Chemoenzymatic synthesis: a strategy to obtain xylitol monoesters

BACKGROUND: Fatty acid sugar esters are used as non-ionic surfactants in cosmetics, foodstuffs and pharmaceuticals. In particular, monoesters of xylitol have attracted industrial interest due to their outstanding biological activities. In this work, xylitol monoesters were obtained by chemoenzymatic synthesis, in which, first, xylitol was made soluble in organic solvent by chemo-protecting reaction, followed by enzymatic esterification reaction using different acyl donors. A commercial immobilized Candida antartica lipase was used as catalyst, and reactions with pure xylitol were carried out to generate data for comparison. RESULTS: t-BuOH was found to be the most suitable solvent to carry out esterification reactions with both pure and protected xylitol. The highest yields were obtained for reactions carried out with pure xylitol, but in this case by-products, such as di- and tri-esters isomers were formed, which required a multi-step purification process. For the systems with protected xylitol, conversions of 86%, 58% and 24% were achieved using oleic, lauric and butyric acids, respectively. The structures of the monoesters were confirmed by (13)C- and (1)H-NMR and microanalysis. CONCLUSION: The chemoenzymatic synthesis of xylitol monoesters avoided laborious downstream processing when compared with reactions performed with pure xylitol. Monoesters production from protected xylitol was shown to be a practical, economical, and clean route for this process, allowing a simple separation, because there are no other products formed besides xylitol monoesters and residual xylitol. (C) 2009 Society of Chemical Industry

Contribution to dynamic characteristics of the cutting temperature in the drilling process considering one dimension heat flow

The machining of hardened steels has always been a great challenge in metal cutting, particularly for drilling operations. Generally, drilling is the machining process that is most difficult to cool due to the tool`s geometry. The aim of this work is to determine the heat flux and the coefficient of convection in drilling using the inverse heat conduction method. Temperature was assessed during the drilling of hardened AISI H13 steel using the embedded thermocouple technique. Dry machining and two cooling/lubrication systems were used, and thermocouples were fixed at distances very close to the hole`s wall. Tests were replicated for each condition, and were carried out with new and worn drills. An analytical heat conduction model was used to calculate the temperature at tool-workpiece interface and to define the heat flux and the coefficient of convection. In all tests using new and worn out drills, the lowest temperatures and decrease of heat flux were observed using the flooded system, followed by the MQL, considering the dry condition as reference. The decrease of temperature was directly proportional to the amount of lubricant applied and was significant in the MQL system when compared to dry cutting. (C) 2011 Elsevier Ltd. All rights reserved.

Contributions of HRM throughout the stages of environmental management: methodological triangulation applied to companies in Brazil

The purpose of this research is to analyze the contribution of human resources management throughout the evolutionary stages of environmental management in Brazilian companies. A theoretical framework concerning environmental management and its evolution and the `greening` of the functional and competitive dimensions of human resource management were developed. A methodological triangulation was developed in two complimentary phases. In the first phase, data were collected from 94 Brazilian companies with ISO 14001 certification. The data collected were analyzed and processed using statistical techniques. The conclusions of the first phase supported the second phase of this empirical research. The second phase consisted of a study of multiple cases in four Brazilian companies. The results show evidence of the first known empirical study of contributions of human resource dimensions throughout the stages of environmental management in Brazilian manufacturing companies.

Dual boundary element formulation applied to analysis of multi-fractured domains

This paper deals with analysis of multiple random crack propagation in two-dimensional domains using the boundary element method (BEM). BEM is known to be a robust and accurate numerical technique for analysing this type of problem. The formulation adopted in this work is based on the dual BEM, for which singular and hyper-singular integral equations are used. We propose an iterative scheme to predict the crack growth path and the crack length increment at each time step. The proposed scheme able us to simulate localisation and coalescence phenomena, which is the main contribution of this paper. Considering the fracture mechanics analysis, the displacement correlation technique is applied to evaluate the stress intensity factors. The propagation angle and the equivalent stress intensity factor are calculated using the theory of maximum circumferential stress. Examples of simple and multi-fractured domains, loaded up to the rupture, are considered to illustrate the applicability of the proposed scheme. (C) 2010 Elsevier Ltd. All rights reserved.

Eucalyptus pulp fibres as alternative reinforcement to engineered cement-based composites

This paper evaluates the advantages of using hardwood short fibre pulp (eucalyptus) as alternative to softwood long fibre pulp (pinus) and polymer fibres, traditionally used in reinforcement of cement-based materials. The effects of cellulose fibre length on microstructure and on mechanical performance of fibre-cement composites were evaluated before and after accelerated ageing cycles. Hardwood pulp fibres were better dispersed in the cement matrix and provided higher number of fibres per unitary weight or volume, in relation to softwood long fibre pulp. The short reinforcing elements lead to an effective crack bridging of the fragile matrix, which contributes to the improvement of the mechanical performance of the composite after ageing. These promising results show the potential of eucalyptus short fibres for reducing costs by both the partial replacement of expensive synthetic fibres in air curing process and the energy savings during pulp refining. (C) 2009 Elsevier B.V. All rights reserved.

A BEM model applied to failure analysis of multi-fractured structures

Due to manufacturing or damage process, brittle materials present a large number of micro-cracks which are randomly distributed. The lifetime of these materials is governed by crack propagation under the applied mechanical and thermal loadings. In order to deal with these kinds of materials, the present work develops a boundary element method (BEM) model allowing for the analysis of multiple random crack propagation in plane structures. The adopted formulation is based on the dual BEM, for which singular and hyper-singular integral equations are used. An iterative scheme to predict the crack growth path and crack length increment is proposed. This scheme enables us to simulate the localization and coalescence phenomena, which are the main contribution of this paper. Considering the fracture mechanics approach, the displacement correlation technique is applied to evaluate the stress intensity factors. The propagation angle and the equivalent stress intensity factor are calculated using the theory of maximum circumferential stress. Examples of multi-fractured domains, loaded up to rupture, are considered to illustrate the applicability of the proposed method. (C) 2011 Elsevier Ltd. All rights reserved.

Influence of concrete strength and length/diameter on the axial capacity of CFT columns

This paper presents an experimental analysis of the confinement effects in steel-concrete composite columns regarding two parameters: concrete compressive strength and column slenderness. Sixteen concrete-filled steel tubular columns with circular cross section were tested under axial loading. The tested columns were filled by concrete with compressive strengths of 30, 60. 80, and 100 MPa, and had length/diameter ratios of 3, 5, 7, and 10. The experimental values of the columns` ultimate load were compared to the predictions of 4 code provisions: the Brazilian Code NBR 8800:2008, Eurocode 4 (EN 1994-1-1:2004), AINSI/AISC 360:2005, and CAN/CSA S16-01:2001. According to the results, the load capacity of the composite columns increased with increasing concrete strength and decreased with increasing length/diameter ratio. In general, the code provisions were highly accurate in the prediction of column capacity. Among them, the Brazilian Code was the most conservative, while Eurocode 4 presented the values closest to the experimental results. (C) 2009 Elsevier Ltd. All rights reserved.

Design of concrete-filled steel tubular columns under axial loading according to NBR 8800:2008 and Eurocode 4:2004: tests results and comparisons

In this paper results of tests on 32 concrete-filled steel tubular columns under axial load are reported. The test parameters were the concrete compressive strength, the column slenderness (L/D) and the wall thickness (t). The test results were compared with predictions from the codes NBR 8800:2008 and EN 1994-1-1:2004 (EC4). The columns were 3, 5, 7 and 10 length to diameter ratios (L/D) and were tested with 30MPa, 60MPa, 80MPa and 100MPa concrete compressive strengths. The results of ultimate strength predicted by codes showed good agreement with experimental results. The results of NBR 8800 code were the most conservative and the EC4 showed the best results, in mean, but it was not conservative for usual concrete-filled short columns.

Effect of Fill Time on the Performance of Pilot-scale ASBR and AnSBBR Applied to Sanitary Wastewater Treatment

Many lab-scale studies have been carried out regarding the effect of feed strategy on the performance of anaerobic sequencing batch reactors (ASBR); however, more detailed pilot-scale studies should be performed to assess the real applicability of this type of operation. Therefore, the objective of this work was to assess the effect of feed strategy or fill time in a 1-m(3) mechanically stirred pilot-scale sequencing batch reactor, treating 0.65 m(3) sanitary wastewater in 8-h cycles at ambient temperature. Two reactor configurations were used: one containing granular biomass (denominated ASBR) and the other immobilized biomass on polyurethane foam as inert support (denominated anaerobic sequencing batch biofilm reactor (AnSBBR)). The reactors were operated under five distinct feed strategies, namely: typical batch and fed-batch for 25%, 50%, 75%, and 100% of the cycle length. Stirring frequency in the ASBR was 40 rpm with two flat-blade turbine impellers and 80 rpm in the AnSBBR with two helix impellers. The results showed that both the ASBR and AnSBBR when operated under typical batch, fed-batch for 50% and 75% of the cycle length, presented improved organic matter removal efficiencies, without significant differences in performance, thus showing important operational flexibility. In addition, the reactors presented operation stability under all conditions.

A safety assessment methodology applied to CNS/ATM-based air traffic control system

In the last decades, the air traffic system has been changing to adapt itself to new social demands, mainly the safe growth of worldwide traffic capacity. Those changes are ruled by the Communication, Navigation, Surveillance/Air Traffic Management (CNS/ATM) paradigm, based on digital communication technologies (mainly satellites) as a way of improving communication, surveillance, navigation and air traffic management services. However, CNS/ATM poses new challenges and needs, mainly related to the safety assessment process. In face of these new challenges, and considering the main characteristics of the CNS/ATM, a methodology is proposed at this work by combining ""absolute"" and ""relative"" safety assessment methods adopted by the International Civil Aviation Organization (ICAO) in ICAO Doc.9689 [14], using Fluid Stochastic Petri Nets (FSPN) as the modeling formalism, and compares the safety metrics estimated from the simulation of both the proposed (in analysis) and the legacy system models. To demonstrate its usefulness, the proposed methodology was applied to the ""Automatic Dependent Surveillance-Broadcasting"" (ADS-B) based air traffic control system. As conclusions, the proposed methodology assured to assess CNS/ATM system safety properties, in which FSPN formalism provides important modeling capabilities, and discrete event simulation allowing the estimation of the desired safety metric. (C) 2011 Elsevier Ltd. All rights reserved.

Effect of the domain spanwise periodic length on the flow around a circular cylinder

We assess the effect of the choice of spanwise periodic length on simulations of the flow around a fixed circular cylinder. The Reynolds number is set to 400 because, at this value, both lift coefficient and shedding frequency show significant drop due to three-dimensional flow structures. From the analysis of the three-dimensionalities of the wake and of the integral quantities such as Strouhal number, RMS of lift coefficient and energy contained in the three-dimensional portion of the flow we obtain an estimate of the minimum spanwise length to satisfactorily represent the flow. Furthermore, we observe a distinct wake behavior when the spanwise length is approximately the mode B instability wavelength. (C) 2011 Elsevier Ltd. All rights reserved.

Reliability concepts applied to cutting tool change time

This paper presents a reliability-based analysis for calculating critical tool life in machining processes. It is possible to determine the running time for each tool involved in the process by obtaining the operations sequence for the machining procedure. Usually, the reliability of an operation depends on three independent factors: operator, machine-tool and cutting tool. The reliability of a part manufacturing process is mainly determined by the cutting time for each job and by the sequence of operations, defined by the series configuration. An algorithm is presented to define when the cutting tool must be changed. The proposed algorithm is used to evaluate the reliability of a manufacturing process composed of turning and drilling operations. The reliability of the turning operation is modeled based on data presented in the literature, and from experimental results, a statistical distribution of drilling tool wear was defined, and the reliability of the drilling process was modeled. (C) 2010 Elsevier Ltd. All rights reserved.

Simulated annealing applied to the irregular rotational placement of shapes over containers with fixed dimensions

This work deals with the problem of minimizing the waste of space that occurs on a rotational placement of a set of irregular two dimensional polygons inside a two dimensional container. This problem is approached with an heuristic based on simulated annealing. Traditional 14 external penalization"" techniques are avoided through the application of the no-fit polygon, that determinates the collision free area for each polygon before its placement. The simulated annealing controls: the rotation applied, the placement and the sequence of placement of the polygons. For each non placed polygon, a limited depth binary search is performed to find a scale factor that when applied to the polygon, would allow it to be fitted in the container. It is proposed a crystallization heuristic, in order to increase the number of accepted solutions. The bottom left and larger first deterministic heuristics were also studied. The proposed process is suited for non convex polygons and containers, the containers can have holes inside. (C) 2009 Elsevier Ltd. All rights reserved.

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.

Replacement of Trays by Packing To Increase the Absorption Capacity of Acetone during Cellulose Acetate Spinning

All textile uses of cellulose acetate involve acetone recovery, which, because of safety issues, results in large installations, in order to work with dilute streams. This compromises the efficiency of all of the involved unit operations, in this case, acetone absorption in cold water, acetone distillation, and water chilling, making them more expensive. The present article proposes the improvement of the absorption of acetone in water, traditionally performed with sieve trays, by using structured packing instead. The advantageous implementation was enabled through the utilization of a calculation methodology based on concepts of thermodynamic equilibrium of the binary acetone/water system and empirical relations that allow the evaluation of the hydrodynamics of the proposed modification.