Nitrate reduction at Pt(1 0 0) single crystals and preferentially oriented nanoparticles in neutral media

The electroreduction of nitrate on Pt(1 0 0) electrodes in phosphate buffer neutral solution, pH 7.2, is reported. The sensitivity of the reaction to the crystallographic order of the surface is studied through the controlled introduction of defects by using stepped surfaces with (1 0 0) terraces of different length separated by monoatomic steps, either with (1 1 1) or (1 1 0) symmetry. The results of this study show that nitrate reduction occurs mainly on the well defined (1 0 0) terraces in the potential region where H adsorption starts to decrease, allowing the nitrate anion to access the surface. Adsorbed NO has been detected as a stable intermediate in this media. An oxidation process observed at 0.8 V has been identified as leading to the formation of adsorbed NO and being responsible for a secondary reduction process observed in the subsequent negative scan. Using in situ FTIRS, ammonium was found to be the main product of nitrate reduction. This species can be oxidized at high potentials resulting in adsorbed NO and nitrate (probably with nitrite as intermediate).

The Single Supervisory Mechanism: A Sound First Step in Europe’s Banking Union? Egmont European Affairs Paper, March 2013

The financial and economic crisis has hit Europe in its core. While the crisis may not have originated in the European Union, it has laid bare structural weaknesses in the EU’s policy framework. Both public finances and the banking sector have been heavily affected. For a long time, the EU failed to take into account sufficiently the perverse link that existed between the two. Negative evolutions in one field of the crisis often dragged along the other in its downward spiral. In June 2012, in the early hours of a yet another EU Summit, the leaders of the eurozone finally decided to address the link between the banking and sovereign debt crises. Faced with soaring public borrowing costs in Spain and Italy, they decided to allow for the direct European recapitalisation of banks when the Member State itself would no longer be in a position to do so. In exchange, supervision of the banking sector would be lifted to the European level by means of a Single Supervisory Mechanism. The Single Supervisory Mechanism, or SSM in the EU jargon, is a first step in the broader revision of policies towards banks in Europe. The eventual goal is the creation of a Banking Union, which is to carry out effective surveillance and – if needed – crisis management of the banking sector. The SSM is to rely on national supervisors and the ECB, with the ECB having final authority on the matter. The involvement of the latter made it clear that the SSM would be centred on the eurozone – while it is to remain open to other Member States willing to join. Due to the ongoing problems and the link between the creation of the SSM and the recapitalisation of banks, the SSM became one of the key legislative priorities of the EU. In December 2012, Member States reached an agreement on the design of the SSM. After discussions with the European Parliament (which were still ongoing at the time of writing), the process towards making the SSM operational can be initiated. The goal is to have the SSM fully up and running in the first half of 2014. The decisions that were taken in June 2012 are likely to have had a bigger impact than the eurozone’s Heads of State and Government could have realised at the time for two important reasons. On the one hand, creating the SSM necessitates a full Banking Union and therefore shared risk. On the other hand, the decisions improved the ECB’s perception of the willingness of governments to take far-reaching measures. This undoubtedly played a significant role in the creation of the Outright Monetary Transactions programme by the ECB, which has led to a substantial easing of the crisis in the short-term. 1 These short-term gains should now be matched with a stable long-term framework for bank supervision and crisis management. The agreement on the SSM should be the first step in the direction of this goal. This paper provides an analysis of the SSM and its role in the creation of a Banking Union. The paper starts with a reminder of why the EU decided to put in place the SSM (§1) and the state of play of the ongoing negotiations on the SSM (§2). Subsequently, the supervisory responsibilities of the SSM are detailed, including its scope and the division of labour between the national supervisors and the ECB (§3). The internal functioning of the SSM (§4) and its relation to the other supervisors are discussed afterwards (§5). As mentioned earlier, the SSM is part of a wider move towards a Banking Union. Therefore, this paper sheds light on the other building blocks of this ambitious project (§6). The transition towards the Banking Union is important and will prove to be a bumpy ride. Before formulating a number of conclusions, this Working Paper therefore provides an overview of the planned road ahead (§7).

The effect of the reduction of carbon content on the toughness of high chromium white irons in the as-cast state

Three high chromium white cast irons were examined in the as-cast state to determine the effect of the carbon content on the fracture toughness. The plane strain fracture toughness K-Ic and the fracture strength were measured for each alloy. X-ray mapping was used to identify the phases on the fracture surfaces. Scanning electron fractography and optical microscopy were used to determine the volume fraction of each phase on the fracture surfaces. It was found that most fracture occurred in the eutectic carbides, but that for the alloys with a reduced volume fraction of eutectic carbides, a small amount of crack propagation occurred in the austenitic dendrites. This change in crack path correlated with an increase in fracture toughness. The Ritchie-Knott-Rice model of brittle fracture was applied. It was found to sensibly predict the critical length for fracture for each alloy. Deep etching was employed to examine the distribution of eutectic carbides. It was found that the eutectic carbides formed a continuous network in each case. (C) 2004 Kluwer Academic Publishers.

Precipitation of chromium containing phases in aluminide coated nickel-base superalloy single crystals

The precipitation of chromium-containing phases, in both the B2 type β-phase coating matrix (nominally NiAl) and the substrate of high-activity-pack-aluminized single crystals of a nickel-base superalloy, is considered in this paper. An ‘edge-on’ transmission electron microscopy (TEM) technique is employed to examine the precipitation of M23X6, σ, α-Cr and other phases after coating and diffusion treatment and subsequent post-coating treatment at 850 and 950 °C. Initial precipitation is dominated by the formation of M23X6 in both the coating and substrate, however, in the case of single-crystal substrates the formation of this carbon-rich phase is not sustained. M23X6 precipitation is superceded by the formation of coherent precipitates of the α-Cr phase which effectively retains the basis but removes the superlattice of the β-matrix. Extensive precipitation of α-Cr has the effect of changing the balance of chromium to molybdenum in solution in the β-phase and further precipitation is dominated by Σ-phase intermetallics and other Cr-Mo-containing phases.

Ex situ sulphate reduction and methane oxidation rates of sediment at the rim of a vesicomyd clam colony in the Japan Deep Sea Trench (dive 956)

Sediment samples were collected from the rim of a large vesicomyid clam colony in the Japan Deep Sea Trench. Immediately after sample recovery onboard, the sediment core was sub-sampled for ex situ rate measurements. Sulfate reduction and anaerobic oxidation of methane were measured ex situ by the whole core injection method with three replicate measurements for each method. We incubated the samples at in situ temperature (1.5°C) for 48 hours with either 14C-methane (dissolved in water, 2.5 kBq) or carrier-free 35S-sulfate (dissolved in water, 50 kBq). Sediment was fixed in 25 ml sodium hydroxide (NaOH) solution (2.5%, w/v) or 20 ml ZnAc solution (20%, w/v) for AOM or SR, respectively. Turnover rates were measured as previously described (Kallmeyer et al., 2004; Treude et al., 2003).

Biogeochemical investigation of sediments at the Hakon Mosby Mud Volcano (Barents Sea)

We have investigated if in a cold seep methane or sulfide is used for chemosynthetic primary production and if significant amounts of the sulfide produced by anaerobic oxidation of methane are oxidized geochemically and hence are not available for chemosynthetic production. Geochemically controlled redox reactions and biological turnover were compared in different habitats of the Håkon Mosby Mud Volcano. The center of the mud volcano is characterized by the highest fluid flow, and most primary production by the microbial community depends on oxidation of methane. The small amount of sulfide produced is oxidized geochemically with oxygen or is precipitated with dissolved iron. In the medium flow peripheral Beggiatoa habitat sulfide is largely oxidized biologically. The oxygen and nitrate supply is high enough that Beggiatoa can oxidize the sulfide completely, and chemical sulfide oxidation or precipitation is not important. An internally stored nitrate reservoir with average concentrations of 110 mmol L-1 enables the Beggiatoa to oxidize sulfide anaerobically. The pH profile indicates sequential sulfide oxidation with elemental sulfur as intermediate. Gray thiotrophic mats associated with perturbed sediments showed a high heterogeneity in sulfate turnover and high sulfide fluxes, balanced by the opposing oxygen and nitrate fluxes so that biological oxidation dominates over geochemical sulfide removal processes. The three habitats indicate substantial small-scale variability in carbon fixation pathways either through direct biological use of methane or through indirect carbon fixation of methane-derived carbon dioxide by chemolithotrophic sulfide oxidation.

A Study of the Microwave Carbothermic Reduction of Chromite Ore

Microwave reduction testing using activated charcoal as a reducing agent was performed on a sample of Black Thor chromite ore from the Ring of Fire deposit in Northern Ontario. First, a thermodynamic model was constructed for the system. Activity coefficients for several species were found in the literature. The model predicted chromium grades of 61.60% and recoveries of 93.43% for a 15% carbon addition. Next, reduction testing on the chromite ore was performed. Tests were performed at increasing power levels and reduction times. Testing atmospheres used were air, argon, and vacuum. The reduced product had maximum grades of 72.89% and recoveries of 80.37%. These maximum values were obtained in the same test where an argon atmosphere was used, with a carbon addition of 15%, optimal power level of 1200 W (actual 1171 W), and a time of 400 seconds. During this test, 17.53% of the initial mass was lost as gas, a carbon grade of 1.95% was found for the sintered core product. Additional work is recommended to try and purify the sintered core product as well as reduce more of the initial sample. Changing reagent schemes or a two step reduction / separation process could be implemented.

Hydrohalite in cold sea ice: Laboratory observations of single crystals, surface accumulations, and migration rates under a temperature gradient, with application to “Snowball Earth"

When NaCl precipitates out of a saturated solution, it forms anhydrous crystals of halite at temperatures above +0.11?C, but at temperatures below this threshold it instead precipitates as the dihydrate ‘‘hydrohalite,’’ NaCl * 2H2O. When sea ice is cooled, hydrohalite begins to precipitate within brine inclusions at about -23C. In this work, hydrohalite crystals are examined in laboratory experiments: their formation, their shape, and their response to warming and desiccation. Sublimation of a sea ice surface at low temperature leaves a lag deposit of hydrohalite, which has the character of a fine powder. The precipitation of hydrohalite in brine inclusions raises the albedo of sea ice, and the subsequent formation of a surface accumulation further raises the albedo. Although these processes have limited climatic importance on the modern Earth, they would have been important in determining the surface types present in regions of net sublimation on the tropical ocean in the cold phase of a Snowball Earth event. However, brine inclusions in sea ice migrate downward to warmer ice, so whether salt can accumulate on the surface depends on the relative rates of sublimation and migration. The migration rates are measured in a laboratory experiment at temperatures from -2C to -32C; the migration appears to be too slow to prevent formation of a salt crust on Snowball Earth.

Experimental study of the mechanical properties of light gauge cold-formed steels at elevated temperatures

In recent times, light gauge cold-formed steel sections have been used extensively as primary load bearing structural members in many applications in the building industry. Fire safety design of structures using such sections has therefore become more important. Deterioration of mechanical properties of yield stress and elasticity modulus is considered the most important factor affecting the performance of steel structures in fires. Hence there is a need to fully understand the mechanical properties of light gauge cold-formed steels at elevated temperatures. A research project based on experimental studies was therefore undertaken to investigate the deterioration of mechanical properties of light gauge cold-formed steels. Tensile coupon tests were undertaken to determine the mechanical properties of these steels made of both low and high strength steels and thicknesses of 0.60, 0.80 and 0.95 mm at temperatures ranging from 20 to 800ºC. Test results showed that the currently available reduction factors are unsafe to use in the fire safety design of cold-formed steel structures. Therefore new predictive equations were developed for the mechanical properties of yield strength and elasticity modulus at elevated temperatures. This paper presents the details of the experimental study, and the results including the developed equations. It also includes details of a stress-strain model for light gauge cold-formed steels at elevated temperatures.

Statistical analysis and reduction of multiple access interference in MC-CDMA systems

Multicarrier code division multiple access (MC-CDMA) is a very promising candidate for the multiple access scheme in fourth generation wireless communi- cation systems. During asynchronous transmission, multiple access interference (MAI) is a major challenge for MC-CDMA systems and significantly affects their performance. The main objectives of this thesis are to analyze the MAI in asyn- chronous MC-CDMA, and to develop robust techniques to reduce the MAI effect. Focus is first on the statistical analysis of MAI in asynchronous MC-CDMA. A new statistical model of MAI is developed. In the new model, the derivation of MAI can be applied to different distributions of timing offset, and the MAI power is modelled as a Gamma distributed random variable. By applying the new statistical model of MAI, a new computer simulation model is proposed. This model is based on the modelling of a multiuser system as a single user system followed by an additive noise component representing the MAI, which enables the new simulation model to significantly reduce the computation load during computer simulations. MAI reduction using slow frequency hopping (SFH) technique is the topic of the second part of the thesis. Two subsystems are considered. The first sub- system involves subcarrier frequency hopping as a group, which is referred to as GSFH/MC-CDMA. In the second subsystem, the condition of group hopping is dropped, resulting in a more general system, namely individual subcarrier frequency hopping MC-CDMA (ISFH/MC-CDMA). This research found that with the introduction of SFH, both of GSFH/MC-CDMA and ISFH/MC-CDMA sys- tems generate less MAI power than the basic MC-CDMA system during asyn- chronous transmission. Because of this, both SFH systems are shown to outper- form MC-CDMA in terms of BER. This improvement, however, is at the expense of spectral widening. In the third part of this thesis, base station polarization diversity, as another MAI reduction technique, is introduced to asynchronous MC-CDMA. The com- bined system is referred to as Pol/MC-CDMA. In this part a new optimum com- bining technique namely maximal signal-to-MAI ratio combining (MSMAIRC) is proposed to combine the signals in two base station antennas. With the applica- tion of MSMAIRC and in the absents of additive white Gaussian noise (AWGN), the resulting signal-to-MAI ratio (SMAIR) is not only maximized but also in- dependent of cross polarization discrimination (XPD) and antenna angle. In the case when AWGN is present, the performance of MSMAIRC is still affected by the XPD and antenna angle, but to a much lesser degree than the traditional maximal ratio combining (MRC). Furthermore, this research found that the BER performance for Pol/MC-CDMA can be further improved by changing the angle between the two receiving antennas. Hence the optimum antenna angles for both MSMAIRC and MRC are derived and their effects on the BER performance are compared. With the derived optimum antenna angle, the Pol/MC-CDMA system is able to obtain the lowest BER for a given XPD.

Food insecurity in Brisbane : the single mother’s struggle

Using a feminist reflexive approach this paper reports on interviews with single mother’s in the Brisbane area about their experiences with food shopping and household food security. Preliminary findings suggest that most experience significant stress around the amount of money they have available for food. As the price of food and other costs of living increase, the only budget item that is flexible – groceries - is squeezed tighter. All women expressed a reluctance to ask for help from strangers at agencies instead relying on the support of family and friends to keep them food secure. Sometimes family and friends had no spare resources to help or were not aware of the extent their friend or relative might be struggling. The increased risks of poverty and food insecurity mean many go without as feeding the children takes precedence. The quality of their diets is variable with many reporting on aiming for quantity rather than being concerned with nutritional balance. Exhaustion and stress from being over-committed doing three roles, mother, father and housekeeper was self-identified as a key factor leading to mental health conditions such as depression, burnout and break down. Female single parent households are vulnerable to reducing welfare benefits as children grow or child support changes. Current policy forces single parents out to work but many can only manage part-time work for lower wages and are barely able to cope with this extra burden often resenting the reduction in benefits it brings. Public perceptions, derision and the notions of choice surrounding single parenting leave the cohort divided and silent for fear of reprisals. In my investigation issues arise about welfare policy that keep benefits low and workplace patriarchal power that can contribute to systemic poverty and the widening of the gender gap in poverty. So far analysis suggests a better support system around community food security including some hands on home help services, nutritional information, cooking classes, community gardening and other social capital building activities are needed for these women in order to avoid long-term health problems and help them better care for the next generation.

Eccentric calf muscle exercise produces a greater acute reduction in Achilles tendon thickness than concentric exercise

Objective: To investigate the acute effects of isolated eccentric and concentric calf muscle exercise on Achilles tendon sagittal thickness. ---------- Design: Within-subject, counterbalanced, mixed design. ---------- Setting: Institutional. ---------- Participants: 11 healthy, recreationally active male adults. ---------- Interventions: Participants performed an exercise protocol, which involved isolated eccentric loading of the Achilles tendon of a single limb and isolated concentric loading of the contralateral, both with the addition of 20% bodyweight. ---------- Main outcome measurements: Sagittal sonograms were acquired prior to, immediately following and 3, 6, 12 and 24 h after exercise. Tendon thickness was measured 2 cm proximal to the superior aspect of the calcaneus. ---------- Results: Both loading conditions resulted in an immediate decrease in normalised Achilles tendon thickness. Eccentric loading induced a significantly greater decrease than concentric loading despite a similar impulse (−0.21 vs −0.05, p<0.05). Post-exercise, eccentrically loaded tendons recovered exponentially, with a recovery time constant of 2.5 h. The same exponential function did not adequately model changes in tendon thickness resulting from concentric loading. Even so, recovery pathways subsequent to the 3 h time point were comparable. Regardless of the exercise protocol, full tendon thickness recovery was not observed until 24 h. ---------- Conclusions: Eccentric loading invokes a greater reduction in Achilles tendon thickness immediately after exercise but appears to recover fully in a similar time frame to concentric loading.

Structural behaviour and design of cold-formed steel beams at elevated temperatures

Cold-formed steel members are extensively used in the building construction industry, especially in residential, commercial and industrial buildings. In recent times, fire safety has become important in structural design due to increased fire damage to properties and loss of lives. However, past research into the fire performance of cold-formed steel members has been limited, and was confined to compression members. Therefore a research project was undertaken to investigate the structural behaviour of compact cold-formed steel lipped channel beams subject to inelastic local buckling and yielding, and lateral-torsional buckling effects under simulated fire conditions and associated section and member moment capacities. In the first phase of this research, an experimental study based on tensile coupon tests was undertaken to obtain the mechanical properties of elastic modulus and yield strength and the stress-strain relationship of cold-formed steels at uniform ambient and elevated temperatures up to 700oC. The mechanical properties deteriorated with increasing temperature and are likely to reduce the strength of cold-formed beams under fire conditions. Predictive equations were developed for yield strength and elastic modulus reduction factors while a modification was proposed for the stressstrain model at elevated temperatures. These results were used in the numerical modelling phases investigating the section and member moment capacities. The second phase of this research involved the development and validation of two finite element models to simulate the behaviour of compact cold-formed steel lipped channel beams subject to local buckling and yielding, and lateral-torsional buckling effects. Both models were first validated for elastic buckling. Lateral-torsional buckling tests of compact lipped channel beams were conducted at ambient temperature in order to validate the finite element model in predicting the non-linear ultimate strength behaviour. The results from this experimental study did not agree well with those from the developed experimental finite element model due to some unavoidable problems with testing. However, it highlighted the importance of magnitude and direction of initial geometric imperfection as well as the failure direction, and thus led to further enhancement of the finite element model. The finite element model for lateral-torsional buckling was then validated using the available experimental and numerical ultimate moment capacity results from past research. The third phase based on the validated finite element models included detailed parametric studies of section and member moment capacities of compact lipped channel beams at ambient temperature, and provided the basis for similar studies at elevated temperatures. The results showed the existence of inelastic reserve capacity for compact cold-formed steel beams at ambient temperature. However, full plastic capacity was not achieved by the mono-symmetric cold-formed steel beams. Suitable recommendations were made in relation to the accuracy and suitability of current design rules for section moment capacity. Comparison of member capacity results from finite element analyses with current design rules showed that they do not give accurate predictions of lateral-torsional buckling capacities at ambient temperature and hence new design rules were developed. The fourth phase of this research investigated the section and member moment capacities of compact lipped channel beams at uniform elevated temperatures based on detailed parametric studies using the validated finite element models. The results showed the existence of inelastic reserve capacity at elevated temperatures. Suitable recommendations were made in relation to the accuracy and suitability of current design rules for section moment capacity in fire design codes, ambient temperature design codes as well as those proposed by other researchers. The results showed that lateral-torsional buckling capacities are dependent on the ratio of yield strength and elasticity modulus reduction factors and the level of non-linearity in the stress-strain curves at elevated temperatures in addition to the temperature. Current design rules do not include the effects of non-linear stress-strain relationship and therefore their predictions were found to be inaccurate. Therefore a new design rule that uses a nonlinearity factor, which is defined as the ratio of the limit of proportionality to the yield stress at a given temperature, was developed for cold-formed steel beams subject to lateral-torsional buckling at elevated temperatures. This thesis presents the details and results of the experimental and numerical studies conducted in this research including a comparison of results with predictions using available design rules. It also presents the recommendations made regarding the accuracy of current design rules as well as the new developed design rules for coldformed steel beams both at ambient and elevated temperatures.