Surface Modification of Transition Metal Dichalcogenide Nanosheets for Intrinsically Self-Healing Hydrogels with Enhanced Mechanical Properties.

Nanocomposites with enhanced mechanical properties and efficient self-healing characteristics can change how the artificially engineered materials' life cycle is perceived. Improved adhesion of nanomaterials with the host matrix can drastically improve the structural properties and confer the material with repeatable bonding/debonding capabilities. In this work, exfoliated 2H-WS2 nanosheets are modified using an organic thiol to impart hydrogen bonding sites on the otherwise inert nanosheets by surface functionalization. These modified nanosheets are incorporated within the PVA hydrogel matrix and analyzed for their contribution to the composite's intrinsic self-healing and mechanical strength. The resulting hydrogel forms a highly flexible macrostructure with an impressive enhancement in mechanical properties and a very high autonomous healing efficiency of 89.92%. Interesting changes in the surface properties after functionalization show that such modification is highly suitable for water-based polymeric systems. Probing into the healing mechanism using advanced spectroscopic techniques reveals the formation of a stable cyclic structure on the surface of nanosheets, mainly responsible for the improved healing response. This work opens an avenue toward the development of self-healing nanocomposites where chemically inert nanoparticles participate in the healing network rather than just mechanically reinforcing the matrix by slender adhesion.

Predicting habitat suitability of filter-feeder communities in a shallow marine environment, New Zealand.

The distribution of benthic ecosystems, dominated by filter-feeding communities, is highly influenced by the seabed geomorphology. However, the spatial variation in settlement of these species is also affected by near-bottom currents and any changes in light, nutrient concentration and food quality often associated with increases of suspended sediment concentrations within the water column. Detailed predictions of the geographic distribution of filter-feeder species and a deeper understanding of the physical processes influencing their distribution patterns is key for effective management and conservation. To date, predictive distribution modelling has been derived essentially from geomorphological parameters, mainly using spatially limited observations. In this study, seabed mapping, oceanographic modelling, hydrographic records and biological observations are integrated to provide high-resolution prediction of filter-feeder habitat distribution within Queen Charlotte Sound/Totaranui and Tory Channel/Kura Te Au, South Island of New Zealand. The aim is to evaluate potential suitable habitat areas for filter-feeders to inform where habitat restoration management should focus efforts to recover communities such as the horse mussel (Atrina zelandica) or the green-lipped mussel (Perna canaliculus), both of which have high economic impact in New Zealand. To accomplish this, Maximum Entropy (MaxEnt) predictive modelling was used to produce Habitat Suitability (HS) maps, using geomorphological parameters and seafloor classification information. Final HS maps also incorporated oceanographic and sediment dynamic information, showing that filter-feeder habitat distribution is highly influenced by the hydrodynamics and sedimentary processes apart from the seafloor geomorphology. Filter-feeder communities inhabit quiescent areas, limited by depth, slope and sediment type; and coincide with regions presenting low near-bottom currents and low turbidity levels. Additionally, the obtained results reveal the effects of the coastal settlements and major marine traffic routes, limiting the suitable habitats to areas with less human impact. This study demonstrates that a multidisciplinary approach is crucial to better predict the spatial distribution of benthic communities, which is key to improve benthic habitat restoration and recovery assessments.

Comparison between thermophysical and tribological properties of two engine lubricant additives: electrochemically exfoliated graphene and molybdenum disulfide nanoplatelets.

Recently graphene and other 2D materials were suggested as nano additives to enhance the performance of nanolubricants and reducing friction and wear-related failures in moving mechanical parts. Nevertheless, to our knowledge there are no previous studies on electrochemical exfoliated nanomaterials as lubricant additives. In this work, engine oil-based nanolubricants were developed via two-steps method using two different 2D nanomaterials: a carbon-based nano additive, graphene nanoplatelets (GNP) and a sulphide nanomaterial, molybdenum disulfide (MoS2) nanoplatelets (MSNP). The influence of these nano additives on the thermophysical properties of the nanolubricants, such as viscosity index, density and wettability, was investigated. The unique features of the electrochemical exfoliated GNP and MSNP allow the formulation of nanolubricant with unusual thermophysical properties. Both the viscosity and density of the nanolubricants decreased by increasing the nanoplatelets loading. The effect of the nano additives loading and temperature on the tribological properties of nanolubricants was investigated using two different test configurations: reciprocating ball-on-plate and rotational ball-on-three-pins. The tribological specimens were analysed by scanning electron microscopy (SEM) and 3D profiler in order to evaluate the wear. The results showed significant improvement in the antifriction and anti-wear properties, for the 2D-materials-based nanolubricants as compared with the engine oil, using different contact conditions. For the reciprocal friction tests, maximum friction and worn area reductions of 20% and 22% were achieved for the concentrations of 0.10 wt% and 0.20 wt% GNP, respectively. Besides, the best anti-wear performance was found for the nanolubricant containing 0.05 wt% MSNP in rotational configuration test, with reductions of 42% and 60% in the scar width and depth, respectively, with respect to the engine oil.

Case study as a means of evaluating the impact of early years leaders: Steps, paths and routes.

The paper argues that case study will need to play an increasingly important role in the evaluation of leadership development programmes as both formal and substantive theories of leadership place greater emphasis upon the role played by organizational context on leaders ability to bring about change. Prolonged engagement within a case study provides researchers with opportunities to capture the dynamics between leaders and their organisational contexts. However, adopting a case study approach is no substitute for inadequate theorization of the link between leadership approaches and leadership effects. The paper argues for the use of inclusive and expansive theoretical notions of leadership and its relationship to organisational context. The evaluation used to illustrate these arguments was based on a longitudinal multi-site case study methodology. The case studies ran over a three-year period and tracked the effect of 42 leaders on the quality of provision in some 30 early years settings. Both individual and collective theoires of leadership were used to trace leaders' steps, paths and routes to improvement. Three overlapping theoretical lenses were used to study the dynamics of these leaders interactions with a key aspect of their organisational contexts - the existing formal and informal leadership structures - and how these affected their attempts to improve the quality of provision of their settings. The analysis, and related findings, were tiered in order to provide progressively more detailed descriptions of the relationships between leaders' approaches and changes in their settings' quality of provision. Each layer of analysis operated with a causal logic that became gradually less general and linear and increasingly more 'local' and complex.

Low-cost oil quality sensor based on changes in complex permittivity.

Real time oil quality monitoring techniques help to protect important industry assets, minimize downtime and reduce maintenance costs. The measurement of a lubricant's complex permittivity is an effective indicator of the oil degradation process and it can be useful in condition based maintenance (CBM) to select the most adequate oil replacement maintenance schedules. A discussion of the working principles of an oil quality sensor based on a marginal oscillator to monitor the losses of the dielectric at high frequencies (>1 MHz) is presented. An electronic design procedure is covered which results in a low cost, effective and ruggedized sensor implementation suitable for use in harsh environments.

Development of an ecologic marine classification in the new zealand region.

We describe here the development of an ecosystem classification designed to underpin the conservation management of marine environments in the New Zealand region. The classification was defined using multivariate classification using explicit environmental layers chosen for their role in driving spatial variation in biologic patterns: depth, mean annual solar radiation, winter sea surface temperature, annual amplitude of sea surface temperature, spatial gradient of sea surface temperature, summer sea surface temperature anomaly, mean wave-induced orbital velocity at the seabed, tidal current velocity, and seabed slope. All variables were derived as gridded data layers at a resolution of 1 km. Variables were selected by assessing their degree of correlation with biologic distributions using separate data sets for demersal fish, benthic invertebrates, and chlorophyll-a. We developed a tuning procedure based on the Mantel test to refine the classification's discrimination of variation in biologic character. This was achieved by increasing the weighting of variables that play a dominant role and/or by transforming variables where this increased their correlation with biologic differences. We assessed the classification's ability to discriminate biologic variation using analysis of similarity. This indicated that the discrimination of biologic differences generally increased with increasing classification detail and varied for different taxonomic groups. Advantages of using a numeric approach compared with geographic-based (regionalisation) approaches include better representation of spatial patterns of variation and the ability to apply the classification at widely varying levels of detail. We expect this classification to provide a useful framework for a range of management applications, including providing frameworks for environmental monitoring and reporting and identifying representative areas for conservation.

The effects of a medializing calcaneal osteotomy with and without superior translation on Achilles tendon elongation and plantar foot pressures.

BACKGROUND: The medial calcaneal osteotomy (MCO) is a frequently used corrective procedure for posterior tibial tendon (PTT) insufficiency; however, patients often complain of lateral foot pain postoperatively. Published findings have documented the usefulness of MCO in off-loading the plantar surface of the first and second metatarsal heads but with a concomitant increase in peak pressure over the lateral forefoot and heel. Achilles tendon elongation revealed a trend toward shortening of the ventromedial aspect of the tendon. It was then hypothesized that translating the osteotomized posterior aspect of the calcaneus medially and superiorly would reduce lateral forefoot pressure and decrease the amount of lengthening of the Achilles tendon while continuing to relieve medial forefoot pressure. METHODS: Twenty-eight fresh-frozen cadaver legs were axially loaded on a load-frame device to 100 lbs to assess the effects of a 1-cm MCO in conjunction with either 0.5-cm or 1-cm superior translation on plantar foot pressures and Achilles tendon elongation. RESULTS: The 0.5-cm superior translation resulted in a greater off-loading of the first and second metatarsals than the MCO alone with a trend toward decreased pressures in the lateral forefoot. The 1-cm superior translation continued to unload the first and second metatarsals; however, lateral forefoot and midfoot pressures were increased. Achilles tendon lengthening remained unchanged in the cadaver foot model. CONCLUSIONS: Our findings suggest that the addition of a 0.5-cm superior translation to the traditional 1-cm MCO should allow some degree of off-loading of the medial forefoot without increasing lateral forefoot or heel pressures.

Effects of medializing calcaneal osteotomy on Achilles tendon lengthening and plantar foot pressures.

Posterior tibial tendon insufficiency, or adult acquired flatfoot deformity, involves collapse of the longitudinal arch of the foot with ensuing changes in the bony architecture of the foot as well. While it is generally accepted that a medializing calcaneal osteotomy (MCO) is a very useful treatment for restoring the fallen arch, questions regarding the effects of this procedure upon plantar foot pressures and Achilles tendon length changes need to be answered. This study focuses on changes in plantar foot pressures and Achilles tendon length as the result of performing a MCO. Fourteen fresh-frozen cadaver legs were used to test the effects of MCO on Achilles tendon length changes 2 cm proximal to the Achilles tendon insertion on the calcaneus. Differential variable reluctance transducers were anchored in ventromedial, dorsomedial, dorsolateral, and ventrolateral positions of the Achilles tendon at the aforementioned level. The effects of the MCO on plantar foot pressures were assessed simultaneously using the Tekscan HR Mat. Axial loading (100 lbs) of each specimen was performed in neutral and dorsiflexion (15 degrees). Data were gathered for Achilles tendon length changes and plantar foot pressures for three trials in both the neutral and dorsiflexed positions. A medializing calcaneal osteotomy (1 cm medial translation) was then performed and testing was repeated in the fashion outlined heretofore. Analysis of the data revealed that there was no significant increase in Achilles tendon length as a result of the MCO. The data also showed that average pressure over the first and second metatarsal regions of the forefoot decreased significantly after MCO. At the same time there was a significant increase in average pressure over the medial and lateral aspect of the heel. These findings suggest that the Achilles tendon aids in inversion of the forefoot without undergoing a significant increase in length change of Achilles tendon fibers in any of the regions tested.