An environmentally friendly flow system for high-sensitivity spectrophotometric determination of free chlorine in natural waters

A green and highly sensitive analytical procedure was developed for the determination of free chlorine in natural waters, based on the reaction with N,N-diethyl-p-phenylenediamine (DPD). The flow system was designed with solenoid micro-pumps in order to improve mixing conditions by pulsed flows and to minimize reagent consumption as well as waste generation. A 100-cm optical path flow cell based on a liquid core waveguide was employed to increase sensitivity. A linear response was observed within the range 10.0 to 100.0 mu g L(-1), with the detection limit, coefficient of variation and sampling rate estimated as 6.8 mu g (99.7% confidence level), 0.9% (n = 20) and 60 determinations per hour, respectively. The consumption of the most toxic reagent (DPD) was reduced 20,000-fold and 30-fold in comparison to the batch method and flow injection with continuous reagent addition, respectively. The results for natural and tap water samples agreed with those obtained by the reference batch spectrophotometric procedure at the 95% confidence level. (C) 2010 Elsevier By. All rights reserved.

A greener and highly sensitive flow-based procedure for carbaryl determination exploiting long pathlength spectrophotometry and photochemical waste degradation

An environmentally friendly analytical procedure with high sensitivity for determination of carbaryl pesticide in natural waters was developed. The flow system was designed with solenoid micro-pumps in order to improve mixing conditions and minimize reagent consumption as well as waste generation. A long pathlength (100 cm) flow cell based on a liquid core waveguide (LCW) was employed to increase the sensitivity in detection of the indophenol formed from the reaction between carbaryl and p-aminophenol (PAP). A clean-up step based on cloud-point extraction was explored to remove the interfering organic matter, avoiding the use of toxic organic solvents. A linear response was observed within the range 5-200 mu g L(-1) and the detection limit, coefficient of variation and sampling rate were estimated as 1.7 mu g L(-1) (99.7% confidence level), 0.7% (n=20) and 55 determinations per hour, respectively. The reagents consumption was 1.9 mu g of PAP and 5.7 mu g of potassium metaperiodate, with volume of 2.6 mL of effluent per determination. The proposed procedure was selective for the determination of carbaryl, without interference from other carbamate pesticides. Recoveries within 84% and 104% were estimated for carbaryl spiked to water samples and the results obtained were also in agreement with those found by a batch spectrophotometric procedure at the 95% confidence level. The waste of the analytical procedure was treated with potassium persulphate and ultraviolet irradiation, yielding a colorless residue and a decrease of 94% of total organic carbon. In addition, the residue after treatment was not toxic for Vibrio fischeri bacteria. (c) 2010 Elsevier B.V. All rights reserved.

A critical evaluation of a long pathlength cell for flow-based spectrophotometric measurements

Coupling of a flow cell based on a liquid core waveguide (LCW) to flow systems for spectro photometric measurements was critically evaluated. Flow-based systems with and without chemical reactions were exploited to estimate the increase in analytical signal in comparison to those obtained with a conventional I cm cell under different experimental conditions. The Schlieren effect associated to intense concentration gradients in the sample zone was investigated with model solutions that do not absorb visible electromagnetic radiation. The effect of radiation scattering was lower than the expected by considering the increase in the optical path, being the magnitude of the perturbation up to 40% higher for the 100-cm LCW cell. Several alternatives for compensation of the Schlieren effect were experimentally investigated. The potentiality of the LCW for turbidimetric measurements and coupling to monosegmented flow analysis was also evaluated. (C) 2008 Elsevier B.V. All rights reserved.

Exploiting Mn(III)/EDTA complex in a flow system with solenoid micro-pumps coupled to long pathlength spectrophotometry for fast manganese determination

The formation of the Mn(III)/EDTA complex in a flow system with solenoid micro-pumps was exploited for fast manganese determination in freshwater. Manganese(II) was oxidized in a solid-phase reactor containing lead dioxide immobilized on polyester. Long pathlength spectrophotometry was exploited to increase sensitivity, aiming to reach the threshold limit established by environmental legislation. A linear response was observed from 25 to 1500 mu g L(-1), with a detection limit of 6 mu g L(-1) (99.7% confidence level). Sample throughput and coefficient of variation were 36 samples/h and 2.6% (n = 10), respectively. EDTA consumption and waste generation were estimated as 500 mu g and 3 mL per determination, respectively. The amount of Pb in the residue corresponds to 250 mu g per determination and a solid-phase reactor could be used for up to 1600 determinations. Adsorption in active charcoal avoided interferences caused by organic matter and the developed procedure was successfully applied for determination of manganese in freshwater samples. Results were in agreement with those attained by GFAAS at the 95% confidence level. (C) 2010 Elsevier B.V. All rights reserved.

Skewness, splitting number and vertex deletion of some toroidal meshes

The skewness sk(G) of a graph G = (V, E) is the smallest integer sk(G) >= 0 such that a planar graph can be obtained from G by the removal of sk(C) edges. The splitting number sp(G) of C is the smallest integer sp(G) >= 0 such that a planar graph can be obtained from G by sp(G) vertex splitting operations. The vertex deletion vd(G) of G is the smallest integer vd(G) >= 0 such that a planar graph can be obtained from G by the removal of vd(G) vertices. Regular toroidal meshes are popular topologies for the connection networks of SIMD parallel machines. The best known of these meshes is the rectangular toroidal mesh C(m) x C(n) for which is known the skewness, the splitting number and the vertex deletion. In this work we consider two related families: a triangulation Tc(m) x c(n) of C(m) x C(n) in the torus, and an hexagonal mesh Hc(m) x c(n), the dual of Tc(m) x c(n) in the torus. It is established that sp(Tc(m) x c(n)) = vd(Tc(m) x c(n) = sk(Hc(m) x c(n)) = sp(Hc(m) x c(n)) = vd(Hc(m) x c(n)) = min{m, n} and that sk(Tc(m) x c(n)) = 2 min {m, n}.

A novel subwavelength plasmon-polariton optical filter based on tilted coupled structures

This work proposes a completely new approach for the design of resonant structures aiming at wavelength-filtering applications. The structure consists of a subwavelength metal-insulator-metal (MIM) waveguide presenting tilted coupled structures transversely arranged in the midpoint between the input and output ports. The cavity-like response of this device has shown that this concept can be particularly attractive for optical filter design for telecom applications. The extra degree of freedom provided by the tilting of the cavity has proved to be not only very effective on improving the quality factor of these structures, but also to be an elegant way of extending the range of applications for tuning multiple wavelengths, if necessary.

Experimental investigation on adaptive robust controller designs applied to a free-floating space manipulator

This paper aims to formulate and investigate the application of various nonlinear H(infinity) control methods to a fiee-floating space manipulator subject to parametric uncertainties and external disturbances. From a tutorial perspective, a model-based approach and adaptive procedures based on linear parametrization, neural networks and fuzzy systems are covered by this work. A comparative study is conducted based on experimental implementations performed with an actual underactuated fixed-base planar manipulator which is, following the DEM concept, dynamically equivalent to a free-floating space manipulator. (C) 2011 Elsevier Ltd. All rights reserved.

A hybrid-mixed finite element formulation for the geometrically exact analysis of three-dimensional framed structures

This paper addresses the development of a hybrid-mixed finite element formulation for the quasi-static geometrically exact analysis of three-dimensional framed structures with linear elastic behavior. The formulation is based on a modified principle of stationary total complementary energy, involving, as independent variables, the generalized vectors of stress-resultants and displacements and, in addition, a set of Lagrange multipliers defined on the element boundaries. The finite element discretization scheme adopted within the framework of the proposed formulation leads to numerical solutions that strongly satisfy the equilibrium differential equations in the elements, as well as the equilibrium boundary conditions. This formulation consists, therefore, in a true equilibrium formulation for large displacements and rotations in space. Furthermore, this formulation is objective, as it ensures invariance of the strain measures under superposed rigid body rotations, and is not affected by the so-called shear-locking phenomenon. Also, the proposed formulation produces numerical solutions which are independent of the path of deformation. To validate and assess the accuracy of the proposed formulation, some benchmark problems are analyzed and their solutions compared with those obtained using the standard two-node displacement/ rotation-based formulation.

Buckling and post-buckling of extensible rods revisited: A multiple-scale solution

An exact non-linear formulation of the equilibrium of elastic prismatic rods subjected to compression and planar bending is presented, electing as primary displacement variable the cross-section rotations and taking into account the axis extensibility. Such a formulation proves to be sufficiently general to encompass any boundary condition. The evaluation of critical loads for the five classical Euler buckling cases is pursued, allowing for the assessment of the axis extensibility effect. From the quantitative viewpoint, it is seen that such an influence is negligible for very slender bars, but it dramatically increases as the slenderness ratio decreases. From the qualitative viewpoint, its effect is that there are not infinite critical loads, as foreseen by the classical inextensible theory. The method of multiple (spatial) scales is used to survey the post-buckling regime for the five classical Euler buckling cases, with remarkable success, since very small deviations were observed with respect to results obtained via numerical integration of the exact equation of equilibrium, even when loads much higher than the critical ones were considered. Although known beforehand that such classical Euler buckling cases are imperfection insensitive, the effect of load offsets were also looked at, thus showing that the formulation is sufficiently general to accommodate this sort of analysis. (c) 2008 Elsevier Ltd. All rights reserved.

Integral Piezoactuator System with Optimum Placement of Functionally Graded Material - A Topology Optimization Paradigm

Piezoactuators consist of compliant mechanisms actuated by two or more piezoceramic devices. During the assembling process, such flexible structures are usually bonded to the piezoceramics. The thin bonding layer(s) between the compliant mechanism and the piezoceramic may induce undesirable behavior, including unusual interfacial nonlinearities. This constitutes a drawback of piezoelectric actuators and, in some applications, such as those associated to vibration control and structural health monitoring (e. g., aircraft industry), their use may become either unfeasible or at least limited. A possible solution to this standing problem can be achieved through the functionally graded material concept and consists of developing `integral piezoactuators`, that is those with no bonding layer(s) and whose performance can be improved by tailoring their structural topology and material gradation. Thus, a topology optimization formulation is developed, which allows simultaneous distribution of void and functionally graded piezoelectric materials (including both piezo and non-piezoelectric materials) in the design domain in order to achieve certain specified actuation movements. Two concurrent design problems are considered, that is the optimum design of the piezoceramic property gradation, and the design of the functionally graded structural topology. Two-dimensional piezoactuator designs are investigated because the applications of interest consist of planar devices. Moreover, material gradation is considered in only one direction in order to account for manufacturability issues. To broaden the range of such devices in the field of smart structures, the design of integral Moonie-type functionally graded piezoactuators is provided according to specified performance requirements.

Computational Method to Determine Reflected Ultrasonic Signals From Arbitrary-Geometry Targets

A computational method based on the impulse response and on the discrete representation computational concept is proposed for the determination of the echo responses from arbitrary-geometry targets. It is supposed that each point of the transducer aperture can be considered as a source radiating hemispherical waves to the reflector. The local interaction with each of the hemispherical waves at the reflector surface can be modeled as a plane wave impinging on a planar surface, using the respective reflection coefficient. The method is valid for all field regions and can be performed for any excitation waveform radiated from an arbitrary acoustic aperture. The effects of target geometry, position, and material on both the amplitude and the shape of the echo response are studied. The model is compared with experimental results obtained using broadband transducers together with plane and cylindrical concave rectangular reflectors (aluminum, brass, and acrylic), as well as a circular cavity placed on a plane surface, in a water medium. The method can predict the measured echoes accurately. This paper shows an improved approach of the method, considering the reflection coefficient for all incident hemispherical waves arriving at each point of the target surface.

A contribution to the exact modal solution of in-plane beam structures

The exact vibration modes and natural frequencies of planar structures and mechanisms, comprised Euler-Bernoulli beams, are obtained by solving a transcendental. nonlinear, eigenvalue problem stated by the dynamic stiffness matrix (DSM). To solve this kind of problem, the most employed technique is the Wittrick-Williams algorithm, developed in the early seventies. By formulating a new type of eigenvalue problem, which preserves the internal degrees-of-freedom for all members in the model, the present study offers an alternative to the use of this algorithm. The new proposed eigenvalue problem presents no poles, so the roots of the problem can be found by any suitable iterative numerical method. By avoiding a standard formulation for the DSM, the local mode shapes are directly calculated and any extension to the beam theory can be easily incorporated. It is shown that the method here adopted leads to exact solutions, as confirmed by various examples. Extensions of the formulation are also given, where rotary inertia, end release, skewed edges and rigid offsets are all included. (C) 2008 Elsevier Ltd. All rights reserved.

Multi-actuated functionally graded piezoelectric micro-tools design: A multiphysics topology optimization approach

Micro-tools offer significant promise in a wide range of applications Such as cell Manipulation, microsurgery, and micro/nanotechnology processes. Such special micro-tools consist of multi-flexible structures actuated by two or more piezoceramic devices that must generate output displacements and forces lit different specified points of the domain and at different directions. The micro-tool Structure acts as a mechanical transformer by amplifying and changing the direction of the piezoceramics Output displacements. The design of these micro-tools involves minimization of the coupling among movements generated by various piezoceramics. To obtain enhanced micro-tool performance, the concept of multifunctional and functionally graded materials is extended by, tailoring elastic and piezoelectric properties Of the piezoceramics while simultaneously optimizing the multi-flexible structural configuration using multiphysics topology optimization. The design process considers the influence of piezoceramic property gradation and also its polarization sign. The method is implemented considering continuum material distribution with special interpolation of fictitious densities in the design domain. As examples, designs of a single piezoactuator, an XY nano-positioner actuated by two graded piezoceramics, and a micro-gripper actuated by three graded piezoceramics are considered. The results show that material gradation plays an important role to improve actuator performance, which may also lead to optimal displacements and coupling ratios with reduced amount of piezoelectric material. The present examples are limited to two-dimensional models because many of the applications for Such micro-tools are planar devices. Copyright (c) 2008 John Wiley & Sons, Ltd.

Intragranular formation of austenite during delta ferrite decomposition in a duplex stainless steel

A Fe-22.5%Cr-4.53%Ni-3.0%Mo duplex stainless steel was solution treated at 1,325 A degrees C for 1 h, quenched in water and isothermally treated at 900 A degrees C for 5,000 s. The crystallography of austenite was studied using EBSD technique. Intragranular austenite particles formed from delta ferrite are shown to nucleate on inclusions, and to be subdivided in twin-related sub-particles. Intragranular austenite appears to have planar-only orientation relationships with the ferrite matrix, close to Kurdjumov-Sachs and Nishyiama-Wassermann, but not related to a conjugate direction. Samples treated at 900 A degrees C underwent sparse formation of sigma phase and pronounced growth of elongated austenite particles, very similar to acicular ferrite.

Macrosegregation of Impurities in Directionally Solidified Silicon

Directional solidification of molten metallurgical-grade Si was carried out in a vertical Bridgman furnace. The effects of changing the mold velocity from 5 to 110 mu m seconds(-1) on the macrosegregation of impurities during solidification were investigated. The macrostructures of the cylindrical Si ingots obtained in the experiments consist mostly of columnar grains parallel to the ingot axis. Because neither cells nor dendrites can be observed on ingot samples, the absence of precipitated particles and the fulfillment of the constitutional supercooling criterion suggest a planar solid-liquid interface for mold velocities a parts per thousand currency sign10 mu m seconds(-1). Concentration profiles of several impurities were measured along the ingots, showing that their bottom and middle are purer than the metallurgical Si from which they solidified. At the ingot top, however, impurities accumulated, indicating the typical normal macrosegregation. When the mold velocity decreases, the macrosegregation and ingot purity increase, changing abruptly for a velocity variation from 20 to 10 mu m seconds(-1). A mathematical model of solute transport during solidification shows that, for mold velocities a parts per thousand yen20 mu m seconds(-1), macrosegregation is caused mainly by diffusion in a stagnant liquid layer assumed at the solid-liquid interface, whereas for lower velocities, macrosegregation increases as a result of more intense convective solute transport.