Transition-metal 13-atom clusters assessed with solid and surface-biased functionals

First-principles density-functional theory studies have reported open structures based on the formation of double simple-cubic (DSC) arrangements for Ru(13), Rh(13), Os(13), and Ir(13), which can be considered an unexpected result as those elements crystallize in compact bulk structures such as the face-centered cubic and hexagonal close-packed lattices. In this work, we investigated with the projected augmented wave method the dependence of the lowest-energy structure on the local and semilocal exchange-correlation (xc) energy functionals employed in density-functional theory. We found that the local-density approximation (LDA) and generalized-gradient formulations with different treatment of the electronic inhomogeneities (PBE, PBEsol, and AM05) confirm the DSC configuration as the lowest-energy structure for the studied TM(13) clusters. A good agreement in the relative total energies are obtained even for structures with small energy differences, e. g., 0.10 eV. The employed xc functionals yield the same total magnetic moment for a given structure, i.e., the differences in the bond lengths do not affect the moments, which can be attributed to the atomic character of those clusters. Thus, at least for those systems, the differences among the LDA, PBE, PBEsol, and AM05 functionals are not large enough to yield qualitatively different results. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3577999]

The role of electron localization in the atomic structure of transition-metal 13-atom clusters: the example of Co(13), Rh(13), and Hf(13)

The crystalline structure of transition-metals (TM) has been widely known for several decades, however, our knowledge on the atomic structure of TM clusters is still far from satisfactory, which compromises an atomistic understanding of the reactivity of TM clusters. For example, almost all density functional theory (DFT) calculations for TM clusters have been based on local (local density approximation-LDA) and semilocal (generalized gradient approximation-GGA) exchange-correlation functionals, however, it is well known that plain DFT fails to correct the self-interaction error, which affects the properties of several systems. To improve our basic understanding of the atomic and electronic properties of TM clusters, we report a DFT study within two nonlocal functionals, namely, the hybrid HSE (Heyd, Scuseria, and Ernzerhof) and GGA + U functionals, of the structural and electronic properties of the Co(13), Rh(13), and Hf(13) clusters. For Co(13) and Rh(13), we found that improved exchange-correlation functionals decrease the stability of open structures such as the hexagonal bilayer (HBL) and double simple-cubic (DSC) compared with the compact icosahedron (ICO) structure, however, DFT-GGA, DFT-GGA + U, and DFT-HSE yield very similar results for Hf(13). Thus, our results suggest that the DSC structure obtained by several plain DFT calculations for Rh(13) can be improved by the use of improved functionals. Using the sd hybridization analysis, we found that a strong hybridization favors compact structures, and hence, a correct description of the sd hybridization is crucial for the relative energy stability. For example, the sd hybridization decreases for HBL and DSC and increases for ICO in the case of Co(13) and Rh(13), while for Hf(13), the sd hybridization decreases for all configurations, and hence, it does not affect the relative stability among open and compact configurations.

Heavy Metal Contamination in Phrynops geoffroanus (Schweigger, 1812) (Testudines: Chelidae) in a River Basin, So Paulo, Brazil

The Piracicaba River basin is considered the most disturbed river basin in the state of So Paulo. Considerable amounts of agricultural residues are seasonally drained into the river, and the region is also highly urbanized and industrialized with an incipient sewage treatment system. The presence of heavy metals has been previously reported for the water and riverbed in Piracicaba river basin. In this study we evaluated 13 heavy metals in the blood of 37 Geoffroy`s side-necked turtles, Phrynops geoffroanus, from Piracicaba River and Piracicamirim Creek, one of its tributaries. Blood levels of As, Co, Cr, Se and Pb varied among sites, whereas Sn varied between males and females. However, no obvious pathology was detected. Serum level of Cu (2,194 ng g(-1)) and Pb (1,150 ng g(-1)) found in this study are the highest ever described for any reptile; however, no clinical symptoms have been detected in the present study. There is no information about the time scale of such contamination, which could be currently subclinical and yet lead to a breakdown in the population reproductive success in a few years. Based on the present study, legal enforcement is urged in order to locate and extirpate heavy metal sources in the Piracicaba River basin. In addition, monitoring should include humans and commercial fish consumed in local markets.

A simulation-based evolutionary multiobjective approach to manufacturing cell formation

The purpose of this paper is to propose a multiobjective optimization approach for solving the manufacturing cell formation problem, explicitly considering the performance of this said manufacturing system. Cells are formed so as to simultaneously minimize three conflicting objectives, namely, the level of the work-in-process, the intercell moves and the total machinery investment. A genetic algorithm performs a search in the design space, in order to approximate to the Pareto optimal set. The values of the objectives for each candidate solution in a population are assigned by running a discrete-event simulation, in which the model is automatically generated according to the number of machines and their distribution among cells implied by a particular solution. The potential of this approach is evaluated via its application to an illustrative example, and a case from the relevant literature. The obtained results are analyzed and reviewed. Therefore, it is concluded that this approach is capable of generating a set of alternative manufacturing cell configurations considering the optimization of multiple performance measures, greatly improving the decision making process involved in planning and designing cellular systems. (C) 2010 Elsevier Ltd. All rights reserved.

Suitability of Daphnia similis as an alternative organism in ecotoxicological tests: implications for metal toxicity

The acute toxicity of metals to Daphnia similis was determined and compared to other daphnid species to evaluate the suitability of this organism in ecotoxicology bioassays. To verify the performance D. similis in toxicity tests, we also investigated the effect of Pseudokirchneriella subcapitata at 1 x 10(5) and 1 x 10(6) cells ml(-1) on Cd and Cr acute toxicity to the cladoceran. Daphnid neonates were exposed to a range of chromium and cadmium concentrations in the absence and presence of the algal cells. Metal speciation calculations using MINEQL(+) showed that total dissolved metal concentrations in zooplankton culture corresponded to 96.2% free Cd and 100% free Cr concentrations. Initial total dissolved metal concentrations were used for 48 h-LC(50) determination. LC(50) for D. similis was 5.15 x 10(-7) mol l(-1) dissolved Cd without algal cells, whereas with 1 x 10(5) cells ml(-1), it was significantly higher (7.15 x 10(-7) mol l(-1) dissolved Cd). For Cr, the 48 h-LC(50) value of 9.17 x 10(-7) mol l(-1) obtained for the cladoceran in tests with 1 x 10(6) cells ml(-1) of P. subcapitata was also significantly higher than that obtained in tests without algal cells (5.28 x 10(-7) mol l(-1) dissolved Cr). The presence of algal cells reduced the toxicity of metals to D. similis, as observed in other studies that investigated the effects of food on metal toxicity to standard cladocerans. Comparing our results to those of literature, we observed that D. similis is as sensitive to metals as other standardized Daphnia species and may serve as a potential test species in ecotoxicological evaluations.

Oxidative stress biomarkers of exposure in the blood of cichlid species from a metal-contaminated river

The oxidative stress biomarkers of exposure, such as reduced glutathione (GSH), activity of superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPx) and the levels of lipid peroxidation (LPO), were measured in the blood of three cichlid fish (Oreochromis niloticus, Tilapia rendalli, and Geophagus brasiliensis) taken during two seasons from two sites, unpolluted and polluted by industrial effluents, to evaluate the effectiveness of these biomarkers in assessing the impact of water contamination. The LPO levels in the blood were higher in fish from the metal-contaminated site and the chronic exposure led to significant changes in GPx, CAT, and SOD activities in all three cichlid species. The considerable variation of responses in these cichlids to water contamination evidenced differences in sensitivity to the metal contamination and/or in the potential to respond to it highlighting the importance of using a set of related biomarkers to assess the impact of water contamination. (C) 2007 Elsevier Inc. All rights reserved.

Digital versus Conventional Radiography for Imaging Fatigue Cracks in Riveted Lap Joints of Hybrid Glass Reinforced Fiber/Metal Laminate

A round robin program zoos conducted to assess the ability of three different X-radiographic systems for imaging internal fatigue cracks in riveted lap joints of composite glass reinforced fiber/metal laminate. From an engineering perspective, conventional film radiography and direct radiography have produced the best results, identifying and characterizing in detail internal damage on metallic faying surfaces of fastened glass reinforced fiber/metal laminate joints. On the other hand, computed radiographic images presented large projected geometric distortions and feature shifts due to the angular incident radiation beam, disclosing only partial internal cracking patterns.

Toxicity-directed approach of polyester manufacturing industry wastewater provides useful information for conducting treatability studies

A broader characterization of industrial wastewaters, especially in respect to hazardous compounds and their potential toxicity, is often necessary in order to determine the best practical treatment (or pretreatment) technology available to reduce the discharge of harmful pollutants to the environment or publicly owned treatment works. Using a toxicity-directed approach, this paper sets the base for a rational treatability study of polyester resin manufacturing. Relevant physical and chemical characteristics were determined. Respirometry was used for toxicity reduction evaluation after physical and chemical effluent fractionation. Of all the procedures investigated, only air stripping was significantly effective in reducing wastewater toxicity. Air stripping in pH 7 reduced toxicity in 18.2%, while in pH 11 a toxicity reduction of 62.5% was observed. Results indicated that toxicants responsible for the most significant fraction of the effluent`s instantaneous toxic effect to unadapted activated sludge were organic compounds poorly or not volatilized in acid conditions. These results led to useful directions for conducting treatability studies which will be grounded on actual effluent properties rather than empirical or based on the rare specific data on this kind of industrial wastewater. (C) 2008 Elsevier B.V. All rights reserved.

Knowledge transfer in product development processes: A case study in small and medium enterprises (SMEs) of the metal-mechanic sector from Sao Paulo, Brazil

This paper reports a research that evaluated the product development methodologies used in Brazilian small and medium-sized metal-mechanic enterprises (SMEs), in a specific region of Sao Paulo. The tool used for collecting the data was a questionnaire, which was developed and applied through interviews conducted by the researchers in 32 companies. The main focus of this paper can be condensed in the synthesis-question ""Is only the company responsible for the development?"" which was analyzed thoroughly. The results obtained from this analysis were evaluated directly (through the respective percentages of answers) and statistically (through the search of an index which demonstrates if two questions are related). The results point to a degree of maturity in SMEs, which allows product development to be conducted in cooperation networks. (C) 2007 Elsevier Ltd. All rights reserved.

Towards modular and coordinated manufacturing systems oriented to services

Nowadays, there is a trend for industry reorganization in geographically dispersed systems, carried out of their activities with autonomy. These systems must maintain coordinated relationship among themselves in order to assure an expected performance of the overall system. Thus, a manufacturing system is proposed, based on ""web services"" to assure an effective orchestration of services in order to produce final products. In addition, it considers special functions, such as teleoperation and remote monitoring, users` online request, among others. Considering the proposed system as discrete event system (DES), techniques derived from Petri nets (PN), including the Production Flow Schema (PFS), can be used in a PFS/PN approach for modeling. The system is approached in different levels of abstraction: a conceptual model which is obtained by applying the PFS technique and a functional model which is obtained by applying PN. Finally, a particular example of the proposed system is presented.

Colloidal Processing of Glass-Ceramics for Laminated Object Manufacturing

Green tapes of Li(2)O-ZrO(2)-SiO(2)-Al(2)O(3) (LZSA) parent glass were produced by aqueous tape casting as the starting material for the laminated object manufacturing (LOM) process. The rheological behavior of the powder suspensions in aqueous media, as well as the mechanical properties of the cast tapes, was evaluated. According to xi potential measurements, the LZSA glass powder particles showed acid surface characteristics and an IEP of around 4 when in aqueous media. The critical volume fraction of solids was about 72 wt% (27 vol%), which hindered the processability of more concentrated slurries. The glass particles also showed an anisometric profile, which contributed to an increase in the interactions between particles during flow. Therefore, the suspensions could not be processed at high solids loadings. Aqueous-based glass suspensions were also characterized by shear thickening after the addition of dispersants. Three slurry compositions were formulated, suitable green tapes were cast, and tapes were successfully laminated by LOM to a gear wheel geometry. A higher tensile strength of the green tapes corresponded to a higher tensile strength of the laminates. Thermal treatment was then applied to the laminates: pyrolysis at 525 degrees C, sintering at 700 degrees C for 1 h, and crystallization at 850 degrees C for 30 min. A 20% volumetric shrinkage was observed, but no surface flaws or inhomogeneous areas were detected. The sintered part maintained the curved edges and internal profile after heat treatment.

Texture and mechanical properties evolution of a deep drawing medium carbon steel during cold rolling and subsequent recrystallization

Medium carbon steels are mostly used for simple applications; however, new applications have been developed for which good sheet metal formability is required. These types of steels have an inherent low formability. A medium-carbon hot-rolled SAE 1050 steel was selected for this study. It has been cold rolled with thickness reductions varying between 7 and 80%. The samples obtained were used to evaluate the strain hardening curve. For samples with a 50 and 80% thickness reduction, an annealing heat treatment was performed to achieve recrystallization. The material was characterized in the ""as-received"", cold rolled and annealed conditions using several methods: optical metallography, X-ray diffraction (texture), Vickers hardness, and tensile testing. For large thickness reductions, the SAE 1050 steel presented low elongation, less than 2%, and yield strength (YS) and tensile strength (TS) around 1400 MPa. Texture in the ""as-received"" condition showed strong components on the {001} plane, in the < 100 >, < 210 > and (110) directions. After cold rolling, the texture did not present any significant changes for small thickness reductions, however. It changed completely for large ones, where gamma, < 111 >//ND, alpha, < 110 > HRD, and gamma prime, < 223 >//ND, fibres were strengthened. After annealing, the microstructure of the SAE 1050 steel was characterized by recrystallized ferrite and globular cementite. There was little change in the alpha fibre for the 50% reduction, whereas for the 80% reduction, its intensity increased. Both gamma and gamma prime fibres vanished upon annealing for 50 and 80% reductions alike. (c) 2008 Elsevier B.V. All rights reserved.

Understanding the strategies of late-movers in International Manufacturing

This paper analyzes the internationalization of new multinationals from emerging countries. It also focuses on Production`s role in firm internationalization, a subject seldom addressed because the discipline of International Manufacturing is still embryonic, while International Business tends to overlook production. The authors integrate International Business and International Manufacturing concepts and frameworks in order to analyze new multinationals from emerging countries, using the empirical evidence of a survey plus case studies of Brazilian multinationals for understanding late-movers` strategies and competences, with emphasis on production. (C) 2009 Elsevier B.V. All rights reserved.

Low-frequency noise and static analysis of the impact of the TiN metal gate thicknesses on n- and p-channel MuGFETs

The impact of the titanium nitride (TIN) gate electrode thickness has been investigated in n and p channel SOI multiple gate field effect transistors (MuGFETs) through low frequency noise charge pumping and static measurements as well as capacitance-voltage curves The results suggest that a thicker TIN metal gate electrode gives rise to a higher EOT a lower mobility and a higher interface trap density The devices have also been studied for different back gate biases where the GIFBE onset occurs at lower front-gate voltage for thinner TIN metal gate thickness and at higher V(GF) In addition it is demonstrated that post deposition nitridation of the MOCVD HfSiO gate dielectric exhibits an unexpected trend with TIN gate electrode thickness where a continuous variation of EOT and an increase on the degradation of the interface quality are observed (C) 2010 Elsevier Ltd All rights reserved