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.

Implementation of a Control Loop Experiment in a Network-Based Control System With LonWorks Technology and IP Networks

Considering the increasing popularity of network-based control systems and the huge adoption of IP networks (such as the Internet), this paper studies the influence of network quality of service (QoS) parameters over quality of control parameters. An example of a control loop is implemented using two LonWorks networks (CEA-709.1) interconnected by an emulated IP network, in which important QoS parameters such as delay and delay jitter can be completely controlled. Mathematical definitions are provided according to the literature, and the results of the network-based control loop experiment are presented and discussed.

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.

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.

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.

Kinetics and Modeling of Fatty Alcohol Ethoxylation in an Industrial Spray Loop Reactor

The kinetics of the ethoxylation of fatty alcohols catalyzed by potassium hydroxide was studied to obtain the rate constants for modeling of the industrial process. Experimental data obtained in a lab-scale semibatch autoclave reactor were used to evaluate kinetic and equilibrium parameters. The kinetic model was employed to model the performance of an industrial-scale spray tower reactor for fatty alcohol ethoxylation. The reactor model considers that mass transfer and reaction occur independently in two distinct zones of the reactor. Good agreement between the model predictions and real data was found. These findings confirm the reliability of the kinetic and reactor model for simulating fatty alcohol ethoxylation processes under industrial conditions.

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

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.

Modeling and Filtering Double-Frequency Jitter in One-Way Master-Slave Chain Networks

One-way master-slave (OWMS) chain networks are widely used in clock distribution systems due to their reliability and low cost. As the network nodes are phase-locked loops (PLLs), double-frequency jitter (DFJ) caused by their phase detectors appears as an impairment to the performance of the clock recovering process found in communication systems and instrumentation applications. A nonlinear model for OWMS chain networks with P + 1 order PLLs as slave nodes is presented, considering the DFJ. Since higher order filters are more effective in filtering DFJ, the synchronous state stability conditions for an OWMS chain network with third-order nodes are derived, relating the loop gain and the filter coefficients. By using these conditions, design examples are discussed.

Phase-Locked Loop design applied to frequency-modulated atomic force microscope

The atomic force microscope (AFM) introduced the surface investigation with true atomic resolution. In the frequency modulation technique (FM-AFM) both the amplitude and the frequency of oscillation of the micro-cantilever must be kept constant even in the presence of tip-surface interaction forces. For that reason, the proper design of the Phase-Locked Loop (PLL) used in FM-AFM is vital to system performance. Here, the mathematical model of the FM-AFM control system is derived considering high order PLL In addition a method to design stable third-order Phase-Locked Loops is presented. (C) 2010 Elsevier B.V. All rights reserved.

Design constraints for third-order PLL nodes in master-slave clock distribution networks

Clock signal distribution in telecommunication commercial systems usually adopts a master-slave architecture, with a precise time basis generator as a master and phase-locked loops (PLLs) as slaves. In the majority of the networks, second-order PLLs are adopted due to their simplicity and stability. Nevertheless, in some applications better transient responses are necessary and, consequently, greater order PLLs need to be used, in spite of the possibility of bifurcations and chaotic attractors. Here a master-slave network with third-order PLLs is analyzed and conditions for the stability of the synchronous state are derived, providing design constraints for the node parameters, in order to guarantee stability and reachability of the synchronous state for the whole network. Numerical simulations are carried out in order to confirm the analytical results. (C) 2009 Elsevier B.V. All rights reserved.

Route to chaos in a third-order phase-locked loop network

Phase-locked loops (PLLs) are widely used in applications related to control systems and telecommunication networks. Here we show that a single-chain master-slave network of third-order PLLs can exhibit stationary, periodic and chaotic behaviors, when the value of a single parameter is varied. Hopf, period-doubling and saddle-saddle bifurcations are found. Chaos appears in dissipative and non-dissipative conditions. Thus, chaotic behaviors with distinct dynamical features can be generated. A way of encoding binary messages using such a chaos-based communication system is suggested. (C) 2009 Elsevier B.V. All rights reserved.

Using bifurcations in the determination of lock-in ranges for third-order phase-locked loops

Transmission and switching in digital telecommunication networks require distribution of precise time signals among the nodes. Commercial systems usually adopt a master-slave (MS) clock distribution strategy building slave nodes with phase-locked loop (PLL) circuits. PLLs are responsible for synchronizing their local oscillations with signals from master nodes, providing reliable clocks in all nodes. The dynamics of a PLL is described by an ordinary nonlinear differential equation, with order one plus the order of its internal linear low-pass filter. Second-order loops are commonly used because their synchronous state is asymptotically stable and the lock-in range and design parameters are expressed by a linear equivalent system [Gardner FM. Phaselock techniques. New York: John Wiley & Sons: 1979]. In spite of being simple and robust, second-order PLLs frequently present double-frequency terms in PD output and it is very difficult to adapt a first-order filter in order to cut off these components [Piqueira JRC, Monteiro LHA. Considering second-harmonic terms in the operation of the phase detector for second order phase-locked loop. IEEE Trans Circuits Syst [2003;50(6):805-9; Piqueira JRC, Monteiro LHA. All-pole phase-locked loops: calculating lock-in range by using Evan`s root-locus. Int J Control 2006;79(7):822-9]. Consequently, higher-order filters are used, resulting in nonlinear loops with order greater than 2. Such systems, due to high order and nonlinear terms, depending on parameters combinations, can present some undesirable behaviors, resulting from bifurcations, as error oscillation and chaos, decreasing synchronization ranges. In this work, we consider a second-order Sallen-Key loop filter [van Valkenburg ME. Analog filter design. New York: Holt, Rinehart & Winston; 1982] implying a third order PLL The resulting lock-in range of the third-order PLL is determined by two bifurcation conditions: a saddle-node and a Hopf. (C) 2008 Elsevier B.V. All rights reserved.

Mutually connected phase-locked loop networks: dynamical models and design parameters

Distribution of timing signals is an essential factor for the development of digital systems for telecommunication networks, integrated circuits and manufacturing automation. Originally, this distribution was implemented by using the master-slave architecture with a precise master clock generator sending signals to phase-locked loops (PLL) working as slave oscillators. Nowadays, wireless networks with dynamical connectivity and the increase in size and operation frequency of the integrated circuits suggest that the distribution of clock signals could be more efficient if mutually connected architectures were used. Here, mutually connected PLL networks are studied and conditions for synchronous states existence are analytically derived, depending on individual node parameters and network connectivity, considering that the nodes are nonlinear oscillators with nonlinear coupling conditions. An expression for the network synchronisation frequency is obtained. The lock-in range and the transmission error bounds are analysed providing hints to the design of this kind of clock distribution system.