Electrospinning and characterization of self-assembled inclusion complexies

L’électrofilage est une technique permettant de fabriquer des fibres polymériques dont le diamètre varie entre quelques nanomètres et quelques microns. Ces fibres ont donc un rapport surface/volume très élevé. Les fibres électrofilées pourraient trouver des applications dans le relargage de médicaments et le génie tissulaire, comme membranes et capteurs chimiques, ou dans les nanocomposites et dispositifs électroniques. L’électrofilage était initialement utilisé pour préparer des toiles de fibres désordonnées, mais il est maintenant possible d’aligner les fibres par l’usage de collecteurs spéciaux. Cependant, il est important de contrôler non seulement l’alignement macroscopique des fibres mais aussi leur orientation au niveau moléculaire puisque l’orientation influence les propriétés mécaniques, optiques et électriques des polymères. Les complexes moléculaires apparaissent comme une cible de choix pour produire des nanofibres fortement orientées. Dans les complexes d’inclusion d’urée, les chaînes polymères sont empilées dans des canaux unidimensionnels construits à partir d’un réseau tridimensionnel de molécules d’urée liées par des ponts hydrogène. Ainsi, les chaînes polymère sonts très allongées à l’échelle moléculaire. Des nanofibres du complexe PEO-urée ont été préparées pour la première fois par électrofilage de suspensions et de solutions. Tel qu’attendu, une orientation moléculaire inhabituellement élevée a été observée dans ces fibres. De tels complexes orientés pourraient être utilisés à la fois dans des études fondamentales et dans la préparation de matériaux hiérarchiquement structurés. La méthode d’électrofilage peut parfois aussi être utilisée pour préparer des matériaux polymériques métastables qui ne peuvent pas être préparés par des méthodes conventionnelles. Ici, l’électrofilage a été utilisé pour préparer des fibres des complexes stables (α) et "métastables" (β) entre le PEO et l’urée. La caractérisation du complexe β, qui était mal connu, révèle un rapport PEO:urée de 12:8 appartenant au système orthorhombique avec a = 1.907 nm, b = 0.862 nm et c = 0.773 nm. Les chaînes de PEO sont orientées selon l’axe de la fibre. Leur conformation est significativement affectée par les ponts hydrogène. Une structure en couches a été suggérée pour la forme β, plutôt que la structure conventionnelle en canaux adoptée par la forme α. Nos résultats indiquent que le complexe β est thermodynamiquement stable avant sa fonte et peut se transformer en forme α et en PEO liquide par un processus de fonte et recristallisation à 89 ºC. Ceci va dans le sens contraire aux observations faites avec le complexe β obtenu par trempe du complexe α fondu. En effet, le complexe β ainsi obtenu est métastable et contient des cristaux d’urée. Il peut subir une transition de phases cinétique solide-solide pour produire du complexe α dans une vaste gamme de températures. Cette transition est induite par un changement de conformation du PEO et par la formation de ponts hydrogène intermoléculaires entre l’urée et le PEO. Le diagramme de phases du système PEO-urée a été tracé sur toute la gamme de compositions, ce qui a permis d’interpréter la formation de plusieurs mélanges qui ne sont pas à l’équilibre mais qui sont été observés expérimentalement. La structure et le diagramme de phases du complexe PEO-thiourée, qui est aussi un complexe très mal connu, ont été étudiés en détail. Un rapport molaire PEO :thiourée de 3:2 a été déduit pour le complexe, et une cellule monoclinique avec a = 0.915 nm, b = 1.888 nm, c = 0.825 nm et β = 92.35º a été déterminée. Comme pour le complexe PEO-urée de forme β, une structure en couches a été suggérée pour le complexe PEO-thiourée, dans laquelle les molécules de thiourée seraient disposées en rubans intercalés entre deux couches de PEO. Cette structure en couches pourrait expliquer la température de fusion beaucoup plus faible des complexes PEO-thiourée (110 ºC) et PEO-urée de forme β (89 ºC) en comparaison aux structures en canaux du complexe PEO-urée de forme α (143 ºC).

A model of the three-dimensional evolution of Arctic melt ponds on first-year and multiyear sea ice

During winter the ocean surface in polar regions freezes over to form sea ice. In the summer the upper layers of sea ice and snow melts producing meltwater that accumulates in Arctic melt ponds on the surface of sea ice. An accurate estimate of the fraction of the sea ice surface covered in melt ponds is essential for a realistic estimate of the albedo for global climate models. We present a melt-pond–sea-ice model that simulates the three-dimensional evolution of melt ponds on an Arctic sea ice surface. The advancements of this model compared to previous models are the inclusion of snow topography; meltwater transport rates are calculated from hydraulic gradients and ice permeability; and the incorporation of a detailed one-dimensional, thermodynamic radiative balance. Results of model runs simulating first-year and multiyear sea ice are presented. Model results show good agreement with observations, with duration of pond coverage, pond area, and ice ablation comparing well for both the first-year ice and multiyear ice cases. We investigate the sensitivity of the melt pond cover to changes in ice topography, snow topography, and vertical ice permeability. Snow was found to have an important impact mainly at the start of the melt season, whereas initial ice topography strongly controlled pond size and pond fraction throughout the melt season. A reduction in ice permeability allowed surface flooding of relatively flat, first-year ice but had little impact on the pond coverage of rougher, multiyear ice. We discuss our results, including model shortcomings and areas of experimental uncertainty.

A continuum model of melt pond evolution on Arctic sea ice

[1] During the Northern Hemisphere summer, absorbed solar radiation melts snow and the upper surface of Arctic sea ice to generate meltwater that accumulates in ponds. The melt ponds reduce the albedo of the sea ice cover during the melting season, with a significant impact on the heat and mass budget of the sea ice and the upper ocean. We have developed a model, designed to be suitable for inclusion into a global circulation model (GCM), which simulates the formation and evolution of the melt pond cover. In order to be compatible with existing GCM sea ice models, our melt pond model builds upon the existing theory of the evolution of the sea ice thickness distribution. Since this theory does not describe the topography of the ice cover, which is crucial to determining the location, extent, and depth of individual ponds, we have needed to introduce some assumptions. We describe our model, present calculations and a sensitivity analysis, and discuss our results.

September Arctic sea-ice minimum predicted by spring melt-pond fraction

The area of Arctic September sea ice has diminished from about 7 million km2 in the 1990s to less than 5 million km2 in five of the past seven years, with a record minimum of 3.6 million km2 in 2012 (ref. 1). The strength of this decrease is greater than expected by the scientific community, the reasons for this are not fully understood, and its simulation is an on-going challenge for existing climate models2, 3. With growing Arctic marine activity there is an urgent demand for forecasting Arctic summer sea ice4. Previous attempts at seasonal forecasts of ice extent were of limited skill5, 6, 7, 8, 9. However, here we show that the Arctic sea-ice minimum can be accurately forecasted from melt-pond area in spring. We find a strong correlation between the spring pond fraction and September sea-ice extent. This is explained by a positive feedback mechanism: more ponds reduce the albedo; a lower albedo causes more melting; more melting increases pond fraction. Our results help explain the acceleration of Arctic sea-ice decrease during the past decade. The inclusion of our new melt-pond model10 promises to improve the skill of future forecast and climate models in Arctic regions and beyond.

Geochemistry of silicate melt inclusions from ODP Holes 137-504B and 140-504B

Geochemical data from plagioclase-hosted silicate melt inclusions from Leg 140, Hole 504B diabase dikes are reported. Hand-picked plagioclase grains were heated to 1260°-1280°C to remelt the glass inclusions and to infer trapping temperatures. The samples were then polished to expose the inclusions, which were analyzed by electron and ion microprobes. Inclusion compositions are mainly in equilibrium with the host plagioclase and are more depleted in incompatible elements than the host rock. Simple crystal-liquid equilibrium calculations show that the melt inclusions could have been in equilibrium with depleted abyssal peridotite diopsides, whereas whole-rock basalt compositions generally could not have been. The melt inclusions are significantly more depleted than normal (N-type) mid-ocean-ridge basalt (MORB) and are consistent with being produced by 8%-16% incremental or open-system melting with 2% residual porosity in the peridotite source. These magmas were formed during pressure-release melting of the mantle over a range of depths between 30 and 15 km.

Composition of melt inclusions and age of zircons of plagiogneisses from the Kola Superdeep Borehole

A comprehensive study of melt inclusions and SHRIMP dating of zircons from trondhjemite gneisses of the sequence VIII from the Kola Superdeep Borehole has revealed presence of old primary magmatic crystals with age up to 2887+/-15 Ma. This is not consistent with the previous view, according to which the oldest zircons from the Archean Complex in SG-3 are products of granulite metamorphism. Primary magmatic zircons of early generation (from 2887 to 2842 Ma) formed in deep-seated magma chambers during partial crystallization of CO2-saturated trondhjemite estimates on duration of generation of tonalite-trondhjemite-granite melts through partial melting of mafic rocks.

Melt climatology estimates for small to giant Antarctic icebergs, links to NetCDF files

We present four melt climatology estimates based on a simulation of Antarctic iceberg drift and melting that includes small, medium-sized, and giant tabular icebergs with a realistic size distribution. Drift and meltdown is simulated using vertical profiles of ocean currents, temperature, and salinity, which goes beyond the present standard in iceberg modeling. The climatology estimates based on simulations of small (SMA), 'small-to-medium'-sized (MED12 & MED123), and small-to-giant icebergs (ALL) exhibit differential characteristics: successive inclusion of larger icebergs leads to a reduced seasonality of iceberg melt and a shift of the mass input to the area north of 58°S, while less melt water is released into the coastal areas. This highlights the necessity to account for larger and giant icebergs in order to obtain accurate melt climatologies. The four monthly melt climatologies [mm/day] are available as netCDF files with 1°x1° spatial resolution and can be used, e.g., for sensitivity studies with uncoupled sea ice-ocean models, or as spatio-temporal templates for the redistribution of land ice from the Antarctic ice sheet over the Southern Ocean in climate models.

Look before you leap : the epistemic violence that sometimes hides behind the word "inclusion"

This paper demonstrates how Indigenous Studies is controlled in some Australian universities in ways that continue the marginalisation, denigration and exploitation of Indigenous peoples. Moreover, it shows how the engagement of white notions of “inclusion” can result in the maintenance of racism, systemic marginalisation, white race privilege and radicalised subjectivity. A case study will be utilised which draws from the experience of two Indigenous scholars who were invited to be part of a panel to review one Australian university’s plan and courses in Indigenous studies. The case study offers the opportunity to destabilise the relationships between oppression and privilege and the epistemology that maintains them. The paper argues for the need to examine exactly what is being offered when universities provide opportunities for “inclusion”.

A framework for assessing social policy inclusion proposals

This document outlines a framework that could be used by government agencies in assessing policy interventions aimed at achieving social outcomes from government construction contracts. The framework represents a rational interpretation of the information gathered during the multi-outcomes construction policies project. The multi-outcomes project focused on the costs and benefits of using public construction contracts to promote the achievement of training and employment and public art objectives. The origin of the policy framework in a cost-benefit appraisal of current policy interventions is evidenced by its emphasis on sensitivity to policy commitment and project circumstances (especially project size and scope).The quantitative and qualitative analysis conducted in the multi-outcomes project highlighted, first, that in the absence of strong industry commitment to policy objectives, policy interventions typically result in high levels of avoidance activity, substantial administrative costs and very few benefits. Thus, for policy action on, for example, training or local employment to be successful compliance issues must be adequately addressed. Currently it appears that pre-qualification schemes (similar to the Priority Access Scheme) and schemes that rely on measuring, for example, the training investments of contractors within particular projects do not achieve high levels of compliance and involve significant administrative costs. Thus, an alternative is suggested in the policy framework developed here: a levy on each public construction project – set as a proportion of the total project costs. Although a full evaluation of this policy alternative was beyond the scope of the multi-outcomes construction policies project, it appears to offer the potential to minimize the transaction costs on contractors whilst enabling the creation of a training agency dedicated to improving the supply of skilled construction labour. A recommendation is thus made that this policy alternative be fully researched and evaluated. As noted above, the outcomes of the multi-outcomes research project also highlighted the need for sensitivity to project circumstances in the development and implementation of polices for public construction projects. Ideally a policy framework would have the flexibility to respond to circumstances where contractors share a commitment to the policy objectives and are able to identify measurable social outcomes from the particular government projects they are involved in. This would involve a project-by-project negotiation of goals and performance measures. It is likely to only be practical for large, longer term projects.