Long-term stability of hydrogen and organic acids production in an anaerobic fluidized-bed reactor using heat treated anaerobic sludge inoculum

This study evaluates the stability of hydrogen and organic acids production in an anaerobic fluidized-bed reactor (AFBR) that contains expanded clay (2.8-3.35 mm in diameter) as a support medium and is operated on a long-term basis. The reactor was inoculated with thermally pre-treated anaerobic sludge and operated with decreasing hydraulic retention time (HRT), from 8 h to 1 h, at a controlled temperature of 30 degrees C and a pH of about 3.8. Glucose (2000 mg L(-1)) was used as the substrate, generating conversion rates of 92-98%. Decreasing the HRT from 8 h to 1 h led to an increase in average hydrogen-production rates, with a maximum value of 1.28 L h(-1) L(-1) for an HRT of 1 h. In general, hydrogen yield production increased as HRT decreased, reaching 2.29 mol of H(2)/mol glucose at an HRT of 2 h and yielding a maximum hydrogen content of 37% in the biogas. No methane was detected in the biogas throughout the period of operation. The main soluble metabolites (SMP) were acetic acid (46.94-53.84% of SMP) and butyric acid (34.51-42.16% of SMP), with less than 15.49% ethanol. The steady performance of the AFBR may be attributed to adequate thermal treatment of the inoculum, the selection of a suitable support medium for microbial adhesion, and the choice of satisfactory environmental conditions imposed on the system. The results show that stable hydrogen production and organic acids production were maintained in the AFBR over a period of 178 days. (C) 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Unsaturated Infinite Slope Stability Considering Surface Flux Conditions

A slope stability model is derived for an infinite slope subjected to unsaturated infiltration flow above a phreatic surface. Closed form steady state solutions are derived for the matric suction and degree of saturation profiles. Soil unit weight, consistent with the degree of saturation profile, is also directly calculated and introduced into the analyzes, resulting in closed-form solutions for typical soil parameters and an infinite series solution for arbitrary soil parameters. The solutions are coupled with the infinite slope stability equations to establish a fully realized safety factor function. In general, consideration of soil suction results in higher factor of safety. The increase in shear strength due to the inclusion of soil suction is analogous to making an addition to the cohesion, which, of course, increases the factor of safety against sliding. However, for cohesive soils, the results show lower safety factors for slip surfaces approaching the phreatic surface compared to those produced by common safety factor calculations. The lower factor of safety is due to the increased soil unit weight considered in the matric suction model but not usually accounted for in practice wherein the soil is treated as dry above the phreatic surface. The developed model is verified with a published case study, correctly predicting stability under dry conditions and correctly predicting failure for a particular storm.

Floquet stability analysis of the flow around an oscillating cylinder

This investigative work is concerned with the flow around a circular cylinder submitted to forced transverse oscillations. The goal is to investigate how the transition to turbulence is initiated in the wake for cases with different Reynolds numbers (Re) and displacement amplitudes (A). For each Re the motion frequency is kept constant, close to the Strouhal number of the flow around a fixed cylinder at the same Re. Stability analysis of two-dimensional periodic flows around a forced-oscillating cylinder is carried out with respect to three-dimensional infinitesimal perturbations. The procedure consists of performing a Floquet type analysis of time-periodic base flows, computed using the spectral/hp element method. With the results of the Floquet calculations, considerations regarding the stability of the system are drawn, and the form of the instability at its onset is obtained. The critical Reynolds number is observed to change with the amplitude of oscillation. With respect to instabilities, unstable modes with the same symmetry as mode A of a fixed cylinder are observed; however, they present different wavelengths. Also, the instabilities observed for the oscillating cylinder are distinctively stronger in the braid shear layers. Other unstable modes similar to mode B are found. Quasi-periodic modes are observed in the 2S wake, and subharmonic mode occurrences are reported in P + S wakes. (C) 2009 Elsevier Ltd. All rights reserved.

Quantification of MgO surface excess on the SnO(2) nanoparticles and relationship with nanostability and growth

In this work, we experimentally showed that the spontaneous segregation of MgO as surface excess in MgO doped SnO(2) nanoparticles plays an important role in the system`s energetics and stability. Using Xray fluorescence in specially treated samples, we quantitatively determined the fraction of MgO forming surface excess when doping SnO(2) with several different concentrations and established a relationship between this amount and the surface energy of the nanoparticles using the Gibbs approach. We concluded that the amount of Mg ions on the surface was directly related to the nanoparticles total free energy, in a sense that the dopant will always spontaneously distribute itself to minimize it if enough diffusion is provided. Because we were dealing with nanosized particles, the effect of MgO on the surface was particularly important and has a direct effect on the equilibrium particle size (nanoparticle stability), such that the lower the surface energy is, the smaller the particle sizes are, evidencing and quantifying the thermodynamic basis of using additives to control SnO(2) nanoparticles stability. (C) 2010 Elsevier B.V. All rights reserved.

Interface Energy Measurement of MgO and ZnO: Understanding the Thermodynamic Stability of Nanoparticles

Nanomaterials have triggered excitement in both fundamental science and technological applications in several fields However, the same characteristic high interface area that is responsible for their unique properties causes unconventional instability, often leading to local collapsing during application Thermodynamically, this can be attributed to an increased contribution of the interface to the free energy, activating phenomena such as sintering and grain growth The lack of reliable interface energy data has restricted the development of conceptual models to allow the control of nanoparticle stability on a thermodynamic basis. Here we introduce a novel and accessible methodology to measure interface energy of nanoparticles exploiting the heat released during sintering to establish a quantitative relation between the solid solid and solid vapor interface energies. We exploited this method in MgO and ZnO nanoparticles and determined that the ratio between the solid solid and solid vapor interface energy is 11 for MgO and 0.7 for ZnO. We then discuss that this ratio is responsible for a thermodynamic metastable state that may prevent collapsing of nanoparticles and, therefore, may be used as a tool to design long-term stable nanoparticles.

Optimal conditions for the wetting balance test

Wetting balance tests of copper sheets submerged in tin solder baths were carried out in a completely automatic wetting balance. Wetting curves were examined for three different values of sheet thickness and four different solder bath temperatures. Most of the wetting curves showed a distorted shape relative to that of a standard curve, preventing calculation of important wetting parameters, such as the wetting rate and the wetting force. The wetting tests showed that the distortion increased for a thicker sheet thickness and a lower solder bath temperature, being the result of solder bath solidification around the submerged sheet substrate. (C) 2008 Elsevier B.V. All rights reserved.

Electron theoretical investigation of the stability of the B2-TiFe compound

The metastable phase diagram of the BCC-based ordering equilibria in the Ti-Fe system has been calculated using a truncated cluster expansion, through the combination of FP-LAPW and cluster variation method (CVM) in the irregular tetrahedron cluster approximation. The results are compared with phenomenological CVM assessments of the system and suggest that the value for the experimental formation enthalpy of the B2-TiFe compound should be significantly more negative than the currently assessed value. (C) 2008 Elsevier B.V. All rights reserved.

Interface excess and polymorphic stability of nanosized zirconia-magnesia

Controlling the phase stability of ZrO2 nanoparticles is of major importance in the development of new ZrO2-based nanotechnologies. Because of the fact that in nanoparticles the surface accounts for a larger fraction of the total atoms, the relative phase stability can be controlled throughout the surface composition, which can be toned by surface excess of one of the components of the system., The objective of this work is to delineate a relationship between surface excess (or solid solution) of MgO relative to ZrO2 and the polymorphic stability of (ZrO2)(1-x) - (MgO), nanopowders, where 0.0 <= x <= 0.6. The nanopowders were prepared by a liquid precursor method at 500 degrees C and characterized by N-2 adsorption (BET), X-ray diffraction (XRD), X-Ray photoelectron spectroscopy (XPS), and Raman spectroscopy. For pure ZrO2 samples, both tetragonal and monoclinic polymorphs were detected, as expected considering the literature. For MgO molar fractions varying from 0.05 to 0.10, extensive solid solution could not be detected, and a ZrO2 surface energy reduction, caused by Mg surface excess detected by XPS, promoted tetragonal polymorph thermodynamic stabilization with relation to monoclinic. For MgO molar fractions higher than 0.10 and up to 0.40, Mg solid solution could be detected and induced cubic phase stabilization. MgO periclase was observed only at x = 0.6. A discussion based on the relationship between the surface excess, surface energy, and polymorph stability is presented.

Evaluation of the effect of ammonium carbamate on the stability of proteins

BACKGROUND: The use of the volatile salt ammonium carbamate in protein downstream processing has recently been proposed. The main advantage of using volatile salts is that they can be removed from precipitates and liquid effluents through pressure reduction or temperature increase. Although previous studies showed that ammonium carbamate is efficient as a precipitant agent, there was evidence of denaturation in some enzymes. In this work, the effect of ammonium carbamate on the stability of five enzymes was evaluated. RESULTS: Activity assays showed that alpha-amylase (1,4-alpha-D-glucan glucanohydrolase, EC 3.2.1.1), lysozyme (1,4-beta-N-acetylmuramoylhydrolase, EC 3.2.1.17) and lipase (triacyl glycerol acyl hydrolase, EC 3.1.1.3) did not undergo activity loss in ammonium carbamate solutions with concentrations from 1.0 to 5.0 mol kg(-1), whereas cellulase complex (1,4-(1,3 : 14)-beta-D-glucan 4-glucano-hydrolase, EC 3.2.1.4) and peroxidase (hydrogen peroxide oxidoreductase, EC 1.11.1.7) showed an average activity loss of 55% and 44%, respectively. Precipitation assays did not show enzyme denaturation or phase separation for alpha-amylase and lipase, while celullase and peroxidase precipitated with some activity reduction. Analysis of similar experiments with ammonium and sodium sulfate did not affect the activity of enzymes. CONCLUSION: Celullase and peroxidase were denatured by ammonium carbamate. While more systematic studies are not available, care must be taken in designing a protein precipitation with this salt. The results suggest that the generally accepted idea that salts that denature proteins tend to solubilize them does not hold for ammonium carbamate. (C) 2010 Society of Chemical Industry

WATER ACTIVITY OF AQUEOUS SOLUTIONS OF ETHYLENE OXIDE-PROPYLENE OXIDE BLOCK COPOLYMERS AND MALTODEXTRINS

The water activity of aqueous solutions of EO-PO block copolymers of six different molar masses and EO/PO ratios and of maltodextrins of three different molar masses was determined at 298.15 K. The results showed that these aqueous solutions present a negative deviation from Raoult`s law. The Flory-Huggins and UNIFAC excess Gibbs energy models were employed to model the experimental data. While a good agreement was obtained with the Flory-Huggins equation, discrepancies were observed when predicting the experimental behavior with the UNIFAC model. The water activities of ternary systems formed by a synthetic polymer, maltodextrin and water were also measured and used to test the predictive capability of both models.

Thermodynamics of aqueous solutions of polyelectrolytes: Experimental results for the activity of water in aqueous solutions of (a single synthetic polyelectrolyte and sodium chloride)

Experimental results for the activity of water in aqueous solutions of 10 single, synthetic polyelectrolytes (polysodium acrylate, polysodium methacrylate, polyammonium acrylate, polysodium ethylene sulfonate, and polysodium styrene sulfonate) and sodium chloride at 298.2 K are presented. The experimental work was performed by applying the isopiestic method with sodium chloride as a reference substance. As expected, the activity of water decreases when the concentration of a polyelectrolyte and/or sodium chloride increases. At constant concentration of a polyelectrolyte and sodium chloride, the activity of water depends on the monomer unit and the molecular mass of the polyelectrolyte. The new data are to be used in future work to develop and test models for the Gibbs excess energy of aqueous solutions of polyelectrolytes.

An extension of the Pitzer equation for the excess Gibbs energy of aqueous electrolyte systems to aqueous polyelectrolyte solutions

Pitzer`s equation for the excess Gibbs energy of aqueous solutions of low-molecular electrolytes is extended to aqueous solutions of polyelectrolytes. The model retains the original form of Pitzer`s model (combining a long-range term, based on the Debye-Huckel equation, with a short-range term similar to the virial equation where the second osmotic virial coefficient depends on the ionic strength). The extension consists of two parts: at first, it is assumed that a constant fraction of the monomer units of the polyelectrolyte is dissociated, i.e., that fraction does not depend on the concentration of the polyelectrolyte, and at second, a modified expression for the ionic strength (wherein each charged monomer group is taken into account individually) is introduced. This modification is to account for the presence of charged polyelectrolyte chains, which cannot be regarded as punctual charges. The resulting equation was used to correlate osmotic coefficient data of aqueous solutions of a single polyelectrolyte as well as of binary mixtures of a single polyelectrolyte and a salt with low-molecular weight. It was additionally applied to correlate liquid-liquid equilibrium data of some aqueous two-phase systems that might form when a polyelectrolyte and another hydrophilic but neutral polymer are simultaneously dissolved in water. A good agreement between the experimental data and the correlation result is observed for all investigated systems. (c) 2008 Elsevier B.V. All rights reserved.

Stochastic stability analysis for the constant-modulus algorithm

We derive an easy-to-compute approximate bound for the range of step-sizes for which the constant-modulus algorithm (CMA) will remain stable if initialized close to a minimum of the CM cost function. Our model highlights the influence, of the signal constellation used in the transmission system: for smaller variation in the modulus of the transmitted symbols, the algorithm will be more robust, and the steady-state misadjustment will be smaller. The theoretical results are validated through several simulations, for long and short filters and channels.

Vibratory noise to the fingertip enhances balance improvement associated with light touch

Light touch of a fingertip on an external stable surface greatly improves the postural stability of standing subjects. The hypothesis of the present work was that a vibrating surface could increase the effectiveness of fingertip signaling to the central nervous system (e.g., by a stochastic resonance mechanism) and hence improve postural stability beyond that achieved by light touch. Subjects stood quietly over a force plate while touching with their right index fingertip a surface that could be either quiescent or randomly vibrated at two low-level noise intensities. The vibratory noise of the contact surface caused a significant decrease in postural sway, as assessed by center of pressure measures in both time and frequency domains. Complementary experiments were designed to test whether postural control improvements were associated with a stochastic resonance mechanism or whether attentional mechanisms could be contributing. A full curve relating body sway parameters and different levels of vibratory noise resulted in a U-like function, suggesting that the improvement in sway relied on a stochastic resonance mechanism. Additionally, no decrease in postural sway was observed when the vibrating contact surface was attached to the subject`s body, suggesting that no attentional mechanisms were involved. These results indicate that sensory cues obtained from the fingertip need not necessarily be associated with static contact surfaces to cause improvement in postural stability. A low-level noisy vibration applied to the contact surface could lead to a better performance of the postural control system.

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.