193 research outputs found

    Diffusive processes in polyacrylic acid hydrogels

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    The aim of this work was to characterise the diffusive properties of superabsorbent polymer systems prepared by free radical crosslinking polymerisation of acrylic acid. The polyelectrolyte nature of these hydrogels gives rise to high swelling capacities, and their ability to absorb and retain water is highly dependent on the precise network structure. Modifying the synthesis formulation results in considerable changes to the dynamic and structural properties of these gels, providing the motive for the work presented here. The influence of two factors, namely the extent of monomer neutralisation and the level of crosslinker in the pre-gel solution, were investigated. The dynamic properties of gels were examined using Quasi-Elastic Light Scattering (QELS), from which the cooperative diffusion coefficient and degree of heterogeneity could be determined. The former was found to increase linearly with neutralisation, due to the introduction of electrostatic interactions. The diffusion coefficient initially remained constant with the addition of crosslinker, due to the dominating influence of physical entanglements, but increased above a threshold crosslinking degree, corresponding to a reduction of the network mesh size. The extent of large-scale inhomogeneity increased for higher ionisations, as both the crosslinker solubility and the efficiency of monomer-crosslinker reaction decreased. However, there was a tendency for concentration fluctuations to be minimised for higher neutralisations, making the gel more microscopically homogeneous. Kinetics of swelling experiments were used to investigate gels of varying composition. The macroscopic diffusion coefficient was found to increase rapidly with increasing neutralisation until the monomer was approximately 35% neutralised, beyond which point counterion condensation caused insignificant variation. This trend was also reflected in the equilibrium swelling ratios, and mode of diffusion. For the majority of gels, the diffusion process was characterised as case II transport. Variation of crosslinking degree caused an overall increase in the diffusion coefficient, reflecting the trend observed in the QELS studies. Nuclear Reaction Analysis (NRA) was used to probe the penetration of heavy water into dry network slabs. The concentration-depth profiles revealed a discontinuity in the diffusion coefficient, corresponding to the transition between glassy and rubbery states, for which the diffusivities differed by several orders of magnitude. The kinetics of plasticisation was assumed to be the rate determining factor in the swelling process, on the timescale of the NRA experiments. The diffusion coefficient for the swollen rubbery region, representative of the macroscopic diffusion process, was found to increase linearly with neutralisation, and decrease with crosslinking degree. The latter observation was explained as due to a reduction in the free volume available for solvent diffusion with higher levels of crosslinker

    Continuum rich-get-richer processes: Mean field analysis with an application to firm size

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    Classical rich-get-richer models have found much success in being able to broadly reproduce the statistics and dynamics of diverse real complex systems. These rich-get-richer models are based on classical urn models and unfold step by step in discrete time. Here, we consider a natural variation acting on a temporal continuum in the form of a partial differential equation (PDE). We first show that the continuum version of Simon\u27s canonical preferential attachment model exhibits an identical size distribution. In relaxing Simon\u27s assumption of a linear growth mechanism, we consider the case of an arbitrary growth kernel and find the general solution to the resultant PDE. We then extend the PDE to multiple spatial dimensions, again determining the general solution. We then relax the zero-diffusion assumption and find an envelope of solutions to the general model in the presence of small fluctuations. Finally, we apply the model to size and wealth distributions of firms. We obtain power-law scaling for both to be concordant with simulations as well as observational data, providing a parsimonious theoretical explanation for these phenomena

    Noncooperative dynamics in election interference

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    Foreign power interference in domestic elections is an existential threat to societies. Manifested through myriad methods from war to words, such interference is a timely example of strategic interaction between economic and political agents. We model this interaction between rational game players as a continuous-time differential game, constructing an analytical model of this competition with a variety of payoff structures. All-or-nothing attitudes by only one player regarding the outcome of the game lead to an arms race in which both countries spend increasing amounts on interference and counterinterference operations. We then confront our model with data pertaining to the Russian interference in the 2016 United States presidential election contest. We introduce and estimate a Bayesian structural time-series model of election polls and social media posts by Russian Twitter troll accounts. Our analytical model, while purposefully abstract and simple, adequately captures many temporal characteristics of the election and social media activity. We close with a discussion of our model\u27s shortcomings and suggestions for future research

    Optical inter-site spin transfer probed by energy and spin-resolved transient absorption spectroscopy

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    Optically driven spin transport is the fastest and most efficient process to manipulate macroscopic magnetization as it does not rely on secondary mechanisms to dissipate angular momentum. In the present work, we show that such an optical inter-site spin transfer (OISTR) from Pt to Co emerges as a dominant mechanism governing the ultrafast magnetization dynamics of a CoPt alloy. To demonstrate this, we perform a joint theoretical and experimental investigation to determine the transient changes of the helicity dependent absorption in the extreme ultraviolet spectral range. We show that the helicity dependent absorption is directly related to changes of the transient spin-split density of states, allowing us to link the origin of OISTR to the available minority states above the Fermi level. This makes OISTR a general phenomenon in optical manipulation of multi-component magnetic systems. Optically driven spin transfer is the fastest process to manipulate magnetism. Here, the authors show that this process emerges as the dominant mechanism in femtosecond spin dynamics enabling to the engineering of functional magnetic systems for future all optical technologies

    The role of flow rotation in the adult right atrium: a 4D flow cardiovascular magnetic resonance study

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    Objective: In healthy adults, the right atrium (RA) serves as a reservoir for the systemic flow return from the superior vena cava (SVC) and inferior vena cava (IVC), preparing the two flows to be transferred to the right ventricle (RV) and pulmonary circulation. This study aims to quantify the haemodynamics of the RA and the associated SVC and IVC inflows, which have not been fully understood to date. Approach: Eighteen adults with structurally normal hearts underwent 4D flow magnetic resonance imaging. The cardiac cycle was resolved to 20 temporal phases with a spatial resolution of 3x3x3mm3. Analysis included objective visualisation of the flow structures in the RA identified by three different vortex identification criteria, kinetic energy (KE), enstrophy and dissipation. KE and helicity flux were also assessed in both caval veins. Main results: Vortex identification methods confirmed that in the majority of subjects the blood flow from the caval veins filling the RA during ventricular systole is not chaotic, but rather forms an organised pattern of a single coherent forward turning vortex structure. Thirteen subjects displayed a single vortex flow structure, four showed multiple vortices and one had a helical flow pattern without a clear vortex structure. A strong positive correlation exists between the flow KE and enstrophy density. Significance: This suggests that flow energy in the RA is mainly rotational, part of which is convected by the highly helical SVC and IVC inflows. Multiple vortices tend to be associated with higher dissipation rates in the central RA region due to turbulence. The rotational nature of the flow in the RA maintains KE better than non-rotational flow. RA flow characteristics are highly related to the helicity content in the caval veins, as well as the KE flux intensity. Lower caval helicity or IVC KE flux dominance tends to favour single vortex formation while the opposite tends to lead to multiple vortices or the rare helical flow patterns. Atria lacking single vortex flow are inclined to have a larger energy input from atrial contraction

    A bio-economic model for cost analysis of alternative management strategies in beef finishing systems.

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    peer-reviewedGlobal population growth together with rising incomes is increasing the demand for meat-based products. This increases the need to optimize livestock production structures, whilst ensuring viable returns for the farmers. On a global scale, beef producers need tools to assist them to produce more high-quality products whilst maintaining economic efficiency. The Grange Scottish Beef Model (GSBM) was customized to simulate beef finishing enterprises using data from Scottish beef finishing studies, as well as agricultural input and output price datasets. Here we describe the model and its use to determine the cost-effectiveness of alternative current management practices (e.g. forage- and cereal-based finishing) and slaughter ages (i.e. short, medium or long finishing duration). To better understand drivers of profitability in beef finishing systems, several scenarios comparing finishing duration, gender, genetic selection of stock for growth rate or feed efficiency, as well as financial support were tested. There are opportunities for profitable and sustainable beef production in Scotland, for both cereal and forage based systems, particularly when aiming for a younger age profile at slaughtering. By careful choice of finishing systems matched to animal potential, as well as future selection of high performing and feed efficient cattle, beef finishers will be able to enhance performance and increase financial returns

    How closely does transient magnetic linear dichroism follow the spin moment?

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    In highly out-of-equilibrium states of matter, such as those induced by a pump laser, the applicability of well established spectroscopic probes of magnetic order are called into question. Here we address the validity of x-ray absorption techniques in pump laser conditions, focusing on magnetic linear dichroism (MLD), a crucial probe of antiferromagnetic (AFM) order. We directly compute the dynamics of the square of the spin moment and compare to those obtained via the MLD response. For AFM FePd the agreement between these distinct routes to the magnetic moment severely degrades at pulse fluences greater than 1 mJ/cm2^2, indicating a breakdown of the MLD response as an accurate probe of the transient moment. This contrasts with the MLD for ferromagnetic FePt which reliably tracks the moment for fluences (and absorbed energies) up to an order of magnitude greater than the breakdown threshold for AFM FePd. The underlying microscopic reason for this we find to be increased laser induced excitations out of the dd-band in AFM FePd, where this increase is made possible by the AFM pseudogap

    The sociospatial factors of death: Analyzing effects of geospatially-distributed variables in a Bayesian mortality model for Hong Kong

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    Human mortality is in part a function of multiple socioeconomic factors that differ both spatially and temporally. Adjusting for other covariates, the human lifespan is positively associated with household wealth. However, the extent to which mortality in a geographical region is a function of socioeconomic factors in both that region and its neighbors is unclear. There is also little information on the temporal components of this relationship. Using the districts of Hong Kong over multiple census years as a case study, we demonstrate that there are differences in how wealth indicator variables are associated with longevity in (a) areas that are affluent but neighbored by socially deprived districts versus (b) wealthy areas surrounded by similarly wealthy districts. We also show that the inclusion of spatially-distributed variables reduces uncertainty in mortality rate predictions in each census year when compared with a baseline model. Our results suggest that geographic mortality models should incorporate nonlocal information (e.g., spatial neighbors) to lower the variance of their mortality estimates, and point to a more in-depth analysis of sociospatial spillover effects on mortality rates.Comment: 26 pages (15 main, 11 appendix), 22 figures (6 main, 11 appendix), 2 table

    Transient spin injection efficiencies at ferromagnet/metal interfaces

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    Spin injection across interfaces driven by ultrashort optical pulses on femtosecond timescales constitutes a new way to design spintronics applications. Targeted utilization of this phenomenon requires knowledge of the efficiency of non-equilibrium spin injection. From a quantitative comparison of ab initio time-dependent density functional theory and interface-sensitive, time-resolved non-linear optical experiment, the spin injection efficiency (SIE) at the Co/Cu(001) interface is determined, and its microscopic origin, i.e., the influence of spin-orbit coupling and the interface electronic structure, is discussed. Moreover, we theoretically predict that the SIE at ferromagnetic–metal interfaces can be optimized through laser pulse and materials parameters, namely the fluence, pulse duration, and substrate material

    Cognitive Restoration in Children Following Exposure to Nature: Evidence From the Attention Network Task and Mobile Eye Tracking

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    Exposure to nature improves cognitive performance through a process of cognitive restoration. However, few studies have explored the effect in children, and no studies have explored how eye movements “in the wild” with mobile eye tracking technology contribute to the restoration process. Our results demonstrated that just a 30-min walk in a natural environment was sufficient to produce a faster and more stable pattern of responding on the Attention Network Task, compared with an urban environment. Exposure to the natural environment did not improve executive (directed) attention performance. This pattern of results supports suggestions that children and adults experience unique cognitive benefits from nature. Further, we provide the first evidence of a link between cognitive restoration and the allocation of eye gaze. Participants wearing a mobile eye-tracker exhibited higher fixation rates while walking in the natural environment compared to the urban environment. The data go some way in uncovering the mechanisms sub-serving the restoration effect in children and elaborate how nature may counteract the effects of mental fatigue
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