Influence of test methodology and probe geometry on nanoscale fatigue mechanisms of diamond-like carbon thin film

The aim of this paper is to investigate the mechanism of nanoscale fatigue using nano-impact and multiple-loading cycle nanoindentation tests, and compare it to previously reported findings of nanoscale fatigue using integrated stiffness and depth sensing approach. Two different film loading mechanism, loading history and indenter shapes are compared to comprehend the influence of test methodology on the nanoscale fatigue failure mechanisms of DLC film. An amorphous 100 nm thick DLC film was deposited on a 500 μm silicon substrate using sputtering of graphite target in pure argon atmosphere. Nano-impact and multiple-load cycle indentations were performed in the load range of 100 μN to 1000 μN and 0.1 mN to 100 mN, respectively. Both test types were conducted using conical and Berkovich indenters. Results indicate that for the case of conical indenter, the combination of nano-impact and multiple-loading cycle nanoindentation tests provide information on the life and failure mechanism of DLC film, which is comparable to the previously reported findings using the integrated stiffness and depth sensing approach. However, the comparison of results is sensitive to the applied load, loading mechanism, test-type and probe geometry. The loading mechanism and load history is therefore critical which also leads to two different definitions of film failure. The choice of exact test methodology, load and probe geometry should therefore be dictated by the in-service tribological conditions, and where necessary both test methodologies can be used to provide better insights of failure mechanism. Molecular dynamics (MD) simulations of the elastic response of nanoindentation is reported, which indicates that the elastic modulus of the film measured using MD simulation was higher than that experimentally measured. This difference is attributed to the factors related to the presence of material defects, crystal structure, residual stress, indenter geometry and loading/unloading rate differences between the MD and experimental results.

X-ray scattering from warm dense iron

We have carried out X-ray scattering experiments on iron foil samples that have been compressed and heated using laser-driven shocks created with the VULCAN laser system at the Rutherford-Appleton Laboratory. This is the highest Z element studied in such experiments so far and the first time scattering from warm dense iron has been reported. Because of the importance of iron in telluric planets, the work is relevant to studies of warm dense matter in planetary interiors. We report scattering results as well as shock breakout results that, in conjunction with hydrodynamic simulations, suggest the target has been compressed to a molten state at several 100 GPa pressure. Initial comparison with modelling suggests more work is needed to understand the structure factor of warm dense iron. (C) 2013 Published by Elsevier B.V.

Comparative study on transport properties for LiFAP and LiPF6 in alkyl-carbonates as electrolytes through conductivity, viscosity and NMR self-diffusion measurements

We present in this work a comparative study on density and transport properties, such as the conductivity (sigma), viscosity (eta) and self-diffusion coefficients (D), for electrolytes based on the lithium hexafluorophosphate, LiPF6; or on the lithium tris(pentafluoroethane)-trifluorophosphate, LiFAP dissolved in a binary mixture of ethylene carbonate (EC) and dimethylcarbonate (DMC) (50:50 wt%). For each electrolyte, the temperature dependence on transport properties over a temperature range from 10 to 80 degrees C and 20 to 70 degrees C for viscosity and conductivity, respectively, exhibits a non-Arrhenius behavior. However, this dependence is correctly correlated by using the Vogel-Tamman-Fulcher (VTF) type fitting equation. In each case, the best-fit parameters, such as the pseudo activation energy and ideal glass transition temperature were then extracted. The self-diffusion coefficients (D) of the Li+ cation and PF6- or FAP(-) anions species, in each studied electrolyte, were then independently determined by observing Li-3, F-19 and P-31 nuclei with the pulsed-gradient spin-echo (PGSE) NMR technique over the same temperature range from 20 to 80 degrees C. Results show that even if the diffusion of the lithium cation is quite similar in both electrolytes, the anions diffusion differs notably. In the case of the LiPF6-based electrolyte, for example at T approximate to 75 degrees C (high temperature), the self-diffusion coefficients of Li+ cations in solution (D (Li+)approximate to 5 x 10(-19) m(2) s(-1)) is 1.6 times smaller than that of PF6- anions (D (PF6-) = 8.5 x 10(-19) m(2) s(-1)), whereas in the case of the LiFAP-based electrolyte, FAP(-) anions diffuse at same rate as the Li+ cations (D (FAP(-)) = 5 x 10(-1) m(2) s(-1)). Based on these experimental results, the transport mobility of ions were then investigated through Stokes-Einstein and Nernst-Einstein equations to determine the transport number of lithium t(Li)(+), effective radius of solvated Li+ and of PF6- and FAP(-) anions, and the degree of dissociation of these lithium salts in the selected EC/DMC (50:50 wt%) mixture over a the temperature range from 20 to 80 degrees C. This study demonstrates the conflicting nature of the requirements and the advantage of the well-balanced properties as ionic mobility and dissociation constant of the selected electrolytes. (C) 2013 Elsevier Ltd. All rights reserved.

Influence of a Single Grain Boundary on Domain Wall Motion in Ferroelectrics

Epitaxial tetragonal 425 and 611 nm thick Pb(ZrTi)O (PZT) films are deposited by pulsed laser deposition on SrRuO-coated (100) SrTiO 24° tilt angle bicrystal substrates to create a single PZT grain boundary with a well-defined orientation. On either side of the bicrystal boundary, the films show square hysteresis loops and have dielectric permittivities of 456 and 576, with loss tangents of 0.010 and 0.015, respectively. Using piezoresponse force microscopy (PFM), a decrease in the nonlinear piezoelectric response is observed in the vicinity (720-820 nm) of the grain boundary. This region represents the width over which the extrinsic contributions to the piezoelectric response (e.g., those associated with the domain density/configuration and/or the domain wall mobility) are influenced by the presence of the grain boundary. Transmission electron microscope (TEM) images collected near and far from the grain boundary indicate a strong preference for (101)/(1-01) type domain walls at the grain boundary, whereas (011)/(01-1) and (101)/(1-01) are observed away from this region. It is proposed that the elastic strain field at the grain boundary interacts with the ferro-electric/elastic domain structure, stabilizing (101)/(1-01) rather than (011)/(01-1) type domain walls, which inhibits domain wall motion under applied field and decreases non-linearity. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Causal knowledge and the development of inductive reasoning

We explored the development of sensitivity to causal relations in children’s inductive reasoning. Children (5-, 8-, and 12-year-olds) and adults were given trials in which they decided whether a property known to be possessed by members of one category was also possessed by members of (a) a taxonomically related category or (b) a causally related category. The direction of the causal link was either predictive (prey → predator) or diagnostic (predator → prey), and the property that participants reasoned about established either a taxonomic or causal context. There was a causal asymmetry effect across all age groups, with more causal choices when the causal link was predictive than when it was diagnostic. Furthermore, context-sensitive causal reasoning showed a curvilinear development, with causal choices being most frequent for 8-year-olds regardless of context. Causal inductions decreased thereafter because 12-year-olds and adults made more taxonomic choices when reasoning in the taxonomic context. These findings suggest that simple causal relations may often be the default knowledge structure in young children’s inductive reasoning, that sensitivity to causal direction is present early on, and that children over-generalize their causal knowledge when reasoning.

Clinical Characteristics of Reticular Pseudodrusen in the Fellow Eye of Patients with Unilateral Neovascular Age-Related Macular Degeneration

Purpose: To describe associations between reticular pseudodrusen, individual characteristics, and retinal function.

Design: Cohort study.

Participants: We recruited 105 patients (age range, 52–93 years) who had advanced neovascular age-related macular degeneration (AMD) in only 1 eye from 3 clinical centers in Europe.

Methods: Minimum follow-up was 12 months. The eye selected for study was the fellow eye without advanced disease. Clinical measures of vision were distance visual acuity, near visual acuity, and results of the Smith-Kettlewell low-luminance acuity test (SKILL). Fundus imaging included color photography, red-free imaging, blue autofluorescence imaging, fluorescein angiography, indocyanine green angiography, and optical coherence tomography using standardized protocols. These were used to detect progression to neovascular AMD in the study eye during follow-up. All imaging outputs were graded for the presence or absence of reticular pseudodrusen (RPD) using a multimodal approach. Choroidal thickness was measured at the foveal center and at 2 other equidistant locations from the fovea (1500 μm) nasally and temporally. Metrics on retinal thickness and volume were obtained from the manufacturer-supplied automated segmentation readouts.

Main Outcome Measures: Presence of RPD, distance visual acuity, near visual acuity, SKILL score, choroidal thickness, retinal thickness, and retinal volume.

Results: Reticular pseudodrusen was found in 43 participants (41%) on 1 or more imaging method. The SKILL score was significantly worse in those with reticular drusen (mean score ± standard deviation [SD, 38±12) versus those without (mean score ± SD, 33±9) (P = 0.034). Parafoveal retinal thickness, parafoveal retinal volume, and all of the choroidal thickness parameters measured were significantly lower in those with reticular drusen than in those without. The presence of RPD was associated with development of neovascular AMD when corrected for age and sex (odds ratio, 5.5; 95% confidence interval, 1.1–28.8; P = 0.042). All participants in whom geographic atrophy developed during follow-up had visible RPD at baseline.

Conclusions: Significant differences in retinal and choroidal anatomic features, visual function, and risk factor profile exist in unilateral neovascular AMD patients with RPD compared with those without; therefore, such patients should be monitored carefully because of the risk of developing bilateral disease.

Climate variability drives anchovies and sardines into the North and Baltic Seas

European anchovy (Engraulis encrasicolus) and sardine (Sardina pilchardus) are southern, warm water species that prefer temperatures warmer than those found in boreal waters. After about 40 years of absence, they were again observed in the 1990s in increasing quantities in the North Sea and the Baltic Sea. Whereas global warming probably played a role in these northward migrations, the North Atlantic Oscillation (NAO), the Atlantic Multidecadal Oscillation (AMO) and the contraction of the subpolar gyre were important influences. Sardine re-invaded the North Sea around 1990, probably mainly as a response to warmer temperatures associated with the strengthening of the NAO in the late 1980s. However, increasing numbers of anchovy eggs, larvae, juveniles and adults have been recorded only since the mid-1990s, when, particularly, summer temperatures started to increase. This is probably a result of the complex dynamics of ocean–atmosphere coupling involving changes in North Atlantic current structures, such as the contraction of the subpolar gyre, and dynamics of AMO. Apparently, climate variability drives anchovies and sardines into the North and Baltic Seas. Here, we elucidate the climatic background of the return of anchovies and sardines to the northern European shelf seas and the changes in the North Sea fish community in the mid-1990s in response to climate variability.

Exploring lay views on physical activity and their implications for public health policy. A case study from East Belfast

It is now recognised that inactive lifestyles underpin much of the disease burden evident in the richer nations of the world. Indeed, the WHO has identified physical inactivity as a 'global public health problem' and has established minimum physical activity (PA) targets for people at different stages of the life-course. Yet, according to WHO, just under 1/3 of working age adults across the globe meet those targets and it is not at all clear how the disjunction between the recommendations of policy makers and the behaviour of ordinary people might be surmounted. Using an opportunity to examine the impact of an urban regeneration project on community residents in East Belfast (Northern Ireland) this paper examines the views of some 113 people on how to increase rates of PA in an area of multiple deprivation. The results of the analysis suggest that lay people rarely consider PA as a discrete issue, or one that centres on individuals and their motivation, but rather as one component in a complex web of concerns, processes and events that include such things as the actions of neighbours and relatives, material and political environments, vandalism, violence, and the weather. We explore and unravel the nature of those concerns using novel methods of content analysis that generate 'issue webs'. Particular attention is paid to the ways in which lay people conceptualize 'activity' and to the manner in which they point to ways of encouraging activity that are rooted in everyday life rather than in the corpocentric, agent-centred and often sport dominated strategies favoured by local policy makers. Our results support those who argue that interventions to increase rates of PA need to move beyond behavioural approaches that focus on individuals and consider the social, political and material contexts in which 'activity' occurs.

Integrating Multiple Point Statistics with Aerial Geophysical Data to assist Groundwater Flow Models

The process of accounting for heterogeneity has made significant advances in statistical research, primarily in the framework of stochastic analysis and the development of multiple-point statistics (MPS). Among MPS techniques, the direct sampling (DS) method is tested to determine its ability to delineate heterogeneity from aerial magnetics data in a regional sandstone aquifer intruded by low-permeability volcanic dykes in Northern Ireland, UK. The use of two two-dimensional bivariate training images aids in creating spatial probability distributions of heterogeneities of hydrogeological interest, despite relatively ‘noisy’ magnetics data (i.e. including hydrogeologically irrelevant urban noise and regional geologic effects). These distributions are incorporated into a hierarchy system where previously published density function and upscaling methods are applied to derive regional distributions of equivalent hydraulic conductivity tensor K. Several K models, as determined by several stochastic realisations of MPS dyke locations, are computed within groundwater flow models and evaluated by comparing modelled heads with field observations. Results show a significant improvement in model calibration when compared to a simplistic homogeneous and isotropic aquifer model that does not account for the dyke occurrence evidenced by airborne magnetic data. The best model is obtained when normal and reverse polarity dykes are computed separately within MPS simulations and when a probability threshold of 0.7 is applied. The presented stochastic approach also provides improvement when compared to a previously published deterministic anisotropic model based on the unprocessed (i.e. noisy) airborne magnetics. This demonstrates the potential of coupling MPS to airborne geophysical data for regional groundwater modelling.

When are total concentrations not total? Factors affecting geochemical analytical techniques for measuring element concentrations in soil

Inductively coupled plasma (ICP) following aqua regia digestion and X-ray fluorescence (XRF) are both geochemical techniques used to determine ‘total’ concentrations of elements in soil. The aim of this study is to compare these techniques, identify elements for which inconsistencies occur and investigate why they arise. A study area (∼14,000 km2) with a variety of total concentration controls and a large geochemical dataset (n = 7950) was selected. Principal component analysis determined underlying variance in a dataset composed of both geogenic and anthropogenic elements. Where inconsistencies between the techniques were identified, further numerical and spatial analysis was completed. The techniques are more consistent for elements of geogenic sources and lead, whereas other elements of anthropogenic sources show less consistency within rural samples. XRF is affected by sample matrix, while the form of element affects ICP concentrations. Depending on their use in environmental studies, different outcomes would be expected from the techniques employed, suggesting the choice of analytical technique for geochemical analyses may be more critical than realised.

Integrated Earth Resistivity Tomography (ERT) and Multilevel Gas Sampling: A Tool to Map Geogenic and Anthropogenic Methane Accumulation on Brownfield Sites

Soil gas emissions of methane and carbon dioxide on brownfield sites are usually attributed to anthropogenic activities; however geogenic sources of soil gas are often not considered during site investigation and risk management strategies. This paper presents a field study at a redeveloped brownfield site on a flood plain to identify accumulations of methane biogas trapped in underlying sediments. The investigation is based on a multidisciplinary approach using direct multi-level sampling measurements and Earth resistivity tomography . Resistivity imaging was applied to evaluate the feasibility of identifying the size and spatial continuity of soil gas accumulations in anthropogenic and naturally occurring deposits. As a result, biogas accumulations are described within both anthropogenic deposits and pristine organic sediments. This result is important to identify the correct approaches to identify and manage risks associated with soil gas emissions on brownfield and pristine sites. The organic-rich sediments in Quaternary fluvial environments of São Paulo Basin in particular the Tietê River, biogas reservoirs can be generated and trapped beneath geogenic and anthropogenic layers, potentially requiring the management of brownfield developments across this region.

The solution structure of 1:2 phenol/N-methylpyridinium bis{(trifluoromethyl)sulfonyl}imide liquid mixtures

Neutron diffraction has been used to investigate the liquid structure of a 1:2 solution of phenol in the ionic liquid N-methylpyridinium bis{(trifluoromethyl)sulfonyl}imide at 60 ◦C, using the empirical potential structure refinement (EPSR) process to model the data obtained from the SANDALS diffractometer at ISIS. Addition of phenol results in suppression of the melting point of the pyridinium salt and formation of a room temperature solution with aromatic phenol–cation and phenol-OH to anion hydrogen-bonding interactions.

Young children's food brand knowledge. Early development and associations with television viewing and parent's diet

Brand knowledge is a prerequisite of children's requests and choices for branded foods. We explored the development of young children's brand knowledge of foods highly advertised on television - both healthy and less healthy. Participants were 172 children aged 3-5 years in diverse socio-economic settings, from two jurisdictions on the island of Ireland with different regulatory environments. Results indicated that food brand knowledge (i) did not differ across jurisdictions; (ii) increased significantly between 3 and 4 years; and (iii) children had significantly greater knowledge of unhealthy food brands, compared with similarly advertised healthy brands. In addition, (iv) children's healthy food brand knowledge was not related to their television viewing, their mother's education, or parent or child eating. However, (v) unhealthy brand knowledge was significantly related to all these factors, although only parent eating and children's age were independent predictors. Findings indicate that effects of food marketing for unhealthy foods take place through routes other than television advertising alone, and are present before pre-schoolers develop the concept of healthy eating. Implications are that marketing restrictions of unhealthy foods should extend beyond television advertising; and that family-focused obesity prevention programmes should begin before children are 3 years of age.

Experimental design and batch experiments for optimization of Cr(VI) removal from aqueous solutions by hydrous cerium oxide nanoparticles

Hydrous cerium oxide (HCO) was synthesized by intercalation of solutions of cerium(III) nitrate and sodium hydroxide and evaluated as an adsorbent for the removal of hexavalent chromium from aqueous solutions. Simple batch experiments and a 2⁵ factorial experimental design were employed to screen the variables affecting Cr(VI) removal efficiency. The effects of the process variables; solution pH, initial Cr(VI) concentration, temperature, adsorbent dose and ionic strength were examined. Using the experimental results, a linear mathematical model representing the influence of the different variables and their interactions was obtained. Analysis of variance (ANOVA) demonstrated that Cr(VI) adsorption significantly increases with decreased solution pH, initial concentration and amount of adsorbent used (dose), but slightly decreased with an increase in temperature and ionic strength. The optimization study indicates 99% as the maximum removal at pH 2, 20 °C, 1.923 mM of metal concentration and a sorbent dose of 4 g/dm³. At these optimal conditions, Langmuir, Freundlich and Redlich–Peterson isotherm models were obtained. The maximum adsorption capacity of Cr(VI) adsorbed by HCO was 0.828 mmol/g, calculated by the Langmuir isotherm model. Desorption of chromium indicated that the HCO adsorbent can be regenerated using NaOH solution 0.1 M (up to 85%). The adsorption interactions between the surface sites of HCO and the Cr(VI) ions were found to be a combined effect of both anion exchange and surface complexation with the formation of an inner-sphere complex.

Automated versus non-automated weaning for reducing the duration of mechanical ventilation for critically ill adults and children: a cochrane systematic review and meta-analysis

IntroductionAutomated weaning systems may improve adaptation of mechanical support for a patient’s ventilatory needs and facilitate systematic and early recognition of their ability to breathe spontaneously and the potential for discontinuation of ventilation. Our objective was to compare mechanical ventilator weaning duration for critically ill adults and children when managed with automated systems versus non-automated strategies. Secondary objectives were to determine differences in duration of ventilation, intensive care unit (ICU) and hospital length of stay (LOS), mortality, and adverse events.MethodsElectronic databases were searched to 30 September 2013 without language restrictions. We also searched conference proceedings; trial registration websites; and article reference lists. Two authors independently extracted data and assessed risk of bias. We combined data using random-effects modelling.ResultsWe identified 21 eligible trials totalling 1,676 participants. Pooled data from 16 trials indicated that automated systems reduced the geometric mean weaning duration by 30% (95% confidence interval (CI) 13% to 45%), with substantial heterogeneity (I2 = 87%, P <0.00001). Reduced weaning duration was found with mixed or medical ICU populations (42%, 95% CI 10% to 63%) and Smartcare/PS™ (28%, 95% CI 7% to 49%) but not with surgical populations or using other systems. Automated systems reduced ventilation duration with no heterogeneity (10%, 95% CI 3% to 16%) and ICU LOS (8%, 95% CI 0% to 15%). There was no strong evidence of effect on mortality, hospital LOS, reintubation, self-extubation and non-invasive ventilation following extubation. Automated systems reduced prolonged mechanical ventilation and tracheostomy. Overall quality of evidence was high.ConclusionsAutomated systems may reduce weaning and ventilation duration and ICU stay. Due to substantial trial heterogeneity an adequately powered, high quality, multi-centre randomized controlled trial is needed.