High performance magnetic separation of gold nanoparticles for catalytic oxidation of alcohols

We present the magnetic separation approach to facilitate the recovery of gold nanoparticle (AuNP) catalysts. The use of magnetically recoverable supports for the immobilization of AuNPs instead of traditional oxides, polymers or carbon based solids guarantees facile, clean, fast and efficient separation of the catalyst at the end of the reaction cycle. Magnetic separation can be considered an environmentally benign separation approach, since it minimizes the use of auxiliary substances and energy for achieving catalyst recovery. The catalyst preparation is based on the immobilization of Au(3+) on the surface of core-shell silica-coated magnetite nanoparticles, followed by metal reduction using two different methods. AuNPs were prepared by thermal reduction in air and by hydrogen reduction at mild temperature. Interestingly, the mean particle size of the supported AuNPs was similar (ca. 5.9 nm), but the polydispersity of the samples is quite different. The catalytic activity of both catalysts in the aerobic oxidation of alcohols was investigated and a distinct selectivity for benzyl alcohol oxidation was observed.

Dynamic transitions in a two dimensional associating lattice gas model

Using Monte Carlo simulations we investigate some new aspects of the phase diagram and the behavior of the diffusion coefficient in an associating lattice gas (ALG) model on different regions of the phase diagram. The ALG model combines a two dimensional lattice gas where particles interact through a soft core potential and orientational degrees of freedom. The competition between soft core potential and directional attractive forces results in a high density liquid phase, a low density liquid phase, and a gas phase. Besides anomalies in the behavior of the density with the temperature at constant pressure and of the diffusion coefficient with density at constant temperature are also found. The two liquid phases are separated by a coexistence line that ends in a bicritical point. The low density liquid phase is separated from the gas phase by a coexistence line that ends in tricritical point. The bicritical and tricritical points are linked by a critical lambda-line. The high density liquid phase and the fluid phases are separated by a second critical tau-line. We then investigate how the diffusion coefficient behaves on different regions of the chemical potential-temperature phase diagram. We find that diffusivity undergoes two types of dynamic transitions: a fragile-to-strong transition when the critical lambda-line is crossed by decreasing the temperature at a constant chemical potential; and a strong-to-strong transition when the critical tau-line is crossed by decreasing the temperature at a constant chemical potential.

Orbital multicriticality in spin-gapped quasi-one-dimensional antiferromagnets

Motivated by the quasi-one-dimensional antiferromagnet CaV(2)O(4), we explore spin-orbital systems in which the spin modes are gapped but orbitals are near a macroscopically degenerate classical transition. Within a simplified model we show that gapless orbital liquid phases possessing power-law correlations may occur without the strict condition of a continuous orbital symmetry. For the model proposed for CaV(2)O(4), we find that an orbital phase with coexisting order parameters emerges from a multicritical point. The effective orbital model consists of zigzag-coupled transverse field Ising chains. The corresponding global phase diagram is constructed using field theory methods and analyzed near the multicritical point with the aid of an exact solution of a zigzag XXZ model.

Microstructural characterization of as-cast Cr-Si alloys

This work presents results of microstructural characterization of as-cast Cr-Si alloys. The alloys were prepared by arc melting pure Cr (min. 99.996%) and Si (min. 99.998%) powder mixtures under argon atmosphere in a water-cooled copper crucible with nonconsumable tungsten electrode and titanium getter. The phases were identified by scanning electron microscopy (SEM), using the back-scattered electron (BSE) image mode and X-ray diffraction (XRD). The results confirm the currently accepted Cr-Si phase diagram in terms of the invariant reactions and solid phases present in this system. Small corrections are proposed for the compositions of the liquid phase in the following reactions: (i) L double left right arrow Cr-ss+Cr3Si, from 15 to 16 at.% Si; (ii) L+alpha Cr5Si3 double left right arrow CrSi, from 51 at.% Si to slightly above 53 at.% Si; (iii) L double left right arrow CrSi+CrSi2, from 56 to slightly above 57 at.% Si; (iv) L double left right arrow CrSi2+Si, from 82 to slightly above 85 at.% Si. (c) 2006 Elsevier Inc. All rights reserved.

Spontaneous infiltrations of compound systems of Y(2)O(3), Sm(2)O(3), RE(2)O(3), Al(2)O(3) and AIN in SiC ceramics

Silicon carbide ceramics (SiC) are used in different applications in the engineering area due to the excellent properties, mainly in high temperatures. They are usually obtained by liquid-phase sintering enabling to form volatile products and, consequently, defects. The present work aims at studying the obtention of SiC ceramics by spontaneous infiltration using a eutectic composition of the Al(2)O(3)/Y(2)O(3), AIN/Y(2)O(3), Al(2)O(3)/Sm(2)O(3), AlN/Sm(2)O(3), Al(2)O(3)/RE(2)O(3) and AlN/RE(2)O(3) Systems. RE(2)O(3) is the concentrate of the rare-earth oxide obtained from Xenotime ore. Infiltration tests were carried out in argon atmosphere, graphite crucibles, in several temperatures near the melting point of each system, varying from 2.5 to 60 min. It was observed that Al(2)O(3)/Y(2)O(3), Al(2)O(3)/SM(2)O(3), AlN/SM(2)O(3) and Al(2)O(3)/RE(2)O(3) systems do not infiltrate appropriately and the AlN/Y(2)O(3) and AlN/RE(2)O(3) systems infiltrated spontaneously more than 20 mm; however, the first one presented a higher degree of infiltration, approximately 97%. (C) 2009 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Toughened ZrO2 ceramics sintered with a La2O3-rich glass as additive

In this study, the influence of the glass addition and sintering parameters on the densification and mechanical properties of tetragonal zirconia polycrystals (3Y-TZP) ceramics were evaluated. High-purity tetragonal ZrO2 powder and La2O3-rich glass were used as starting powders. Two compositions based on ZrO2 and containing 5wt.% and 10wt.% of La2O3-rich glass were studied in this work. The starting powders were mixed/milled by planetary milling, dried at 90 degrees C for 24 h, sieved through a 60 mesh screen and uniaxially cold pressed under 80 MPa. The samples were sintered in air at 1200 degrees C, 1300 degrees C, 1400 degrees C for 60 min and at 1450 degrees C for 120 min, with heating and cooling rates of 10 degrees C/min. Sintered samples were characterized by relative density, X-ray diffraction (XRD) and scanningelectron microscopy (SEM). Hardness and fracture toughness were obtained by Vickers indentation method. Dense sintered samples were obtained for all conditions. Furthermore, only tetragonal-ZrO2 was identified as crystalline phase in sintered samples, independently of the conditions studied. Samples sintered at 1300 degrees C for 60 min presented the optimal mechanical properties with hardness and fracture toughness values near to 12 GPa and 8.5 MPa m(1/2) respectively. (c) 2007 Elsevier B.V, All rights reserved.

Infiltration of Al2O3/Y2O3 mix into SiC ceramic preforms

Silicon carbide ceramics are very interesting materials to engineering applications because of their properties. These ceramics are produced by liquid phase sintering (LPS), where elevated temperature and time are necessary, and generally form volatile products that promote defects and damage their mechanical properties. In this work was studied the infiltration process to produce SiC ceramics, using shorter time and temperature than LPS, thereby reducing the undesirable chemical reactions. SiC powder was pressed at 300 MPa and pre-sintered at 1550 degrees C for 30 min. Unidirectional and spontaneous infiltration of this preform by Al2O3/Y2O3 liquid was done at 1850 degrees C for 5, 10, 30 and 60 min. The kinetics of infiltration was studied, and the infiltration equilibrium happened when the liquid infiltrated 12 mm into perform. The microstructures show grains of the SiC surrounded by infiltrated additives. The hardness and fracture toughness are similar to conventional SiC ceramics obtained by LPS. (c) 2007 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Strength improvement of LPS-SiC ceramics by oxidation treatment

In this work, SiC ceramics were liquid phase sintered (LPS), using AIN-Y(2)O(3) as additives, and oxidized at 1400 degrees C in air for up to 120 h. Oxidation was monitored by the weight gain of the samples as function of exposition time and temperature. A parabolic growth of the oxidation layer has been observed and the coefficient of the growth rate has been determined by relating the weight gain and the surface area. The effect of oxidation on strength has been determined by 4-point bending tests. Phase analysis by Xray diffraction and microstructural observation by scanning electron microscopy indicated the formation of a uniform and dense oxidation layer. The elimination of surface flaws and pores and the generation of compressive stresses in the surface resulted in a strength increase of the oxidized samples. (C) 2009 Published by Elsevier Ltd.

AnSBBR Applied to a Personal Care Industry Wastewater Treatment: Effects of Fill Time, Volume Treated Per Cycle, and Organic Load

A study was performed regarding the effect of the relation between fill time, volume treated per cycle, and influent concentration at different applied organic loadings on the stability and efficiency of an anaerobic sequencing batch reactor containing immobilized biomass on polyurethane foam with recirculation of the liquid phase (AnSBBR) applied to the treatment of wastewater from a personal care industry. Total cycle length of the reactor was 8 h (480 min). Fill times were 10 min in the batch operation, 4 h in the fed-batch operation, and a 10-min batch followed by a 4-h fed batch in the mixed operation. Settling time was not necessary since the biomass was immobilized and decant time was 10 min. Volume of liquid medium in the reactor was 2.5 L, whereas volume treated per cycle ranged from 0.88 to 2.5 L in accordance with fill time. Influent concentration varied from 300 to 1,425 mg COD/L, resulting in an applied volumetric organic load of 0.9 and 1.5 g COD/L.d. Recirculation flow rate was 20 L/h, and the reactor was maintained at 30 A degrees C. Values of organic matter removal efficiency of filtered effluent samples were below 71% in the batch operations and above 74% in the operations of fed batch followed by batch. Feeding wastewater during part of the operational cycle was beneficial to the system, as it resulted in indirect control over the conversion of substrate into intermediates that would negatively interfere with the biochemical reactions regarding the degradation of organic matter. As a result, the average substrate consumption increased, leading to higher organic removal efficiencies in the fed-batch operations.

Effect of impeller type and stirring frequency on the behavior of an AnSBBR in the treatment of low-strength wastewater

The influence of impeller type and stirring frequency on the performance of a mechanically stirred anaerobic sequencing batch reactor containing immobilized biomass on an inert support (AnSBBR - Anaerobic Sequencing Batch Biofilm Reactor) was evaluated. The biomass was immobilized on polyurethane foam cubes placed in a stainless-steel basket inside a glass cylinder. Each 8-h batch run consisted of three stages: feed (10 min), reaction (460 min) and discharge (10 min) at 30 degrees C. Experiments were performed with four impeller types, i.e., helical, flat-blade, inclined-blade and curved-blade turbines, at stirring frequencies ranging from 100 to 1100 rpm. Synthetic wastewater was used in all experiments with an organic-matter concentration of 530 +/- 37 mg/L measured as chemical oxygen demand (COD). The reactor achieved an organic-matter removal efficiency of around 87% under all investigated conditions. Analysis of the four impeller types and the investigated stirring frequencies showed that mass transfer in the liquid phase was affected not only by the applied stirring frequency but also by the agitation mode imposed by each impeller type. The best reactor performance at all stirring frequencies was obtained when agitation was provided by the flat-blade turbine impeller. (C) 2010 Elsevier Ltd. All rights reserved.

Effect of Organic Load on the Performance and Methane Production of an AnSBBR Treating Effluent from Biodiesel Production

Currently, there is an increasing demand for the production of biodiesel and, consequently, there will be an increasing need to treat wastewaters resulting from the production process of this biofuel. The main objective of this work was, therefore, to investigate the effect of applied volumetric organic load (AVOL) on the efficiency, stability, and methane production of an anaerobic sequencing batch biofilm reactor applied to the treatment of effluent from biodiesel production. As inert support, polyurethane foam cubes were used in the reactor and mixing was accomplished by recirculating the liquid phase. Increase in AVOL resulted in a drop in organic matter removal efficiency and increase in total volatile acids in the effluent. AVOLs of 1.5, 3.0, 4.5 and 6.0 g COD L(-1) day(-1) resulted in removal efficiencies of 92%, 81%, 67%, and 50%, for effluent filtered samples, and 91%, 80%, 63%, and 47%, for non-filtered samples, respectively, whereas total volatile acids concentrations in the effluent amounted to 42, 145, 386 and 729 mg HAc L(-1), respectively. Moreover, on increasing AVOL from 1.5 to 4.5 g COD L(-1) day(-1) methane production increased from 29.5 to 55.5 N mL CH(4) g COD(-1). However, this production dropped to 36.0 N mL CH(4) g COD(-1) when AVOL was increased to 6.0 g COD L(-1) day(-1), likely due to the higher concentration of volatile acids in the reactor. Despite the higher concentration of volatile acids at the highest AVOL, alkalinity supplementation to the influent, in the form of sodium bicarbonate, at a ratio of 0.5-1.3 g NaHCO(3) g COD (fed) (-1) , was sufficient to maintain the pH near neutral and guarantee process stability during reactor operation.

Effect of specific feed volume on the performance of an anaerobic sequencing batch biofilm reactor (AnSBBR) with circulation treating different wastewaters under different organic loads

The objective of this research was to study the behavior of two anaerobic sequencing batch reactors, containing immobilized biomass (AnSBBR), as a function of the ratio of the volume of treated medium in each cycle to the total volume of reaction medium. The reactors, in which mixing was accomplished by recirculation of the liquid phase, were maintained at 30 +/- 1 degrees C and treated different wastewaters in 8-h cycles. The operational conditions imposed had the objective to investigate whether maintenance of a residual volume in the reactor would affect, at the end of each cycle, process efficiency and stability, as well as to verify the intensity of the effect for different types of wastewaters and organic loading rates. The first reactor, with work volume of 2.5 L, treated reconstituted cheese whey at an organic loading rate of 12 g COD.L(-1).d(-1) and presented similar effluent quality for the four conditions under which it was operated: renewal of 100, 70, 50 and 25 % of its work volume at each cycle. Despite the fact that reduction in the renewed volume did not significantly affect effluent quality, in quantitative terms, this reduction resulted in an increase in the amount of organic matter removed by the first reactor. The second reactor, with work volume of 1.8 L, treated synthetic wastewater at organic loading rates of 3 and 5 g COD.L(-1).d(-1) and operated under two conditions for each loading: renewal of 100 and 50 % of its work volume. At the organic loading rate of 3 g COD.L(-1).d(-1), the results showed that both effluent quality and amount of organic matter removed by the second reactor were independent of the treated volume per cycle. At the organic loading rate of 5 g COD.L(-1).d(-1), although the reduction in the renewed volume did not affect the amount of organic matter removed by the reactor, effluent quality improved during reactor operation with total discharge of its volume. In general, results showed process stability under all conditions, evidencing reactor flexibility and the potential to apply this technology in the treatment of different types of wastewater.

Effects of Feed Time, Organic Loading and Shock Loads in Anaerobic Whey Treatment by an AnSBBR with Circulation

The aim of this work was to investigate the effect of different feeding times (2, 4, and 6 h) and organic loading rates (3, 6 and 12 gCOD l(-1) day(-1)) on the performance of an anaerobic sequencing batch reactor containing immobilized biomass, as well as to verify the minimum amount of alkalinity that can be added to the influent. The reactor, in which mixing was achieved by recirculation of the liquid phase, was maintained at 30 +/- 1A degrees C, possessed 2.5 l reactional volume and treated 1.5 l cheese whey in 8-h cycles. Results showed that the effect of feeding time on reactor performance was more pronounced at higher values of organic loading rates (OLR). During operation at an OLR of 3 gCOD l(-1) day(-1), change in feeding time did not affect efficiency of organic matter removal from the reactor. At an OLR of 6 gCOD l(-1) day(-1), reactor efficiency improved in relation to the lower loading rate and tended to drop at longer feeding times. At an OLR of 12 gCOD l(-1) day(-1) the reactor showed to depend more on feeding time; higher feeding times resulted in a decrease in reactor efficiency. Under all conditions shock loads of 24 gCOD l(-1) day(-1) caused an increase in acids concentration in the effluent. However, despite this increase, the reactor regained stability readily and alkalinity supplied to the influent showed to be sufficient to maintain pH close to neutral during operation. Regardless of applied OLR, operation with feeding time of 2 h was which provided improved stability and rendered the process less susceptible to shock loads.

Temperature and feed strategy effects on sulfate and organic matter removal in an AnSBB

The objective of this work was to analyze the interaction effects between temperature, feed strategy and COD/[SO(4)(2-)] levels, maintaining the same ratio, on sulfate and organic matter removal efficiency from a synthetic wastewater. This work is thus a continuation of Archilha et al. (2010) who studied the effect of feed strategy at 30 degrees C using different COD/[SO] ratios and levels. A 3.7-L anaerobic sequencing batch reactor with recirculation of the liquid phase and which contained immobilized biomass on polyurethane foam (AnSBBR) was used to treat 2.0 L synthetic wastewater in 8 h cycles. The temperatures of 15, 22.5 and 30 degrees C with two feed strategies were assessed: (a) batch and (b) batch followed by fed-batch. In strategy (a) the reactor was fed in 10 min with 2 L wastewater containing sulfate and carbon sources. In strategy (b) 1.2 L wastewater (containing only the sulfate source) was fed during the first 10 min of the cycle and the remaining 0.8 L (containing only the carbon source) in 240 min. Based on COD/[SO(4)(2-)] = 1 and on the organic matter (0.5 and 1.5 gCOD/L) and sulfate (0.5 and 1.5 gSO(4)(2-)/L) concentrations, the sulfate and organic matter loading rates applied were 1.5 and 4.5 g/L.d, i.e., same COD/[SO(4)(2-)] ratio (=1) but different levels (1.5/1.5 and 4.5/4.5 gCOD/gSO(4)(2-)). When reactor feed was 1.5 gCOD/L.d and 1.5 gSO(4)(2-)/L.d, gradual feeding (strategy b) showed to favor sulfate and organic matter removal in the investigated temperature range, indicating improved utilization of the electron donor for sulfate reduction. Sulfate removal efficiencies were 87.9; 86.3 and 84.4%, and organic matter removal efficiencies 95.2; 86.5 and 80.8% at operation temperatures of 30; 22.5 and 15 degrees C, respectively. On the other hand, when feeding was 4.5 gCOD/L.d and 4.5 gSO(4)(2-)/L.d, gradual feeding did not favor sulfate removal, indicating that gradual feeding of the electron donor did not improve sulfate reduction. (C) 2011 Elsevier Ltd. All rights reserved.

Heterogeneous modeling of an anaerobic sequencing batch biofilm reactor (ASBBR)

The objective of this study was to estimate the first-order intrinsic kinetic constant (k(1)) and the liquid-phase mass transfer coefficient (k(c)) in a bench-scale anaerobic sequencing batch biofilm reactor (ASBBR) fed with glucose. A dynamic heterogeneous mathematical model, considering two phases (liquid and solid), was developed through mass balances in the liquid and solid phases. The model was adjusted to experimental data obtained from the ASBBR applied for the treatment of glucose-based synthetic wastewater with approximately 500 mg L-1 of glucose, operating in 8 h batch cycles, at 30 degrees C and 300 rpm. The values of the parameters obtained were 0.8911 min(-1) for k(1) and 0.7644 cm min(-1) for kc. The model was validated utilizing the estimated parameters with data obtained from the ASBBR operating in 3 h batch cycles, with a good representation of the experimental behavior. The solid-phase mass transfer flux was found to be the limiting step of the overall glucose conversion rate.