Linear viscoelasticity of styrenic block copolymers-clay nanocomposites

In this work, the rheological behavior of block copolymers with different morphologies (lamellar, cylindrical, spherical, and disordered) and their clay-containing nanocomposites was studied using small amplitude oscillatory shear. The copolymers studied were one asymmetric starblock styrene-butadiene-styrene copolymer and four styrene-ethylene/butylenes-styrene copolymers with different molecular architectures, one of them being modified with maleic anhydride. The nanocomposites of those copolymers were prepared by adding organophilic clay using three different preparation techniques: melt mixing, solution casting, and a hybrid melt mixing-solution technique. The nanocomposites were characterized by X-ray diffraction and transmission electron microscopy, and their viscoelastic properties were evaluated and compared to the ones of the pure copolymers. The influence of copolymer morphology and presence of clay on the storage modulus (G`) curves was studied by the evaluation of the changes in the low frequency slope of log G` x log omega (omega: frequency) curves upon variation of temperature and clay addition. This slope may be related to the degree of liquid- or solid-like behavior of a material. It was observed that at temperatures corresponding to the ordered state, the rheological behavior of the nanocomposites depended mainly on the viscoelasticity of each type of ordered phase and the variation of the slope due to the addition of clay was small. For temperatures corresponding to the disordered state, however, the rheological behavior of the copolymer nanocomposites was dictated mostly by the degree of clay dispersion: When the clay was well dispersed, a strong solid-like behavior corresponding to large G` slope variations was observed.

Insufficient uracil supply in fully aerobic chemostat cultures of Saccharomyces cerevisiae leads to respiro-fermentative metabolism and double nutrient-limitation

A combination of chemostat cultivation and a defined medium was used to demonstrate that uracil limitation leads to a drastic alteration in the physiology of auxotrophic cells of Saccharomyces cerevisiae. Under this condition, the carbon source is dissimilated mainly to ethanol and acetate, even in fully aerobic cultures grown at 0.1 h(-1), which is far below the critical dilution rate. Differently from nitrogen-, sulphur-, or phosphate-limited cultures, uracil limitation leads to residual sugar (either glucose or sucrose) concentrations below 2 mM, which characterizes a situation of double-limitation: by the carbon source and by uracil. Furthermore, the specific rates of CO(2) production and O(2) consumption are increased when compared to the corresponding prototrophic strain. We conclude that when auxotrophic strains are to be used for quantitative physiological studies, special attention must be paid to the cultivation conditions, mainly regarding medium formulation, in order to avoid limitation of growth by the auxotrophic nutrient.

A mechanistic kinetic model for phenol degradation by the Fenton process

The objective of this paper is to develop and validate a mechanistic model for the degradation of phenol by the Fenton process. Experiments were performed in semi-batch operation, in which phenol, catechol and hydroquinone concentrations were measured. Using the methodology described in Pontes and Pinto [R.F.F. Pontes, J.M. Pinto, Analysis of integrated kinetic and flow models for anaerobic digesters, Chemical Engineering journal 122 (1-2) (2006) 65-80], a stoichiometric model was first developed, with 53 reactions and 26 compounds, followed by the corresponding kinetic model. Sensitivity analysis was performed to determine the most influential kinetic parameters of the model that were estimated with the obtained experimental results. The adjusted model was used to analyze the impact of the initial concentration and flow rate of reactants on the efficiency of the Fenton process to degrade phenol. Moreover, the model was applied to evaluate the treatment cost of wastewater contaminated with phenol in order to meet environmental standards. (C) 2009 Elsevier B.V. All rights reserved.

DEVELOPMENT OF STATIC MIXERS FOR MISCIBLE FLUIDS IN LAMINAR FLOW WITH THE USE OF COMPUTATIONAL FLUID DYNAMICS (CFD)

Static mixers with improved performance were developed from CFD simulations in a stepwise approach. The relevant geometric features of simple mixer designs and the corresponding mixing mechanisms-laminar shear, elongational flow, and distributive mixing-were identified first. This information was used to formulate guidelines for the development of new geometries. The solid elements of the static mixer should: (a) provide restrictions to the flow; (b) deflect the flow; (c) be sequentially rotated around the flow direction to provide symmetry; (d) extend from the center of the pipe to the vicinity of the walls to avoid short-circuiting; and (e) distribute and remix the flow. Based on these guidelines, two improved mixer designs were developed: the DS A-I mixer has a good mixing efficiency and an acceptable pressure drop; the Fins 35 degrees mixer is more efficient and compact, but requires a larger pressure drop. Their performance indicates that their use is possible on industrial applications.

The Penicillium chrysogenum aclA gene encodes a broad-substrate-specificity acyl-coenzyme A ligase involved in activation of adipic acid, a side-chain precursor for cephem antibiotics

Activation of the cephalosporin side-chain precursor to the corresponding CoA-thioester is an essential step for its incorporation into the P-lactam backbone. To identify an acyl-CoA ligase involved in activation of adipate, we searched in the genome database of Penicillium chrysogenum for putative structural genes encoding acyl-CoA ligases. Chemostat-based transcriptome analysis was used to identify the one presenting the highest expression level when cells were grown in the presence of adipate. Deletion of the gene renamed aclA, led to a 32% decreased specific rate of adipate consumption and a threefold reduction of adipoyl-6-aminopenicillanic acid levels, but did not affect penicillin V production. After overexpression in Escherichia coli, the purified protein was shown to have a broad substrate range including adipate. Finally, protein-fusion with cyan-fluorescent protein showed co-localization with microbody-borne acyl-transferase. Identification and functional characterization of aclA may aid in developing future metabolic engineering strategies for improving the production of different cephalosporins. (C) 2009 Elsevier Inc. All rights reserved.

A systemic approach for optimal cooling tower operation

The thermal performance of a cooling tower and its cooling water system is critical for industrial plants, and small deviations from the design conditions may cause severe instability in the operation and economics of the process. External disturbances such as variation in the thermal demand of the process or oscillations in atmospheric conditions may be suppressed in multiple ways. Nevertheless, such alternatives are hardly ever implemented in the industrial operation due to the poor coordination between the utility and process sectors. The complexity of the operation increases because of the strong interaction among the process variables. In the present work, an integrated model for the minimization of the operating costs of a cooling water system is developed. The system is composed of a cooling tower as well as a network of heat exchangers. After the model is verified, several cases are studied with the objective of determining the optimal operation. It is observed that the most important operational resources to mitigate disturbances in the thermal demand of the process are, in this order: the increase in recycle water flow rate, the increase in air flow rate and finally the forced removal of a portion of the water flow rate that enters the cooling tower with the corresponding make-up flow rate. (C) 2009 Elsevier Ltd. All rights reserved.

Optimal synthesis of anaerobic digester networks

The objective of this paper is to develop a mathematical model for the synthesis of anaerobic digester networks based on the optimization of a superstructure that relies on a non-linear programming formulation. The proposed model contains the kinetic and hydraulic equations developed by Pontes and Pinto [Chemical Engineering journal 122 (2006) 65-80] for two types of digesters, namely UASB (Upflow Anaerobic Sludge Blanket) and EGSB (Expanded Granular Sludge Bed) reactors. The objective function minimizes the overall sum of the reactor volumes. The optimization results show that a recycle stream is only effective in case of a reactor with short-circuit, such as the UASB reactor. Sensitivity analysis was performed in the one and two-digester network superstructures, for the following parameters: UASB reactor short-circuit fraction and the EGSB reactor maximum organic load, and the corresponding results vary considerably in terms of digester volumes. Scenarios for three and four-digester network superstructures were optimized and compared with the results from fewer digesters. (C) 2009 Elsevier B.V. All rights reserved.

Robust model predictive control with zone control

Model predictive control (MPC) is usually implemented as a control strategy where the system outputs are controlled within specified zones, instead of fixed set points. One strategy to implement the zone control is by means of the selection of different weights for the output error in the control cost function. A disadvantage of this approach is that closed-loop stability cannot be guaranteed, as a different linear controller may be activated at each time step. A way to implement a stable zone control is by means of the use of an infinite horizon cost in which the set point is an additional variable of the control problem. In this case, the set point is restricted to remain inside the output zone and an appropriate output slack variable is included in the optimisation problem to assure the recursive feasibility of the control optimisation problem. Following this approach, a robust MPC is developed for the case of multi-model uncertainty of open-loop stable systems. The controller is devoted to maintain the outputs within their corresponding feasible zone, while reaching the desired optimal input target. Simulation of a process of the oil re. ning industry illustrates the performance of the proposed strategy.

A stable MPC with zone control

Several MPC applications implement a control strategy in which some of the system outputs are controlled within specified ranges or zones, rather than at fixed set points [J.M. Maciejowski, Predictive Control with Constraints, Prentice Hall, New Jersey, 2002]. This means that these outputs will be treated as controlled variables only when the predicted future values lie outside the boundary of their corresponding zones. The zone control is usually implemented by selecting an appropriate weighting matrix for the output error in the control cost function. When an output prediction is inside its zone, the corresponding weight is zeroed, so that the controller ignores this output. When the output prediction lies outside the zone, the error weight is made equal to a specified value and the distance between the output prediction and the boundary of the zone is minimized. The main problem of this approach, as long as stability of the closed loop is concerned, is that each time an output is switched from the status of non-controlled to the status of controlled, or vice versa, a different linear controller is activated. Thus, throughout the continuous operation of the process, the control system keeps switching from one controller to another. Even if a stabilizing control law is developed for each of the control configurations, switching among stable controllers not necessarily produces a stable closed loop system. Here, a stable M PC is developed for the zone control of open-loop stable systems. Focusing on the practical application of the proposed controller, it is assumed that in the control structure of the process system there is an upper optimization layer that defines optimal targets to the system inputs. The performance of the proposed strategy is illustrated by simulation of a subsystem of an industrial FCC system. (C) 2008 Elsevier Ltd. All rights reserved.

A Functional Verification Methodology Based on Parameter Domains for Efficient Input Stimuli Generation and Coverage Modeling

Modern Integrated Circuit (IC) design is characterized by a strong trend of Intellectual Property (IP) core integration into complex system-on-chip (SOC) architectures. These cores require thorough verification of their functionality to avoid erroneous behavior in the final device. Formal verification methods are capable of detecting any design bug. However, due to state explosion, their use remains limited to small circuits. Alternatively, simulation-based verification can explore hardware descriptions of any size, although the corresponding stimulus generation, as well as functional coverage definition, must be carefully planned to guarantee its efficacy. In general, static input space optimization methodologies have shown better efficiency and results than, for instance, Coverage Directed Verification (CDV) techniques, although they act on different facets of the monitored system and are not exclusive. This work presents a constrained-random simulation-based functional verification methodology where, on the basis of the Parameter Domains (PD) formalism, irrelevant and invalid test case scenarios are removed from the input space. To this purpose, a tool to automatically generate PD-based stimuli sources was developed. Additionally, we have developed a second tool to generate functional coverage models that fit exactly to the PD-based input space. Both the input stimuli and coverage model enhancements, resulted in a notable testbench efficiency increase, if compared to testbenches with traditional stimulation and coverage scenarios: 22% simulation time reduction when generating stimuli with our PD-based stimuli sources (still with a conventional coverage model), and 56% simulation time reduction when combining our stimuli sources with their corresponding, automatically generated, coverage models.

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.

Nitrogen doping of SiC thin films deposited by RF magnetron sputtering

Silicon carbide thin films (Si(x)C(y)) were deposited in a RF (13.56 MHz) magnetron sputtering system using a sintered SiC target (99.5% purity). In situ doping was achieved by introducing nitrogen into the electric discharge during the growth process of the films. The N(2)/Ar flow ratio was adjusted by varying the N(2) flow rate and maintaining constant the Ar flow rate. The structure, composition and bonds formed in the nitrogen-doped Si (x) C (y) thin films were investigated by X-ray diffraction (XRD), Rutherford backscattering spectroscopy (RBS), Raman spectroscopy and Fourier transform infrared spectrometry (FTIR) techniques. RBS results indicate that the carbon content in the film decreases as the N(2)/Ar flow ratio increases. Raman spectra clearly reveal that the deposited nitrogen-doped SiC films are amorphous and exhibited C-C bonds corresponding to D and G bands. After thermal annealing, the films present structural modifications that were identified by XRD, Raman and FTIR analyses.

AUTOMATIC CORONARY WALL SEGMENTATION IN INTRAVASCULAR ULTRASOUND IMAGES USING BINARY MORPHOLOGICAL RECONSTRUCTION

Intravascular ultrasound (IVUS) image segmentation can provide more detailed vessel and plaque information, resulting in better diagnostics, evaluation and therapy planning. A novel automatic segmentation proposal is described herein; the method relies on a binary morphological object reconstruction to segment the coronary wall in IVUS images. First, a preprocessing followed by a feature extraction block are performed, allowing for the desired information to be extracted. Afterward, binary versions of the desired objects are reconstructed, and their contours are extracted to segment the image. The effectiveness is demonstrated by segmenting 1300 images, in which the outcomes had a strong correlation to their corresponding gold standard. Moreover, the results were also corroborated statistically by having as high as 92.72% and 91.9% of true positive area fraction for the lumen and media adventitia border, respectively. In addition, this approach can be adapted easily and applied to other related modalities, such as intravascular optical coherence tomography and intravascular magnetic resonance imaging. (E-mail: matheuscardosomg@hotmail.com) (C) 2011 World Federation for Ultrasound in Medicine & Biology.

A vaccination game based on public health actions and personal decisions

Susceptible-infective-removed (SIR) models are commonly used for representing the spread of contagious diseases. A SIR model can be described in terms of a probabilistic cellular automaton (PCA), where each individual (corresponding to a cell of the PCA lattice) is connected to others by a random network favoring local contacts. Here, this framework is employed for investigating the consequences of applying vaccine against the propagation of a contagious infection, by considering vaccination as a game, in the sense of game theory. In this game, the players are the government and the susceptible newborns. In order to maximize their own payoffs, the government attempts to reduce the costs for combating the epidemic, and the newborns may be vaccinated only when infective individuals are found in their neighborhoods and/or the government promotes an immunization program. As a consequence of these strategies supported by cost-benefit analysis and perceived risk, numerical simulations show that the disease is not fully eliminated and the government implements quasi-periodic vaccination campaigns. (C) 2011 Elsevier B.V. All rights reserved.

Valve friction and nonlinear process model closed-loop identification

Among several process variability sources, valve friction and inadequate controller tuning are supposed to be two of the most prevalent. Friction quantification methods can be applied to the development of model-based compensators or to diagnose valves that need repair, whereas accurate process models can be used in controller retuning. This paper extends existing methods that jointly estimate the friction and process parameters, so that a nonlinear structure is adopted to represent the process model. The developed estimation algorithm is tested with three different data sources: a simulated first order plus dead time process, a hybrid setup (composed of a real valve and a simulated pH neutralization process) and from three industrial datasets corresponding to real control loops. The results demonstrate that the friction is accurately quantified, as well as ""good"" process models are estimated in several situations. Furthermore, when a nonlinear process model is considered, the proposed extension presents significant advantages: (i) greater accuracy for friction quantification and (ii) reasonable estimates of the nonlinear steady-state characteristics of the process. (C) 2010 Elsevier Ltd. All rights reserved.