The study of ternary carbides formation during SPS consolidation process in the WC-Co-steel system

Tungsten carbide has a wide range of applications, mainly cemented carbides made of WC and Co, as wear resistant materials. However, the high cost of WC-Co powders encourages the use of a substrate to manufacture a functionally graded material (FGM) tool made of WC-Co and a tool steel. These materials join the high wear resistance of the cemented carbide and the toughness of the steel. This work deals with the study interaction of the WC-Co and H13 steel to design a functionally graded material by means of spark plasma sintering (SPS). The SPS, a novel sintering technique reaching the consolidation of the powders at relatively low temperatures and short dwell times, is a promising technique in processing materials. In this study, WC, H13 steel, WC-Co, WC-H13 steel and WC-Co-H13 steel bulk samples were investigated using scanning electron microscopy and X-ray diffraction techniques to evaluate the phase transformations involved during SPS consolidation process. The W(2)C and W(3)Fe(3)C precipitation were identified after the SPS consolidation of the WC and WC-H13 steel samples, respectively. The precipitation Of W(4)Co(2)C was also identified in the WC-Co and WC-Co-H13 steel samples. The WC-H 13 steel and WC-Co-H13 steel were also evaluated after heat treatments at 1100 degrees C for 9 h, which enhanced the chemical interaction and the precipitation of W(3)Fe(3)C and W(4)Co(2)C, respectively. (C) 2009 Elsevier Ltd. All rights reserved.

MODELING ELECTRODIALYSIS AND A PHOTOCHEMICAL PROCESS FOR THEIR INTEGRATION IN SALINE WASTEWATER TREATMENT

Oxidation processes can be used to treat industrial wastewater containing non-biodegradable organic compounds. However, the presence of dissolved salts may inhibit or retard the treatment process. In this study, wastewater desalination by electrodialysis (ED) associated with an advanced oxidation process (photo-Fenton) was applied to an aqueous NaCl solution containing phenol. The influence of process variables on the demineralization factor was investigated for ED in pilot scale and a correlation was obtained between the phenol, salt and water fluxes with the driving force. The oxidation process was investigated in a laboratory batch reactor and a model based on artificial neural networks was developed by fitting the experimental data describing the reaction rate as a function of the input variables. With the experimental parameters of both processes, a dynamic model was developed for ED and a continuous model, using a plug flow reactor approach, for the oxidation process. Finally, the hybrid model simulation could validate different scenarios of the integrated system and can be used for process optimization.

USE OF SOLAR ENERGY IN THE TREATMENT OF WATER CONTAMINATED WITH PHENOL BY PHOTOCHEMICAL PROCESSES

The solar driven photo-Fenton process for treating water containing phenol as a contaminant has been evaluated by means of pilot-scale experiments with a parabolic trough solar reactor (PTR). The effects of Fe(II) (0.04-1.0 mmol L(-1)), H(2)O(2) (7-270 mmol L(-1)), initial phenol concentration (100 and 500 mg C L(-1)), solar radiation, and operation mode (batch and fed-batch) on the process efficiency were investigated. More than 90% of the dissolved organic carbon (DOC) was removed within 3 hours of irradiation or less, a performance equivalent to that of artificially-irradiated reactors, indicating that solar light can be used either as an effective complementary or as an alternative source of photons for the photo-Fenton degradation process. A non-linear multivariable model based on a neural network was fit to the experimental results of batch-mode experiments in order to evaluate the relative importance of the process variables considered on the DOC removal over the reaction time. This included solar radiation, which is not a controlled variable. The observed behavior of the system in batch-mode was compared with fed-batch experiments carried out under similar conditions. The main contribution of the study consists of the results from experiments under different conditions and the discussion of the system behavior. Both constitute important information for the design and scale-up of solar radiation-based photodegradation processes.

Optimal synthesis of Fenton reactor networks for phenol degradation

There is an increasing need to treat effluents contaminated with phenol with advanced oxidation processes (AOPs) to minimize their impact on the environment as well as on bacteriological populations of other wastewater treatment systems. One of the most promising AOPs is the Fenton process that relies on the Fenton reaction. Nevertheless, there are no systematic studies on Fenton reactor networks. The objective of this paper is to develop a strategy for the optimal synthesis of Fenton reactor networks. The strategy is based on a superstructure optimization approach that is represented as a mixed integer non-linear programming (MINLP) model. Network superstructures with multiple Fenton reactors are optimized with the objective of minimizing the sum of capital, operation and depreciation costs of the effluent treatment system. The optimal solutions obtained provide the reactor volumes and network configuration, as well as the quantities of the reactants used in the Fenton process. Examples based on a case study show that multi-reactor networks yield decrease of up to 45% in overall costs for the treatment plant. (C) 2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Vortex configuration flow cell based on low temperature cofired ceramics as a compact chemiluminescence microsystern

The integration of optical detection methods in continuous flow microsystems can highly extend their range of application, as long as some negative effects derived from their scaling down can be minimized. Downsizing affects to a greater extent the sensitivity of systems based on absorbance measurements than the sensitivity of those based on emission ones. However, a careful design of the instrumental setup is needed to maintain the analytical features in both cases. In this work, we present the construction and evaluation of a simple miniaturized optical system, which integrates a novel flow cell configuration to carry out chemiluminescence (CL) measurements using a simple photodiode. It consists of a micro-mixer based on a vortex structure, which has been constructed by means of the low-temperature cofired ceramics (LTCC) technology. This mixer not only efficiently promotes the CL reaction due to the generated high turbulence but also allows the detection to be carried out in the same area, avoiding intensity signal losses. As a demonstration, a flow injection system has been designed and optimized for the detection of cobalt(H) in water samples. It shows a linear response between 2 and 20 mu M with a correlation of r > 0.993, a limit of detection of 1.1 mu M, a repeatability of RSD = 12.4 %, and an analysis time of 17 s. These results demonstrate the suitability of the proposal to the determination of compounds involved in CL reactions by means of an easily constructed versatile device based on low-cost instrumentation.

Thermodynamic modelling of an Al(2)O(3)-MnO system using the ionic model

The thermodynamic assessment of an Al(2)O(3)-MnO pseudo-binary system has been carried out with the use of an ionic model. The use of the electro-neutrality principles in addition to the constitutive relations, between site fractions of the species on each sub-lattice, the thermodynamics descriptions of each solid phase has been determined to make possible the solubility description. Based on the thermodynamics descriptions of each phase in addition to thermo-chemical data obtained from the literature, the Gibbs energy functions were optimized for each phase of the Al(2)O(3)-MnO system with the support of PARROT(R) module from ThemoCalc(R) package. A thermodynamic database was obtained, in agreement with the thermo-chemical data extracted from the literature, to describe the Al(2)O(3)-MnO system including the solubility description of solid phases. (C) 2009 Elsevier Ltd. All rights reserved.

Sweet Basil (Ocimum basilicum) Extracts Obtained by Supercritical Fluid Extraction (SFE): Global Yields, Chemical Composition, Antioxidant Activity, and Estimation of the Cost of Manufacturing

In this work, supercritical technology was used to obtain extracts from Ocimum basilicum (sweet basil) with CO(2) and the cosolvent H(2)O at 1, 10, and 20% (w/w). The raw material was obtained from hydroponic cultivation. The extract`s global yield isotherms, chemical compositions, antioxidant activity, and cost of manufacturing were determined. The extraction assays were done for pressures of 10 to 30 MPa at 303 to 323 K. The identification of the compounds present in the extracts was made by GC-MS and ESI-MS. The antioxidant activity of extracts was determined using the coupled reaction of beta-carotene and linolenic acid. At 1% of cosolvent, the largest global yield was obtained at 10 MPa and 303 K (2%, dry basis-d.b.); at 10% of cosolvent the largest global yield was obtained at 10 and 15 MPa (11%, d.b.), and at 20% of cosolvent the largest global yield was detected at 30 MPa and 303 K (24%, d.b.). The main components identified in the extracts were eugenol, germacrene-D, epi-alpha-cadinol, malic acid, tartaric acid, ramnose, caffeic acid, quinic acid, kaempferol, caffeoylquinic acid, and kaempferol 3-O-glucoside. Sweet basil extracts exhibited high antioxidant activity compared to beta-carotene. Three types of SFE extracts from sweet basil were produced, for which the estimated cost of manufacturing (class 5 type) varied from US$ 47.96 to US$ 1,049.58 per kilogram of dry extract.

Extractive Fermentation of Clavulanic Acid by Streptomyces DAUFPE 3060 Using Aqueous Two-Phase System

The influence of four variables, specifically PEG molar mass (400, 1,000, and 8,000 g/mol), concentrations of PEG and phosphate salts (15, 20, and 25% for both), and agitation intensity (110, 150, and 200 rpm), on clavulanic acid (CA) extraction by extractive fermentation with PEG/phosphate salts aqueous two-phase system was investigated in shaken flasks using a 2(4-1)-fractional factorial design. After selection of the two most significant variables (agitation intensity and PEG molar mass), an optimization study conducted according to a 2(2)-central composite design revealed that 25% PEG 8,000 g/mol and phosphate salts at 240 rpm (run 6) were the best conditions for the extractive fermentation, leading to the best results in terms of partition coefficient (k = 8.2), yield of CA in the PEG-rich phase (eta(T) = 93%) and productivity (P = 5.3 mg/Lh). As a first attempt to make a scale-up of these results, the effectiveness of the extractive fermentation was then checked in a bench-scale bioreactor under conditions as close as possible to the optimum ones determined in flasks. The highest CA concentration obtained in the PEG-rich phase (691 mg/L) was 30% higher than in flasks, thus demonstrating the potential of such a new process, integrating the production and extraction steps, as a promising, low-cost tool to obtain high yields of this and similar products. (C) 2010 American Institute of Chemical Engineers Biotechnol. Prog., 27: 95-103, 2011

LPS Removal from an E. Coli Fermentation Broth Using Aqueous Two-Phase Micellar System

In biotechnology, endotoxin (LPS) removal from recombinant proteins is a critical and challenging step in the preparation of injectable therapeutics, as endotoxin is a natural component of bacterial expression systems widely used to manufacture therapeutic proteins. The viability of large-scale industrial production of recombinant biomolecules of pharmaceutical interest significantly depends on the separation and purification techniques used. The aim of this work was to evaluate the use of aqueous two-phase micellar system (ATPMS) for endotoxin removal from preparations containing recombinant proteins of pharmaceutical interest, such as green fluorescent protein (GFPuv). Partition assays were carried out initially using pure LPS, and afterwards in the presence of E. coli cell lysate. The ATPMS technology proved to be effective in GFPuv recovery, preferentially into the micelle-poor phase (K(GFPuv) < 1.00), and LPS removal into the micelle-rich phase (%REM(LPS) > 98.00%). Therefore, this system can be exploited as the first step for purification in biotechnology processes for removal of higher LPS concentrations. (C) 2010 American Institute of Chemical Engineers Biotechnol. Prog., 26: 1644-1653, 2010

EFFECT OF CHEMICAL INTERESTERIFICATION ON PHYSICOCHEMICAL PROPERTIES AND INDUSTRIAL APPLICATIONS OF CANOLA OIL AND FULLY HYDROGENATED COTTONSEED OIL BLENDS

Blends of canola oil (CO) and fully hydrogenated cottonseed oil (FHCSO), with 20, 25, 30, 35 and 40% FHCSO (w/w) were interesterified under the following conditions: 0.4% sodium methoxide, 500 rpm stirring, 100C, 20 min. The original and interesterified blends were examined for triacylglycerol composition, melting point, solid fat content (SFC) and consistency. Interesterification caused considerable rearrangement of triacylglycerol species, reduction of trisaturated triacylglycerol content and increase in disaturated-monounsaturated and monosaturated-diunsaturated triacylglycerols in all blends, resulting in lowering of respective melting points. The interesterified blends showed reduced SFC at all temperatures and more linear melting profiles if compared with the original blends. Consistency, expressed as yield value, significantly decreased after the reaction. Iso-solid curves indicated eutectic interactions for the original blends, which were eliminated after randomization. The 80:20, 75:25, 70:30 and 65:35 (w/w) CO: FHCSO interesterified blends showed characteristics which are appropriate for their application as soft margarines, spreads, fat for bakery/all-purpose shortenings, and icing shortenings, respectively. PRACTICAL APPLICATIONS Recently, a number of studies have suggested a direct relationship between trans isomers and increased risk of vascular disease. In response, many health organizations have recommended reducing consumption of foods containing trans fatty acids. In this connection, chemical interesterification has proven the main alternative for obtaining plastic fats that have low trans isomer content or are even trans isomer free. This work proposes to evaluate the chemical interesterification of binary blends of canola oil and fully hydrogenated cottonseed oil and the specific potential application of these interesterified blends in food products.

Zero trans fats from soybean oil and fully hydrogenated soybean oil: Physico-chemical properties and food applications

Blends of soybean oil (50) and fully hydrogenated soybean oil (FHSBO), with 10%, 20%, 30%, 40% and 50% FHSBO (w/w) content were interesterified under the following conditions: 0.4% sodium methoxide, 500 rpm stirring, 100 degrees C, 20 min. The original and interesterified blends were examined for triacylglycerol composition, melting point, solid fat content (SFC) and consistency. Interesterification caused considerable rearrangement of triacylglycerol species, reduction of trisaturated triacylglycerol content and increase in monounsaturated and diunsaturated triacylglycerols, resulting in lowering of respective melting points. The interesterified blends displayed reduced SFC at all temperatures and more linear melting profiles as compared with the original blends. Yield values showed increased plasticity in the blends after the reaction. Isosolid diagrams before and after the reaction showed no eutectic interactions. The 90:10, 80:20, 70:30 and 60:40 interesterified SO:FHSBO blends displayed characteristics suited to application, respectively, as liquid shortening, table margarine, baking/confectionery fat and all-purpose shortenings/biscuit-filing base. (C) 2009 Elsevier Ltd. All rights reserved.

Continuous extraction of alpha-toxin from a fermented broth of Clostridium perfringens Type A in perforated rotating disc contactor using aqueous two-phase PEG-phosphate system

A 2(3-1) factorial experimental design was used to evaluate the performance of a perforated rotating disc contactor to extract alpha-toxin from the fermented broth of Clostridium perfringens Type A by aqueous two-phase system of polyethylene glycol-phosphate salts. The influence of three independent variables, specifically the dispersed phase flowrate, the continuous phase flowrate and the disc rotational speed, was investigated on the hold up, the mass transfer coefficient, the separation efficiency and the purification factor, taken as the response variables. The optimum dispersed phase flowrate was 3.0 mL/min for all these responses. Besides, maximum values of hold up (0.80), separation efficiency (0. 10) and purification factor (2.4) were obtained at this flowrate using the lowest disc rotational speed (35 rpm), while the optimum mass transfer coefficient (0. 165 h(-1)) was achieved at the highest agitation level (140 rpm). The results of this study demonstrated that the dispersed phase flowrate strongly influenced the performance of PRDC, in that both the mass transfer coefficient and hold up increased with this parameter. (c) 2007 Elsevier B. V. All rights reserved.

Liquid-liquid extraction of proteases from fermented broth by PEG/citrate aqueous two-phase system

This work deals with the use of an aqueous two-phase system (ATPS) of PEG/citrate to remove proteases from a Clostridium perfringens fermentation broth. To plan the experimental tests and evaluate the corresponding results, three successive experimental designs were employed, for which the PEG molar mass (M-PEG) and concentration (C-PEG), the citrate concentration (C-C) and the pH were selected as independent variables, while the purification factor (PF), the partition coefficient (K), the activity yield (Y) and the selectivity (S) were selected as responses. PF of proteases in the top phase was shown to increase with increasing MPEG and decreasing Cc, whereas a completely opposite trend was observed for K. On the other hand, Y was favored by simultaneous decreases in both these variables, while S decreased with increasing Cc. Therefore, selecting a simultaneous increase in PF and Y as the most desirable result, the best performance of the system was obtained using M-PEG = 10-000 g/mol C-PEG = 22% (w/w) and C-c = 8.0% (w/w) at pH 8.5. Under these conditions, the activity yield was very high (131 %) but the purification factor (4.2) and the selectivity (4.3) were lower than those ensured by more selective purification methods. According to these results, the ATPS seems to be an interesting alternative primary concentration/decontamination step for vaccine preparation from C. perfringens fermented broth. (C) 2007 Elsevier B.V. All rights reserved.

Application of high-resolution electrospray mass spectrometry for the elucidation of the disproportionation reaction of iodobenzene diacetate

Disproportionation reactions take place in solution of (diacetoxyiodo)benzene (DIB) in acetonitrile in the presence of water, giving iodine(V) and iodine(l) species. This redox reaction is accelerated by the presence of water and by increasing the temperature. Several species of the solution of DIB were identified by high-resolution ESI-MS/MS, which allowed the elucidation of the mechanisms of disproportionation for DIB in gas phase and in solution. Key species in the process are the dimers [PhI(CH)OlPh](+) at m/z 440.8864, [PhI(OAc)OlPh](+) at m/z 482.8947, and [PhI(O)(OAc)OlPh](+) at m/z 498.8887. (C) 2008 Elsevier B.V. All rights reserved.

Nestmate recognition in a stingless bee: does the similarity of chemical cues determine guard acceptance?

The ability to discriminate nestmates from non-nestmates is critical to the maintenance of the integrity of social insect colonies. Guard workers compare the chemical cues of an incoming individual with their internal template to determine whether the entrant belongs to their colony. In contrast to honeybees, Apis mellifera, stingless bees have singly mated queens and, therefore, are expected to have a higher chemical homogeneity in their colonies. We tested whether aggressive behaviour of Frieseomelitta varia guards towards nestmate and non-nestmate foragers reflects chemical similarities and dissimilarities, respectively, of cuticular hydrocarbon profiles. We also introduced individuals of Lestrimelitta limao, an obligatory robber species, to test the ability of guards to react effectively to intruders from other taxa. We verified that foraging nestmates were almost invariably accepted, while heterospecific and conspecific non-nestmates were rejected at relatively high rates. However, non-nestmate individuals with higher chemical profile similarity were likely to be accepted by guards. We conclude that guards compare the chemical cuticular blend of incoming individuals and make acceptance decisions according to the similarity of the compounds between the colonies. (c) 2007 The Association for the Study of Animal Behaviour. Published by Elsevier Ltd. All rights reserved.