Unconventional gas: potential energy market impacts in the European Union

In the interest of effective policymaking, this report seeks to clarify certain controversies and identify key gaps in the evidence-base relating to unconventional gas. The scope of this report is restricted to the economic impact of unconventional gas on energy markets. As such, it principally addresses such issues as the energy mix, energy prices, supplies, consumption, and trade flows. Whilst this study touches on coal bed methane and tight gas, its predominant focus is on shale gas, which the evidence at this time suggests will be the form of unconventional gas with the most growth potential in the short- to medium-term. This report considers the prospects for the indigenous production of shale gas within the EU-27 Member States. It evaluates the available evidence on resource size, extractive technology, resource access and market access. This report also considers the implications for the EU of large-scale unconventional gas production in other parts of the world. This acknowledges the fact that many changes in the dynamics of energy supply can only be understood in the broader global context. It also acknowledges that the EU is a major importer of energy, and that it is therefore heavily affected by developments in global energy markets that are largely out of its control.JRC.F.3-Energy securit

Controlling the Self-Assembly of Binary Copolymer Mixtures in Solution through Molecular Architecture

We present a combined experimental and theoretical study on the role of copolymer architecture in the self-assembly of binary PEO–PCL mixtures in water–THF and show that altering the chain geometry and composition of the copolymers can control the form of the self-assembled structures and lead to the formation of novel aggregates. First, using transmission electron microscopy and turbidity measurements, we study a mixture of sphere-forming and lamella-forming PEO–PCL copolymers and show that increasing the molecular weight of the lamella-former at a constant ratio of its hydrophilic and hydrophobic components leads to the formation of highly curved structures even at low sphere-former concentrations. This result is explained using a simple argument based on the effective volumes of the two sections of the diblock and is reproduced in a coarse-grained mean-field model: self-consistent field theory (SCFT). Using further SCFT calculations, we study the distribution of the two copolymer species within the individual aggregates and discuss how this affects the self-assembled structures. We also investigate a binary mixture of lamella-formers of different molecular weights and find that this system forms vesicles with a wall thickness intermediate to those of the vesicles formed by the two copolymers individually. This result is also reproduced using SCFT. Finally, a mixture of sphere-former and a copolymer with a large hydrophobic block is shown to form a range of structures, including novel elongated vesicles

Controlling the micellar morphology of binary PEO-PCL block copolymers in water-THF through controlled blending

We study both experimentally and theoretically the self-assembly of binary polycaprolactone–polyethylene oxide (PCL–PEO) block copolymers in dilute solution, where self-assembly is triggered by changing the solvent from the common good solvent THF to the selective solvent water, and where the two species on their own in water form vesicles and spherical micelles respectively. We find that in water the inter-micellar exchange of these block copolymers is extremely slow so that the resultant self-assembled structures are in local but not in global equilibrium (i.e., they are non-ergodic). This opens up the possibility of controlling micelle morphology both thermodynamically and kinetically. Specifically, when the two species are first molecularly dissolved in THF before mixing and self-assembly (‘pre-mixing’) by dilution with water, the morphology of the formed structures is found to depend on the mixing ratio of the two species, going gradually on a route of decreasing surface curvature from vesicles via an intermediate regime of micelles in the shape of ‘bulbed’ rods, rings, Y-junctions and finally to spherical micelles as we increase the proportion of the “sphere formers”. On the other hand, if the two species are first partially self-assembled (by partial exchange of the solvent with water) before mixing and further self-assembly (‘intermediate mixing’), novel metastable structures, including nanoscopic ‘pouches’, emerge. These experimental results are corroborated by Self-Consistent Field Theory (SCFT) calculations which reproduce the sequence of morphologies seen in the pre-mixing experiments. SCFT also reveals a clear coupling between polymer composition and aggregate curvature, with regions of positive and negative curvature being stabilized by an enrichment and depletion of sphere formers respectively. Our study demonstrates that both thermodynamic and kinetic blending of block copolymers are effective design parameters to control the resulting structures and allow us to access a much richer range of nano-morphologies than is possible with monomodal block copolymer solutions

On the mechanism of formation of vesicles from poly(ethylene oxide)-block-poly(caprolactone) copolymers

Micelles, worm-like micelles and vesicles were prepared from poly(ethylene oxide)-b-poly(caprolactone) block copolymersvia a solvent switch method, and characterised by light scattering, X-ray scattering and cryo-transmission electron microscopy. The volume fraction of ethylene oxide, as the hydrophilic part in these polymers, determined the morphology in dilute solution, with spherical micelles, worm-like micelles, vesicles and precipitate being formed as the volume fraction decreased. The mechanism by which vesicles were formed in these systems during sequential dilution of the initial THF-rich solution with water was probed. It was shown that vesicles formed via a sequence of morphologies. The transitions between different self-assembled structures were followed using dynamic cryo-TEM. The behaviour of the PEO-b-PCL system was compared with the well-studied poly(acrylic acid)-b-poly(styrene) system; the behaviour was shown to differ in the final stage during the transition from worm-like micelles to vesicles

Controlling the micellar morphology of binary PEO-PCL block copolymers in water-THF through controlled blending

We study both experimentally and theoretically the self-assembly of binary polycaprolactone-polyethylene oxide (PCL-PEO) block copolymers in dilute solution, where self-assembly is triggered by changing the solvent from the common good solvent THF to the selective solvent water, and where the two species on their own in water form vesicles and spherical micelles respectively. We find that in water the inter-micellar exchange of these block copolymers is extremely slow so that the resultant self-assembled structures are in local but not in global equilibrium (i.e., they are non-ergodic). This opens up the possibility of controlling micelle morphology both thermodynamically and kinetically. Specifically, when the two species are first molecularly dissolved in THF before mixing and self-assembly ('pre-mixing') by dilution with water, the morphology of the formed structures is found to depend on the mixing ratio of the two species, going gradually on a route of decreasing surface curvature from vesicles via an intermediate regime of micelles in the shape of 'bulbed' rods, rings, Y-junctions and finally to spherical micelles as we increase the proportion of the "sphere formers". On the other hand, if the two species are first partially self-assembled (by partial exchange of the solvent with water) before mixing and further self-assembly ('intermediate mixing'), novel metastable structures, including nanoscopic 'pouches', emerge. These experimental results are corroborated by Self-Consistent Field Theory (SCFT) calculations which reproduce the sequence of morphologies seen in the pre-mixing experiments. SCFT also reveals a clear coupling between polymer composition and aggregate curvature, with regions of positive and negative curvature being stabilized by an enrichment and depletion of sphere formers respectively. Our study demonstrates that both thermodynamic and kinetic blending of block copolymers are effective design parameters to control the resulting structures and allow us to access a much richer range of nano-morphologies than is possible with monomodal block copolymer solutions