Simulation of multicomponent gas transport through mixed-matrix membranes

We extend the Maxwell-Stefan (M-S) formulation of irreversible thermodynamics to multicomponent transport in mixed-matrix membranes (MMMs), using a simulation-based rigorous modeling approach (SMA) through finite-element method (FEM) solution of the three-dimensional (3-d) transport problem in full-scale MMMs. In the new approach, we generalize the dual-mode/partial immobilization (DM/PI) theory for the local permeability in glassy polymers to describe multicomponent permeation in pure glassy polymer membranes and MMMs, by reformulating the M-S constitutive equations in the Onsager formalism considering concentration-dependent transport diffusivities and non-uniform concentration gradients across the MMM. In this way, the new M-S formulation explicitly considers effects of intrinsic MMM features such as finite filler particle size and isotherm nonlinearity in the MMM constituent phases, as well as mixture-related effects, such as competitive adsorption and friction amongst permeants, on the calculation of the mixture fluxes (permeabilities). This is achieved without introduction of empirical fitting parameters in the MMM permeability calculation and only requiring single-gas experimental or simulation-based adsorption and permeation data on the individual MMM materials to predict the mixture perm-selectivity in the MMM as a whole. Further, we validate the new approach by using available experimental permeation data for the separation of an equimolar binary mixture of propylene (C H ) and propane (C H ) in ZIF‑8/PIM-6FDA-OH MMMs, with the rigorous simulation results showing very good agreement with both experimental single and mixed-gas permeabilities and perm-selectivities

Improved pore connectivity by the reduction of cobalt oxide silica membranes

This work investigated the permeation of binary gas mixtures in non-reducing (He/CO2) and reducing (H-2/Ar) conditions at temperatures ranging from 200 to 500 degrees C. A common performance aspect under both non-reducing and reducing conditions was that the He and H-2 purity in the permeate stream was independent of temperature for the tested binary gas mixtures, except at very high He/CO2 or H-2/Ar concentrations (>= 90/10) in the retentate stream. Under non-reducing conditions, the transport of gases was consistent with molecular sieving properties of silica derived membranes, and He permeance was constant irrespective of the He/CO2 binary concentration tested. An anomalous H-2 transport was observed under reduced conditions, as unexpectedly the H-2 permeance was higher for gas mixtures instead of single gas. Further tests showed that H-2 permeance increased 170% as the gas mixture changed from single H-2 gas to H-2/Ar gas mixtures. This was attributed to the experimental procedure, as the membranes were partially reduced each day and tested for gas permeation from pure H-2 to lower H-2 concentration in gas mixtures. Under these partial reducing conditions, H-2 slowly reacts with the surface of the dense Co3O4 particle, thus forming a porous CoO region. The increase in H-2 permeance was therefore attributed to improved pore connectivity between the silica structure and the porous CoO region. (C) 2015 Elsevier B.V. All rights reserved

A method for the objective selection of landscape-scale study regions and sites at the national level

1. Ecological processes operating on large spatio-temporal scales are difficult to disentangle with traditional empirical approaches. Alternatively, researchers can take advantage of ‘natural’ experiments, where experimental control is exercised by careful site selection. Recent advances in developing protocols for designing these ‘pseudo-experiments’ commonly do not consider the selection of the focal region and predictor variables are usually restricted to two. Here, we advance this type of site selection protocol to study the impact of multiple landscape scale factors on pollinator abundance and diversity across multiple regions. 2. Using datasets of geographic and ecological variables with national coverage, we applied a novel hierarchical computation approach to select study sites that contrast as much as possible in four key variables, while attempting to maintain regional comparability and national representativeness. There were three main steps to the protocol: (i) selection of six 100 9 100 km2 regions that collectively provided land cover representative of the national land average, (ii) mapping of potential sites into a multivariate space with axes representing four key factors potentially influencing insect pollinator abundance, and (iii) applying a selection algorithm which maximized differences between the four key variables, while controlling for a set of external constraints. 3. Validation data for the site selection metrics were recorded alongside the collection of data on pollinator populations during two field campaigns. While the accuracy of the metric estimates varied, the site selection succeeded in objectively identifying field sites that differed significantly in values for each of the four key variables. Between-variable correlations were also reduced or eliminated, thus facilitating analysis of their separate effects. 4. This study has shown that national datasets can be used to select randomized and replicated field sites objectively within multiple regions and along multiple interacting gradients. Similar protocols could be used for studying a range of alternative research questions related to land use or other spatially explicit environmental variables, and to identify networks of field sites for other countries, regions, drivers and response taxa in a wide range of scenarios

Rapid thermal treatment of interlayer-free ethyl silicate 40 derived membranes for desalination

This work demonstrates for the first time the preparation of interlayer-free silica membranes by the Rapid Thermal Processing (RTP) method at 630 degrees C using ethyl silicate (ES40) as a silica precursor. RTP resulted in water being retained inside the xerogel pores at higher temperatures, thus favouring condensation reactions and the formation of siloxane bridges. As a result, RTP ES40 xerogels were stronger than their conventional thermal processing (CTP) counterparts and also had higher pore volumes and surface areas. Nevertheless, RTP ES40 xerogels were characterised by a tri-modal pore size distribution. The majority of pores were in the microporous domain with a minor fraction of mesopores. Successful preparation of membranes without a conventional interlayer was dependent on the pH of the sol-gel, as sols with a pH 4 or 6 were able to penetrate into the alpha-alumina substrate allowing strong adhesion to the support and formed a defect free top layer. The best interlayer-free RTP silica membrane was prepared with a pH 4 sol reaching high water fluxes of 17.8 kg m(-2) h(-1) at 60 degrees C and high salt rejection (> 99%) for desalination of 3.5 wt% NaCl synthetic seawater. The dilution of the sol with ethanol also played an important role in the membrane stability. Membranes prepared from a sol of pH 4 with EtOH:Si ratio 255:4 were stable for 120 h, but a reduction in this ratio to 200:4 increased the stability to 300 h. This improvement was attributed to thicker films derived from more viscous sols. (C) 2016 Elsevier B.V. All rights reserved

Binary gas mixture and hydrothermal stability investigation of cobalt silica membranes

This work investigates the influence of hydrothermal exposure on the separation performance of sal gel derived cobalt oxide silica membranes for both single gases (He, H-2, CO2 and N-2) and binary gas mixtures (He/CO2). The surface area of the materials slightly decreased after exposed to 25 mol% water vapour at 550 degrees C for 100 h. The membranes complied with activation transport mechanism before and after hydrothermal treatment (HT), and for both single gas and gas mixture permeation. Best values were achieved for He permeance of 3.3 x 10(7) Mol m(-2) s(-1) Pa-1 at 500 degrees C and permselectivity of 479 for He/CO2. After HT, the permeance of He and H-2 decreased by 28% and 22% at 500 degrees C, respectively, while the permeance of CO2 increased and resulting in a lower He/CO2 permselectivity of 190. For gas mixtures, the He purity in the permeate side increased from 62% to 97% at 200 degrees C when the He feed molar concentration increased from 10% to 50% before HT. The He permeance remained unchanged with respect to He feed concentrations and was unaffected by the presence of CO2, although a reduction of He permeance was observed after HT exposure. The He purity in the permeate side was similar before and after HT exposure as a function of the He concentration in the feed side. Hence, the membrane matrix underwent densification though the overall pore size distribution did not broaden after hydrothermal treatment. (C) 2015 Elsevier B.V. All rights reserved

Vacuum-assisted tailoring of pore structures of phenolic resin derived carbon membranes

This work shows the preparation and separation performance assessment of carbon membranes derived from phenolic resin by a vacuum-assisted method and carbonisation in an inert atmosphere. The vacuum time played an important role in tailoring the structure of the membranes. For instance, pore volumes and surface areas increased from 0.81 and 834 to 2.2 cmgand 1910 mg, respectively, as the vacuum time exposure increased from 0 to 1200 s. The significant structural changes correlated very well with water permeation, as fluxes increased by 91% as the vacuum time increased from 0 to 1200 s reaching up to 169 L mhat 5 bar. Molecular weight cut-off tests showed no rejection for the smaller glucose and sucrose molecules, though this increased to ~ 80% and full rejection for 36 kDa and 400 kDa polyvinyl pyrrolidine. Interestingly, FTIR spectra showed that the peaks of C–H stretching vibration (2800–3200 cm) and C–O stretching (1030 cm) became more pronounced as a function of increasing vacuum time, strongly suggesting that the use of vacuum further assisted in the polycondensation of phenolic oligomers. Based on these outcomes, a cluster to cluster model is proposed, whereby vacuum application promoted crosslinking reactions of the phenolic resin, creating microporous regions within the clusters, and mesoporous regions between the clusters

Elevated <scp>CO₂</scp> interacts with nutrient inputs to restructure plant communities in phosphorus‐limited grasslands

AbstractGlobally pervasive increases in atmospheric CO2 and nitrogen (N) deposition could have substantial effects on plant communities, either directly or mediated by their interactions with soil nutrient limitation. While the direct consequences of N enrichment on plant communities are well documented, potential interactions with rising CO2 and globally widespread phosphorus (P) limitation remain poorly understood. We investigated the consequences of simultaneous elevated CO2 (eCO2) and N and P additions on grassland biodiversity, community and functional composition in P‐limited grasslands. We exposed soil‐turf monoliths from limestone and acidic grasslands that have received &gt;25 years of N additions (3.5 and 14 g m−2 year−1) and 11 (limestone) or 25 (acidic) years of P additions (3.5 g m−2 year−1) to eCO2 (600 ppm) for 3 years. Across both grasslands, eCO2, N and P additions significantly changed community composition. Limestone communities were more responsive to eCO2 and saw significant functional shifts resulting from eCO2–nutrient interactions. Here, legume cover tripled in response to combined eCO2 and P additions, and combined eCO2 and N treatments shifted functional dominance from grasses to sedges. We suggest that eCO2 may disproportionately benefit P acquisition by sedges by subsidising the carbon cost of locally intense root exudation at the expense of co‐occurring grasses. In contrast, the functional composition of the acidic grassland was insensitive to eCO2 and its interactions with nutrient additions. Greater diversity of P‐acquisition strategies in the limestone grassland, combined with a more functionally even and diverse community, may contribute to the stronger responses compared to the acidic grassland. Our work suggests we may see large changes in the composition and biodiversity of P‐limited grasslands in response to eCO2 and its interactions with nutrient loading, particularly where these contain a high diversity of P‐acquisition strategies or developmentally young soils with sufficient bioavailable mineral P.</jats:p

Spatial patterns and environmental constraints on ecosystem services at a catchment scale

Improved understanding and prediction of the fundamental environmental controls on ecosystem service supply across the landscape will help to inform decisions made by policy makers and land-water managers. To evaluate this issue for a local catchment case study, we explored metrics and spatial patterns of service supply for water quality regulation, agriculture production, carbon storage, and biodiversity for the Macronutrient Conwy catchment. Methods included using ecosystem models such as LUCI and JULES, integration of national scale field survey datasets, earth observation products and plant trait databases, to produce finely resolved maps of species richness and primary production. Analyses were done with both 1x1 km gridded and subcatchment data. A common single gradient characterised catchment scale ecosystem services supply with agricultural production and carbon storage at opposing ends of the gradient as reported for a national-scale assessment. Species diversity was positively related to production due to the below national average productivity levels in the Conwy combined with the unimodal relationship between biodiversity and productivity at the national scale. In contrast to the national scale assessment, a strong reduction in water quality as production increased was observed in these low productive systems. Various soil variables were tested for their predictive power of ecosystem service supply. Soil carbon, nitrogen, their ratio and soil pH all had double the power of rainfall and altitude, each explaining around 45% of variation but soil pH is proposed as a potential metric for ecosystem service supply potential as it is a simple and practical metric which can be carried out in the field with crowd-sourcing technologies now available. The study emphasises the importance of considering multiple ecosystem services together due to the complexity of covariation at local and national scales, and the benefits of exploiting a wide range of metrics for each service to enhance data robustness

Search for squarks and gluinos in events with isolated leptons, jets and missing transverse momentum at s√=8 TeV with the ATLAS detector

The results of a search for supersymmetry in final states containing at least one isolated lepton (electron or muon), jets and large missing transverse momentum with the ATLAS detector at the Large Hadron Collider are reported. The search is based on proton-proton collision data at a centre-of-mass energy s√=8 TeV collected in 2012, corresponding to an integrated luminosity of 20 fb−1. No significant excess above the Standard Model expectation is observed. Limits are set on supersymmetric particle masses for various supersymmetric models. Depending on the model, the search excludes gluino masses up to 1.32 TeV and squark masses up to 840 GeV. Limits are also set on the parameters of a minimal universal extra dimension model, excluding a compactification radius of 1/R c = 950 GeV for a cut-off scale times radius (ΛR c) of approximately 30

Evidence for the Higgs-boson Yukawa coupling to tau leptons with the ATLAS detector

Results of a search for H → τ τ decays are presented, based on the full set of proton-proton collision data recorded by the ATLAS experiment at the LHC during 2011 and 2012. The data correspond to integrated luminosities of 4.5 fb−1 and 20.3 fb−1 at centre-of-mass energies of √s = 7 TeV and √s = 8 TeV respectively. All combinations of leptonic (τ → `νν¯ with ` = e, µ) and hadronic (τ → hadrons ν) tau decays are considered. An excess of events over the expected background from other Standard Model processes is found with an observed (expected) significance of 4.5 (3.4) standard deviations. This excess provides evidence for the direct coupling of the recently discovered Higgs boson to fermions. The measured signal strength, normalised to the Standard Model expectation, of µ = 1.43 +0.43 −0.37 is consistent with the predicted Yukawa coupling strength in the Standard Model