LaMO₃ and LaNi_0.5M_0.5O₃ (M = Ni, Co, Fe, Mn and Cr) perovskite oxide electrocatalysts were synthesized by a combined ethylenediaminetetraacetic acid-citrate complexation technique and subsequent calcinations at 1000 °C in air. Their powder X-ray diffraction patterns demonstrate the formation of a specific crystalline structure for each composition. The catalytic property of these materials toward the oxygen reduction reaction (ORR) was studied in alkaline potassium hydroxide solution using the rotating disk and rotating ring-disk electrode techniques. Carbon is considered to be a crucial additive component because its addition into perovskite oxide leads to optimized ORR current density. For LaMO₃ (M = Ni, Co, Fe, Mn and Cr)), in terms of the ORR current densities, the performance is enhanced in the order of LaCrO₃, LaFeO₃, LaNiO₃, LaMnO₃, and LaCoO3. For LaNi_0.5M_0.5O₃, the ORR current performance is enhanced in the order of LaNi_0.5Fe_0.5O₃, LaNi_0.5Co_0.5O₃, LaNi_0.5Cr_0.5O₃, and LaNi_0.5Mn_0.5O₃. Overall, LaCoO₃ demonstrates the best performance. Most notably, substituting half of the nickel with cobalt, iron, manganese, or chromium translates the ORR to a more positive onset potential, suggesting the beneficial catalytic effect of two transition metal cations with Mn as the most promising candidate. Koutecky–Levich analysis on the ORR current densities of all compositions indicates that the four-electron pathway is favored on these oxides, which are consistent with hydroperoxide ion formation of <2%.