Modifications of MCM-22 zeolite through sequential post-synthesis treatments. Implications on the acidic and catalytic behaviour

Desilication and a combination of alkaline followed by acid treatment were applied to MCM-22 zeolite using two different base concentrations. The samples were characterised by powder X-ray diffraction, Al-27 and Si-29 MAS-NMR spectroscopy, SEM, TEM and low temperature N-2 adsorption. The acidity of the samples was study through pyridine adsorption followed by FTIR spectroscopy and by the analyses of the hydroxyl region. The catalytic behaviour, anticipated by the effect of post-synthesis treatments on the acidity and space available inside the two internal pore systems was evaluated by using the model reaction of m-xylene transformation. The generation of mesoporosity was achieved upon alkaline treatment with 0.05 M NaOH solution and practically no additional gain was obtained when the more concentrate solution, 0.1 M, was used. Instead, Al extraction takes place along with Si, as shown by Si-29 and Al-27 MAS-NMR data, followed by Al deposition as extraframework species. Samples submitted to alkaline plus acid treatments present distinct behaviour. When the lowest NaOH solution was used no relevant effect was observed on the textural characteristics. Additionally, when the acid treatment was performed on an already fragilized MCM-22 structure, due to previous desilication with 0.1 M NaOH solution, the extraction of Al from both internal pore systems promotes their interconnection, evolving from a 2-D to a 3-D porous structure. This transformation has a marked effect in the catalytic behaviour, allowing an increase of m-xylene conversion as a consequence of an easier and faster molecular traffic in the 3-D structure. On the other hand, the continuous deposition of extraframework Al species inside the pores leads to a shape selective effect that privileges the formation of the more valuable isomer p-xylene.

Synthesis and structural characterization of new Piano-stool Ruthenium(II) complexes bearing 1-Butylimidazole heteroaromatic ligand

New cationic ruthenium(II) complexes with the formula [Ru(eta(5)-C5H5)(LL)(1-BuIm)] [Z], with (LL) = 2PPh(3) or DPPE, and Z = CF3SO3-, PF6-, BPh4-, have been synthesized and fully characterized. Spectroscopic and electrochemical studies revealed that the electronic properties of the coordinated 1-butylimidazole were clearly influenced by the nature of the phosphane coligands (LL) and also by the different counter ions. The solid state structures of the six complexes determined by X-ray crystallographic studies, confirmed the expected distorted three-legged piano stool structure. However the geometry of the 1-butylimidazole ligand was found considerably different in all six compounds, being governed by the stereochemistry of the mono and bidentate coligands (PPh3 or DPPE).

Synthesis of organometallic Ruthenium(II) complexes with strong activity against several human canceer cell lines

A new family of "RuCp" (Cp=eta(5)-C5H5) derivatives with bidentate N,O and N,N'-heteroaromatic ligands revealed outstanding cytotoxic properties against several human cell lines namely, A2780, A2780CisR, HT29, MCF7, MDAMB231, and PD. IC50 values were much lower than those found for cisplatin. Crystal structure of compound 4 was determined by X-ray diffraction studies. Density functional theory (DFT) calculations performed for compound 1 showed electronic flow from the ruthenium center to the coordinated bidentate ligand, in agreement with the electrochemical studies and the existence of a metal-to-ligand charge-transfer (MLCT) band evidenced by spectroscopic data.

Evidences for direct magnetic patterning via diffusive transformations using femtosecond laser interferometry

The application of femtosecond laser interferometry to direct patterning of thin-film magnetic alloys is demonstrated. The formation of stripe gratings with submicron periodicities is achieved in Fe1-xVx (x=18-34wt. %) layers, with a difference in magnetic moments up to Delta mu/mu similar to 20 between adjacent stripes but without any significant development of the topographical relief (<1% of the film thickness). The produced gratings exhibit a robust effect of their anisotropy shape on magnetization curves in the film plane. The obtained data witness ultrafast diffusive transformations associated with the process of spinodal decomposition and demonstrate an opportunity for producing magnetic nanostructures with engineered properties upon this basis.

Synthesis of titanate nanostructures using amorphous precursor material and their adsorption/photocatalytic properties

This article reports on a new and swift hydrothermal chemical route to prepare titanate nanostructures (TNS) avoiding the use of crystalline TiO2 as starting material. The synthesis approach uses a commercial solution of TiCl3 as titanium source to prepare an amorphous precursor, circumventing the use of hazardous chemical compounds. The influence of the reaction temperature and dwell autoclave time on the structure and morphology of the synthesised materials was studied. Homogeneous titanate nanotubes with a high length/diameter aspect ratio were synthesised at 160 degrees C and 24 h. A band gap of 3.06 +/- 0.03 eV was determined for the TNS samples prepared in these experimental conditions. This value is red shifted by 0.14 eV compared to the band gap value usually reported for the TiO2 anatase. Moreover, such samples show better adsorption capacity and photocatalytic performance on the dye rhodamine 6G (R6G) photodegradation process than TiO2 nanoparticles. A 98% reduction of the R6G concentration was achieved after 45 min of irradiation of a 10 ppm dye aqueous solution and 1 g L-1 of TNS catalyst.

Optimal design for active damping in sandwich structures using the Direct MultiSearch method

This paper addresses the problem of optimal positioning of surface bonded piezoelectric patches in sandwich plates with viscoelastic core and laminated face layers. The objective is to maximize a set of modal loss factors for a given frequency range using multiobjective topology optimization. Active damping is introduced through co-located negative velocity feedback control. The multiobjective topology optimization problem is solved using the Direct MultiSearch Method. An application to a simply supported sandwich plate is presented with results for the maximization of the first six modal loss factors. The influence of the finite element mesh is analyzed and the results are, to some extent, compared with those obtained using alternative single objective optimization.

Predictors of infant positive, negative and self-direct coping during face to face still-face in a Portuguese preterm sample

Past studies found three types of infant coping behaviour during Face-to-Face Still-Face paradigm (FFSF): a Positive Other-Directed Coping; a Negative Other-Directed Coping and a Self-Directed Coping. In the present study, we investigated whether those types of coping styles are predicted by: infants’ physiological responses; maternal representations of their infant’s temperament; maternal interactive behaviour in free play; and infant birth and medical status. The sample consisted of 46, healthy, prematurely born infants and their mothers. At one month, infant heart rate was collected in basal. At three months old (corrected age), infant heart-rate was registered during FFSF episodes. Mothers described their infants’ temperament using a validated Portuguese temperament scale, at infants three months of corrected age. As well, maternal interactive behaviour was evaluated during a free play situation using CARE-Index. Our findings indicate that positive coping behaviours were correlated with gestational birth weight, heart rate (HR), gestational age, and maternal sensitivity in free play. Gestational age and maternal sensitivity predicted Positive Other-Direct Coping behaviours. Moreover, Positive Other-Direct coping was negatively correlated with HR during Still-Face Episode. Self-directed behaviours were correlated with HR during Still-Face Episode and Recover Episode and with maternal controlling/intrusive behaviour. However, only maternal behaviour predicted Self-direct coping. Early social responses seem to be affected by infants’ birth status and by maternal interactive behaviour. Therefore, internal and external factors together contribute to infant ability to cope and to re-engage after stressful social events.

Aryleneethynylene Trimers Bearing Calix[4]arenes: synthesis, optical properties and self-assembling studies

New homoditopic bis-calix[4]arene-carbazole conjugates, armed with hydrophilic carboxylic acid functions at their lower rims, are disclosed. Evidence for their self-association in solution was gathered from solvatochromic and thermochromic studies, as well as from gel-permeation chromatography analysis. Their ability to function as highly sensitive sensors toward polar electron-deficient aromatic compounds is demonstrated.

Preliminary study of synthesis gas production from water electrolysis, using the ELECTROFUEL (R) concept

This paper describes preliminary work on the generation of synthesis gas from water electrolysis using graphite electrodes without the separation of the generated gases. This is an innovative process, that has no similar work been done earlier. Preliminary tests allowed to establish correlations between the applied current to the electrolyser and flow rate and composition of the generated syngas, as well as a characterisation of generated carbon nanoparticles. The obtained syngas can further be used to produce synthetic liquid fuels, for example, methane, methanol or DME (dimethyl ether) in a catalytic reactor, in further stages of a present ongoing project, using the ELECTROFUEL® concept. The main competitive advantage of this project lies in the built-in of an innovative technology product, from RE (renewable energy) power in remote locations, for example, islands, villages in mountains as an alternative for energy storage for mobility constraints.

Synthesis of titanate nanofibers co-sensitized with ZnS and Bi2S3 nanocrystallites and their application on pollutants removal

The synthesis of nanocomposite materials combining titanate nanofibers (TNF) with nanocrystalline ZnS and Bi2S3 semiconductors is described in this work. The TNF were produced via hydrothermal synthesis and sensitized with the semiconductor nanoparticles, through a single-source precursor decomposition method. ZnS and Bi2S3 nanoparticles were successfully grown onto the TNF's surface and Bi2S3-ZnS/TNF nanocomposite materials with different layouts. The samples' photocatalytic performance was first evaluated through the production of the hydroxyl radical using terephthalic acid as probe molecule. All the tested samples show photocatalytic ability for the production of this oxidizing species. Afterwards, the samples were investigated for the removal of methylene blue. The nanocomposite materials with best adsorption ability were the ZnS/TNF and Bi2S3ZnS/TNF. The dye removal was systematically studied, and the most promising results were obtained considering a sequential combination of an adsorption-photocatalytic degradation process using the Bi2S3ZnS/TNF powder as a highly adsorbent and photocatalyst material. (C) 2015 Elsevier Ltd. All rights reserved.

Matrix converter as unified power flow controller: design and implementation of decoupled direct power controllers

This paper presents the design and implementation of direct power controllers for three-phase matrix converters (MC) operating as Unified Power Flow Controllers (UPFC). Theoretical principles of the decoupled linear power controllers of the MC-UPFC to minimize the cross-coupling between active and reactive power control are established. From the matrix converter based UPFC model with a modified Venturini high frequency PWM modulator, decoupled controllers for the transmission line active (P) and reactive (Q) power direct control are synthesized. Simulation results, obtained from Matlab/Simulink, are presented in order to confirm the proposed approach. Results obtained show decoupled power control, zero error tracking, and fast responses with no overshoot and no steady-state error.

GLODS: Global and Local Optimization using Direct Search

Locating and identifying points as global minimizers is, in general, a hard and time-consuming task. Difficulties increase in the impossibility of using the derivatives of the functions defining the problem. In this work, we propose a new class of methods suited for global derivative-free constrained optimization. Using direct search of directional type, the algorithm alternates between a search step, where potentially good regions are located, and a poll step where the previously located promising regions are explored. This exploitation is made through the launching of several instances of directional direct searches, one in each of the regions of interest. Differently from a simple multistart strategy, direct searches will merge when sufficiently close. The goal is to end with as many direct searches as the number of local minimizers, which would easily allow locating the global extreme value. We describe the algorithmic structure considered, present the corresponding convergence analysis and report numerical results, showing that the proposed method is competitive with currently commonly used global derivative-free optimization solvers.

Materials selection for a set of multiple parts considering manufacturing costs and weight reduction with structural isoperformance using direct multisearch optimization

Materials selection is a matter of great importance to engineering design and software tools are valuable to inform decisions in the early stages of product development. However, when a set of alternative materials is available for the different parts a product is made of, the question of what optimal material mix to choose for a group of parts is not trivial. The engineer/designer therefore goes about this in a part-by-part procedure. Optimizing each part per se can lead to a global sub-optimal solution from the product point of view. An optimization procedure to deal with products with multiple parts, each with discrete design variables, and able to determine the optimal solution assuming different objectives is therefore needed. To solve this multiobjective optimization problem, a new routine based on Direct MultiSearch (DMS) algorithm is created. Results from the Pareto front can help the designer to align his/hers materials selection for a complete set of materials with product attribute objectives, depending on the relative importance of each objective.

Multiobjective optimization of viscoelastic laminated sandwich structures using the Direct MultiSearch method

A multiobjective approach for optimization of passive damping for vibration reduction in sandwich structures is presented in this paper. Constrained optimization is conducted for maximization of modal loss factors and minimization of weight of sandwich beams and plates with elastic laminated constraining layers and a viscoelastic core, with layer thickness and material and laminate layer ply orientation angles as design variables. The problem is solved using the Direct MultiSearch (DMS) solver for derivative-free multiobjective optimization and solutions are compared with alternative ones obtained using genetic algorithms.

Optimization of cruciform specimens for biaxial fatigue loading with direct multi search

In order to correctly assess the biaxial fatigue material properties one must experimentally test different load conditions and stress levels. With the rise of new in-plane biaxial fatigue testing machines, using smaller and more efficient electrical motors, instead of the conventional hydraulic machines, it is necessary to reduce the specimen size and to ensure that the specimen geometry is appropriate for the load capacity installed. At the present time there are no standard specimen's geometries and the indications on literature how to design an efficient test specimen are insufficient. The main goal of this paper is to present the methodology on how to obtain an optimal cruciform specimen geometry, with thickness reduction in the gauge area, appropriate for fatigue crack initiation, as a function of the base material sheet thickness used to build the specimen. The geometry is optimized for maximum stress using several parameters, ensuring that in the gauge area the stress distributions on the loading directions are uniform and maximum with two limit phase shift loading conditions (delta = 0 degrees and (delta = 180 degrees). Therefore the fatigue damage will always initiate on the center of the specimen, avoiding failure outside this region. Using the Renard Series of preferred numbers for the base material sheet thickness as a reference, the reaming geometry parameters are optimized using a derivative-free methodology, called direct multi search (DMS) method. The final optimal geometry as a function of the base material sheet thickness is proposed, as a guide line for cruciform specimens design, and as a possible contribution for a future standard on in-plane biaxial fatigue tests