959 resultados para Non-minimum phase systems
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Ring opening metathesis polymerization (ROMP) is a variant of olefin metathesis used to polymerize strained cyclic olefins. Ruthenium-based Grubbs’ catalysts are widely used in ROMP to produce industrially important products. While highly efficient in organic solvents such as dichloromethane and toluene, these hydrophobic catalysts are not typically applied in aqueous systems. With the advancements in emulsion and miniemulsion polymerization, it is promising to conduct ROMP in an aqueous dispersed phase to generate well-defined latex nanoparticles while improving heat transfer and reducing the use of volatile organic solvents (VOCs). Herein I report the efforts made using a PEGylated ruthenium alkylidene as the catalyst to initiate ROMP in an oil-in-water miniemulsion. 1H NMR revealed that the synthesized PEGylated catalyst was stable and reactive in water. Using 1,5-cyclooctadiene (COD) as monomer, we showed the highly efficient catalyst yielded colloidally stable polymer latexes with ~ 100% conversion at room temperature. Kinetic studies demonstrated first-order kinetics with good livingness as confirmed by the shift of gel permeation chromatography (GPC) traces. Depending on the surfactants used, the particle sizes ranged from 100 to 300 nm with monomodal distributions. The more strained cyclic olefin norbornene (NB) could also be efficiently polymerized with a PEGylated ruthenium alkylidene in miniemulsion to full conversion and with minimal coagulum formation.
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Veterinary medicines (VMs) from agricultural industry can enter the environment in a number of ways. This includes direct exposure through aquaculture, accidental spillage and disposal, and indirect entry by leaching from manure or runoff after treatment. Many compounds used in animal treatments have ecotoxic properties that may have chronic or sometimes lethal effects when they come into contact with non-target organisms. VMs enter the environment in mixtures, potentially having additive effects. Traditional ecotoxicology tests are used to determine the lethal and sometimes reproductive effects on freshwater and terrestrial organisms. However, organisms used in ecotoxicology tests can be unrepresentative of the populations that are likely to be exposed to the compound in the environment. Most often the tests are on single compound toxicity but mixture effects may be significant and should be included in ecotoxicology testing. This work investigates the use, measured environmental concentrations (MECs) and potential impact of sea lice treatments on salmon farms in Scotland. Alternative methods for ecotoxicology testing including mixture toxicity, and the use of in silico techniques to predict the chronic impact of VMs on different species of aquatic organisms were also investigated. The Scottish Environmental Protection Agency (SEPA) provided information on the use of five sea lice treatments from 2008-2011 on Scottish salmon farms. This information was combined with the recently available data on sediment MECs for the years 2009-2012 provided by SEPA using ArcGIS 10.1. In depth analysis of this data showed that from a total of 55 sites, 30 sites had a MEC higher than the maximum allowable concentration (MAC) as set out by SEPA for emamectin benzoate and 7 sites had a higher MEC than MAC for teflubenzuron. A number of sites that were up to 16 km away from the nearest salmon farm reported as using either emamectin benzoate or teflubenzuron measured positive for the two treatments. There was no relationship between current direction and the distribution of the sea lice treatments, nor was there any evidence for alternative sources of the compounds e.g. land treatments. The sites that had MECs higher than the MAC could pose a risk to non-target organisms and disrupt the species dynamics of the area. There was evidence that some marine protected sites might be at risk of exposure to these compounds. To complement this work, effects on acute mixture toxicity of the 5 sea lice treatments, plus one major metabolite 3-phenoxybenzoic acid (3PBA), were measured using an assay using the bioluminescent bacteria Aliivibrio fischeri. When exposed to the 5 sea lice treatments and 3PBA A. fischeri showed a response to 3PBA, emamectin benzoate and azamethiphos as well as combinations of the three. In order to establish any additive effect of the sea lice treatments, the efficacy of two mixture prediction equations, concentration addition (CA) and independent action ii(IA) were tested using the results from single compound dose response curves. In this instance IA was the more effective prediction method with a linear regression confidence interval of 82.6% compared with 22.6% of CA. In silico molecular docking was carried out to predict the chronic effects of 15 VMs (including the five used as sea lice control). Molecular docking has been proposed as an alternative screening method for the chronic effects of large animal treatments on non-target organisms. Oestrogen receptor alpha (ERα) of 7 non-target bony fish and the African clawed frog Xenopus laevis were modelled using SwissModel. These models were then ‘docked’ to oestradiol, the synthetic oestrogen ethinylestradiol, two known xenoestrogens dichlorodiphenyltrichloroethane (DDT) and bisphenol A (BPA), the antioestrogen breast cancer treatment tamoxifen and 15 VMs using Auto Dock 4. Based on the results of this work, four VMs were identified as being possible xenoestrogens or anti-oestrogens; these were cypermethrin, deltamethrin, fenbendazole and teflubenzuron. Further investigation, using in vitro assays, into these four VMs has been suggested as future work. A modified recombinant yeast oestrogen screen (YES) was attempted using the cDNA of the ERα of the zebrafish Danio rerio and the rainbow trout Oncorhynchus mykiss. Due to time and difficulties in cloning protocols this work was unable to be completed. Use of such in vitro assays would allow for further investigation of the highlighted VMs into their oestrogenic potential. In conclusion, VMs used as sea lice treatments, such as teflubenzuron and emamectin benzoate may be more persistent and have a wider range in the environment than previously thought. Mixtures of sea lice treatments have been found to persist together in the environment, and effects of these mixtures on the bacteria A. fischeri can be predicted using the IA equation. Finally, molecular docking may be a suitable tool to predict chronic endocrine disrupting effects and identify varying degrees of impact on the ERα of nine species of aquatic organisms.
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This paper is on the use and performance of M-path polyphase Infinite Impulse Response (IIR) filters for channelisation, conventionally where Finite Impulse Response (FIR) filters are preferred. This paper specifically focuses on the Discrete Fourier Transform (DFT) modulated filter banks, which are known to be an efficient choice for channelisation in communication systems. In this paper, the low-pass prototype filter for the DFT filter bank has been implemented using an M-path polyphase IIR filter and we show that the spikes present at the stopband can be avoided by making use of the guardbands between narrowband channels. It will be shown that the channelisation performance will not be affected when polyphase IIR filters are employed instead of their counterparts derived from FIR prototype filters. Detailed complexity and performance analysis of the proposed use will be given in this article.
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This paper studies the impact of in-phase and quadrature-phase imbalance (IQI) in two-way amplify-and-forward (AF) relaying systems. In particular, the effective signal-to-interference-plus-noise ratio (SINR) is derived for each source node, considering four different linear detection schemes, namely, uncompensated (Uncomp) scheme, maximal-ratio-combining (MRC), zero-forcing (ZF) and minimum mean-square error (MMSE) based schemes. For each proposed scheme, the outage probability (OP) is investigated over independent, non-identically distributed Nakagami-m fading channels, and exact closed-form expressions are derived for the first three schemes. Based on the closed-form OP expressions, an adaptive detection mode switching scheme is designed for minimizing the OP of both sources. An important observation is that, regardless of the channel conditions and transmit powers, the ZF-based scheme should always be selected if the target SINR is larger than 3 (4.77dB), while the MRC-based scheme should be avoided if the target SINR is larger than 0.38 (-4.20dB).
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Presented in this report is an investigation of the use of "sand-lightweight" concrete in prestressed concrete structures. The sand-lightweight concrete consists of 100% sand substitution for fines, along with Idealite coarse and medium lightweight aggregate and Type I Portland Cement.
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In the past decades, social-ecological systems (SESs) worldwide have undergone dramatic transformations with often detrimental consequences for livelihoods. Although resilience thinking offers promising conceptual frameworks to understand SES transformations, empirical resilience assessments of real-world SESs are still rare because SES complexity requires integrating knowledge, theories, and approaches from different disciplines. Taking up this challenge, we empirically assess the resilience of a South African pastoral SES to drought using various methods from natural and social sciences. In the ecological subsystem, we analyze rangelands’ ability to buffer drought effects on forage provision, using soil and vegetation indicators. In the social subsystem, we assess households’ and communities’ capacities to mitigate drought effects, applying agronomic and institutional indicators and benchmarking against practices and institutions in traditional pastoral SESs. Our results indicate that a decoupling of livelihoods from livestock-generated income was initiated by government interventions in the 1930s. In the post-apartheid phase, minimum-input strategies of herd management were adopted, leading to a recovery of rangeland vegetation due to unintentionally reduced stocking densities. Because current livelihood security is mainly based on external monetary resources (pensions, child grants, and disability grants), household resilience to drought is higher than in historical phases. Our study is one of the first to use a truly multidisciplinary resilience assessment. Conflicting results from partial assessments underline that measuring narrow indicator sets may impede a deeper understanding of SES transformations. The results also imply that the resilience of contemporary, open SESs cannot be explained by an inward-looking approach because essential connections and drivers at other scales have become relevant in the globalized world. Our study thus has helped to identify pitfalls in empirical resilience assessment and to improve the conceptualization of SES dynamics.
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Phase change problems arise in many practical applications such as air-conditioning and refrigeration, thermal energy storage systems and thermal management of electronic devices. The physical phenomenon in such applications are complex and are often difficult to be studied in detail with the help of only experimental techniques. The efforts to improve computational techniques for analyzing two-phase flow problems with phase change are therefore gaining momentum. The development of numerical methods for multiphase flow has been motivated generally by the need to account more accurately for (a) large topological changes such as phase breakup and merging, (b) sharp representation of the interface and its discontinuous properties and (c) accurate and mass conserving motion of the interface. In addition to these considerations, numerical simulation of multiphase flow with phase change introduces additional challenges related to discontinuities in the velocity and the temperature fields. Moreover, the velocity field is no longer divergence free. For phase change problems, the focus of developmental efforts has thus been on numerically attaining a proper conservation of energy across the interface in addition to the accurate treatment of fluxes of mass and momentum conservation as well as the associated interface advection. Among the initial efforts related to the simulation of bubble growth in film boiling applications the work in \cite{Welch1995} was based on the interface tracking method using a moving unstructured mesh. That study considered moderate interfacial deformations. A similar problem was subsequently studied using moving, boundary fitted grids \cite{Son1997}, again for regimes of relatively small topological changes. A hybrid interface tracking method with a moving interface grid overlapping a static Eulerian grid was developed \cite{Juric1998} for the computation of a range of phase change problems including, three-dimensional film boiling \cite{esmaeeli2004computations}, multimode two-dimensional pool boiling \cite{Esmaeeli2004} and film boiling on horizontal cylinders \cite{Esmaeeli2004a}. The handling of interface merging and pinch off however remains a challenge with methods that explicitly track the interface. As large topological changes are crucial for phase change problems, attention has turned in recent years to front capturing methods utilizing implicit interfaces that are more effective in treating complex interface deformations. The VOF (Volume of Fluid) method was adopted in \cite{Welch2000} to simulate the one-dimensional Stefan problem and the two-dimensional film boiling problem. The approach employed a specific model for mass transfer across the interface involving a mass source term within cells containing the interface. This VOF based approach was further coupled with the level set method in \cite{Son1998}, employing a smeared-out Heaviside function to avoid the numerical instability related to the source term. The coupled level set, volume of fluid method and the diffused interface approach was used for film boiling with water and R134a at the near critical pressure condition \cite{Tomar2005}. The effect of superheat and saturation pressure on the frequency of bubble formation were analyzed with this approach. The work in \cite{Gibou2007} used the ghost fluid and the level set methods for phase change simulations. A similar approach was adopted in \cite{Son2008} to study various boiling problems including three-dimensional film boiling on a horizontal cylinder, nucleate boiling in microcavity \cite{lee2010numerical} and flow boiling in a finned microchannel \cite{lee2012direct}. The work in \cite{tanguy2007level} also used the ghost fluid method and proposed an improved algorithm based on enforcing continuity and divergence-free condition for the extended velocity field. The work in \cite{sato2013sharp} employed a multiphase model based on volume fraction with interface sharpening scheme and derived a phase change model based on local interface area and mass flux. Among the front capturing methods, sharp interface methods have been found to be particularly effective both for implementing sharp jumps and for resolving the interfacial velocity field. However, sharp velocity jumps render the solution susceptible to erroneous oscillations in pressure and also lead to spurious interface velocities. To implement phase change, the work in \cite{Hardt2008} employed point mass source terms derived from a physical basis for the evaporating mass flux. To avoid numerical instability, the authors smeared the mass source by solving a pseudo time-step diffusion equation. This measure however led to mass conservation issues due to non-symmetric integration over the distributed mass source region. The problem of spurious pressure oscillations related to point mass sources was also investigated by \cite{Schlottke2008}. Although their method is based on the VOF, the large pressure peaks associated with sharp mass source was observed to be similar to that for the interface tracking method. Such spurious fluctuation in pressure are essentially undesirable because the effect is globally transmitted in incompressible flow. Hence, the pressure field formation due to phase change need to be implemented with greater accuracy than is reported in current literature. The accuracy of interface advection in the presence of interfacial mass flux (mass flux conservation) has been discussed in \cite{tanguy2007level,tanguy2014benchmarks}. The authors found that the method of extending one phase velocity to entire domain suggested by Nguyen et al. in \cite{nguyen2001boundary} suffers from a lack of mass flux conservation when the density difference is high. To improve the solution, the authors impose a divergence-free condition for the extended velocity field by solving a constant coefficient Poisson equation. The approach has shown good results with enclosed bubble or droplet but is not general for more complex flow and requires additional solution of the linear system of equations. In current thesis, an improved approach that addresses both the numerical oscillation of pressure and the spurious interface velocity field is presented by featuring (i) continuous velocity and density fields within a thin interfacial region and (ii) temporal velocity correction steps to avoid unphysical pressure source term. Also I propose a general (iii) mass flux projection correction for improved mass flux conservation. The pressure and the temperature gradient jump condition are treated sharply. A series of one-dimensional and two-dimensional problems are solved to verify the performance of the new algorithm. Two-dimensional and cylindrical film boiling problems are also demonstrated and show good qualitative agreement with the experimental observations and heat transfer correlations. Finally, a study on Taylor bubble flow with heat transfer and phase change in a small vertical tube in axisymmetric coordinates is carried out using the new multiphase, phase change method.
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The study of quantum degenerate gases has many applications in topics such as condensed matter dynamics, precision measurements and quantum phase transitions. We built an apparatus to create 87Rb Bose-Einstein condensates (BECs) and generated, via optical and magnetic interactions, novel quantum systems in which we studied the contained phase transitions. For our first experiment we quenched multi-spin component BECs from a miscible to dynamically unstable immiscible state. The transition rapidly drives any spin fluctuations with a coherent growth process driving the formation of numerous spin polarized domains. At much longer times these domains coarsen as the system approaches equilibrium. For our second experiment we explored the magnetic phases present in a spin-1 spin-orbit coupled BEC and the contained quantum phase transitions. We observed ferromagnetic and unpolarized phases which are stabilized by the spin-orbit coupling’s explicit locking between spin and motion. These two phases are separated by a critical curve containing both first-order and second-order transitions joined at a critical point. The narrow first-order transition gives rise to long-lived metastable states. For our third experiment we prepared independent BECs in a double-well potential, with an artificial magnetic field between the BECs. We transitioned to a single BEC by lowering the barrier while expanding the region of artificial field to cover the resulting single BEC. We compared the vortex distribution nucleated via conventional dynamics to those produced by our procedure, showing our dynamical process populates vortices much more rapidly and in larger number than conventional nucleation.
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Harmful algal blooms of Alexandrium spp. dinoflagellates regularly occur in French coastal waters contaminating shellfish. Studies have demonstrated that toxic Alexandrium spp. disrupt behavioural and physiological processes in marine filter-feeders, but molecular modifications triggered by phycotoxins are less well understood. This study analyzed the mRNA levels of 7 genes encoding antioxidant/detoxifying enzymes in gills of Pacific oysters (Crassostrea gigas) exposed to a cultured, toxic strain of A. minutum, a producer of paralytic shellfish toxins (PST) or fed Tisochrysis lutea (T. lutea, formerly Isochrysis sp., clone Tahitian (T. iso)), a non-toxic control diet, in four repeated experiments. Transcript levels of sigma-class glutathione S-transferase (GST), glutathione reductase (GR) and ferritin (Fer) were significantly higher in oysters exposed to A. minutum compared to oysters fed T. lutea. The detoxification pathway based upon glutathione (GSH)-conjugation of toxic compounds (phase II) is likely activated, and catalyzed by GST. This system appeared to be activated in gills probably for the detoxification of PST and/or extra-cellular compounds, produced by A. minutum. GST, GR and Fer can also contribute to antioxidant functions to prevent cellular damage from increased reactive oxygen species (ROS) originating either from A. minutum cells directly, from oyster hemocytes during immune response, or from other gill cells as by-products of detoxification.
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A detailed non-equilibrium state diagram of shape-anisotropic particle fluids is constructed. The effects of particle shape are explored using Naive Mode Coupling Theory (NMCT), and a single particle Non-linear Langevin Equation (NLE) theory. The dynamical behavior of non-ergodic fluids are discussed. We employ a rotationally frozen approach to NMCT in order to determine a transition to center of mass (translational) localization. Both ideal and kinetic glass transitions are found to be highly shape dependent, and uniformly increase with particle dimensionality. The glass transition volume fraction of quasi 1- and 2- dimensional particles fall monotonically with the number of sites (aspect ratio), while 3-dimensional particles display a non-monotonic dependence of glassy vitrification on the number of sites. Introducing interparticle attractions results in a far more complex state diagram. The ideal non-ergodic boundary shows a glass-fluid-gel re-entrance previously predicted for spherical particle fluids. The non-ergodic region of the state diagram presents qualitatively different dynamics in different regimes. They are qualified by the different behaviors of the NLE dynamic free energy. The caging dominated, repulsive glass regime is characterized by long localization lengths and barrier locations, dictated by repulsive hard core interactions, while the bonding dominated gel region has short localization lengths (commensurate with the attraction range), and barrier locations. There exists a small region of the state diagram which is qualified by both glassy and gel localization lengths in the dynamic free energy. A much larger (high volume fraction, and high attraction strength) region of phase space is characterized by short gel-like localization lengths, and long barrier locations. The region is called the attractive glass and represents a 2-step relaxation process whereby a particle first breaks attractive physical bonds, and then escapes its topological cage. The dynamic fragility of fluids are highly particle shape dependent. It increases with particle dimensionality and falls with aspect ratio for quasi 1- and 2- dimentional particles. An ultralocal limit analysis of the NLE theory predicts universalities in the behavior of relaxation times, and elastic moduli. The equlibrium phase diagram of chemically anisotropic Janus spheres and Janus rods are calculated employing a mean field Random Phase Approximation. The calculations for Janus rods are corroborated by the full liquid state Reference Interaction Site Model theory. The Janus particles consist of attractive and repulsive regions. Both rods and spheres display rich phase behavior. The phase diagrams of these systems display fluid, macrophase separated, attraction driven microphase separated, repulsion driven microphase separated and crystalline regimes. Macrophase separation is predicted in highly attractive low volume fraction systems. Attraction driven microphase separation is charaterized by long length scale divergences, where the ordering length scale determines the microphase ordered structures. The ordering length scale of repulsion driven microphase separation is determined by the repulsive range. At the high volume fractions, particles forgo the enthalpic considerations of attractions and repulsions to satisfy hard core constraints and maximize vibrational entropy. This results in site length scale ordering in rods, and the sphere length scale ordering in Janus spheres, i.e., crystallization. A change in the Janus balance of both rods and spheres results in quantitative changes in spinodal temperatures and the position of phase boundaries. However, a change in the block sequence of Janus rods causes qualitative changes in the type of microphase ordered state, and induces prominent features (such as the Lifshitz point) in the phase diagrams of these systems. A detailed study of the number of nearest neighbors in Janus rod systems reflect a deep connection between this local measure of structure, and the structure factor which represents the most global measure of order.
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International audience
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Herbicide runoff from cropping fields has been identified as a threat to the Great Barrier Reef ecosystem. A field investigation was carried out to monitor the changes in runoff water quality resulting from four different sugarcane cropping systems that included different herbicides and contrasting tillage and trash management practices. These include (i) Conventional - Tillage (beds and inter-rows) with residual herbicides used; (ii) Improved - only the beds were tilled (zonal) with reduced residual herbicides used; (iii) Aspirational - minimum tillage (one pass of a single tine ripper before planting) with trash mulch, no residual herbicides and a legume intercrop after cane establishment; and (iv) New Farming System (NFS) - minimum tillage as in Aspirational practice with a grain legume rotation and a combination of residual and knockdown herbicides. Results suggest soil and trash management had a larger effect on the herbicide losses in runoff than the physico-chemical properties of herbicides. Improved practices with 30% lower atrazine application rates than used in conventional systems produced reduced runoff volumes by 40% and atrazine loss by 62%. There were a 2-fold variation in atrazine and >10-fold variation in metribuzin loads in runoff water between reduced tillage systems differing in soil disturbance and surface residue cover from the previous rotation crops, despite the same herbicide application rates. The elevated risk of offsite losses from herbicides was illustrated by the high concentrations of diuron (14mugL-1) recorded in runoff that occurred >2.5months after herbicide application in a 1st ratoon crop. A cropping system employing less persistent non-selective herbicides and an inter-row soybean mulch resulted in no residual herbicide contamination in runoff water, but recorded 12.3% lower yield compared to Conventional practice. These findings reveal a trade-off between achieving good water quality with minimal herbicide contamination and maintaining farm profitability with good weed control.
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The Amazon river prawn (Macrobrachium amazonicum) is a native species with great potential for aquaculture, based on promising results obtained from experimental culture trials in Brazil. The influence of different stocking densities on the development of prawns reared in cages in the nursery phase as well as on their growth when transferred to grow-out net pens at lower densities was evaluated. In the nursery phase, juveniles I (0.157 +/- 0.014 g, 47 days old) were stocked in 0.5 m(-2) cages at densities of 400, 800 and 1200 m(-2). After 71 days, prawns were transferred to grow-out net pens of 2.0 m(-2), at a density of 20 juveniles II m(-2). The treatments were determined by the mean weights registered for the prawns (118 days old) previously stocked at 400, 800 and 1200 juveniles I m(-2) in the nursery phase: 0.94 +/- 0.07 g (T1), 0.61 +/- 0.04 g (T2) and 0.48 +/- 0.07 g (T3), respectively. In the nursery phase, mean survival was above 96%, whereas mean weights were significantly higher (P<0.05) for the density of 400 prawns m(-2). The highest biomass (276.7 g) and productivity (1152 juveniles II m(-2)) were registered at the density of 1200 prawns m(-2), differing significantly (P<0.05) from the lower densities. One month after the transfer of the animals to the net pens, there was recovery in the specific growth rate (SGR) of prawns in all treatments which was significantly higher (P<0.05) in T3 (4.01 +/- 0.36% day(-1)) and T2 (3.60 +/- 0.18% day(-1)). The feed conversion efficiency (FCE) in the first month after the transfer was also significantly higher (P<0.05) in T3 (78.2 +/- 19.1%) when compared to T1 (39.8 +/- 9.5%). These results suggest the occurrence of a compensatory growth in M. amazonicum after transferring them to lower densities, which can point out high densities for nursery cages as a viable practice. After 277 days of grow-out phase in net pens in the cold season, survival, mean weight and biomass did not differ significantly among the treatments, indicating the viability of using net pens in stocking prawns during autumn and winter, since the minimum temperature does not drop below 17 degrees C. Influence of stocking density during the nursery phase on the grow-out of prawns was not observed. The population structure in prawns reared in net-pens was similar to that observed in earthen ponds. (C) 2012 Elsevier B.V. All rights reserved.