Phase Equilibrium and Optimization Tools: Application for Enhanced Structured Lipids for Foods

Solid-liquid phase equilibrium modeling of triacylglycerol mixtures is essential for lipids design. Considering the alpha polymorphism and liquid phase as ideal, the Margules 2-suffix excess Gibbs energy model with predictive binary parameter correlations describes the non ideal beta and beta` solid polymorphs. Solving by direct optimization of the Gibbs free energy enables one to predict from a bulk mixture composition the phases composition at a given temperature and thus the SFC curve, the melting profile and the Differential Scanning Calorimetry (DSC) curve that are related to end-user lipid properties. Phase diagram, SFC and DSC curve experimental data are qualitatively and quantitatively well predicted for the binary mixture 1,3-dipalmitoyl-2-oleoyl-sn-glycerol (POP) and 1,2,3-tripalmitoyl-sn-glycerol (PPP), the ternary mixture 1,3-dimyristoyl-2-palmitoyl-sn-glycerol (MPM), 1,2-distearoyl-3-oleoyl-sn-glycerol (SSO) and 1,2,3-trioleoyl-sn-glycerol (OOO), for palm oil and cocoa butter. Then, addition to palm oil of Medium-Long-Medium type structured lipids is evaluated, using caprylic acid as medium chain and long chain fatty acids (EPA-eicosapentaenoic acid, DHA-docosahexaenoic acid, gamma-linolenic-octadecatrienoic acid and AA-arachidonic acid), as sn-2 substitutes. EPA, DHA and AA increase the melting range on both the fusion and crystallization side. gamma-linolenic shifts the melting range upwards. This predictive tool is useful for the pre-screening of lipids matching desired properties set a priori.

Modeling Vinyl Acetate and n-Butyl Acrylate Emulsion Copolymerization Process

This work presents a mathematical model for the vinyl acetate and n-butyl acrylate emulsion copolymerization process in batch reactors. The model is able to explain the effects of simultaneous changes in emulsifier concentration, initiator concentration, monomer-to-water ratio, and monomer feed composition on monomer conversion, copolymer composition and, to lesser extent, average particle size evolution histories. The main features of the system, such as the increase in the rate of polymerization as temperature, emulsifier, and initiator concentrations increase are correctly represented by the model. The model accounts for the basic features of the process and may be useful for practical applications, despite its simplicity and a reduced number of adjustable parameters.

FLOW PROPERTIES AND TUBE FRICTION FACTOR OF MILK CREAM: INFLUENCE OF TEMPERATURE AND FAT CONTENT

The rheological behavior of milk cream was studied for different fat contents (0.10 to 0.31) and for a wide temperature range (2 and 87C) using a rotational rheometer. Newtonian behavior was observed, except for fat content between 0.20 and 0.31 and temperature between 2 and 33C, where viscoplastic behavior was remarkable. The rheological parameters (Newtonian viscosity, plastic viscosity and yield stress) and density were well correlated to temperature and fat content. Tube friction factor during flow of cream was experimentally obtained at various flow rates, temperatures and tube diameters (86 < Re < 2.3 x 104, 38 < Re(B) < 8.8 x 103, 1.1 x 103 < He < 6.7 x 103). The proposed correlations for density and rheological parameters were applied for the prediction of friction factor for laminar and turbulent flow of cream using well-known equations for Newtonian and viscoplastic flow. The good agreement between experimental and predicted values confirms the reliability of the proposed correlations for describing the flow behavior of cream. PRACTICAL APPLICATIONS This paper presents correlations for the calculation of density and rheological parameters (Newtonian viscosity, Bingham plastic viscosity and yield stress) of milk cream as functions of temperature (2-87C) and fat content (0.10-0.31). Because of the large temperature range, the proposed correlations are useful for process design and optimization in dairy processing. An example of practical application is presented in the text, where the correlations were applied for the prediction of friction factor for laminar and turbulent tube flow of cream using well-known equations for Newtonian and viscoplastic flow, which are summarized in the text. The comparison with experimental data obtained at various flow rates, temperatures and tube diameters showed a good agreement, which confirms the reliability of the proposed correlations.

Coalescence of Water Droplets in Crude Oil Emulsions: Analytical Solution

In petroleum refineries, water is used in desalting units to remove the salt contained in crude oil. Typically, 7% of the volume of hot crude oil is water, forming a water-and-oil emulsion. The emulsion flows between two electrodes and is subjected to an electric field. The electrical forces promote the coalescence of small droplets of water dispersed in crude oil, and these form bigger droplets. This paper calculates the forces acting on the droplets, highlighting particularly the mechanisms proposed for droplet-droplet coalescence under the influence of an applied electric field. Moreover, a model is developed in order to calculate the displacement speed of the droplets and the time between droplet collisions. Thus, it is possible to simulate and optimize the process by changing the operational variables (temperature, electrical field, and water quantity). The main advantage of this study is to show that it is feasible to increase the volume of water recycled in desalting processes, thus reducing the use of freshwater and the generation of liquid effluents in refineries.

Phase equilibria for salt-induced lysozyme precipitation: Effect of salt type and temperature

The salt-induced precipitation of lysozyme from aqueous solutions was studied through precipitation assays in which the equilibrium compositions of the coexisting phases were determined. Lysozyme precipitation experiments were carried out at 5, 15 and 25 degrees C and pH 7.0 with ammonium sulfate, sodium sulfate and sodium chloride as precipitating agents. In these experiments a complete separation of the coexisting phases (liquid and solid) could not be achieved. Nevertheless it was possible to determine the composition of the precipitate. The enzymatic activity of lysozyme in the supernatant phase as well as in the precipitate phase was also determined. The activity balance suggests that there is a relationship between the composition of the true precipitate and the total activity recovery. (C) 2009 Elsevier B.V. All rights reserved.

Replacement of Trays by Packing To Increase the Absorption Capacity of Acetone during Cellulose Acetate Spinning

All textile uses of cellulose acetate involve acetone recovery, which, because of safety issues, results in large installations, in order to work with dilute streams. This compromises the efficiency of all of the involved unit operations, in this case, acetone absorption in cold water, acetone distillation, and water chilling, making them more expensive. The present article proposes the improvement of the absorption of acetone in water, traditionally performed with sieve trays, by using structured packing instead. The advantageous implementation was enabled through the utilization of a calculation methodology based on concepts of thermodynamic equilibrium of the binary acetone/water system and empirical relations that allow the evaluation of the hydrodynamics of the proposed modification.

Temperature influence on the gate-induced floating body effect parameters in fully depleted SOI nMOSFETs

The temperature influence on the gate-induced floating body effect (GIFBE) in fully depleted (FD) silicon-on-insulator (SOI) nMOSFETs is investigated, based on experimental results and two-dimensional numerical simulations. The GIFBE behavior will be evaluated taking into account the impact of carrier recombination and of the effective electric field mobility degradation on the second peak in the transconductance (gm). This floating body effect is also analyzed as a function of temperature. It is shown that the variation of the studied parameters with temperature results in a ""C"" shape of the threshold voltage corresponding with the second peak in the gm curve. (C) 2008 Elsevier Ltd. All rights reserved.

Vortex configuration flow cell based on low temperature cofired ceramics as a compact chemiluminescence microsystern

The integration of optical detection methods in continuous flow microsystems can highly extend their range of application, as long as some negative effects derived from their scaling down can be minimized. Downsizing affects to a greater extent the sensitivity of systems based on absorbance measurements than the sensitivity of those based on emission ones. However, a careful design of the instrumental setup is needed to maintain the analytical features in both cases. In this work, we present the construction and evaluation of a simple miniaturized optical system, which integrates a novel flow cell configuration to carry out chemiluminescence (CL) measurements using a simple photodiode. It consists of a micro-mixer based on a vortex structure, which has been constructed by means of the low-temperature cofired ceramics (LTCC) technology. This mixer not only efficiently promotes the CL reaction due to the generated high turbulence but also allows the detection to be carried out in the same area, avoiding intensity signal losses. As a demonstration, a flow injection system has been designed and optimized for the detection of cobalt(H) in water samples. It shows a linear response between 2 and 20 mu M with a correlation of r > 0.993, a limit of detection of 1.1 mu M, a repeatability of RSD = 12.4 %, and an analysis time of 17 s. These results demonstrate the suitability of the proposal to the determination of compounds involved in CL reactions by means of an easily constructed versatile device based on low-cost instrumentation.

Development and fabrication of an optimized thermo-electro-optic device using a Mach-Zehnder interferometer

The development and fabrication of a thermo-electro-optic sensor using a Mach-Zehnder interferometer and a resistive micro-heater placed in one of the device`s arms is presented. The Mach-Zehnder structure was fabricated on a single crystal silicon substrate using silicon oxynitride and amorphous hydrogenated silicon carbide films to form an anti-resonant reflective optical waveguide. The materials were deposited by Plasma enhanced chemical vapor deposition technique at low temperatures (similar to 320 degrees C). To optimize the heat transfer and increase the device response with current variation, part of the Mach-Zehnder sensor arm was suspended through front-side bulk micromachining of the silicon substrate in a KOH solution. With the temperature variation caused by the micro-heater, the refractive index of the core layer of the optical waveguide changes due to the thermo-optic effect. Since this variation occurs only in one of the Mach-Zehnder`s arm, a phase difference between the arms is produced, leading to electromagnetic interference. In this way, the current applied to the micro-resistor can control the device output optical power. Further, reactive ion etching technique was used in this work to define the device`s geometry, and a study of SF6 based etching rates on different composition of silicon oxynitride films is also presented. (C) 2007 Elsevier B.V. All rights reserved.

Sensory Stability of Ultra-High Temperature Milk in Polyethylene Bottle

The objective of this study was to evaluate the sensory stability of ultra-high temperature (UHT) milk subjected to different heat treatments and stored at room temperature in white high density polyethylene bottles (HDPE) pigmented with titanium dioxide. Two lots of 300 units each were processed, respectively, at 135 and 141 degrees C/10 s using indirect heating and subsequently aseptically filled in an ISO class 7 clean room. These experimental lots were evaluated for appearance, aroma, flavor, and overall appreciation and compared to samples of commercial UHT milk purchased from local commercial stores. The time-temperature combinations investigated did not affect either the acceptability or the shelf life of the milk. Despite the limited light barrier properties of HDPE bottles, the product contained in the package tested exhibited good stability, with a shelf life ranging from 4 to 11 wk. Within this time period, the acceptability of the experimental lots was similar to that of the commercial products. The results achieved in this study contribute to turn the low-cost UHT system investigated into a technically viable option for small-size dairy processing plants.

Piezooptical effects in the tellurite glasses doped by europium and gold

We present the temperature dependence of piezooptical coefficients for three samples of TeO(2)-GeO(2)-PbO glasses doped with 0.5% of Eu(2)O(3), 0.5% and 1% of Au(2)O(3), after different thermoannealing times. We have established that there exist two temperatures singularities - minima in the range 655-695 K and maxima - at 850 K. It is crucial that for the glasses annealed during 61 h, at temperatures about 850 K, the anomaly of piezooptical coefficient disappears. Simultaneously the minima within the range 655-695 K changed depending on the duration of the thermoannealing which leads to low temperature shift of the minima. Towards lower temperature the piezooptical maxima occurs around 850 K and disappears after the increase of the annealing time. It is also crucial that the values of the piezooptical coefficients decrease with the enhancement of the thermoannealing. The observed temperature dependence with the piezooptical coefficients has a good correlation with the temperature dependences of the DSC. We have found that the pure glasses and glasses doped only by Au(2)O(3) and Eu(2)O(3) possess the piezooptical coefficients one order less with respect to the samples possessing simultaneously Au(2)O(3) and Eu(2)O(3). (C) 2008 Elsevier B.V. All rights reserved.

Piezoresistive response of ITO films deposited at room temperature by magnetron sputtering

Indium tin oxide (ITO) thin films have been deposited on (100) Si substrates by RF magnetron sputtering from a compact target (90% In(2)O(3)-10% SnO(2) in weight) with 6 in. in diameter. In order to perform electromechanical characterizations of these films, strain gauges were fabricated. An experimental set-up based on bending beam theory was developed to determine the longitudinal piezoresistive coefficient (pi(1)) of the strain gauges fabricated. It has been confirmed that electrical resistance of the strain gauges decreases with load increases which results a negative gauge factor. A model based on the activation energy was used to explain the origin of this negative signal. The influence of the temperature on piezoresistive properties of ITO films was also evaluated.

Structure and properties of an austenitic stainless steel AISI 316L grade ASTM F138 after low temperature plasma nitriding

Austenitic stainless steels cannot be conventionally nitrided at temperatures near 550 degrees C due to the intense precipitation of chromium nitrides in the diffusion zone. The precipitation of chro-mium nitrides increases the hardness but severely impairs corrosion resistance. Plasma nitriding allows introducing nitrogen in the steel at temperatures below 450 degrees C, forming pre-dominantly expanded austenite (gamma(N)), with a crystalline structure best represented by a special triclin-ic lattice, with a very high nitrogen atomic concentration promoting high compressive residual stresses at the surface, increasing substrate hardness from 4 GPa up to 14 GPa on the nitrided case.

Predicting the columnar-to-equiaxed transition for a distribution of nucleation undercoolings

A deterministic mathematical model for steady-state unidirectional solidification is proposed to predict the columnar-to-equiaxed transition. In the model, which is an extension to the classic model proposed by Hunt [Hunt JD. Mater Sci Eng 1984;65:75], equiaxed grains nucleate according to either a normal or a log-normal distribution of nucleation undercoolings. Growth maps are constructed, indicating either columnar or equiaxed solidification as a function of the velocity of isotherms and temperature gradient. The fields A columnar and equiaxed growth change significantly with the spread of the nucleation undercooling distribution. Increasing the spread Favors columnar solidification if the dimensionless velocity of the isotherms is larger than 1. For a velocity less than 1, however, equiaxed solidification is initially favored, but columnar solidification is enhanced for a larger increase in the spread. This behavior was confirmed by a stochastic model, which showed that an increase in the distribution spread Could change the grain structure from completely columnar to 50% columnar grains. (c) 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Structural and physicochemical characterization of RS prepared using hydrolysis and heat treatments of chickpea starch

The aim of this study was to evaluate the production and the structural and physicochemical properties of RS obtained by molecular mass reduction (enzyme or acid) and hydrothermal treatment of chickpea starch. Native and gelatinized starch were submitted to acid (2 M HCl for 2.5 h) or enzymatic hydrolysis (pullulanase, 40 U/g per 10 h), autoclaved (121 degrees C/30 min), stored under refrigeration (4 degrees C/24 h), and lyophilized. The hydrolysis of starch increased the RS content from 16% to values between 20 and 32%, and the enzymatic treatment of the gelatinized starch was the most efficient. RS showed an increase in water absorption and water solubility indexes due to hydrolytic and thermal process. The processes for obtaining RS changed the crystallinity pattern from C to B. Hydrolysis treatments caused an increase in relative crystallinity due to the greater retrogradation caused by the reduction in MW. RS obtained from hydrolysis showed a reduction in viscosity, indicating the rupture of molecules. The viscosity seemed to be inversely proportional to the RS content in the sample.