Density Functional Theory and Molecular Dynamics Studies on Energetics and Kinetics for Electro-Active Polymers: PVDF and P(VDF-TrFE)

We use first principles methods to study static and dynamical mechanical properties of the ferroelectric polymer Poly(vinylidene fluoride) (PVDF) and its copolymer with trifluoro ethylene (TrFE). We use density functional theory [within the generalized gradient approximation (DFT-GGA)] to calculate structures and energetics for various crystalline phases for PVDF and P(VDF-TrFE). We find that the lowest energy phase for PVDF is a non-polar crystal with a combination of trans (T) and gauche (G) bonds; in the case of the copolymer the role of the extra (bulkier) F atoms is to stabilize T bonds. This leads to the higher crystallinity and piezoelectricity observed experimentally. Using the MSXX first principles-based force field (FF) with molecular dynamics (MD), we find that the energy barrier necessary to nucleate a kink (gauche pairs separated by trans bonds) in an all-T crystal is much lower (14.9 kcal/mol) in P(VDF-TrFE) copolymer than in PVDF (24.8 kcal/mol). This correlates with the observation that the polar phase of the copolymer exhibits a solid-solid a transition to a non-polar phase under heating while PVDF directly melts. We also studied the mobility of an interface between a polar and non-polar phases under uniaxial stress; we find a lower threshold stress and a higher mobility in the copolymer as compared with PVDF. Finally, considering plastic deformation under applied shear, we find that the chains for P(VDF-TrFE) have a very low resistance to sliding, particularly along the chain direction. The atomistic characterization of these "unit mechanisms" provides essential input to mesoscopic or macroscopic models of electro-active polymers.Comment: 15 pages 9 figures Electro-active polyme

Spatially and Temporally Explicit Energy System Modelling to Support the Transition to a Low Carbon Energy Infrastructure – Case Study for Wind Energy in the UK

Renewable energy sources and electricity demand vary with time and space and the energy system is constrained by the location of the current infrastructure in place. The transitioning to a low carbon energy society can be facilitated by combining long term planning of infrastructure with taking spatial and temporal characteristics of the energy system into account. There is a lack of studies addressing this systemic view. We soft-link two models in order to analyse long term investment decisions in generation, transmission and storage capacities and the effects of short-term fluctuation of renewable supply: The national energy system model UKTM (UK TIMES model) and a dispatch model. The modelling approach combines the benefits of two models: an energy system model to analyse decarbonisation pathways and a power dispatch model that can evaluate the technical feasibility of those pathways and the impact of intermittent renewable energy sources on the power market. Results give us the technical feasibility of the UKTM solution from 2010 until 2050. This allows us to determine lower bounds of flexible elements and feeding them back in an iterative process (e.g. storage, demand side control, balancing). We apply the methodology to study the long-term investments of wind infrastructure in the United Kingdom

Attempts to synthesize kainic acid

Attempts were made to synthesise a conformationally restricted analogue of kainic acid wherein the double bond was confined in a ring-system. The stratagem involved an intramolecular Diels-Alder reaction but could not be tested as the precursors to the cycloaddition reaction could not be prepared. Attempts were made to develop a general route to kainic acid and analogues by employing a 1,3-dipolar cycloaddition reaction between aziridines and olefins. Triazolines were used as a precursor to aziridines because of the ease of formation from alkyl azides and olefins. The required dipolar cycloaddition was found to occur but produced various side-products from the triazoline thermolysis. The subsequent Grignard reaction on the cycloaddition product gave problems as the compound epimerised under basic conditions and did not undergo reaction with methyl Grignard or methyl lithium. An attempt to prepare kainic acid and analogues by an intramolecular 1,3-dipolar cycloaddition or a 1,3-sigmatropic shift reaction failed when the basic precursors for the reaction could not be prepared

U-Pn geochronology of deformed metagranites in central Sutherland, Scotland: evidence for widespread late Silurian metamorphism and ductile deformation of the Moine Supergroup during the Caledonian orogeny

Within the Caledonides of central Sutherland, Scotland, the Neoproterozoic metasedimentary rocks of the Moine Supergroup record NW-directed D2 ductile thrusting and nappe assembly, accompanied by widespread tight-to-isoclinal folding and amphibolite-facies metamorphism. A series of metagranite sheets which were emplaced and penetratively deformed during D2 have been dated using SHRIMP UâPb geochronology. Zircon ages of 424 8 Ma (Vagastie Bridge granite), 420 6 Ma (Klibreck granite) and 429 11 Ma (Strathnaver granite) are interpreted to date emplacement, and hence regional D2 deformation, during mid- to late Silurian time. Titanite ages of 413 3 Ma (Vagastie Bridge granite) and 416 3 Ma (Klibreck granite) are thought to date post-metamorphic cooling through a blocking temperature of c. 550â 500 8C. A mid- to late Silurian age for D2 deformation supports published models that have viewed the internal ductile thrusts of this part of the orogen as part of the same kinematically linked system of forelandpropagating thrusts as the marginal Moine Thrust Zone. The new data contrast with previous interpretations that have viewed the dominant structures and metamorphic assemblages within the Moine Supergroup as having formed during the early to mid-Ordovician Grampian arcâcontinent orogeny. The mid-to late Silurian D2 nappe stacking event in Sutherland is probably a result of the collision of Baltica with the Scottish segment of Laurentia

Series of experiments for empirical validation of solar gain modelling in building energy simulation codes - experimental setup, test cell characterization, specifications and uncertainty analysis

Empirical validation of building energy simulation codes is an important component in understanding the capacity and limitations of the software. Within the framework of Task 34/Annex 43 of the International Energy Agency (IEA), a series of experiments was performed in an outdoor test cell. The objective of these experiments was to provide a high-quality data set for code developers and modelers to validate their solar gain models for windows with and without shading devices. A description of the necessary specifications for modeling these experiments is provided in this paper, which includes information about the test site location, experimental setup, geometrical and thermophysical cell properties including estimated uncertainties. Computed overall thermal cell properties were confirmed by conducting a steady-state experiment without solar gains. A transient experiment, also without solar gains, and corresponding simulations from four different building energy simulation codes showed that the provided specifications result in accurate thermal cell modeling. A good foundation for the following experiments with solar gains was therefore accomplished

A strategic study of energy efficient and hybrid energy system options for a multi-family building in Korea

This study is to identify performance of energy efficiency measures and to match low-carbon and renewable energy (RE) systems supplies to demands in the context of multi-family residential buildings in Korea. An approach to the evaluation of the hybrid energy systems was investigated, including consideration of heat and power demand profiles, energy system combinations, building design options and strategies for matching supply to demand. The approach is encapsulated within an integrated software environment. Building energy simulation technology was exploited to make virtual energy use data. Low-carbon and RE system modelling techniques were used to predict energy supply profiles. A series of demand/supply matching-based analyses were made to identify the effect of energy efficient demand measures (e.g. roof-top gardens, innovative underfloor heating system) and evaluate the capacity utilisation factor from the hybrid energy systems. On the basis of performance information obtained at the conceptual design stage, the design team can pinpoint the most energy efficient demand/supply combination, and consequently, maximise the impact of hybrid energy systems adoption

Empirical validation of models to compute solar irradiance on inclined surfaces for building energy simulation

Accurately computing solar irradiance on external facades is a prerequisite for reliably predicting thermal behavior and cooling loads of buildings. Validation of radiation models and algorithms implemented in building energy simulation codes is an essential endeavor for evaluating solar gain models. Seven solar radiation models implemented in four building energy simulation codes were investigated: (1) isotropic sky, (2) Klucher, (3) Hay-Davies, (4) Reindl, (5) Muneer, (6) 1987 Perez, and (7) 1990 Perez models. The building energy simulation codes included: EnergyPlus, DOE-2.1E, TRNSYS-TUD, and ESP-r. Solar radiation data from two 25 days periods in October and March/April, which included diverse atmospheric conditions and solar altitudes, measured on the EMPA campus in a suburban area in Duebendorf, Switzerland, were used for validation purposes. Two of the three measured components of solar irradiances - global horizontal, diffuse horizontal and direct-normal - were used as inputs for calculating global irradiance on a south-west façade. Numerous statistical parameters were employed to analyze hourly measured and predicted global vertical irradiances. Mean absolute differences for both periods were found to be: (1) 13.7% and 14.9% for the isotropic sky model, (2) 9.1% for the Hay-Davies model, (3) 9.4% for the Reindl model, (4) 7.6% for the Muneer model, (5) 13.2% for the Klucher model, (6) 9.0%, 7.7%, 6.6%, and 7.1% for the 1990 Perez models, and (7) 7.9% for the 1987 Perez model. Detailed sensitivity analyses using Monte Carlo and fitted effects for N-way factorial analyses were applied to assess how uncertainties in input parameters propagated through one of the building energy simulation codes and impacted the output parameter. The implications of deviations in computed solar irradiances on predicted thermal behavior and cooling load of buildings are discussed

The dispersive self-dual Einstein equations and the Toda lattice

The Boyer-Finley equation, or $SU(\infty)$-Toda equation is both a reduction of the self-dual Einstein equations and the dispersionlesslimit of the $2d$-Toda lattice equation. This suggests that there should be a dispersive version of the self-dual Einstein equation which both contains the Toda lattice equation and whose dispersionless limit is the familiar self-dual Einstein equation. Such a system is studied in this paper. The results are achieved by using a deformation, based on an associative $\star$-product, of the algebra $sdiff(\Sigma^2)$ used in the study of the undeformed, or dispersionless, equations.Comment: 11 pages, LaTeX. To appear: J. Phys.

Costs and effects of two public sector delivery channels for long-lasting insecticidal nets in Uganda.

BACKGROUND: In Uganda, long-lasting insecticidal nets (LLIN) have been predominantly delivered through two public sector channels: targeted campaigns or routine antenatal care (ANC) services. Their combination in a mixed-model strategy is being advocated to quickly increase LLIN coverage and maintain it over time, but there is little evidence on the efficiency of each system. This study evaluated the two delivery channels regarding LLIN retention and use, and estimated the associated costs, to contribute towards the evidence-base on LLIN delivery channels in Uganda. METHODS: Household surveys were conducted 5-7 months after LLIN distribution, combining questionnaires with visual verification of LLIN presence. Focus groups and interviews were conducted to further investigate determinants of LLIN retention and use. Campaign distribution was evaluated in Jinja and Adjumani while ANC distribution was evaluated only in the latter district. Costs were calculated from the provider perspective through retrospective analysis of expenditure data, and effects were estimated as cost per LLIN delivered and cost per treated-net-year (TNY). These effects were calculated for the total number of LLINs delivered and for those retained and used. RESULTS: After 5-7 months, over 90% of LLINs were still owned by recipients, and between 74% (Jinja) and 99% (ANC Adjumani) were being used. Costing results showed that delivery was cheapest for the campaign in Jinja and highest for the ANC channel, with economic delivery cost per net retained and used of USD 1.10 and USD 2.31, respectively. Financial delivery costs for the two channels were similar in the same location, USD 1.04 for campaign or USD 1.07 for ANC delivery in Adjumani, but differed between locations (USD 0.67 for campaign delivery in Jinja). Economic cost for ANC distribution were considerably higher (USD 2.27) compared to campaign costs (USD 1.23) in Adjumani. CONCLUSIONS: Targeted campaigns and routine ANC services can both achieve high LLIN retention and use among the target population. The comparatively higher economic cost of delivery through ANC facilities was at least partially due to the relatively short time this system had been in existence. Further studies comparing the cost of well-established ANC delivery with LLIN campaigns and other delivery channels are thus encouraged