Electrochemical impedance spectroscopy investigation of the electrochemical behaviour of copper coated with artificial patina layers and submitted to wet and dry cycles

Due to rain events historical monuments exposed to the atmosphere are frequently submitted to wet and dry cycles. During drying periods wetness is maintained in some confined regions and the corrosion product layer, generally denominated patinas, builds up and gets thicker. The aim of this study is to use electrochemical impedance spectroscopy (EIS) to investigate the electrochemical behaviour of pure copper coated with two artificial patina layers and submitted either to continuous or to intermittent immersion tests, this latter aiming to simulate wet and dry cycles. The experiments were performed in 0.1 mol dm(-3) NaCl solution and in artificial rainwater containing the most significant pollutants of the city of Sao Paulo. The results of the continuous immersion tests in the NaCl solution have shown that the coated samples behave like a porous electrode with finite pore length. On the other hand, in the intermittent tests a porous electrode response with semi-infinite pore length can be developed. The results were interpreted based on the model of de Levie and a critical comparison with previous interpretations reported in the literature for similar systems is presented. (C) 2011 Elsevier Ltd. All rights reserved.

Development of a Continuous Emulsion Copolymerization Process in a Tubular Reactor

This contribution describes the development of a continuous emulsion copolymerization processs for vinyl acetate and n-butyl acrylate in a tubular reactor. Special features of this reactor include the use of oscillatory (pulsed) flow and internals (sieve plates) to prevent polymer fouling and promote good radial mixing, along with a controlled amount of axial mixing. The copolymer system studied (vinyl acetate and butyl acrylate) is strongly prone to composition drift due to very different reactivity ratios. An axially dispersed plug flow model, based on classical free radical copolymerization kinetics, was developed for this process and used successfully to optimize the lateral feeding profile to reduce compositional drift. An energy balance was included in the model equations to predict the effect of temperature variations on the process. The model predictions were validated with experimental data for monomer conversion, copolymer composition, average particle size, and temperature measured along the reactor length.

AN ASSESSMENT ON THE USE OF THE DEBYE-HUCKEL EQUATION FOR THE THERMODYNAMIC MODELING OF AQUEOUS SYSTEMS CONTAINING POLYMERS AND SALTS

In this work, a study on the role of the long-range term of excess Gibbs energy models in the modeling of aqueous systems containing polymers and salts is presented. Four different approaches on how to account for the presence of polymer in the long-range term were considered, and simulations were conducted considering aqueous solutions of three different salts. The analysis of water activity curves showed that, in all cases, a liquid-phase separation may be introduced by the sole presence of the polymer in the long-range term, regardless of how it is taken into account. The results lead to the conclusion that there is no single exact solution for this problem, and that any kind of approach may introduce inconsistencies.

MPC for tracking zone regions

This paper deals with the problem of tracking target sets using a model predictive control (MPC) law. Some MPC applications require a control strategy in which some system outputs are controlled within specified ranges or zones (zone control), while some other variables - possibly including input variables - are steered to fixed target or set-point. In real applications, this problem is often overcome by including and excluding an appropriate penalization for the output errors in the control cost function. In this way, throughout the continuous operation of the process, the control system keeps switching from one controller to another, and 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. From a theoretical point of view, the control objective of this kind of problem can be seen as a target set (in the output space) instead of a target point, since inside the zones there are no preferences between one point or another. In this work, a stable MPC formulation for constrained linear systems, with several practical properties is developed for this scenario. The concept of distance from a point to a set is exploited to propose an additional cost term, which ensures both, recursive feasibility and local optimality. The performance of the proposed strategy is illustrated by simulation of an ill-conditioned distillation column. (C) 2010 Elsevier Ltd. All rights reserved.

Investigation of Cationic Polymerization of beta-Pinene Using Calorimetric Measurements

An experimental investigation of the kinetics of cationic polymerization of beta-pinene was performed using two different initiator systems under two different operating conditions (shot additions of initiator, and continuous feeding of monomer). The experiments were done using calorimetric measurements under isoperibolic conditions. The heat of polymerization of beta-pinene was found to be -30.6 kcal . mol(-1). A simple kinetic model was tentatively proposed, and the model fit reasonably well to the different experimental runs. Different values of the fitting parameters were obtained for runs carried out under different conditions, which can probably be ascribed to the presence of adventitious impurities in the commercial-grade monomer used.

Stable Model Predictive Control for Integrating Systems with Optimizing Targets

This paper concern the development of a stable model predictive controller (MPC) to be integrated with real time optimization (RTO) in the control structure of a process system with stable and integrating outputs. The real time process optimizer produces Optimal targets for the system inputs and for Outputs that Should be dynamically implemented by the MPC controller. This paper is based oil a previous work (Comput. Chem. Eng. 2005, 29, 1089) where a nominally stable MPC was proposed for systems with the conventional control approach where only the outputs have set points. This work is also based oil the work of Gonzalez et at. (J. Process Control 2009, 19, 110) where the zone control of stable systems is studied. The new control for is obtained by defining ail extended control objective that includes input targets and zone controller the outputs. Additional decision variables are also defined to increase the set of feasible solutions to the control problem. The hard constraints resulting from the cancellation of the integrating modes Lit the end of the control horizon are softened,, and the resulting control problem is made feasible to a large class of unknown disturbances and changes of the optimizing targets. The methods are illustrated with the simulated application of the proposed,approaches to a distillation column of the oil refining industry.

Integrated analysis of cooling water systems: Modeling and experimental validation

Cooling towers are widely used in many industrial and utility plants as a cooling medium, whose thermal performance is of vital importance. Despite the wide interest in cooling tower design, rating and its importance in energy conservation, there are few investigations concerning the integrated analysis of cooling systems. This work presents an approach for the systemic performance analysis of a cooling water system. The approach combines experimental design with mathematical modeling. An experimental investigation was carried out to characterize the mass transfer in the packing of the cooling tower as a function of the liquid and gas flow rates, whose results were within the range of the measurement accuracy. Then, an integrated model was developed that relies on the mass and heat transfer of the cooling tower, as well as on the hydraulic and thermal interactions with a heat exchanger network. The integrated model for the cooling water system was simulated and the temperature results agree with the experimental data of the real operation of the pilot plant. A case study illustrates the interaction in the system and the need for a systemic analysis of cooling water system. The proposed mathematical and experimental analysis should be useful for performance analysis of real-world cooling water systems. (C) 2009 Elsevier Ltd. All rights reserved.

Photoinduced Degradation of the Herbicide Clomazone Model Reactions for Natural and Technical Systems

The photodegradation of the herbicide clomazone in the presence of S(2)O(8)(2-) or of humic substances of different origin was investigated. A value of (9.4 +/- 0.4) x 10(8) m(-1) s(-1) was measured for the bimolecular rate constant for the reaction of sulfate radicals with clomazone in flash-photolysis experiments. Steady state photolysis of peroxydisulfate, leading to the formation of the sulfate radicals, in the presence of clomazone was shown to be an efficient photodegradation method of the herbicide. This is a relevant result regarding the in situ chemical oxidation procedures involving peroxydisulfate as the oxidant. The main reaction products are 2-chlorobenzylalcohol and 2-chlorobenzaldehyde. The degradation kinetics of clomazone was also studied under steady state conditions induced by photolysis of Aldrich humic acid or a vermicompost extract (VCE). The results indicate that singlet oxygen is the main species responsible for clomazone degradation. The quantum yield of O(2)(a(1)Delta(g)) generation (lambda = 400 nm) for the VCE in D(2)O, Phi(Delta) = (1.3 +/- 0.1) x 10(-3), was determined by measuring the O(2)(a(1)Delta(g)) phosphorescence at 1270 nm. The value of the overall quenching constant of O(2)(a(1)Delta(g)) by clomazone was found to be (5.7 +/- 0.3) x 10(7) m(-1) s(-1) in D(2)O. The bimolecular rate constant for the reaction of clomazone with singlet oxygen was k(r) = (5.4 +/- 0.1) x 10(7) m(-1) s(-1), which means that the quenching process is mainly reactive.

Liquid-Liquid Equilibrium of Aqueous Two-Phase Systems Containing Some Synthetic Polyelectrolytes and Polyethylene Glycol

Experimental results are presented for the liquid-liquid equilibrium of aqueous two-phase systems containing a synthetic polyelectrolyte (polysodium acrylate, polysodium methacrylate, and polysodium ethylene sulfonate) and polyethylene glycol at (298.2 and 323.2) K. A total of 40 phase diagrams were obtained, comprising data both of the binodal curve (obtained through cloud-point measurements) and of equilibrium compositions. The influences of temperature, the nature of the polyelectrolyte monomer unit, and the chain length of both types of polymers are analyzed and discussed.

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.

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.

Signals in Communication Engineering History

This paper is a study of various electric signals, which have been employed throughout the history of communication engineering in its two main landmarks: the telegraph and the telephone. The signals are presented in their time and frequency domain representations. The historical order has been followed in the presentation: wired systems, spark gap wireless, continuous wave (CW) and amplitude modulation (AM), detection by rectification, and frequency modulation (FM). The analysis of these signals is meant to lead into a better understanding of the evolution of communication technology. The material presented in this work could be used to illustrate ""Signals and Systems"" and ""Communication Systems"" courses by taking advantage of its technical as well as historical contents.

Probing Individual Quantum Dots: Noise in Self-Assembled Systems

In this work we explore the noise characteristics in lithographically-defined two terminal devices containing self-assembled InAs/InP quantum dots. The experimental ensemble of InAs dots show random telegraph noise (RTN) with tuneable relative amplitude-up to 150%-in well defined temperature and source-drain applied voltage ranges. Our numerical simulation indicates that the RTN signature correlates with a very low number of quantum dots acting as effective charge storage centres in the structure for a given applied voltage. The modulation in relative amplitude variation can thus be associated to the altered electrostatic potential profile around such centres and enhanced carrier scattering provided by a charged dot.

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.

The Policy Iteration Algorithm for Average Continuous Control of Piecewise Deterministic Markov Processes

The main goal of this paper is to apply the so-called policy iteration algorithm (PIA) for the long run average continuous control problem of piecewise deterministic Markov processes (PDMP`s) taking values in a general Borel space and with compact action space depending on the state variable. In order to do that we first derive some important properties for a pseudo-Poisson equation associated to the problem. In the sequence it is shown that the convergence of the PIA to a solution satisfying the optimality equation holds under some classical hypotheses and that this optimal solution yields to an optimal control strategy for the average control problem for the continuous-time PDMP in a feedback form.