156 resultados para PRECIPITATION POLYMERIZATION


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We separate and quantify the sources of uncertainty in projections of regional (*2,500 km) precipitation changes for the twenty-first century using the CMIP3 multi-model ensemble, allowing a direct comparison with a similar analysis for regional temperature changes. For decadal means of seasonal mean precipitation, internal variability is the dominant uncertainty for predictions of the first decade everywhere, and for many regions until the third decade ahead. Model uncertainty is generally the dominant source of uncertainty for longer lead times. Scenario uncertainty is found to be small or negligible for all regions and lead times, apart from close to the poles at the end of the century. For the global mean, model uncertainty dominates at all lead times. The signal-to-noise ratio (S/N) of the precipitation projections is highest at the poles but less than 1 almost everywhere else, and is far lower than for temperature projections. In particular, the tropics have the highest S/N for temperature, but the lowest for precipitation. We also estimate a ‘potential S/N’ by assuming that model uncertainty could be reduced to zero, and show that, for regional precipitation, the gains in S/N are fairly modest, especially for predictions of the next few decades. This finding suggests that adaptation decisions will need to be made in the context of high uncertainty concerning regional changes in precipitation. The potential to narrow uncertainty in regional temperature projections is far greater. These conclusions on S/N are for the current generation of models; the real signal may be larger or smaller than the CMIP3 multi-model mean. Also note that the S/N for extreme precipitation, which is more relevant for many climate impacts, may be larger than for the seasonal mean precipitation considered here.

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Current changes in tropical precipitation from satellite data and climate models are assessed. Wet and dry regions of the tropics are defined as the highest 30% and lowest 70% of monthly precipitation values. Observed tropical ocean trends in the wet regime (1.8%/decade) and the dry regions (−2.6%/decade) according to the Global Precipitation Climatology Project (GPCP) over the period including Special Sensor Microwave Imager (SSM/I) data (1988–2008), where GPCP is believed to be more reliable, are of smaller magnitude than when including the entire time series (1979–2008) and closer to model simulations than previous comparisons. Analysing changes in extreme precipitation using daily data within the wet regions, an increase in the frequency of the heaviest 6% of events with warming for the SSM/I observations and model ensemble mean is identified. The SSM/I data indicate an increased frequency of the heaviest events with warming, several times larger than the expected Clausius–Clapeyron scaling and at the upper limit of the substantial range in responses in the model simulations.

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A method to estimate the size and liquid water content of drizzle drops using lidar measurements at two wavelengths is described. The method exploits the differential absorption of infrared light by liquid water at 905 nm and 1.5 μm, which leads to a different backscatter cross section for water drops larger than ≈50 μm. The ratio of backscatter measured from drizzle samples below cloud base at these two wavelengths (the colour ratio) provides a measure of the median volume drop diameter D0. This is a strong effect: for D0=200 μm, a colour ratio of ≈6 dB is predicted. Once D0 is known, the measured backscatter at 905 nm can be used to calculate the liquid water content (LWC) and other moments of the drizzle drop distribution. The method is applied to observations of drizzle falling from stratocumulus and stratus clouds. High resolution (32 s, 36 m) profiles of D0, LWC and precipitation rate R are derived. The main sources of error in the technique are the need to assume a value for the dispersion parameter μ in the drop size spectrum (leading to at most a 35% error in R) and the influence of aerosol returns on the retrieval (≈10% error in R for the cases considered here). Radar reflectivities are also computed from the lidar data, and compared to independent measurements from a colocated cloud radar, offering independent validation of the derived drop size distributions.

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The development of shallow cellular convection in warm orographic clouds is investigated through idealized numerical simulations of moist flow over topography using a cloud-resolving numerical model. Buoyant instability, a necessary element for moist convection, is found to be diagnosed most accurately through analysis of the moist Brunt–Väisälä frequency (N_m) rather than the vertical profile of θ_e. In statically unstable orographic clouds (N_m^2) < 0), additional environmental and terrain-related factors are shown to have major effects on the amount of cellularity that occurs in 2D simulations. One of these factors, the basic-state wind shear, may suppress convection in 2D yet allow for longitudinal convective roll circulations in 3D. The presence of convective structures within an orographic cloud substantially enhanced the maximum rainfall rates, precipitation efficiencies, and precipitation accumulations in all simulations.

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Optical data are compared with EISCAT radar observations of multiple Naturally Enhanced Ion-Acoustic Line (NEIAL) events in the dayside cusp. This study uses narrow field of view cameras to observe small-scale, short-lived auroral features. Using multiple-wavelength optical observations, a direct link between NEIAL occurrences and low energy (about 100 eV) optical emissions is shown. This is consistent with the Langmuir wave decay interpretation of NEIALs being driven by streams of low-energy electrons. Modelling work connected with this study shows that, for the measured ionospheric conditions and precipitation characteristics, growth of unstable Langmuir (electron plasma) waves can occur, which decay into ion-acoustic wave modes. The link with low energy optical emissions shown here, will enable future studies of the shape, extent, lifetime, grouping and motions of NEIALs.

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1. Changes in the frequency of extreme events, such as droughts, may be one of the most significant impacts of climate change for ecosystems. Models predict more frequent summer droughts in much of England: this paper investigates the impact on different types of plants in an ex-arable grassland community. 2. A long-term experiment simulated increased and decreased summer precipitation. Substantial interannual variation allowed the effects of summer drought to be tested in combination with wet and dry weather in other seasons. This is important, as climate models predict increased winter precipitation. 3. Total cover abundance in early summer increased with increasing water supply in the previous summer; there was no effect of winter precipitation. Productivity is therefore likely to decrease with more frequent summer droughts, with no mitigating effect of wetter winters. 4. The percentage cover of perennial grasses declined during a natural drought in 1995-97; this was exacerbated by the experimental drought treatment and reduced by supplemented rainfall. Simultaneously, short-lived ruderal species increased; this was greatest in drought treatments and least with supplemented rainfall. 4. These trends were subsequently reversed during several years of unusually wet weather, with perennial grasses increasing and short-lived forbs decreasing. This occurred even in experimentally droughted plots, and we propose that it resulted from rapid coverage of gaps during wet autumns and winters. 6. Deep-rooted species generally proved to be more drought resistant, but there were exceptions. 7. We conclude that increased frequency of summer droughts could have serious implications for the establishment and successional development of ex-arable grasslands. Increased winter precipitation would moderate the impact on species composition, but not on productivity.

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We describe the nature of recent (50 year) rainfall variability in the summer rainfall zone, South Africa, and how variability is recognised and responded to on the ground by farmers. Using daily rainfall data and self-organising mapping (SOM) we identify 12 internally homogeneous rainfall regions displaying differing parameters of precipitation change. Three regions, characterised by changing onset and timing of rains, rainfall frequencies and intensities, in Limpopo, North West and KwaZulu Natal provinces, were selected to investigate farmer perceptions of, and responses to, rainfall parameter changes. Village and household level analyses demonstrate that the trends and variabilities in precipitation parameters differentiated by the SOM analysis were clearly recognised by people living in the areas in which they occurred. A range of specific coping and adaptation strategies are employed by farmers to respond to climate shifts, some generic across regions and some facilitated by specific local factors. The study has begun to understand the complexity of coping and adaptation, and the factors that influence the decisions that are taken.

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With the current concern over climate change, descriptions of how rainfall patterns are changing over time can be useful. Observations of daily rainfall data over the last few decades provide information on these trends. Generalized linear models are typically used to model patterns in the occurrence and intensity of rainfall. These models describe rainfall patterns for an average year but are more limited when describing long-term trends, particularly when these are potentially non-linear. Generalized additive models (GAMS) provide a framework for modelling non-linear relationships by fitting smooth functions to the data. This paper describes how GAMS can extend the flexibility of models to describe seasonal patterns and long-term trends in the occurrence and intensity of daily rainfall using data from Mauritius from 1962 to 2001. Smoothed estimates from the models provide useful graphical descriptions of changing rainfall patterns over the last 40 years at this location. GAMS are particularly helpful when exploring non-linear relationships in the data. Care is needed to ensure the choice of smooth functions is appropriate for the data and modelling objectives. (c) 2008 Elsevier B.V. All rights reserved.

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A physically motivated statistical model is used to diagnose variability and trends in wintertime ( October - March) Global Precipitation Climatology Project (GPCP) pentad (5-day mean) precipitation. Quasi-geostrophic theory suggests that extratropical precipitation amounts should depend multiplicatively on the pressure gradient, saturation specific humidity, and the meridional temperature gradient. This physical insight has been used to guide the development of a suitable statistical model for precipitation using a mixture of generalized linear models: a logistic model for the binary occurrence of precipitation and a Gamma distribution model for the wet day precipitation amount. The statistical model allows for the investigation of the role of each factor in determining variations and long-term trends. Saturation specific humidity q(s) has a generally negative effect on global precipitation occurrence and with the tropical wet pentad precipitation amount, but has a positive relationship with the pentad precipitation amount at mid- and high latitudes. The North Atlantic Oscillation, a proxy for the meridional temperature gradient, is also found to have a statistically significant positive effect on precipitation over much of the Atlantic region. Residual time trends in wet pentad precipitation are extremely sensitive to the choice of the wet pentad threshold because of increasing trends in low-amplitude precipitation pentads; too low a choice of threshold can lead to a spurious decreasing trend in wet pentad precipitation amounts. However, for not too small thresholds, it is found that the meridional temperature gradient is an important factor for explaining part of the long-term trend in Atlantic precipitation.

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Blends of the poly(ether sulfone) derived from 4,4'-biphenol and 4,4'-dichlorodiphenylsulfone (Radel-R(TM)) with its homologous macrocyclic oligomers show greatly lowered melt viscosities relative to that of the parent polymer, potentially enabling more facile production and fabrication of fiber-reinforced composite materials. The macrocycles can then undergo entropically driven ring-opening polymerization in situ. The required blends can be obtained easily in one step, by carrying out polycondensations at concentrations lower than those usually used for polymer synthesis.

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An amorphous, catechol-based analogue of PEEK ("o-PEEK") has been prepared by a classical step-growth polymerization reaction between catechol and 4,4'-difluorobenzophenone and shown to be readily soluble in a range of organic solvents. Copolymers with p-PEEK have been investigated, including an amorphous 50: 50 composition and a semicrystalline though still organic-soluble material comprising 70% p-PEEK. o-PEEK has also been obtained by entropy-driven ring-opening polymerization of the macrocyclic oligomers (MCO's) formed by cyclo-condensation of catechol with 4,4'-difluorobenzophenone under pseudo-high-dilution conditions. The principal products of this latter reaction were the cyclic dimer 3a (20 wt %), cyclic trimer 3b (16%) cyclic tetramer 3c (14%), cyclic pentamer 3d (13%) and cyclic hexamer 3e (12%). Macrocycles 3a-c were isolated as pure compounds by gradient column chromatography, and the structures of the cyclic dimer 3a and cyclic tetramer 3c were analyzed by single-crystal X-ray diffraction. A mixture of MCO's, 3, of similar composition, was obtained by cyclodepolymerization of high molar mass o-PEEK in dilute soluion.

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A homologous series of macrocyclic oligoamides has been prepared in high yield by reaction of isophthaloyl chloride with m-phenylenediamine under pseudo-high-dilution conditions. The products were characterized by infrared and H-1 NMR spectroscopies, matrix assisted laser desorption-ionization time-of-flight mass spectrometry, and gel permeation chromatography (GPC). A series of linear oligomers was prepared for comparison. The macrocycles ranged in size from the cyclic trimer up to at least the cyclic nonamer (90 ring atoms). The same homologous series of macrocyclic oligomers was prepared in high yield by the cyclodepolymerization of poly(m-phenylene isophthalamide) (Nomex). Cyclodepolymerization was best achieved by treating a 1% w/v solution of the polymer in dimethyl sulfoxide containing calcium chloride or lithium chloride with 3-4 mol % of sodium hydride or the sodium salt of benzanilide at 150 degreesC for 70 h. Treatment of a concentrated solution of the macrocyclic oligomers (25% w/v) with 4 mol % of sodium hydride or the sodium salt of benzanilide in a solution of lithium chloride in dimethyl sulfoxide at 170 degreesC for 6 h resulted in efficient entropically driven ring-opening polymerizations to give poly(m-phenylene isophthalamide), characterized by infrared and H-1 NMR spectroscopies and by GPC. The molecular weights obtained were comparable with those of the commercial polymer.

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Highly strained macrocyclic ether-ketones obtained by nickel-catalyzed cyclization of linear precursor oligomers undergo ring-opening polyinerization via ether exchange in the presence of nucleophilic initiators such as fluoride or phenoxide anions. Strain enthapies of these macrocycles, from DSC analyses of their exothermic ring-opening polymerization are in the range 50-90 kJ mol(-1). Melt-phase polymerization generally affords slightly cross-linked materials, but solution-phase polymerization at high macrocycle concentrations gives fully soluble, high molar mass polymers with inherent viscosities of up to 1.78 dL g(-1). Sequence-analysis of the resulting polymers by C-13 NMR shows that alternating or random monomer sequences may be obtained, depending on whether one or both aromatic rings adjacent to the ether linkages are activated toward nucleophilic attack.

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Polymerizable macrocyclic biarylene-ether-ketones and biarylene-ether-sulfones are accessible from linear, bis(chloro)-terminated oligomers via nickel-catalyzed, intramolecular coupling under pseudo-high-dilution conditions. Single-crystal X-ray analyses of the resulting cyclo-oligomers reveal extremely distorted and highly strained geometries, with 4,4 '-biphenylene units showing deviations of up to 70 degrees from linearity.