Algorithms for scheduling parallel batch processing machines with non-identical job ready times

This research is motivated by a practical application observed at a printed circuit board (PCB) manufacturing facility. After assembly, the PCBs (or jobs) are tested in environmental stress screening (ESS) chambers (or batch processing machines) to detect early failures. Several PCBs can be simultaneously tested as long as the total size of all the PCBs in the batch does not violate the chamber capacity. PCBs from different production lines arrive dynamically to a queue in front of a set of identical ESS chambers, where they are grouped into batches for testing. Each line delivers PCBs that vary in size and require different testing (or processing) times. Once a batch is formed, its processing time is the longest processing time among the PCBs in the batch, and its ready time is given by the PCB arriving last to the batch. ESS chambers are expensive and a bottleneck. Consequently, its makespan has to be minimized. ^ A mixed-integer formulation is proposed for the problem under study and compared to a formulation recently published. The proposed formulation is better in terms of the number of decision variables, linear constraints and run time. A procedure to compute the lower bound is proposed. For sparse problems (i.e. when job ready times are dispersed widely), the lower bounds are close to optimum. ^ The problem under study is NP-hard. Consequently, five heuristics, two metaheuristics (i.e. simulated annealing (SA) and greedy randomized adaptive search procedure (GRASP)), and a decomposition approach (i.e. column generation) are proposed—especially to solve problem instances which require prohibitively long run times when a commercial solver is used. Extensive experimental study was conducted to evaluate the different solution approaches based on the solution quality and run time. ^ The decomposition approach improved the lower bounds (or linear relaxation solution) of the mixed-integer formulation. At least one of the proposed heuristic outperforms the Modified Delay heuristic from the literature. For sparse problems, almost all the heuristics report a solution close to optimum. GRASP outperforms SA at a higher computational cost. The proposed approaches are viable to implement as the run time is very short. ^

Ferroelectric and dielectric properties of Nd2−xCexTi2O7 ceramics

The solid solution system Nd2−xCexTi2O7 has been investigated. The solubility limit of Ce in Nd2−xCexTi2O7 was found to be 0·5–0·75 according to X-ray diffraction and X-ray photoelectron spectroscopy results. Ce substitution increases the b and c axes and the volume of the unit cell due to its larger ionic radius. Nd2−xCexTi2O7 (x  = 0·05, 0·25, 0·5, 0·75) textured ceramics were fabricated using spark plasma sintering. The ferroelectric and dielectric properties of the ceramics were studied. Ce substitution decreases the Curie point Tc of Nd2−xCexTi2O7 compounds. The results suggest that the Tc of Ce2Ti2O7 is <1445°C.

Game-Theoretically Allocating Resources to Catch Evaders and Payments to Stabilize Teams

Allocating resources optimally is a nontrivial task, especially when multiple

self-interested agents with conflicting goals are involved. This dissertation

uses techniques from game theory to study two classes of such problems:

allocating resources to catch agents that attempt to evade them, and allocating

payments to agents in a team in order to stabilize it. Besides discussing what

allocations are optimal from various game-theoretic perspectives, we also study

how to efficiently compute them, and if no such algorithms are found, what

computational hardness results can be proved.

The first class of problems is inspired by real-world applications such as the

TOEFL iBT test, course final exams, driver's license tests, and airport security

patrols. We call them test games and security games. This dissertation first

studies test games separately, and then proposes a framework of Catcher-Evader

games (CE games) that generalizes both test games and security games. We show

that the optimal test strategy can be efficiently computed for scored test

games, but it is hard to compute for many binary test games. Optimal Stackelberg

strategies are hard to compute for CE games, but we give an empirically

efficient algorithm for computing their Nash equilibria. We also prove that the

Nash equilibria of a CE game are interchangeable.

The second class of problems involves how to split a reward that is collectively

obtained by a team. For example, how should a startup distribute its shares, and

what salary should an enterprise pay to its employees. Several stability-based

solution concepts in cooperative game theory, such as the core, the least core,

and the nucleolus, are well suited to this purpose when the goal is to avoid

coalitions of agents breaking off. We show that some of these solution concepts

can be justified as the most stable payments under noise. Moreover, by adjusting

the noise models (to be arguably more realistic), we obtain new solution

concepts including the partial nucleolus, the multiplicative least core, and the

multiplicative nucleolus. We then study the computational complexity of those

solution concepts under the constraint of superadditivity. Our result is based

on what we call Small-Issues-Large-Team games and it applies to popular

representation schemes such as MC-nets.

The phase diagram of the mercury-indium alloy system

The mercury-indium phase diagram has been investigated over the whole composition range from -78°C to the melting point of indium, using thermal analysis, X-ray and superconductivity techniques. This is believed to be the first application of superconductivity measurements to phase diagram investigations. A compound, HgIn, of very limited range of composition, melts congruently at -19.3°C; and gives rise to eutectics at 61.5 at. % indium and -31°C, and at 34.7% indium and -37.2°C. The β phase extends from 2.5 to 19.1 % indium and has a maximum melting point of -14.2°C at 14.2% indium. It forms a peritectic or eutectic at a temperature indistinguishable from the melting point of pure mercury with a solid solution in mercury containing some, but less than 0.3%, indium. A transition from face-centred tetragonal to face-centred cubic in the indium-rich solid solutions at about 93% indium gives rise to a peritectic at 108°C. The solubility of mercury in this face-centred cubic phase falls from about 22% at-31°C to 13% at -78°C. © 1963.

Selluloosamembraanien kehittäminen ja testaus

Tämän työn tavoitteena oli selvittää, kuinka selluloosan lisääminen vaikuttaa polysulfonirunkoisiin membraaneihin. Lisäksi työssä selvitettiin selluloosamembraanien modifiointia kitosaanilla ja bentoniitilla. Työssä muodostettiin membraanit faasi-inversiotekniikalla. Selluloosamembraanien valmistuksessa jauhettu selluloosa liuotettiin ioniseen nesteeseen. Sekä polysulfonista että selluloosasta valmistetuille membraaneille määritettiin puhdasvesivuot ja retentiot. Retention määrittämiseen käytettiin malliaineena dekstraanin vesiliuosta. Lisäksi määriteltiin polysulfonipohjaisten membraanien hydrofiilisyys tutkimalla membraanien pintojen ja vesipisaroiden välisiä kontaktikulmia. Polysulfonimembraaneihin lisätyn selluloosan havaittiin pienentävän puhdasvesivuota ja kasvattavan hydrofiilisyyttä mitä enemmän selluloosaa oli membraanimatriisissa. Kaikkien selluloosalla modifioitujen membraanien retentiot olivat suurempia kuin modifioimattoman polysulfonimembraanin. Kitosaanilla modifioitujen selluloosamembraanien valmistus ei onnistunut johtuen luultavasti kitosaanin liian suuresta partikkelikoosta. Bentoniitilla modifioitujen membraanien vuot olivat merkittävästi suuremmat sekä niiden retentiot pienemmät verrattuna modifioimattomaan selluloosamembraaniin. Tämä johtui luultavasti siitä, että bentoniitin lisääminen aiheutti membraanirakenteeseen reikiä.

Coupling of magnetic, strain and electric polarization fields in the structure of multiferroic material

The comprehensive study on the coupling of magnetism, electrical polarization and the crystalline lattice with the off-stoichiometric effects in self-doped multiferroic hexagonal h-LuMnxO3±δ (0.92≤x≤1.12) ceramic oxides was carried out for the PhD work. There is a complex coupling of the three ferroic degrees. The cancelation of the magnetic moments of ions in the antiferromagnetic order, electric polarization with specific vortex/antivortex topology and lattice properties have pushed researchers to find out ways to disclose the underlying physics and chemistry of magneto-electric and magneto-elastic couplings of h-RMnO3 multiferroic materials. In this research work, self-doping of Lu-sites or Mn-sites of h-LuMnxO3±δ ceramics prepared via solid state route was done to pave a way for deeper understanding of the antiferromagnetic transition, the weak ferromagnetism often reported in the same crystalline lattices and the ferroelectric properties coupled to the imposed lattice changes. Accordingly to the aim of the PhD thesis, the objectives set for the sintering study in the first chapter on experimental results were two. First, study of sintering off-stoichiometric samples within conditions reported in the bibliography and also extracted from the phase diagrams of the LuMnxO3±δ, with a multiple firings ending with a last high temperature step at 1300ºC for 24 hours. Second, explore longer annealing times of up to 240 hours at the fixed temperature of 1300 ºC in a search for improving the properties of the solid solution under study. All series of LuMnxO3±δ ceramics for each annealing time were characterized to tentatively build a framework enabling comparison of measured properties with results of others available in literature. XRD and Rietveld refinement of data give the evolution the lattice parameters as a function to x. Shrinkage of the lattice parameters with increasing x values was observed, the stability limit of the solid solution being determined by analysis of lattice parameters. The evolution of grain size and presence of secondary phases have been investigated by means of TEM, SEM, EDS and EBSD techniques. The dependencies of grain growth and regression of secondary phases on composition x and time were further characterized. Magnetic susceptibility of samples and magnetic irreversibility were extensively examined in the present work. The dependency of magnetic susceptibility, Neel ordering transition and important magnetic parameters are determined and compared to observation in other multiferroics in the following chapter of the thesis. As a tool of high sensitivity to detect minor traces of the secondary phase hausmannite, magnetic measurements are suggested for cross-checking of phase diagrams. Difficulty of previous studies on interpreting the magnetic anomaly below 43 K in h-RMnO3 oxides was discussed and assigned to the Mn3O4 phase, with supported of the electron microscopy. Magneto-electric coupling where AFM ordering is coupled to dielectric polarization is investigated as a function of x and of sintering condition via frequency and temperature dependent complex dielectric constant measurements in the final chapter of the thesis. Within the limits of solid solubility, the crystalline lattice of off-stoichiometric ceramics was shown to preserve the magneto-electric coupling at TN. It represents the first research work on magneto-electric coupling modified by vacancy doping to author’s knowledge. Studied lattices would reveal distortions at the atomic scale imposed by local changes of x dependent on sintering conditions which were widely inspected by using TEM/STEM methods, complemented with EDS and EELS spectroscopy all together to provide comprehensive information on cross coupling of distortions, inhomogeneity and electronic structure assembled and discussed in a specific chapter. Internal interfaces inside crystalline grains were examined. Qualitative explanations of the measured magnetic and ferroelectric properties were established in relation to observed nanoscale features of h-LuMnxO3±δ ceramics. Ferroelectric domains and topological defects are displayed both in TEM and AFM/PFM images, the later technique being used to look at size, distribution and switching of ferroelectric domains influenced by vacancy doping at the micron scale bridging to complementary TEM studies on the atomic structure of ferroelectric domains. In support to experimental study, DFT simulations using Wien2K code have been carried out in order to interpret the results of EELS spectra of O K-edge and to obtain information on the cation hybridization to oxygen ions. The L3,2 edges of Mn is used to access the oxidation state of the Mn ions inside crystalline grains. In addition, rehybridization driven ferroelectricity is also evaluated by comparing the partial density of states of the orbitals of all ions of the samples, also the polarization was calculated and correlated to the off-stoichiometric effect.

Nurse Rostering with Genetic Algorithms

In recent years genetic algorithms have emerged as a useful tool for the heuristic solution of complex discrete optimisation problems. In particular there has been considerable interest in their use in tackling problems arising in the areas of scheduling and timetabling. However, the classical genetic algorithm paradigm is not well equipped to handle constraints and successful implementations usually require some sort of modification to enable the search to exploit problem specific knowledge in order to overcome this shortcoming. This paper is concerned with the development of a family of genetic algorithms for the solution of a nurse rostering problem at a major UK hospital. The hospital is made up of wards of up to 30 nurses. Each ward has its own group of nurses whose shifts have to be scheduled on a weekly basis. In addition to fulfilling the minimum demand for staff over three daily shifts, nurses’ wishes and qualifications have to be taken into account. The schedules must also be seen to be fair, in that unpopular shifts have to be spread evenly amongst all nurses, and other restrictions, such as team nursing and special conditions for senior staff, have to be satisfied. The basis of the family of genetic algorithms is a classical genetic algorithm consisting of n-point crossover, single-bit mutation and a rank-based selection. The solution space consists of all schedules in which each nurse works the required number of shifts, but the remaining constraints, both hard and soft, are relaxed and penalised in the fitness function. The talk will start with a detailed description of the problem and the initial implementation and will go on to highlight the shortcomings of such an approach, in terms of the key element of balancing feasibility, i.e. covering the demand and work regulations, and quality, as measured by the nurses’ preferences. A series of experiments involving parameter adaptation, niching, intelligent weights, delta coding, local hill climbing, migration and special selection rules will then be outlined and it will be shown how a series of these enhancements were able to eradicate these difficulties. Results based on several months’ real data will be used to measure the impact of each modification, and to show that the final algorithm is able to compete with a tabu search approach currently employed at the hospital. The talk will conclude with some observations as to the overall quality of this approach to this and similar problems.

Biossorção do corante têxtil preto reafix super 2R com bagaço de malte

Na indústria têxtil grandes volumes de efluentes são gerados, os quais são caracterizados por serem coloridos e poluentes , devido à presença de corantes em sua composição. Com a necessidade de descontaminação, diferentes métodos são utilizados no tratamento, sendo um deles, a biossorção. Este consiste na remoção das substâncias tóxicas recorrendo a biossorventes obtidos a partir de resíduos agrícolas e sub-produtos de processos industriais. O objetivo principal deste trabalho foi estudar a remoção do corante Preto Reafix Super 2R em soluções aquosas por meio de biossorção com bagaço de malte. Baseando-se sobretudo no estudo da cinética e equilíbrio entre o biossorvente e o corante. Numa primeira fase foi estudada a influência dos parâmetros operacionais, como a influência do diâmetro médio das partículas do biossorvente, o pH da solução e a velocidade de agitação da solução. Sendo as condições ótimas de biossorção definidas a pH 2, velocidade de agitação de 150 rpm e biomassa sem peneiramento. Posteriormente, ajustaram-se os modelos cinéticos de Pseudo-primeira ordem, Pseudo-segunda ordem e de Difusão intrapartícula aos resultados experimentais obtidos pela cinética de adsorção avaliando também a influência da temperatura no tempo de contato para se alcançar o equilibrio. O modelo de Pseudo-segunda ordem conduziu ao melhor ajuste, com um coeficiente de correlação (R2) de apróximadamente 1. A partir dos testes de equilíbrio realizados com diferentes concentrações de corante, foram ajustadas as isotermas de Langmuir, Freundlich, Tempkin aos resultados experimentais tendo-se obtido parâmetros bastante significativos para o modelo Langmuir, cuja capacidade máxima de remoção (qmax) obtida foi de 40,16 mg.g-1. A análise dos parâmetros termodinâmicos permitiram avaliar que o processo de adsorção ocorre espontaneamente, sendo endotérmico e que ao longo do processo aumenta a aleatoriedade na interface sólido/solução, devido à desorganização do processo em virtude das interações que ocorrem.

Comportamento da adição do carbeto de nióbio (nBC) na matriz metálica do aço ferrítico 15kH2mfa

The 15Kh2MFA steel is a kind of Cr-Mo-V family steels and can be used in turbines for energy generation, pressure vessels, nuclear reactors or applications where the range of temperature that the material works is between 250 to 450°C. To improve the properties of these steels increasing the service temperature and the thermal stability is add a second particle phase. These particles can be oxides, carbides, nitrites or even solid solution of some chemical elements. On this way, this work aim to study the effect of addition of 3wt% of niobium carbide in the metallic matrix of 15Kh2MFA steel. Powder metallurgy was the route employed to produce this metallic matrix composite. Two different milling conditions were performed. Condition 1: milling of pure 15Kh2MFA steel and condition 2: milling of 15Kh2MFA steel with addition of niobium carbide. A high energy milling was carried out during 5 hours. Then, these two powders were sintered in a vacuum furnace (10-4torr) at 1150 and 1250°C during 60 minutes. After sintering the samples were normalized at 950°C per 3 minutes followed by air cooling to obtain a desired microstructure. Results show that the addition of niobium carbide helps to mill faster the particles during the milling when compared with that steel without carbide. At the sintering, the niobium carbide helps to sinter increasing the density of the samples reaching a maximum density of 7.86g/cm³, better than the melted steel as received that was 7,81g/cm³. In spite this good densification, after normalizing, the niobium carbide don t contributed to increase the microhardness. The best microhardness obtained to the steel with niobium carbide was 156HV and to pure 15Kh2MFA steel was 212HV. It happened due when the niobium carbide is added to the steel a pearlitic structure was formed, and the steel without niobium carbide submitted to the same conditions reached a bainitic structure

Platinum–tin/carbon catalysts for ethanol oxidation: Influence of Sn content on the electroactivity and structural characteristics

Carbon-supported Pt–Sn catalysts commonly contain Pt–Sn alloy and/or Pt–Sn bimetallic systems (Sn oxides). Nevertheless, the origin of the promotion effect due to the presence of Sn in the Pt–Sn/C catalyst towards ethanol oxidation in acid media is still under debate and some contradictions. Herein, a series of Ptx–Sny/C catalysts with different atomic ratios are synthesized by a deposition process using formic acid as the reducing agent. Catalysts structure and chemical compositions are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) and their relationship with catalytic behavior towards ethanol electro-oxidation was established. Geometric structural changes are producing by highest Sn content (Pt1–Sn1/C) promoted the interaction of Pt and Sn forming a solid solution of Pt–Sn alloy phase, whereas, the intermediate and lowest Sn content (Pt2–Sn1/C and Pt3–Sn1/C, respectively) promoted the electronic structure modifications of Pt by Sn addition without the formation of a solid solution. The amount of Sn added affects the physical and chemical characteristics of the bimetallic catalysts as well as reducing the amount of Pt in the catalyst composition and maintaining the electrocatalytic activities at the anode. However, the influence of the Sn oxidation state in Pt–Sn/C catalysts surfaces and the alloy formation between Pt and Sn as well as with the atomic ratio on their catalytic activity towards ethanol oxidation appears minimal. Similar methodologies applied for synthesis of Ptx–Sny/C catalysts with a small change show differences with the results obtained, thus highlighting the importance of the conditions of the preparation method.

Adesão ao regime medicamentoso dos adolescentes submetidos a transplante hepático: fatores motivacionais.

Introduction: In liver transplantation the immunosuppression is essential for the survival of the graft and of the receiver. Although characteristics of adolescent development may influence medication non-adherence, the literature on the subject is scarce. The high prevalence and consequences of non-adherence makes it essential to identify the non-adherent adolescent with the intention of promoting medication adherence. Methods: The aim of this descriptive cross-sectional study is to characterize adolescents undergoing liver transplantation, and to determine the degree of medication non-adherence, using the Measure Treatment Adherence (MAT) scale and immunosuppression blood values. Moreover, the study seeks to explore the relationship between adherence and motivation - using the Treatment Self-Regulation Questionnaire (TSRQ), and adherence and competency - using Perceived Competence Scale (PCS). Results: The sample consisted of 32 adolescents (Age M=14,44 (SD=2,66); 56,3% (n=18) male) who underwent liver transplantation at a Portuguese pediatric hospital. Adolescents self-reported medication adherence scores in the MAT were significantly higher (100%) than what was expected based on the mean value of the three blood values of tacrolimus obtained within one year prior to completing the questionnaire (66,7%). As a subjective self-reported measure, the MAT is prone to bias and inflated self assessed adherence is commonly found in the literature. On the other hand, the mean value of the three blood levels of tacrolimus obtained widely and considered objective adherences measure, they may individually vary in terms of pharmacokinetic response and absorption. Adolescents showed a predominantly autonomous motivation to fulfill the medication prescription, being that motivation high (TSRQ autonomous motivation subscale presents an average value of 6.5, in a range of 1 to 7). They showed themselves confident and believing in their capacity to follow the medication regimen, due to the high perceived competence (PCS presents an average value of 6.65, in a range of 1 to 7). Opposed to what was postulated by the Self-determination Theory and other investigation's results, motivation and perceived competence are not related to adherence to the medication regimen in this study (rs=,119 p=,523; rs=,283 p=,123, respectively). Thus, perceived competence seems to have a positive influence on the autonomous motivation of these adolescents (rs=,482 p=,006). Conclusion: This study shows that medication adherence when evaluated subjectively scores higher compared to the blood values of immunosuppression. Also, Motivation and Perceived Competence do not seem to influence the adherence to the medication regimen. More multi-centre studies are needed, based on solid theory to examine adherence behaviour more.

Nuovi processi catalitici per la produzione di syngas

The study of the combined Steam/Dry Reforming (S/DR) process for the production of syngas (CO + H2) from clean biogas was carried out using Ni/Ir bimetallic catalysts on Mg and Al mixed-oxides, obtained by calcination of hydrotalcite-type precursors (Ht) prepared by co-precipitation. The presence of small amounts of Ir promoted the catalytic activity and limited the deactivation phenomena through the formation of a bimetallic alloy, which does the catalyst very active even at lowest temperature and in lack of steam. By integrating a High Temperature–WGS unit (HTS) after the S/DR reactor it was possible to increase the H2 yield of the process. The performance of the Zn/Al/Cu-based catalyst was improved using a templating agent during the synthesis of the catalyst, which increased the catalyst’s structural properties and activity especially at lowest temperatures and at highest contact times. Finally, starting from the laboratory data, it was possible to simulate the S/DR process on industrial scale, evaluating its scalability and environmental impact. The results showed that, using the S/DR technology instead of the current processes, it was possible to reduce the energy costs and the atmospheric emissions of the plant.

Jeans modeling of massive early-type galaxies with observed stellar kinematic profiles up to 2-3 effective radii

A recent integral-field spectroscopic (IFS) survey, the MASSIVE survey (Ma et al. 2014), observed the 116 most massive (MK < −25.3 mag, stellar mass M∗ > 10^11.6 M⊙) early-type galaxies (ETGs) within 108 Mpc, out to radii as large as 40 kpc, that correspond to ∼ 2 − 3 effective radii (Re). One of the major findings of the MASSIVE survey is that the galaxy sample is split nearly equally among three groups showing three different velocity dispersion profiles σ(R) outer of a radius ∼ 5 kpc (falling, flat and rising with radius). The purpose of this thesis is to model the kinematic profiles of six ETGs included in the MASSIVE survey and representative of the three observed σ(R) shapes, with the aim of investigating their dynamical structure. Models for the chosen galaxies are built using the numerical code JASMINE (Posacki, Pellegrini, and Ciotti 2013). The code produces models of axisymmetric galaxies, based on the solution of the Jeans equations for a multicomponent gravitational potential (supermassive black hole, stars and dark matter halo). With the aim of having a good agreement between the kinematics obtained from the Jeans equations, and the observed σ and rotation velocity V of MASSIVE (Veale et al. 2016, 2018), I derived constraints on the dark matter distribution and orbital anisotropy. This work suggests a trend of the dark matter amount and distribution with the shape of the velocity dispersion profiles in the outer regions: the models of galaxies with flat or rising velocity dispersion profiles show higher dark matter fractions fDM both within 1 Re and 5 Re. Orbital anisotropy alone cannot account for the different observed trends of σ(R) and has a minor effect compared to variations of the mass profile. Galaxies with similar stellar mass M∗ that show different velocity dispersion profiles (from falling to rising) are successfully modelled with a variation of the halo mass Mh.

Preconcentration of copper from natural water samples using ligand-less in situ surfactant-based solid phase extraction prior to FAAS determination

In the present work, a simple and rapid ligand-less, in situ, surfactant-based solid phase extraction for the preconcentration of copper in water samples was developed. In this method, a cationic surfactant (n-dodecyltrimethylammonium bromide) was dissolved in an aqueous sample followed by the addition of an appropriate ion-pairing agent (ClO4-). Due to the interaction between the surfactant and ion-pairing agent, solid particles were formed and subsequently used for the adsorption of Cu(OH)2 and CuI. After centrifugation, the sediment was dissolved in 1.0 mL of 1 mol L-1 HNO3 in ethanol and aspirated directly into the flame atomic absorption spectrometer. In order to obtain the optimum conditions, several parameters affecting the performance of the LL-ISS-SPE, including the volumes of DTAB, KClO4, and KI, pH, and potentially interfering ions, were optimized. It was found that KI and phosphate buffer solution (pH = 9) could extract more than 95% of copper ions. The amount of copper ions in the water samples varied from 3.2 to 4.8 ng mL-1, with relative standard deviations of 98.5%-103%. The determination of copper in water samples was linear over a concentration range of 0.5-200.0 ng mL-1. The limit of detection (3Sb/m) was 0.1 ng mL-1 with an enrichment factor of 38.7. The accuracy of the developed method was verified by the determination of copper in two certified reference materials, producing satisfactory results.

Copper determination in ethanol fuel by differential pulse anodic stripping voltammetry at a solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica

Solid paraffin-based carbon paste electrodes modified with 2-aminothiazole organofunctionalized silica have been applied to the anodic stripping determination of copper ions in ethanol fuel samples without any sample treatment. The proposed method comprised four steps: (1) copper ions preconcentration at open circuit potential directly in the ethanol fuel sample; (2) exchange of the solution and immediate cathodic reduction of the absorbate at controlled potential; (3) differential pulse anodic stripping voltammetry; (4) electrochemical surface regeneration by applying a positive potential in acid media. Factors affecting the preconcentration, reduction and stripping steps were investigated and the optimum conditions were employed to develop the analytical procedure. Using a preconcentration time of 20 min and reduction time of 120 s at -0.3 V versus Ag/AgCl(sat) a linear range from 7.5 x 10(-8) to 2.5 x 10(-6) mol L(-1) with detection limit of 3.1 x 10(-8) mol L(-1) was obtained. Interference studies have shown a decrease in the interference effect according to the sequence: Ni > Zn > Cd > Pb > Fe. However, the interference effects of these ions have not forbidden the application of the proposed method. Recovery values between 98.8 and 102.3% were obtained for synthetic samples spiked with known amounts of Cu(2+) and interfering metallic ions. The developed electrode was successfully applied to the determination of Cu(2+) in commercial ethanol fuel samples. The results were compared to those obtained by flame atomic absorption spectroscopy by using the F-test and t-test. Neither F-value nor t-value have exceeded the critical values at 95% confidence level, confirming that there are no significant differences between the results obtained by both methods. (c) 2006 Elsevier B.V. All rights reserved.