The Interaction of Glymes with Surfactant Micelles

The critical micelle concentrations (CMC) values and counterion dissociation (α values) have been determined for a number of mixed micellar systems consisting of two typical ionic surfactants and glycol ethers (glymes) as cosurfactants, namely diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. Conductance experiments were used to determine the CMC and α values of the mixed micelles as a function of glyme concentration in the aqueous mixed solvent. Favorable interactions between sodium dodecyl sulfate micelles and glyme cosurfactants were deduced from the decreases in the CMC values and the large increase in the α values of these systems as a function of increasing glyme concentration in the mixed solvents. In contrast to the anionic surfactant/glyme systems, in general, there appeared to be little favorable interactions between the surfactant and glymes when micelles of the cationic surfactant dodecyltrimethylammonium bromide were formed in water/glyme solvent systems containing an increasing amount of the glymes. The interaction of glymes with the surfactant micelles was examined closely via ¹³C nuclear magnetic resonance (NMR) chemical shifts for both surfactant and glyme carbons; these chemical shifts changes were interpreted in terms of the distribution and the localization of the glymes in the aggregates. Finally, partition constants, determined from two-dimensional diffusion-oriented spectroscopy (2D-DOSY) experiments, were used to calculate thermodynamic quantities of transfer of the glymes between the bulk phase and the self-assembled aggregates. All these results are interpreted in terms of the key contributions that both the glyme ethoxylated groups and alkyl endgroups make to the hydrophobic interactions.     

Effect of DAG on milk fat TAG crystallization

The effect of milk fat and standard DAG on the crystallization behavior of milk fat TAG (MF-TAG) was investigated. When milk fat DAG were added to MF-TAG at the 0.1 wt% level, crystallization was delayed. Racemic purity was shown to be an important factor in the ability of DAG to influence TAG crystallization. Only sn-1,2 isomers of blends of MF-TAG with 0.1 wt% of the racemic mixtures of dipalmitin and diolein increased the activation free energy barrier to MF-TAG nucleation (ΔG _c ) and delayed the subsequent crystallization process by increasing the crystallization induction time (τ_SFC) determined from solid fat content-time measurements. Although crystallization kinetics were affected, the properties of the resulting network structures remained unchanged upon addition of milk fat minor components at the 0.1 wt% level     

Restructuring butterfat through blending and chemical interesterification. 3. Rheology

Interesterified and noninteresterified butterfat-canola oil blends, ranging from 100% butterfat to 60∶40 butterfat-canola oil (w/w) in 10% increments, were evaluated for hardness index (HI), dropping point, viscosity, and viscoelastic properties at small deformation. Both blending and chemical interesterification diminished HI in a nonlinear fashion. HI changes in interesterified blends were more pronounced than in noninteresterified blends. Dropping points yielded information on the structure of the blends. Butterfat’s dropping point (DP) was 34.4°C, whereas that of interesterified butterfat was 37.0°C, which is indicative of a more structured network for the latter. DP values of blends with 60–90% butterfat (interesterified vs. noninteresterified) were not significantly different (P<0.05). Interesterified blends had a higher crystallization onset temperature than did noninteresterified blends. All blends in the liquid state displayed Newtonian behavior. Oscillatory frequency sweep measurements at small amplitude showed that interesterified blends generally had lower storage moduli (G′) than their noninteresterified counterparts. BothG′ andG″ were frequency-dependent. Replacement of 30% butterfat by canola oil led to notable changes in small deformation measurements, whereas replacement of 20% butterfat led to big changes in large deformation measurements.     

Distributed Control Strategy with Smith's Predictor in a Pilot-Scale Diabatic Distillation Unit

Intrinsic characteristics of distillation such as dead time and high nonlinearities do not allow the complete elimination of transient times when any external disturbance or set-point change occurs. Thus, aiming at the use of easy-tuning systems, a distributed-action control in trays of a diabatic distillation unit with Smith's predictor was implemented in the Simulink environment to further reduce transient times and out-of-specification product. The distributed-action strategy with Smith's predictor led to a reduction of 33.3 min (33 %) in the transient time of the top temperature control loop and 66 % in out-of-specification product, when compared with the conventional strategy, and thus is shown to be an efficient approach to increasing the productivity of distillation plants.     

Effect of rheology and humic acids on the transport of environmental fluids: Potential implications for soil remediation revealed through microfluidics

This study investigated the potential effect of shear rheology and humic acids (HA) on the subsurface transport of polymeric fluids used for the remediation of contaminants. Polymeric fluids were prepared with guar, scleroglucan, and carboxymethyl cellulose (CMC). Guar fluids can be used to suspend reactive particles for contaminant degradation. Fluids prepared with 2.5 g/L of guar in water were viscous, and the crosslinker borax (1 g/L) made them viscoelastic. Microfluidics experiments showed that the increase in elasticity blocked the flow of guar in 350 μm channels. Guar, CMC, or scleroglucan fluids containing sodium thiosulfate can be used to trap toxic Cr(VI) in the subsurface and reduce it to harmless Cr(III). Trapping of Cr(VI) is achieved by the gelation of the fluids upon contact with chromium. Before mixing with chromium, HA did not affect the flow of CMC, guar, and scleroglucan in microfluidic channels. Quartz-crystal microbalance with dissipation monitoring experiments indicates that HA reduced sorption of guar onto silica, potentially promoting the transport of guar fluids in sandy aquifers. While HA slightly decreased the rate of gelation of CMC and scleroglucan upon contact with chromium, it did not affect the fast gelation rate of guar. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48465.     

Porous,Sintered Glass‐Ceramics from Inorganic Polymers Based on Fayalite Slag

The present paper deals with the synthesis of porous, sintered glass‐ceramics obtained at temperatures below 1150°C, originating from inorganic polymers based on fayalite slag. Firing led to the evaporation of water, dehydroxylation, and oxidation of Fe²⁺ above 345°C. For heating >700°C, the Si–O stretching band shifted from the 1160 and 750 cm^?1 to the 1255 and 830 cm^?1 region, due to a structural reorganization of the amorphous phase, whereas Fe–O bands appeared at 550 cm^?1. The final microstructure consisted predominantly of an amorphous phase, hematite, and franklinite. The open porosity and compressive strength decreased and increased, respectively, as the firing temperature increased. The final values suggest properties comparable to that of structural lightweight concrete, still, the materials synthesized herein, are lighter, and made primarily from secondary resources.     

Fractal Dimensions of Simulated and Real Fat Crystal Networks in 3D Space

The microstructure of fat crystal networks is closely related to rheological properties of fat products, and thus is of particular interest to food scientists. The fractal dimensions of fat crystal networks calculated by microscopy methods such as box-counting, D _b, particle-counting, D _f, and mass fractal dimension, D _m, have been extensively employed to quantify the microstructure of fats. This work revealed the microstructural basis of D _b, D _f, and D _m in 3D space through both computer simulation and experiments on the high melting fraction of milk fat crystal networks. Similar to our previous simulation study on the fractal dimensions of fat crystal networks in 2D space, D _b is sensitive to crystal size, area fraction, and not sensitive to distribution orderliness of crystals, which is the percentage of evenly distributed fat crystals within the simulated fat crystal networks. D _f and D _m were not affected by any of the microstructural factors studied in the simulation.     

Identifying key structural indicators of mechanical strength in networks of fat crystals

The mechanical properties of edible fats can be influenced by a series of factors, including the amount of solids, the polymorphism of the solid-state, as well as the microstructure of networks of polycrystalline particles created upon crystallization. This work demonstrates that for binary mixtures of the high-melting fraction of milk fat (HMF) with cocoa butter as well as for mixtures of HMF with the middle-melting fraction of milk fat, changes in the storage shear modulus (G′) are mostly controlled by the solid fat content (SFC), and the material’s microstructure. The SFC, in turn is a function of the phase behavior of the mixtures in the solid state. Experimental techniques used in the characterization of the different levels of structure are presented in this work. A model developed to explain mechanical properties of these materials taking into account all levels of structure is proposed. The polymorphism of the solid state did not seem to influence the mechanical properties of the fats, indicative of this material being structured as a network of weakly-attractive polycrystalline particles. Moreover, the mass fractal dimension of the network was closely related to the polymorphism of the solid state.     

Rheological Properties of Milkfat and Butter

ABSTRACT: Butter and milkfat are examples of plastic materials for which texture is a critical factor in determining functionality and consumer acceptance. The methods by which butter rheology is characterized are discussed, including large deformation techniques such as cone penetrometry, compression, sectility and extrusion, and methods which involve testing at low levels of strain. Correlations between instrumental tests and sensory-evaluated properties of the fats are explored. Rheological properties, including hardness, spreadability, setting, work softening, and thixotropy are described, and the models which have been proposed to characterize these behaviors are reviewed. Techniques which have been devised recently to quantitatively relate structural measurements to rheology are also examined. Modification of butter's rheological properties can be accomplished through alterations in composition or in the manufacturing process. These approaches are discussed and evaluated.