Strong-segregation limit of the self-consistent field theory for diblock copolymer melts

The self-consistent field theory (SCFT) introduced by Helfand for diblock copolymer melts is expected to converge to the strong-segregation theory (SST) of Semenov in the asymptotic limit, $\chi N \rightarrow \infty$. However, past extrapolations of the lamellar/cylinder and cylinder/sphere phase boundaries, within the standard unit-cell approximation, have cast some doubts on whether or not this is actually true. Here we push the comparison further by extending the SCFT calculations to $\chi N = 512,000$, by accounting for exclusion zones in the coronae of the cylindrical and spherical unit cells, and by examining finite-segregation corrections to SST. In doing so, we provide the first compelling evidence that SCFT does indeed reduce to SST.

Condition number estimates for combined potential integral operators in acoustics and their boundary element discretisation

We consider the classical coupled, combined-field integral equation formulations for time-harmonic acoustic scattering by a sound soft bounded obstacle. In recent work, we have proved lower and upper bounds on the $L^2$ condition numbers for these formulations, and also on the norms of the classical acoustic single- and double-layer potential operators. These bounds to some extent make explicit the dependence of condition numbers on the wave number $k$, the geometry of the scatterer, and the coupling parameter. For example, with the usual choice of coupling parameter they show that, while the condition number grows like $k^{1/3}$ as $k\to\infty$, when the scatterer is a circle or sphere, it can grow as fast as $k^{7/5}$ for a class of `trapping' obstacles. In this paper we prove further bounds, sharpening and extending our previous results. In particular we show that there exist trapping obstacles for which the condition numbers grow as fast as $\exp(\gamma k)$, for some $\gamma>0$, as $k\to\infty$ through some sequence. This result depends on exponential localisation bounds on Laplace eigenfunctions in an ellipse that we prove in the appendix. We also clarify the correct choice of coupling parameter in 2D for low $k$. In the second part of the paper we focus on the boundary element discretisation of these operators. We discuss the extent to which the bounds on the continuous operators are also satisfied by their discrete counterparts and, via numerical experiments, we provide supporting evidence for some of the theoretical results, both quantitative and asymptotic, indicating further which of the upper and lower bounds may be sharper.

Synthesis, structure and magnetic properties of mono- and di-nuclear nickel(II) thiocyanate complexes with tridentate N3 donor Schiff bases

The 1:1 condensation of N-methyl-1,3-diaminopropane and N,N-diethyl-1,2-diminoethane with 2-acetylpyridine, respectively at high dilution gives the tridentate mono-condensed Schiff bases N-methyl-N'-(1-pyridin-2-yl-ethylidene)-propane-1,3-diamine (L-1) and N,N-diethyl-N'-(1-pyridin-2-yl-ethylidene)-ethane-1,2-diamine (L-2). The tridentate ligands were allowed to react with methanol solutions of nickel(II) thiocyanate to prepare the complexes [Ni(L-1)(SCN)(2)(OH2) (1) and [{Ni(L-2)(SCN)}(2)] (2). Single crystal X-ray diffraction was used to confirm the structures of the complexes. The nickel(II) in complex 1 is bonded to three nitrogen donor atoms of the ligand L-1 in a mer orientation, together with two thiocyanates bonded through nitrogen and a water molecule, and it is the first Schiff base complex of nickel(II) containing both thiocyanate and coordinated water. The coordinated water initiates a hydrogen bonded 2D network. In complex 2, the nickel ion occupies a slightly distorted octahedral coordination sphere, being bonded to three nitrogen atoms from the ligand L-2, also in a mer orientation, and two thiocyanate anions through nitrogen. In contrast to 1, the sixth coordination site is occupied by a sulfur atom from a thiocyanate anion in an adjacent molecule, thus creating a centrosymmetric dimer. A variable temperature magnetic study of complex 2 indicates the simultaneous presence of zero-field splitting, weak intramolecular ferromagnetic coupling and intermolecular antiferromagnetic interactions between the nickel(II) centers.

Rheology of magmas with bimodal crystal size and shape distributions: insights from analog experiments

Magmas in volcanic conduits commonly contain microlites in association with preexisting phenocrysts, as often indicated by volcanic rock textures. In this study, we present two different experiments that inves- tigate the flow behavior of these bidisperse systems. In the first experiments, rotational rheometric methods are used to determine the rheology of monodisperse and polydisperse suspensions consisting of smaller, prolate particles (microlites) and larger, equant particles (phenocrysts) in a bubble‐free Newtonian liquid (silicate melt). Our data show that increasing the relative proportion of prolate microlites to equant pheno- crysts in a magma at constant total particle content can increase the relative viscosity by up to three orders of magnitude. Consequently, the rheological effect of particles in magmas cannot be modeled by assuming a monodisperse population of particles. We propose a new model that uses interpolated parameters based on the relative proportions of small and large particles and produces a considerably improved fit to the data than earlier models. In a second series of experiments we investigate the textures produced by shearing bimodal suspensions in gradually solidifying epoxy resin in a concentric cylinder setup. The resulting textures show the prolate particles are aligned with the flow lines and spherical particles are found in well‐organized strings, with sphere‐depleted shear bands in high‐shear regions. These observations may explain the measured variation in the shear thinning and yield stress behavior with increasing solid fraction and particle aspect ratio. The implications for magma flow are discussed, and rheological results and tex- tural observations are compared with observations on natural samples.

Synthesis, X-ray crystal structure and catalytic activity of the manganese(II) complex [Mn(bdoa)(H2O)3](bdoaH2 =benzene-1,2-dioxyacetic acid)

Benzene-1,2-dioxyacetic acid (bdoaH2) reacts with Mn(CH3CO2)2·4H2O in an ethanol-water mixture to give the manganese(II) complex [Mn(bdoa)(H2O)3]. The X-ray crystal structure of the complex shows the metal to be pseudo seven-coordinate. The quadridentate bdoa2− dicar☐ylate ligand forms an essentially planar girdle around the metal, being strongly bondedtransoid by a car☐ylate oxygen atom from each of the two car☐ylate moieties (mean MnO 2.199A˚) and also weakly chelated by the two internal ether oxygen atoms (mean MnO 2.413A˚). The coordination sphere about the manganese is completed by three water molecules (mean MnO 2.146A˚) lying in a meridional plane orthogonal to that of the bdoa2− ligand. Magnetic, conductivity and voltammetry data for the complex are given, and its use as a catalyst for the disproportionisation of H2O2 is described.

Effect of water-soluble polymers, polyethylene glycol and poly(vinylpyrrolidone),on the gelation of aqueous micellar solutions of Pluronic copolymer F127

The micellization of F127 (E98P67E98) in dilute aqueous solutions of polyethylene glycol (PEG6000 and PEG35000) and poly(vinylpyrrolidone) (PVP K30 and PVP K90) is studied. The average hydrodynamic radius (rh,app) obtained from the dynamic light scattering technique increased with increase in PEG concentration but decreased on addition of PVP, results which are consistent with interaction of the micelles with PEG and the formation of micelles clusters, but no such interaction occurs with PVP. Tube inversion was used to determine the onset of gelation. The critical concentration of F127 for gelation increased on addition of PEG and of PVP K30 but decreased on addition of PVP K90. Small-angle X-ray scattering (SAXS) was used to show that the 30 wt% F127 gel structure (fcc) was independent of polymer type and concentration, as was the d-spacing and so the micelle hard-sphere radius. The maximum elastic modulus (G0 max) of 30 wt% F127 decreased from its value for water alone as PEG was added, but was little changed by adding PVP. These results are consistent with the packed-micelles in the 30 wt% F127 gel being effectively isolated from the polymer solution on the microscale while, especially for the PEG, being mixed on the macroscale.

Safeguarding livelihoods or exacerbating poverty?: Artisanal mining and formalization in West Africa

In recent years, policy mechanisms to support a formalized artisanal and small-scale mining (ASM) sector in sub-Saharan Africa have gained increasing currency. Proponents of formalization argue that most social and environmental problems associated with the sector stem from the fact that ASM is predominantly unregulated and operates outside the legal sphere. This paper critically examines recent efforts to formalize artisanal and small-scale mining inWest Africa, drawing upon recent fieldwork carried out in Sierra Leone, Ghana and Mali. In exploring the sector’s livelihood dimensions, the analysis suggests that bringing unregulated, informal mining activities into the legal domain remains a considerable challenge. The paper concludes by confirming the urgent need to refocus formalization strategies on the main livelihood challenges and constraints of small-scale miners themselves, if poverty is to be alleviated and more benefits are to accrue to depressed communities in mineral-rich regions.

Computational modes and grid imprinting on five quasi-uniform spherical C-grids

Currently, most operational forecasting models use latitude-longitude grids, whose convergence of meridians towards the poles limits parallel scaling. Quasi-uniform grids might avoid this limitation. Thuburn et al, JCP, 2009 and Ringler et al, JCP, 2010 have developed a method for arbitrarily-structured, orthogonal C-grids (TRiSK), which has many of the desirable properties of the C-grid on latitude-longitude grids but which works on a variety of quasi-uniform grids. Here, five quasi-uniform, orthogonal grids of the sphere are investigated using TRiSK to solve the shallow-water equations. We demonstrate some of the advantages and disadvantages of the hexagonal and triangular icosahedra, a Voronoi-ised cubed sphere, a Voronoi-ised skipped latitude-longitude grid and a grid of kites in comparison to a full latitude-longitude grid. We will show that the hexagonal-icosahedron gives the most accurate results (for least computational cost). All of the grids suffer from spurious computational modes; this is especially true of the kite grid, despite it having exactly twice as many velocity degrees of freedom as height degrees of freedom. However, the computational modes are easiest to control on the hexagonal icosahedron since they consist of vorticity oscillations on the dual grid which can be controlled using a diffusive advection scheme for potential vorticity.

Shaping children’s mobilities: expectations of gendered parenting in the English rural idyll

This paper explores the impact of local parenting practices and children's everyday use of public space within two villages in the rural South West of England, an issue that has been underexplored in recent research. Drawing upon the concept of hybridity, it explores the interplay between the social, natural and material in shaping local cultures of rural parenting. The paper begins by drawing upon recent research on parenting in the global North, the gendering of rural space and hybridity to show how these bodies of work can be interlinked to better understand rural parenting practices and norms. Through empirical research that focused on the relationships between gendered parenting strategies, idealised notions of rural motherhood and materiality, the paper explores the diverse ways in which a group of working and middle-class mothers construct and define ideas about their children's lives and mobilities. Whilst dominant discourses of rurality focus upon the idyll, and gendered identities of rural women still remain within the domestic sphere, so we examine how these deeply embedded notions of ‘normality’ can be powerful social tools in rural villages, mobilised through discourses of materiality and anxiety. In our conclusions, we argue that the hybrid integration of the material and social provides a useful framework for understanding the everyday geographies of rural parenting.

Temperature dependent SANS from ferritin and apoferritin

SANS from deuterated ferritin and apoferritin solutions over the temperature range 5 to 300 K is presented. Above the freezing point the SANS is well described by Percus-Yevick hard sphere packing. On freezing, highly correlated, partially crystallised, clusters of the proteins form and grow with decreasing temperature. The resulting scattering, characterised by a squared Lorentzian structure factor, indicates a spatial extent of 1000 8, for the protein clusters.

Innovation in construction: a sociology of technology approach

An alternative approach to understanding innovation is made using two intersecting ideas. The first is that successful innovation requires consideration of the social and organizational contexts in which it is located. The complex context of construction work is characterized by inter-organizational collaboration, a project-based approach and power distributed amongst collaborating organizations. The second is that innovations can be divided into two modes: ‘bounded’, where the implications of innovation are restricted within a single, coherent sphere of influence, and ‘unbounded’, where the effects of implementation spill over beyond this. Bounded innovations are adequately explained within the construction literature. However, less discussed are unbounded innovations, where many firms' collaboration is required for successful implementation, even though many innovations can be considered unbounded within construction's inter-organizational context. It is argued that unbounded innovations require an approach to understand and facilitate the interactions both within a range of actors and between the actors and technological artefacts. The insights from a sociology of technology approach can be applied to the multiplicity of negotiations and alignments that constitute the implementation of unbounded innovation. The utility of concepts from the sociology of technology, including ‘system building’ and ‘heterogeneous engineering’, is demonstrated by applying them to an empirical study of an unbounded innovation on a major construction project (the new terminal at Heathrow Airport, London, UK). This study suggests that ‘system building’ contains outcomes that are not only transformations of practices, processes and systems, but also the potential transformation of technologies themselves.

Collision prediction of a moving object within a virtual world

This paper provides a solution for predicting moving/moving and moving/static collisions of objects within a virtual environment. Feasible prediction in real-time virtual worlds can be obtained by encompassing moving objects within a sphere and static objects within a convex polygon. Fast solutions are then attainable by describing the movement of objects parametrically in time as a polynomial.

Controlling the computational modes of the arbitrarily structured C-grid

The arbitrarily structured C-grid, TRiSK (Thuburn, Ringler, Skamarock and Klemp, 2009, 2010) is being used in the ``Model for Prediction Across Scales'' (MPAS) and is being considered by the UK Met Office for their next dynamical core. However the hexagonal C-grid supports a branch of spurious Rossby modes which lead to erroneous grid-scale oscillations of potential vorticity (PV). It is shown how these modes can be harmlessly controlled by using upwind-biased interpolation schemes for PV. A number of existing advection schemes for PV are tested, including that used in MPAS, and none are found to give adequate results for all grids and all cases. Therefore a new scheme is proposed; continuous, linear-upwind stabilised transport (CLUST), a blend between centred and linear-upwind with the blend dependent on the flow direction with respect to the cell edge. A diagnostic of grid-scale oscillations is proposed which gives further discrimination between schemes than using potential enstrophy alone and indeed some schemes are found to destroy potential enstrophy while grid-scale oscillations grow. CLUST performs well on hexagonal-icosahedral grids and unrotated skipped latitude-longitude grids of the sphere for various shallow water test cases. Despite the computational modes, the hexagonal icosahedral grid performs well since these modes are easy and harmless to filter. As a result TRiSK appears to perform better than a spectral shallow water model.

‘The Apostolate of the Pen’: Mgr De Ségur and the mobilization of Catholic opinion in Second Empire France

This article contends that the papacy and ultramontane Catholicism played a pivotal role in the democratization of culture in Second Empire France. Drawing upon recent scholarship, which argues that religion played an important role in the constitution of mass democracies in modern Europe, this article revisits the pamphlet campaign led by Mgr Gaston de Ségur at the height of the Italian question in February 1860. Ségur made the most of the freedom of expression enjoyed by the Catholic Church in France in an attempt to direct Catholic opinion, and place pressure on the French government over its diplomatic relations with the pope. New archive material, notably Ségur’s correspondence with the leading Catholic journalist of the time, Louis Veuillot, sheds further light on Rome’s interventions in French culture and politics and its consequences. The article demonstrates that one of the most important, if unintended, results of the ultramontane campaign was to trigger reforms to the cultural sphere, and the granting of freedoms to their political enemies: the Republicans and freethinkers.

A multidisciplinary literature review of low and zero carbon technologies into new housing

The UK Government is committed to all new homes being zero-carbon from 2016. The use of low and zero carbon (LZC) technologies is recognised by housing developers as being a key part of the solution to deliver against this zero-carbon target. The paper takes as its starting point that the selection of new technologies by firms is not a phenomenon which takes place within a rigid sphere of technical rationality (for example, Rip and Kemp, 1998). Rather, technology forms and diffusion trajectories are driven and shaped by myriad socio-technical structures, interests and logics. A literature review is offered to contribute to a more critical and systemic foundation for understanding the socio-technical features of the selection of LZC technologies in new housing. The problem is investigated through a multidisciplinary lens consisting of two perspectives: technological and institutional. The synthesis of the perspectives crystallises the need to understand that the selection of LZC technologies by housing developers is not solely dependent on technical or economic efficiency, but on the emergent ‘fit’ between the intrinsic properties of the technologies, institutional logics and the interests and beliefs of various actors in the housing development process.