Solution Polymerization of N-vinylcaprolactam in 1,4-dioxane. Kinetic Dependence on Temperature, Monomer, and Initiator Concentrations

The kinetics of the solution free radical polymerization of N-vinylcaprolactam, in 1,4-dioxane and under various polymerization conditions was studied. Azobisisobutyronitrile and 3-mercaptopropionic acid were used as initiator and as chain transfer agent (CTA), respectively. The influence of monomer and initiator concentrations and polymerization temperature on the rate of polymerizations (R(p)) was investigated. In general, high conversions were obtained. The order with respect to initiator was consistent with the classical kinetic rate equation, while the order with respect to the monomer was greater than unity. The overall activation energy of 53.6 kJ mol(-1) was obtained in the temperature range 60-80 degrees C. The decreasing of the absolute molecular weights when increasing the CIA concentration was confirmed by GPC/SEC/LALS analyses. It was confirmed by UV-visible analyses the effect of molecular weights on the lower critical solution temperature of the polymers. It was also verified that the addition of the CTA influenced the kinetic of the polymerizations. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 118: 229-240, 2010

Obtaining and stability verification of superconducting phases of the Nb-Al and Nb-Sn systems by mechanical alloying and low-temperature heat treatments

The development of Nb(3)Al and Nb(3)Sn superconductors is of great interest for the applied superconductivity area. These intermetallics composites are obtained normally by heat treatment reactions at high temperature. Processes that allow formation of the superconducting phases at lower temperatures (<1000 degrees C), particularly for Nb(3)Al, are of great interest. The present work studies phase formation and stability of Nb(3)Al and Nb(3)Sn superconducting phases using mechanical alloying (high energy ball milling). Our main objective was to form composites near stoichiometry, which could be transformed into the superconducting phases using low-temperature heat treatments. High purity Nb-Sn and Nb-Al powders were mixed to generate the required superconducting phases (Nb-25at.%Sn and Nb-25at.%Al) in an argon atmosphere glove-box. After milling in a Fritsch mill, the samples were compressed in a hydraulic uniaxial press and encapsulated in evacuated quartz tubes for heat treatment. The compressed and heat treated samples were characterized using X-ray diffractometry. Microstructure and chemical analysis were accomplished using scanning electron microscopy and energy dispersive spectrometry. Nb(3)Al XRD peaks were observed after the sintering at 800 degrees C for the sample milled for 30 h. Nb(3)Sn XRD peaks could be observed even before the heat treatment. (C) 2009 Elsevier B.V. All rights reserved.

Improved xylitol production in media containing phenolic aldehydes: application of response surface methodology for optimization and modeling of bioprocess

BACKGROUND: The combined effects of vanillin and syringaldehyde on xylitol production by Candida guilliermondii using response surface methodology (RSM) have been studied. A 2(2) full-factorial central composite design was employed for experimental design and analysis of the results. RESULTS: Maximum xylitol productivities (Q(p) = 0.74 g L(-1) h(-1)) and yields (Y(P/S) = 0.81 g g(-1)) can be attained by adding only vanillin at 2.0 g L(-1) to the fermentation medium. These data were closely correlated with the experimental results obtained (0.69 +/- 0.04 g L(-1) h(-1) and 0.77 +/- 0.01 g g(-1)) indicating a good agreement with the predicted value. C. guilliermondii was able to convert vanillin completely after 24 h of fermentation with 94% yield of vanillyl alcohol. CONCLUSIONS: The bioconversion of xylose into xylitol by C. guilliermondii is strongly dependent on the combination of aldehydes and phenolics in the fermentation medium. Vanillin is a source of phenolic compound able to improve xylitol production by yeast. The conversion of vanillin to alcohol vanilyl reveals the potential of this yeast for medium detoxification. (C) 2009 Society of Chemical Industry

Thermal expansion of the V(5)Si(3) and T(2) phases of the V-Si-B system investigated by high-temperature X-ray diffraction

The thermal expansion anisotropy of the V(5)Si(3) and T(2)-phase of the V-Si-B system were determined by high-temperature X-ray diffraction from 298 to 1273 K. Alloys with nominal compositions V(62.5)Si(37.5) (V5Si3 phase) and V(63)Si(12)B(25) (T(2)-phase) were prepared from high-purity materials through arc-melting followed by heat-treatment at 1873 K by 24 h, under argon atmosphere. The V(5)Si(3) phase exhibits thermal expansion anisotropy equals to 1.3, with thermal expansion coefficients along the a and c-axis equal to 9.3 x 10(-6) K(-1) and 11.7 x 10(-6) K(-1), respectively. Similarly, the thermal expansion anisotropy value of the T(2)-phase is 0.9 with thermal expansion coefficients equal to 8.8 x 10(-6) K(-1) and 8.3 x 10(-6) K(-1) along the, a and c-axis respectively. Compared to other isostructural silicides of the 5:3 type and the Ti(5)Si(3) phase, the V(5)Si(3) phase presents lower thermal expansion anisotropy. The T(2)-phase present in the V-Si-B system exhibits low thermal expansion anisotropy, as the T(2)-phase of the Mo-Si-B, Nb-Si-B and W-Si-B systems. (C) 2009 Elsevier Ltd. All rights reserved.

Modeling associations between genetic markers using Bayesian networks

Motivation: Understanding the patterns of association between polymorphisms at different loci in a population ( linkage disequilibrium, LD) is of fundamental importance in various genetic studies. Many coefficients were proposed for measuring the degree of LD, but they provide only a static view of the current LD structure. Generative models (GMs) were proposed to go beyond these measures, giving not only a description of the actual LD structure but also a tool to help understanding the process that generated such structure. GMs based in coalescent theory have been the most appealing because they link LD to evolutionary factors. Nevertheless, the inference and parameter estimation of such models is still computationally challenging. Results: We present a more practical method to build GM that describe LD. The method is based on learning weighted Bayesian network structures from haplotype data, extracting equivalence structure classes and using them to model LD. The results obtained in public data from the HapMap database showed that the method is a promising tool for modeling LD. The associations represented by the learned models are correlated with the traditional measure of LD D`. The method was able to represent LD blocks found by standard tools. The granularity of the association blocks and the readability of the models can be controlled in the method. The results suggest that the causality information gained by our method can be useful to tell about the conservability of the genetic markers and to guide the selection of subset of representative markers.

A Study on Unconditionally Stable FDTD Methods for the Modeling of Metamaterials

We assess the performance of three unconditionally stable finite-difference time-domain (FDTD) methods for the modeling of doubly dispersive metamaterials: 1) locally one-dimensional FDTD; 2) locally one-dimensional FDTD with Strang splitting; and (3) alternating direction implicit FDTD. We use both double-negative media and zero-index media as benchmarks.

Modeling and analysis of laminate composite plates with embedded active-passive piezoelectric networks

The objective of this work is to present the finite element modeling of laminate composite plates with embedded piezoelectric patches or layers that are then connected to active-passive resonant shunt circuits, composed of resistance, inductance and voltage source. Applications to passive vibration control and active control authority enhancement are also presented and discussed. The finite element model is based on an equivalent single layer theory combined with a third-order shear deformation theory. A stress-voltage electromechanical model is considered for the piezoelectric materials fully coupled to the electrical circuits. To this end, the electrical circuit equations are also included in the variational formulation. Hence, conservation of charge and full electromechanical coupling are guaranteed. The formulation results in a coupled finite element model with mechanical (displacements) and electrical (charges at electrodes) degrees of freedom. For a Graphite-Epoxy (Carbon-Fibre Reinforced) laminate composite plate, a parametric analysis is performed to evaluate optimal locations along the plate plane (xy) and thickness (z) that maximize the effective modal electromechanical coupling coefficient. Then, the passive vibration control performance is evaluated for a network of optimally located shunted piezoelectric patches embedded in the plate, through the design of resistance and inductance values of each circuit, to reduce the vibration amplitude of the first four vibration modes. A vibration amplitude reduction of at least 10 dB for all vibration modes was observed. Then, an analysis of the control authority enhancement due to the resonant shunt circuit, when the piezoelectric patches are used as actuators, is performed. It is shown that the control authority can indeed be improved near a selected resonance even with multiple pairs of piezoelectric patches and active-passive circuits acting simultaneously. (C) 2010 Elsevier Ltd. All rights reserved.

Hybrid modeling of convective laminar flow in a permeable tube associated with the cross-flow process

The confined flows in tubes with permeable surfaces arc associated to tangential filtration processes (microfiltration or ultrafiltration). The complexity of the phenomena do not allow for the development of exact analytical solutions, however, approximate solutions are of great interest for the calculation of the transmembrane outflow and estimate of the concentration, polarization phenomenon. In the present work, the generalized integral transform technique (GITT) was employed in solving the laminar and permanent flow in permeable tubes of Newtonian and incompressible fluid. The mathematical formulation employed the parabolic differential equation of chemical species conservation (convective-diffusive equation). The velocity profiles for the entrance region flow, which are found in the connective terms of the equation, were assessed by solutions obtained from literature. The velocity at the permeable wall was considered uniform, with the concentration at the tube wall regarded as variable with an axial position. A computational methodology using global error control was applied to determine the concentration in the wall and concentration boundary layer thickness. The results obtained for the local transmembrane flux and the concentration boundary layer thickness were compared against others in literature. (C) 2007 Elsevier B.V. All rights reserved.

A state-space modeling approach for active structural acoustic control

The demands for improvement in sound quality and reduction of noise generated by vehicles are constantly increasing, as well as the penalties for space and weight of the control solutions. A promising approach to cope with this challenge is the use of active structural-acoustic control. Usually, the low frequency noise is transmitted into the vehicle`s cabin through structural paths, which raises the necessity of dealing with vibro-acoustic models. This kind of models should allow the inclusion of sensors and actuators models, if accurate performance indexes are to be accessed. The challenge thus resides in deriving reasonable sized models that integrate structural, acoustic, electrical components and the controller algorithm. The advantages of adequate active control simulation strategies relies on the cost and time reduction in the development phase. Therefore, the aim of this paper is to present a methodology for simulating vibro-acoustic systems including this coupled model in a closed loop control simulation framework that also takes into account the interaction between the system and the control sensors/actuators. It is shown that neglecting the sensor/actuator dynamics can lead to inaccurate performance predictions.

Contribution to dynamic characteristics of the cutting temperature in the drilling process considering one dimension heat flow

The machining of hardened steels has always been a great challenge in metal cutting, particularly for drilling operations. Generally, drilling is the machining process that is most difficult to cool due to the tool`s geometry. The aim of this work is to determine the heat flux and the coefficient of convection in drilling using the inverse heat conduction method. Temperature was assessed during the drilling of hardened AISI H13 steel using the embedded thermocouple technique. Dry machining and two cooling/lubrication systems were used, and thermocouples were fixed at distances very close to the hole`s wall. Tests were replicated for each condition, and were carried out with new and worn drills. An analytical heat conduction model was used to calculate the temperature at tool-workpiece interface and to define the heat flux and the coefficient of convection. In all tests using new and worn out drills, the lowest temperatures and decrease of heat flux were observed using the flooded system, followed by the MQL, considering the dry condition as reference. The decrease of temperature was directly proportional to the amount of lubricant applied and was significant in the MQL system when compared to dry cutting. (C) 2011 Elsevier Ltd. All rights reserved.

Parametrical study of masonry walls subjected to in-plane loading through numerical modeling

This paper deals with the numerical assessment of the influence of parameters such as pre-compression level, aspect ratio, vertical and horizontal reinforcement ratios and boundary conditions on the lateral strength of masonry walls under in-plane loading. The numerical study is performed through the software DIANA (R) based on the Finite Element Method. The validation of the numerical model is carried out from a database of available experimental results on masonry walls tested under cyclic lateral loading. Numerical results revealed that boundary conditions play a central role on the lateral behavior of masonry walls under in-plane loading and determine the influence of level of pre-compression as well as the reinforcement ratio on the wall strength. The lateral capacity of walls decreases with the increase of aspect ratio and with the decrease of pre-compression. Vertical steel bars appear to have almost no influence in the shear strength of masonry walls and horizontal reinforcement only increases the lateral strength of masonry walls if the shear response of the walls is determinant for failure, which is directly related to the boundary conditions. (C) 2011 Elsevier Ltd. All rights reserved.

Effects of temperature at different organic loading levels on the performance of a fluidized-bed anaerobic sequencing batch bioreactor

An investigation was performed on the effect of temperature and organic load on the stability and efficiency of a 1.8-L fluidized-bed anaerobic sequencing batch reactor (ASBR), containing granulated biomass. Assays were carried out employing superficial up How velocity of 7 m/h, total cycle length of 6 h and synthetic wastewater volume of 1.3 L per cycle. The fluidized-bed ASH was operated at 15, 20, 25 and 30 degrees C with influent organic matter concentrations of 500 and 1000 mgCOD/L The system showed stability under all conditions and presented filtered samples removal efficiency ranging from 79 to 86%. A first-order kinetic model could be fitted to the experimental values of the organic matter concentration profiles. The specific kinetic parameter values of this model ranged from 0.0435 to 0.2360 L/(gTVS h) at the implemented operation conditions. in addition, from the slope of an Arrhenius plot, the activation energy values were calculated to be 16,729 and 12,673 cal/mol for operation with 500 and 1000 mgCOD/L, respectively. These results show that treatment of synthetic wastewater. with concentration of 500 mgCOD/L, was more sensitive to temperature variations than treatment of the same residue with concentration of 1000 mgCOD/L. Comparing the activation energy value for operation at 500 mgCOD/L with the value obtained by Agibert et al. (S.A. Agibert, M.B. Moreira, S.M. Ratusznei, J.A.D. Rodrigues, M. Zaiat, E. Foresti. Influence of temperature on performance of an ASBBR with circulation applied to treatment of low-strength wastewater. journal of Applied Biochemistry and Biotechnology, 136 (2007) 193-206) in an ASBBR treating the same wastewater at the same concentration, the value obtained in the fluidized-bed ASBR showed to be superior, indicating that treatment of synthetic wastewater in a reactor containing granulated biomass was more sensitive to temperature variations than the treatment using immobilized biomass. (c) 2008 Elsevier B.V. All rights reserved.

Temperature and feed strategy effects on sulfate and organic matter removal in an AnSBB

The objective of this work was to analyze the interaction effects between temperature, feed strategy and COD/[SO(4)(2-)] levels, maintaining the same ratio, on sulfate and organic matter removal efficiency from a synthetic wastewater. This work is thus a continuation of Archilha et al. (2010) who studied the effect of feed strategy at 30 degrees C using different COD/[SO] ratios and levels. A 3.7-L anaerobic sequencing batch reactor with recirculation of the liquid phase and which contained immobilized biomass on polyurethane foam (AnSBBR) was used to treat 2.0 L synthetic wastewater in 8 h cycles. The temperatures of 15, 22.5 and 30 degrees C with two feed strategies were assessed: (a) batch and (b) batch followed by fed-batch. In strategy (a) the reactor was fed in 10 min with 2 L wastewater containing sulfate and carbon sources. In strategy (b) 1.2 L wastewater (containing only the sulfate source) was fed during the first 10 min of the cycle and the remaining 0.8 L (containing only the carbon source) in 240 min. Based on COD/[SO(4)(2-)] = 1 and on the organic matter (0.5 and 1.5 gCOD/L) and sulfate (0.5 and 1.5 gSO(4)(2-)/L) concentrations, the sulfate and organic matter loading rates applied were 1.5 and 4.5 g/L.d, i.e., same COD/[SO(4)(2-)] ratio (=1) but different levels (1.5/1.5 and 4.5/4.5 gCOD/gSO(4)(2-)). When reactor feed was 1.5 gCOD/L.d and 1.5 gSO(4)(2-)/L.d, gradual feeding (strategy b) showed to favor sulfate and organic matter removal in the investigated temperature range, indicating improved utilization of the electron donor for sulfate reduction. Sulfate removal efficiencies were 87.9; 86.3 and 84.4%, and organic matter removal efficiencies 95.2; 86.5 and 80.8% at operation temperatures of 30; 22.5 and 15 degrees C, respectively. On the other hand, when feeding was 4.5 gCOD/L.d and 4.5 gSO(4)(2-)/L.d, gradual feeding did not favor sulfate removal, indicating that gradual feeding of the electron donor did not improve sulfate reduction. (C) 2011 Elsevier Ltd. All rights reserved.

Heterogeneous modeling of an anaerobic sequencing batch biofilm reactor (ASBBR)

The objective of this study was to estimate the first-order intrinsic kinetic constant (k(1)) and the liquid-phase mass transfer coefficient (k(c)) in a bench-scale anaerobic sequencing batch biofilm reactor (ASBBR) fed with glucose. A dynamic heterogeneous mathematical model, considering two phases (liquid and solid), was developed through mass balances in the liquid and solid phases. The model was adjusted to experimental data obtained from the ASBBR applied for the treatment of glucose-based synthetic wastewater with approximately 500 mg L-1 of glucose, operating in 8 h batch cycles, at 30 degrees C and 300 rpm. The values of the parameters obtained were 0.8911 min(-1) for k(1) and 0.7644 cm min(-1) for kc. The model was validated utilizing the estimated parameters with data obtained from the ASBBR operating in 3 h batch cycles, with a good representation of the experimental behavior. The solid-phase mass transfer flux was found to be the limiting step of the overall glucose conversion rate.

Solution of a heterogeneous modeling of a horizontal-flow anaerobic immobilized biomass (HAIB) reactor by the sequencing method

A modeling study was completed to develop a methodology that combines the sequencing and finite difference methods for the simulation of a heterogeneous model of a tubular reactor applied in the treatment of wastewater. The system included a liquid phase (convection diffusion transport) and a solid phase (diffusion reaction) that was obtained by completing a mass balance in the reactor and in the particle, respectively. The model was solved using a pilot-scale horizontal-flow anaerobic immobilized biomass (HAIB) reactor to treat domestic sewage, with the concentration results compared with the experimental data. A comparison of the behavior of the liquid phase concentration profile and the experimental results indicated that both the numerical methods offer a good description of the behavior of the concentration along the reactor. The advantage of the sequencing method over the finite difference method is that it is easier to apply and requires less computational time to model the dynamic simulation of outlet response of HAIB.