Four batches of pasteurized process cheese were prepared from the same Cheddar cheese by cooking to 82C in the presence of sodium citrate, disodium phosphate, tetrasodium pyrophosphate or sodium aluminum phosphate. Each batch contained the same moisture (40.6%) and emulsifying salt concentration (2.5%). The process cheese was sampled for microstructural and rheological examination after 0, 5, 10, 20 and 40 min in the cooker at 82C. Even though each emulsifying salt affected the physical properties of the process cheese differently, the cheese generally became firmer, stiffer, more elastic and less meltable as cooking time increased from 0 to 40 min. These changes were accompanied by a decrease in the dimension of fat masses and an increase in the degree of emulsification as evidenced by scanning electron microscopy and transmission electron microscopy. The degree of emulsification (fineness of fat particles) seemed directly related to firmness, poor meltability, toughness, breaking force, apparent stiffness modulus, degree of elasticity , apparent ultimate stress and inversely related to hysteresis and apparent ultimate strain. Tetrasodium pyrophosphate produced the most rapid emulsification of the fat in the cheese and sodium aluminum phosphate the slowest. The effect of the other salts was intermediate. The softest most meltable cheese was poorly emulsified while the firmest most sliceable was well emulsified. Sodium citrate and tetrasodium pyrophosphate crystals remained undissolved in the cheese after 40 min in the cooker while sodium aluminum phosphate crystals were still undissolved after 10 min. There was a close statistical relationship among several of the rheological measurements viz. meltability and firmness, toughness and breaking force, and meltability and breaking force. Future rheological studies on process cheese should not require all of the above measurements. An increase in the fineness of the fat emulsion as determined by scanning electron microscopy was generally accompanied by increased firmness, poorer meltability and increased toughness.

Highly concentrated micellar casein concentrate (HC-MCC), a potential ingredient for cheese making, containing ~20% casein with ~70% of serum proteins removed by microfiltration, and diafiltration of skim milk, and then further concentrated by vacuum evaporation. The objectives of this research were to investigate solubilization, cold gelation, rennet coagulation properties of recombined HC-MCC and cream for its use in cheese making. In Chapter 3, either mixing thawed HC-MCC in water at high temperature (~50C) or addition of trisodium citrate can achieve complete dispersion and more than 80% solubility of HC-MCC in water (3% protein). Overnight storage helps to fully disperse HC-MCC, but only reaches ~30% of solubility at 20C. Cold-gelation of HCMCC is thermally reversible and reducing protein levels in HC-MCC can decrease its CGT. The HC-MCC with less than 16% of protein does not gel at 5C. We propose that cold-gelation of HC-MCC occurs when the kinetic energy of the casein micelles is sufficiently reduced to inhibit their mobility in relation to adjacent casein micelles. In Chapter 4, the recombined concentrated milk (RCM) by mixing thawed frozen HC-MCC and cream with 12% casein at pH 6.6 does not gel until cooled below 12°C. Addition of either sodium citrate or high levels of calcium increased CGT, although low levels of calcium did not impact CGT. Cold gelation of RCM was thermally reversible, even when citrate was added to partially chelate calcium. We propose that cold gelation of RCM occurs when protein strands that have been partially released from the casein micelles entangle, restrict their mobility and form a fine stranded gel network. The RCM at a casein level of 12% (wt/wt) has potential for use in cheese making. In Chapter 5, reducing rennet level can increase coagulation time of RCM (11% casein) without impact on curd firmness or firming rate. Decreased coagulation temperature helps to increase coagulation time and decrease curd firmness rate, but also increases the initial viscosity of RCM. Pre-acidified RCM has no advantage in increasing coagulation time, decreasing curd firmness or firming rate. Microstructure of RCM and its coagulum indicates that the increased curd firmness probably results from the highly inter-linked and longer protein strands in RCM curd. Reducing rennet level can be applied to slow down rennet coagulation of RCM (11% casein) in cheese making.

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In this work flow properties of dendrimers are studied with the aid of molecular simulations. For the first time the results of the nonequilibrium molecular dynamics simulations of the dendrimers in the melt are reported. Molecules are modelled at the coarse-grained level using the bead-spring model. The objective of this research is to analyse the influence of the molecular topology in the macroscopic flow behaviour of the melts. Systems of dendrimers of generations 1 to 4 undergoing planar shear are compared to the melts composed of linear chain polymers. The internal structure and shape of dendrimers is extensively analysed. The response of the molecules to the shearing in the form of stretching and alignment is studied. The correlation between the onset of shear thinning and the onset of deformation of molecules is observed. The changes in the fractal dimensionality of dendrimers due to shearing are also analysed. Dendrimers, due to their highly branched structure and compact globular conformations in the melt, are found to behave differently when sheared, compared to traditional linear polymers. Unlike linear polymers, they do not undergo transition form the Rouse to the reptation regimes. This effect is explained in terms of the suppressed entanglement between molecules. Moreover, dendrimers when compared to linear chain systems exhibit lower Newtonian viscosity, onset of the shear thinning at higher strain rates, and less pronounced shear thinning in the non-Newtonian regime. They can be used as rheology modifiers, as it is shown in the preliminary results obtained from the simulations of the dendrimers-linear polymer blends. In agreement with other theoretical and experimental studies, dendrimers in the melt are found to have compact space-filling structure with terminal groups distributed throughout the interior of the molecule. Suggestions for the further study of dendrimers via molecular simulations are made.

Tailings (mining waste) disposal is a significant consideration for the mining industry, with the majority of the ore processed in most mining operations ending up as tailings. This creates large volumes of tailings, which must be handled and stored responsibly to avoid potential environmental catastrophes. The most common form of tailings storage facility is the impoundment, where tailings are contained within a basin, with beaches forming around the perimeter of the impoundment and a pond standing in the middle. A relatively new method of tailings storage is to create a 'stack', whereby the tailings solids form a large heap, with the discharge of tailings slurry from the apex of the heap. It is of significant value for mine operators and tailings engineers to be able to predict the shape of the beach that forms in either of these disposal scenarios. The key to being able to do this relies on a method of prediction of the beach slope. The aim of this work is to develop a method of tailings beach slope prediction for tailings slurries that are sub-aerially discharged from a pipe. In this thesis a literature review is undertaken, investigating existing methods for the prediction of tailings beach slopes. These methods are validated against relevant industrial and experimental data. Two separate phases of experimental work have taken place in an effort to investigate tailings deposition behaviour, one at mine sites and the other in a laboratory on a small scale. Three new tailings beach slope prediction models are presented; a simple empirical model enabling quick approximate predictions; an a priori tailings beach slope prediction model based on existing theories of open channel flow, sediment transport and rheology, which is more powerful due to the greater degree of theory in its foundation; and a new semi-empirical model that shares some of the theoretical aspects of the a priori model but offers better predictions due to its empirical calibration to the experimental data. The experimental results, along with 3 other independently collected sets of relevant industrial and experimental data, are used to validate the beach slope prediction models found in the literature, as well as the new beach slope models presented in this thesis. Statistical evaluation of the performance of all of these models is presented to enable comparison. Finally, a new beach shape model is presented for the three dimensional geometric forecasting of the beach surface of a tailings stack. Historic tailings discharge data is run through the beach shape model, and the shapes predicted by the model are compared with aerial survey data of a real tailings stack for validation of the shape model. This work not only presents a new method of tailings stack shape prediction, but also a plausible theory for explaining the concavity of tailings beaches. The stack shape model also has the potential to be developed further for the three dimensional modelling of tailings beaches formed in other types of storage facilities, such as impoundments or valleys.

Transport properties of concentrated suspensions are of interest to many industries. Mineral slurries at higher solids concentrations have shown some rheologically interesting characteristics such as shear thickening, the increase of viscosity of a multi-phase mixture with increasing shear rate. The general literature on the rheology of suspensions records the presence of yield stresses, shear thinning and normal stress differences. Little is said specifically about shear thickening behaviour except for colloidal suspensions. The aim of this study is to examine the behaviour of coarse shear thickening suspensions and determine the causes of this phenomenon. The study intended to achieve the following objectives to; develop the appropriate techniques for rheometric studies of shear thickening suspensions; investigate the nature of particle-fluid interaction; develop a model of shear thickening behaviour as it occurs in non-colloidal suspensions and to develop a method of applying the rheology results to flows and flow geometries of practical relevance. The effects of wall slip dominate much of the literature of shear thickening materials. To investigate this aspect a significant portion of the experimental work examined the effect of shear thickening on torsional flow. The rheogram produced from parallel plate rheometry was reassessed as a non-controlled flow and a rheology model dependant analysis demonstrated that the effects of slip are considerably more problematic for shear thickening suspensions, particularly as wall slip is an increasing function of shear stress. As a consequence of the rheometric method described above it was observed that the rate of change of the first normal stress difference, N1, with shear rate changes as shear thickening commences for non-colloidal suspensions. N1 is initially negative and is increasingly negative at low shear rates. Additional rheometric analysis examined the transient effects in the behaviour of a non-colloidal shear thickening suspension. By employing large angle oscillating strain tests the strain required to initiate a shear thickening response was determined. Coherent back scattering of laser light experiments were able to show the change in orientation of the particles with respect to its rotation around the vorticity axis. After a viscosity minimum was reached the orientation became more random as particle rotation and lamina disruption occurred. This was considered to be the cause of the measured shear thickening. A model of shear thickening in concentrated, non-colloidal suspensions of non-spherical particles was developed. Based on hydrodynamic interaction in the Stokes flow regime, the flow of interstitial fluid subjected the adjacent particles to lubricating and Couette type forces, acting as a couple. When a series of force balances on a particle contained between two moving laminae are conducted as a time sequence, the particle orientation and motion can be observed. The model has qualitative agreement with several aspects of the experimentally observed behaviour of shear thickening suspensions, such as viscosity change with shear rate and concentration, and the first normal stress difference increasing with shear rate. Pipe line flow experiments were conducted on the model suspension. Particle settling produces unusual patterns in shear thickening suspensions, with an annulus of delayed settling near the wall.

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Optimization of comminuting and heating conditions for surimi gel preparation obtained from three fish species: Alaska pollock (AP) (Theragra chalcogramma), Pacific whiting (PW) (Merluccius productus), and threadfin bream (TB) (Nemipterus spp.) was the focus of this study. Three parameters during comminution were separately evaluated: chopping time, chopping temperature, and salting time. Results from fracture gel analysis suggested a strong relation between the fish's environmental habitat and optimal final chopping temperature. Extending chopping time to 15 min under strictly controlled temperature at 0 ��C was preferable for cold water fish AP surimi. Even though high chopping temperature (20 ��C) for a shorter time (12 min) surprisingly resulted in strong gel texture similar to that of 0 ��C for 15 min, high chopping temperature should not be employed for AP surimi. AP could set as a gel at this temperature within a shorter time in a holding tank which could subsequently cause a problem when extruded on the cooking belt. Temperate water fish Pacific whiting, demonstrated its maximum gel strength when chopped at 15-20 ��C. The optimum comminution condition for warm water fish threadfin bream surimi was to chop the surimi until the paste temperature reached between 25-30 ��C. Prolongation of chopping once the surimi hit its threshold (optimum) temperature diminished the quality of the resulting protein gel. Cooling system connected to the chopping bowl is strongly recommended as it will allow the comminution process to be extended as long as possible until the surimi paste reaches its target temperature. Raman spectroscopy disclosed the different level of protein unfolding based on secondary structure of ��-helix and ��-sheet during various comminuting conditions. Unfolding of protein was facilitated by increased chopping temperature to a greater degree than extended chopping time. Extending chopping could denature the light meromyosin structure as it could not form a semi gel-like structure at temperatures between 32-40 ��C. Protein solubility of surimi paste in salt solution always decreased with prolonged chopping time. The decrease rate accelerated with increased chopping temperature. The formation of disulfide interchange gradually took place during chopping as observed from Raman spectroscopy. Also the surface hydrophobicity increased with extended chopping time. However, gel strength behaved differently according to the various chopping conditions indicating the lack of its relationship between salt soluble protein, disulfide formation, and surface hydrophobicity to gel strength. During extending chopping time, not only more mechanical force is applied to unfold protein structure, but proteins also have longer time to be extracted more by salt. Addition of salt at a different time during chopping process was therefore conducted using threadfin bream surimi due to its higher thermostability. Extending chopping time without salt followed by salt addition at the last step resulted in lower gel texture compared to the conventional chopping protocol where salt is always added at the early stage of comminution. Mechanical chopping could unfold protein structure; however, proteins, rather than staying solubilized, would precipitate and form a randomized structure under the chopping condition without salt. The heating condition greatly affected the gelation and rheological properties of AP surimi. The highest elastic modulus was obtained with the slowest heating rate at 1 ��C/min. Increased heating rate did not only shorten the time for proteins to unfold and form a well-organized network, it also interfered with the protein network through the vibration of water molecules as phase angle increased. This suggested that AP surimi gained more viscous properties and failed to form an elastic gel. Adjusting moisture content along with applying various frequencies did not alter the pattern of G' formation when paste was heated at different heating rates. AP surimi favored the slow heating. / Graduation date: 2013