Acidified dairy products are one of the oldest types of food products. Unfortunately all of them are low in dietary fibre. Thus, to improve health benefit of these products the idea of fortifying them with dietary fibre seems attractive. However dairy products enriched with Glucagel (a commercial product that is high in barley β-glucan) were found to suffer from textural defects. When the Glucagel concentration exceeded a certain value (5 g/L), dramatic phase separation was observed in set yogurt and yogurt drink with volume fraction of casein micelles greater then 0.108. To investigate interactions of β-glucan polymers and casein micelles in the milk prior to setting of yogurt, mixtures of yogurt milk and Glucagel were systematically studied. Depending on the volume fraction of casein micelles and the Glucagel concentration, a stable phase or a gel or a sedimented material could exist. The driving force for phase separation was depletion flocculation of casein micelles in the presence of β-glucan. The phase separation responsible for textural defects in yogurt systems supplemented with high amounts of Glucagel can be avoided by the reduction of β-glucan molecular weight, a process that limits the range of attraction between micelles. Incubation of Glucagel with lichenase for 90 min resulted in homogeneous (stable) yogurt systems with Glucagel concentrations as high as 10 g/L.

Acidified dairy products are one of the oldest types of food products. Unfortunately all of them are low in dietary fibre. Thus, to improve health benefit of these products the idea of fortifying them with dietary fibre seems attractive. However dairy products enriched with Glucagel (a commercial product that is high in barley β-glucan) were found to suffer from textural defects. When the Glucagel concentration exceeded a certain value (5 g/L), dramatic phase separation was observed in set yogurt and yogurt drink with volume fraction of casein micelles greater then 0.108. To investigate interactions of β-glucan polymers and casein micelles in the milk prior to setting of yogurt, mixtures of yogurt milk and Glucagel were systematically studied. Depending on the volume fraction of casein micelles and the Glucagel concentration, a stable phase or a gel or a sedimented material could exist. The driving force for phase separation was depletion flocculation of casein micelles in the presence of β-glucan. The phase separation responsible for textural defects in yogurt systems supplemented with high amounts of Glucagel can be avoided by the reduction of β-glucan molecular weight, a process that limits the range of attraction between micelles. Incubation of Glucagel with lichenase for 90 min resulted in homogeneous (stable) yogurt systems with Glucagel concentrations as high as 10 g/L.

Polymers of various types are added to crude oils and oil products to prevent wax deposition, break water-in-oil emulsions, reduce drag in pipelines and to stabilize asphaltenes. In mixtures where a polymer does not adsorb on colloids, two stable liquid phases can arise due to depletion flocculation. Asphaltenes in heavy oils and toluene mixtures form sterically stabilized colloidal particles. In this work, the addition of a non-adsorbing polymer (polystyrene) to C5 Maya asphaltene + toluene mixtures was investigated experimentally and theoretically. As concentrated asphaltene + toluene mixtures are opaque to visible light, phase volumes and compositions were detected using ultrasound. The sensors comprised two commercial 64 element phased-array acoustic probes. The operation of the view cell, and kinetic and equilibrium data processing procedures were validated using mixtures of methanol + alkanes. Acoustic speed and attenuation profiles were found to provide independent measures of phase separation. At equilibrium, acoustic speed profiles are uniform in each phase with a step change at the interface. Acoustic wave attenuation profiles exhibit a sharp peak/spike at liquid-liquid interfaces. Mixtures of asphaltenes + polystyrene + toluene are shown to exhibit liquid-liquid phase behavior over broad ranges of composition. This is the first report of liquid-liquid phase behavior for such mixtures. One phase is asphaltene rich and the other phase is polystyrene rich. Liquid-liquid critical points were also identified along the liquid-liquid/liquid phase boundary for mixtures with two mean molar masses of polystyrene. Compositions of co-existing phases were computed using phase volume variations along dilution lines, acoustic speed data and a mass balance model. A parameter was introduced to improve the agreement between calculated and experimental speeds of sound. The results of the model indicate that more than half of the asphaltenes, by volume, participate in the depletion flocculation process. Phase compositions were measured independently using UV-visible spectrophotometry. The nominal size of asphaltene colloidal particles participating in the phase separation mechanism was estimated by comparing calculated phase boundaries with the experimental phase diagram. The estimated size of asphaltene colloidal particles is in agreement with the expected size of asphaltenes in toluene mixtures obtained exogenously. / Chemical and Materials Engineering

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Rheology modifiers such as hydrophobically-modified ethoxylated urethane (HEUR)thickeners are included in waterborne latex coatings to optimize shear-rate dependent viscosity and other rheological properties. While these HEUR polymers are commonly used in industry, the complex chemical interactions that contribute to rheological properties are still not completely understood. Prior work in this area has focused on understanding latex-HEUR and latex-surfactant-HEUR interactions that affect rheological properties. Additionally, studies have been previously conducted to understand the relaxation mechanisms of complex interactions present in HEUR-thickened waterborne latex coatings under various dynamic conditions. The objective of this work is to extend the experimental work to fully-formulated coatings and determine the effects of additional ingredients in a fully-formulated system. Coating formulations were prepared with a target 90 KU (Kreb Units) viscosity, having 0.23wt% HEUR. The pigment volume concentration (PVC) and non-volatiles by volume (NVV) were kept constant at 19.87% and 30.47%, respectively. An analysis of phase stability (presence or absence of syneresis), flow sweep (10-2 to 103 s-1), oscillatory strain (10-2 to 102 %), and oscillatory frequency (10-2 to 102 Hz) data was carried out in an attempt to determine connections among these properties. Furthermore, brief comparisons were made with previous results on latex-HEUR and latex-HEUR-surfactant systems that utilized the same HEUR thickener and latex used in this study. In the fully-formulated system, 0.23wt% HEUR was found to be in excess of what is needed to saturate latex surfaces. This HEUR level is less than half of the level needed to saturate latex surfaces in simpler latex-HEUR systems in previous studies. Fully-formulated coatings, in addition to having TiO2 and other ingredients are more crowded than the previous systems. It appeared that a depletion flocculation mechanism dominated at low surfactant concentrations for fully-formulated systems in this study as evident from syneresis; large HEUR aggregates appear to build enough osmotic pressure to drive aggregation of latex and pigment particles resulting in depletion flocculation. At increasing surfactant levels, the depletion flocculation mechanism was negated allowing the associative HEUR bridge networks to dominate and stabilize the system. Phase stability for fully-formulated systems in this study were associated with Newtonian viscosity plateaus on flow sweeps, strain hardening on oscillatory strain sweeps, and formation of high frequency moduli plateaus in frequency sweeps. Further increase of surfactant concentration appeared to disrupt the stable latex-HEUR network due to competitive adsorption of surfactant on latex particles, resulting in syneresis from bridging flocculation. Possible correlations between phase stability and high relaxation times were seen, although further analysis of relaxation time data and simulations will need to be carried out to better understand the behavior of HEUR in fully-formulated systems.