High performance polyester-based materials

Biaxially oriented films produced from semi-crystalline, semi-aromatic polyesters are utilised extensively as components within various applications, including the specialist packaging, flexible electronic and photovoltaic markets. However, the thermal performance of such polyesters, specifically poly(ethylene terephthalate) (PET) and poly(ethylene-2,6-naphthalate) (PEN), is inadequate for several applications that require greater dimensional stability at higher operating temperatures. The work described in this project is therefore primarily focussed upon the copolymerisation of rigid comonomers with PET and PEN, in order to produce novel polyester-based materials that exhibit superior thermomechanical performance, with retention of crystallinity, to achieve biaxial orientation. Rigid biphenyldiimide comonomers were readily incorporated into PEN and poly(butylene-2,6-naphthalate) (PBN) via a melt-polycondensation route. For each copoly(ester-imide) series, retention of semi-crystalline behaviour is observed throughout entire copolymer composition ratios. This phenomenon may be rationalised by cocrystallisation between isomorphic biphenyldiimide and naphthalenedicarboxylate residues, which enables statistically random copolymers to melt-crystallise despite high proportions of imide sub-units being present. In terms of thermal performance, the glass transition temperature, Tg, linearly increases with imide comonomer content for both series. This facilitated the production of several high performance PEN-based biaxially oriented films, which displayed analogous drawing, barrier and optical properties to PEN. Selected PBN copoly(ester-imide)s also possess the ability to either melt-crystallise, or form a mesophase from the isotropic state depending on the applied cooling rate. An equivalent synthetic approach based upon isomorphic comonomer crystallisation was subsequently applied to PET by copolymerisation with rigid diimide and Kevlar®-type amide comonomers, to afford several novel high performance PET-based copoly(ester-imide)s and copoly(ester-amide)s that all exhibited increased Tgs. Retention of crystallinity was achieved in these copolymers by either melt-crystallisation or thermal annealing. The initial production of a semi-crystalline, PET-based biaxially oriented film with a Tg in excess of 100 °C was successful, and this material has obvious scope for further industrial scale-up and process development.

Seasonal surface urban energy balance and wintertime stability simulated using three land-surface models in the high-latitude city Helsinki

The performance of three urban land surface models, run in offline mode, with their default external parameters, is evaluated for two distinctly different sites in Helsinki: Torni and Kumpula. The former is a dense city centre site with 22% vegetation, while the latter is a suburban site with over 50% vegetation. At both locations the models are compared against sensible and latent heat fluxes measured using the eddy covariance technique, along with snow depth observations. The cold climate experienced by the city causes strong seasonal variations that include snow cover and stable atmospheric conditions. Most of the time the three models are able to account for the differences between the study areas as well as the seasonal and diurnal variability of the energy balance components. However, the performances are not systematic across the modelled components, season and surface type. The net all-wave radiation is well simulated, with the greatest uncertainties related to snowmelt timing, when the fraction of snow cover has a key role, particularly in determining the surface albedo. For the turbulent fluxes, more variation between the models is seen which can partly be explained by the different methods in their calculation and partly by surface parameter values. For the sensible heat flux, simulation of wintertime values was the main problem, which also leads to issues in predicting near-surface stabilities particularly at the dense city centre site. All models have the most difficulties in simulating latent heat flux. This study particularly emphasizes that improvements are needed in the parameterization of anthropogenic heat flux and thermal parameters in winter, snow cover in spring and evapotranspiration in order to improve the surface energy balance modelling in cold climate cities.

Sampling uncertainty in gridded sea surface temperature products and Advanced Very High Resolution Radiometer (AVHRR) Global Area Coverage (GAC) data

Sea surface temperature (SST) data are often provided as gridded products, typically at resolutions of order 0.05 degrees from satellite observations to reduce data volume at the request of data users and facilitate comparison against other products or models. Sampling uncertainty is introduced in gridded products where the full surface area of the ocean within a grid cell cannot be fully observed because of cloud cover. In this paper we parameterise uncertainties in SST as a function of the percentage of clear-sky pixels available and the SST variability in that subsample. This parameterisation is developed from Advanced Along Track Scanning Radiometer (AATSR) data, but is applicable to all gridded L3U SST products at resolutions of 0.05-0.1 degrees, irrespective of instrument and retrieval algorithm, provided that instrument noise propagated into the SST is accounted for. We also calculate the sampling uncertainty of ~0.04 K in Global Area Coverage (GAC) Advanced Very High Resolution Radiometer (AVHRR) products, using related methods.