Modelling the performance and dynamics of vapour compression refrigeration systems

This thesis was submitted for the degree of Doctor of Philosophy and awarded by Brunel University.The impact of refrigeration systems on the environment can be reduced by the use of alternative reffigerants which are less harmful to the atmosphere and the optimisation of systems and control strategies to deliver increased levels of energy efficiency. Mathematical modelling offers the opportunity to test the performance of systems under different operating conditions and with alternative refrigerants. Dynamic models allow comparison of both transient and steady-state behaviour and this is of particular importance for liquid chillers, since these systems can operate under transient conditions for long periods. This thesis details the development of a general dynamic model for the simulation of liquid chillers. Mathematical models of the reciprocating compressor, expansion valve, evaporator and condenser are presented. The models are integrated to form the overall system model by passing conditions from one component to another. A series of steady-state and transient experimental tests were carried out on a liquid chiller and the model was used to simulate these tests. Validation was carried out by comparison of these measured results to those predicted by the simulation for both the steady-state and transient tests. Once validated, the model was used to investigate the steady-state and dynamic performance of liquid chillers operating with various refrigerants. The effect of the mass of the system refrigerant charge was examined for a number of refrigerants. The steady-state performance for a range of evaporator and condenser coolant temperatures was also investigated. Finally, the effect of different system refrigerants on start-up transients was examined and the losses in cooling capacity due to cycling quantified. The effect of the expansion valve's initial superheat spring setting on the dynamic response and transient losses was also investigated

Exploiting the Extended {\pi}-System of Perylene Bisimide for Label-free Single-Molecule Sensing

We demonstrate the potential of perylene bisimide (PBI) for label-free sensing of organic molecules by investigating the change in electronic properties of five symmetric and asymmetric PBI derivatives, which share a common backbone, but are functionalised with various bay-area substituents. Density functional theory was combined with a Greens function scattering approach to compute the electrical conductance of each molecule attached to two gold electrodes by pyridyl anchor groups. We studied the change in their conductance in response to the binding of three analytes, namely TNT, BEDT-TTF and TCNE, and found that the five different responses provided a unique fingerprint for the discriminating sensing of each analyte. This ability to sense and discriminate was a direct consequence of the extended {\pi} system of the PBI backbone, which strongly binds the analytes, combined with the different charge distribution of the five PBI derivatives, which leads to a unique electrical response to analyte binding.Comment: J. Mater. Chem. C, 201

Tuning the thermoelectric properties of metallo-porphyrins

We investigated the thermoelectric properties of metalloporphyrins connected by thiol anchor groups to gold electrodes. By varying the transition metal-centre over the family Mn, Co, Ni, Cu, Fe, and Zn we are able to tune the molecular energy levels relative to the Fermi energy of the electrodes. The resulting single-molecule room-temperature thermopowers range from almost zero for Co and Cu centres, to +80 μV K−1 and +230 μV K−1 for Ni and Zn respectively. In contrast, the thermopowers with Mn(II) or Fe(II) metal centres are negative and lie in the range −280 to −260 μV K−1. Complexing these with a counter anion to form Fe(III) and Mn(III) changes both the sign and magnitude of their thermopowers to +218 and +95 respectively. The room-temperature power factors of Mn(II), Mn(III), Fe(III), Zn and Fe(II) porphyrins are predicted to be 5.9 × 10−5 W m−1 K−2, 5.4 × 10−4 W m−1 K−2, 9.5 × 10−4 W m−1 K−2, 1.6 × 10−4 W m−1 K−2 and 2.3 × 10−4 W m−1 K−2 respectively, which makes these attractive materials for molecular-scale thermoelectric devices

Thermoelectric Performance of various Benzo-difuran Wires

Using a first principles approach to electron transport, we calculate the electrical and thermoelectrical transport properties of a series of molecular wires containing benzo-difuran subunits. We demonstrate that the side groups introduce Fano resonances, the energy of which is changing with the electronegativity of selected atoms in it. We also study the relative effect of single, double or triple bonds along the molecular backbone and find that single bonds yield the highest thermopower, approximately 22$\mu$V/K at room temperature, which is comparable with the highest measured values for single-molecule thermopower reported to date.Comment: 7 pages, 8 figure

A spatial and temporal analysis of risk factors associated with sporadic Shiga toxin-producing Escherichia coli O157 infection in England between 2009 and 2015

Infection with STEC O157 is relatively rare but has potentially serious sequelae, particularly for children. Large outbreaks have prompted considerable efforts designed to reduce transmission primarily from food and direct animal contact. Despite these interventions, numbers of infections have remained constant for many years and the mechanisms leading to many sporadic infections remain unclear. Here, we show that two-thirds of all cases reported in England between 2009 and 2015 were sporadic. Crude rates of infection differed geographically and were highest in rural areas during the summer months. Living in rural areas with high densities of cattle, sheep or pigs and those served by private water supplies were associated with increased risk. Living in an area of lower deprivation contributed to increased risk but this appeared to be associated with reported travel abroad. Fresh water coverage and residential proximity to the coast were not risk factors. To reduce the overall burden of infection in England, interventions designed to reduce the number of sporadic infections with STEC should focus on the residents of rural areas with high densities of livestock and the effective management of non-municipal water supplies. The role of sheep as a reservoir and potential source of infection in humans should not be overlooked

A Sm(II)-mediated cascade approach to Dibenzoindolo[3,2-b]carbazoles:synthesis and evaluation

Previously unstudied dibenzoindolo[3,2-b]carbazoles have been prepared by two-directional, phase tag-assisted synthesis utilizing a connective-Pummerer cyclization and a SmI2-mediated tag cleavage-cyclization cascade. The use of a phase tag allows us to exploit unstable intermediates that would otherwise need to be avoided. The novel materials were characterized by X-ray, cyclic voltammetry, UV-vis spectroscopy, TGA, and DSC. Preliminary studies on the performance of OFET devices are also described