Shear effects on the properties and separation characteristics of whey protein precipitates

Selective isoelectric whey protein precipitation and aggregation is carried out at laboratory scale in a standard configuration batch agitation vessel. Geometric scale-up of this operation is implemented on the basis of constant impeller power input per unit volume and subsequent clarification is achieved by high speed disc-stack centrifugation. Particle size and fractal geometry are important in achieving efficient separation while aggregates need to be strong enough to resist the more extreme levels of shear that are encountered during processing, for example through pumps, valves and at the centrifuge inlet zone. This study investigates how impeller agitation intensity and ageing time affect aggregate size, strength, fractal dimension and hindered settling rate at laboratory scale in order to determine conditions conducive for improved separation. Particle strength is measured by observing the effects of subjecting aggregates to moderate and high levels of process shear in a capillary rig and through a partially open ball-valve respectively. The protein precipitate yield is also investigated with respect to ageing time and impeller agitation intensity. A pilot scale study is undertaken to investigate scale-up and how agitation vessel shear affects centrifugal separation efficiency. Laboratory scale studies show that precipitates subject to higher impeller shear-rates during the addition of the precipitation agent are smaller but more compact than those subject to lower impeller agitation and are better able to resist turbulent breakage. They are thus more likely to provide a better feed for more efficient centrifugal separation. Protein precipitation yield improves significantly with ageing, and 50 minutes of ageing is required to obtain a 70 - 80% yield of α-lactalbumin. Geometric scale-up of the agitation vessel at constant power per unit volume results in aggregates of broadly similar size exhibiting similar trends but with some differences due to the absence of dynamic similarity due to longer circulation time and higher tip speed in the larger vessel. Disc stack centrifuge clarification efficiency curves show aggregates formed at higher shear-rates separate more efficiently, in accordance with laboratory scale projections. Exposure of aggregates to highly turbulent conditions, even for short exposure times, can lead to a large reduction in particle size. Thus, improving separation efficiencies can be achieved by the identification of high shear zones in a centrifugal process and the subsequent elimination or amelioration of such.

First principles modelling of nucleation and growth during atomic layer deposition onto III-V substrates

Atomic layer deposition (ALD) is now used in semiconductor fabrication lines to deposit nanometre-thin oxide films, and has thus enabled the introduction of high-permittivity dielectrics into the CMOS gate stack. With interest increasing in transistors based on high mobility substrates, such as GaAs, we are investigating the surface treatments that may improve the interface characteristics. We focus on incubation periods of ALD processes on III-V substrates. We have applied first principles Density Functional Theory (DFT) to investigate detailed chemistry of these early stages of growth, specifically substrate and ALD precursor interaction. We have modelled the ‘clean-up’ effect by which organometallic precursors: trimethylaluminium (TMA) or hafnium and titanium amides clean arsenic oxides off the GaAs surface before ALD growth of dielectric commences and similar effect on Si3N4 substrate. Our simulations show that ‘clean-up’ of an oxide film strongly depends on precursor ligand, its affinity to the oxide and the redox character of the oxide. The predominant pathway for a metalloid oxide such as arsenic oxide is reduction, producing volatile molecules or gettering oxygen from less reducible oxides. An alternative pathway is non-redox ligand exchange, which allows non-reducible oxides (e.g. SiO2) to be cleaned-up. First principles study shows also that alkylamides are more susceptible to decomposition rather than migration on the oxide surface. This improved understanding of the chemical principles underlying ‘clean-up’ allows us to rationalize and predict which precursors will perform the reaction. The comparison is made between selection of metal chlorides, methyls and alkylamides precursors.

Echoes of existentialism in the works of Carlos Fuentes

In this thesis I have set out to trace the echoes of existentialism in the work of the Mexican novelist, Carlos Fuentes scrutinizing, in particular, La región más transparente, La muerte de Artemio Cruz and Cambio de piel. In the opening segment of the thesis I outline the essential tenets of existentialist thought and how it became the predominant philosophical and literary movement of the early part of the twentieth-century. Stemming from the work of Sören Kierkegaard in Denmark towards the end of the nineteenth-century, it challenged the arid philosophies of previous generations and provided a new way of looking at man and the human condition. In this opening chapter, I study the works of the more important philosophers in this regard such as Heidegger, Sartre, Jaspers, Marcel, Unamuno, and Ortega y Gasset and show how each in his own way contributed to the further development of the new philosophy. Chapter 2 is concerned with the spread of existentialism to the Latin American continent. In the early part of the twentieth-century, Mexico was emerging from a turbulent revolutionary period and seeking a solution to the fractured nature of its society. The Spanish philosopher, Ortega y Gasset, and the many Spanish intellectuals who sought refuge from Franco’s dictatorship in Mexico, helped to popularise the new philosophy and these lively debates about existentialism served to underpin ideas around mexicanidad or Mexican national identity. Carlos Fuentes was deeply immersed in the debate of his time, positioned as he was as a prominent public intellectual. In La muerte de Artemio Cruz he shows us how great wealth and power are a poor recompense for the loss of love and compassion and lead only to alienation and selfishness. In his other best known novel, La región más transparente, he explores the rise of modern Mexico and its society – an inauthentic society that is corrupted by a scramble for wealth and self-aggrandizement. The final chapter is devoted to the study of Cambio de piel which is concerned with violence and alienation as central pillars of existence. The violence depicted here precipitates a crisis in the human condition and an accompanying sense of alienation. The thesis seeks to establish that existentialism is central not only to Fuentes’s literary concerns but also forms a part of his ethics as an artist.