Bistable regime of surface magnetoplasma waves excitation at a semiconductor-metal interface

The theoretical analysis of the bistability associated with the excitation of surface magnetoplasma waves (SWs) propagating across an external magnetic field at the semiconductor-metal interface by the attenuated total reflection (ATR) method is presented. The Kretschmann-Raether configuration of the ATR method is considered, i.e. a plane electromagnetic wave is incident onto a metal surface through a coupling prism. The third-order nonlinearity of the semiconductor medium is considered in the general form using the formalism of the third-order nonlinear susceptibilities and of the perturbation theory. The examples of the nonlinear mechanisms which influence the SW propagation are given. The analytical and numerical analyses show that the realization of bistable regimes of the SW excitation is possible. The SW amplitude values providing bistability in the structure are evaluated and are reasonably low to provide the experimental observation.

Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic-hydrophobic metal-organic framework

Formed by linking metals or metal clusters through organic linkers, metal-organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal-organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal-organic frameworks in molecular synthetic chemistry as 'protecting groups' to accomplish selective transformations that are difficult using standard chemistry techniques.

Thumb-bangers : exploring the cultural bond between video games and heavy metal

« Heavy Metal Generations » is the fourth volume in the series of papers drawn from the 2012 Music, Metal and Politics international conference (http://www.inter-disciplinary.net/publishing/product/heavy-metal-generations/).

Transition metal complexes derived from ketone based N(4)-substituted thiosemicarbazones: Crystal structures and spectral studies

Thiosemicarbazones have recently attracted considerable attention due to their ability to form tridentate chelates with transition metal ions through either two nitrogen and sulfur atoms, N–N–S or oxygen, nitrogen and sulfur atoms, O–N–S. Considerable interest in thiosemicarbazones and their transition metal complexes has also grown in the areas of biology and chemistry due to biological activities such as antitumoral, fungicidal, bactericidal, antiviral and nonlinear optical properties. They have been used for metal analyses, for device applications related to telecommunications, optical computing, storage and information processing.The versatile applications of metal complexes of thiosemicarbazones in various fields prompted us to synthesize the tridentate NNS-donor thiosemicarbazones and their metal complexes. As a part of our studies on transition metal complexes with these ligands, the researcher undertook the current work with the following objectives. 1. To synthesize and physico-chemically characterize the following thiosemicarbazone ligands: a. Di-2-pyridyl ketone-N(4)-methyl thiosemicarbazone (HDpyMeTsc) b. Di-2-pyridyl ketone-N(4)-ethyl thiosemicarbazone (HDpyETsc) 2. To synthesize oxovanadium(IV), manganese(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes using the synthesized thiosemicarbazones as principal ligands and some anionic coligands. 3. To study the coordination modes of the ligands in metal complexes by using different physicochemical methods like partial elemental analysis, thermogravimetry and by different spectroscopic techniques. 4. To establish the structure of compounds by single crystal XRD studies

Two-dimensional correlation localized surface plasmon resonance spectroscopy for analysis of the interaction between metal nanoparticles and bovine serum albumin

Time-resolved extinction spectra assisted with two-dimensional correlation spectroscopy (2DCOS) analysis and principal component analysis (PCA) were employed to investigate the interaction between bovine serum albumin (BSA) and metal nanoparticles (NPs). A series of localized surface plasmon resonance (LSPR) spectra of metal NPs were measured just after a small amount of BSA was added into metal colloids. Through 2DCOS analysis, remarkable changes in the intensities of the LSPR were observed. The interaction process was totally divided into three periods according to the PCA. Transmission electron microscopy, dynamic light scattering, and ζ-potential measurements were also employed to characterize the interaction between BSA and metal NPs. The addition of BSA brings silver NPs to aggregate through the electrostatic interaction between them, but it has less effect on gold NPs. In a gold and silver mixed system, gold NPs can affect the interaction of silver NPs and BSA, leading it to weaken. The combination of 2DCOS analysis and LSPR spectroscopy is powerful for exploring the LSPR spectra of the metal NP involved systems. This combined technique holds great potential in LSPR sensing through analysis of slight, slim spectral changes of metal colloids

Four new metal complexes with the amino acid deoxyalliin

The solid complexes [Co(C6H10NO2S) 2], [Ni(C6H10NO2S)2], [Cu(C6H10NO2S)2] and [Fe(C 6H10NO2S)2] were obtained from the reaction of cobalt(II), nickel(II), copper(II) and iron(II) salts with the potassium salt of the amino acid deoxyalliin (S-allyl-L-cysteine). Electronic absorption spectra of the complexes are typical of octahedral structures. Infrared spectroscopy confirms the ligand coordination to the metal ions through (COO-) and (NH2) groups. EPR spectrum of the Cu(II) complex indicates a slight distortion of its octahedral symmetry. Mössbauer parameters permitted to identify the presence of iron(II) and iron(III) species in the same sample, both of octahedral geometry. Thermal decomposition of the complexes lead to the formation of CoO, NiO, CuO and Fe2O3 as final products. The compounds show poor solubility in water and in the common organic solvents. ©2005 Sociedade Brasileira de Química.

Caratterizzazione e simulazione di processi di colata in sabbia di ghise sferoidali

L’oggetto principale delle attività di tesi è la caratterizzazione numerico-sperimentale di processi di colata in sabbia di ghisa sferoidale. Inizialmente è stata effettuata un’approfondita indagine bibliografica per comprendere appieno le problematiche relative all’influenza dei parametri del processo fusorio (composizione chimica, trattamento del bagno, velocità di raffreddamento) sulle proprietà microstrutturali e meccaniche di getti ottenuti e per valutare lo stato dell’arte degli strumenti numerici di simulazione delle dinamiche di solidificazione e di previsione delle microstrutture. Sono state definite, realizzate ed impiegate attrezzature sperimentali di colata per la caratterizzazione di leghe rivolte alla misura ed alla differenziazione delle condizioni di processo, in particolare le velocità di raffreddamento, ed atte a validare strumenti di simulazione numerica e modelli previsionali. Inoltre sono stati progettati ed impiegati diversi sistemi per l’acquisizione ed analisi delle temperature all’interno di getti anche di grandi dimensioni. Lo studio, mediante analisi metallografica, di campioni di materiale ottenuto in condizioni differenziate ha confermato l’effetto dei parametri di processo considerati sulle proprietà microstrutturali quali dimensioni dei noduli di grafite e contenuto di ferrite e perlite. In getti di grandi dimensioni si è riscontrata anche una forte influenza dei fenomeni di macrosegregazione e convezione della lega su microstrutture e difettologie dei getti. Le attività si sono concentrate principalmente nella simulazione numerica FEM dei processi fusori studiati e nell’impiego di modelli empirico-analitici per la previsione delle microstrutture. I dati misurati di temperature di processo e di microstrutture sono stati impiegati per la validazione ed ottimizzazione degli strumenti numerici previsionali impiegati su un ampio intervallo di condizioni di processo. L’impiego di strumenti affidabili di simulazione del processo fusorio, attraverso l’implementazione di correlazioni sperimentali microstrutture-proprietà meccaniche, permette la valutazione di proprietà e difettologie dei getti, fornendo un valido aiuto nell’ottimizzazione del prodotto finito e del relativo processo produttivo.

Valutazione numerica del comportamento di materiali compositi sottoposti ad impatti "near edge"

Simulazione numerica con software Abaqus di impatti a bassa energia su laminati di fibra di carbonio con matrice epossidica per la previsione della formazione di delaminazioni interne. Confronto tra impatti centrali al provino e in prossimità del bordo.

Fracture strength of drilled wafers: study of the stress concentration factor and determination of the weibull distribution of the fracture stress

In the photovoltaic field, the back contact solar cells technology has appeared as an alternative to the traditional silicon modules. This new type of cells places both positive and negative contacts on the back side of the cells maximizing the exposed surface to the light and making easier the interconnection of the cells in the module. The Emitter Wrap-Through solar cell structure presents thousands of tiny holes to wrap the emitter from the front surface to the rear surface. These holes are made in a first step over the silicon wafers by means of a laser drilling process. This step is quite harmful from a mechanical point of view since holes act as stress concentrators leading to a reduction in the strength of these wafers. This paper presents the results of the strength characterization of drilled wafers. The study is carried out testing the samples with the ring on ring device. Finite Element models are developed to simulate the tests. The stress concentration factor of the drilled wafers under this load conditions is determined from the FE analysis. Moreover, the material strength is characterized fitting the fracture stress of the samples to a three-parameter Weibull cumulative distribution function. The parameters obtained are compared with the ones obtained in the analysis of a set of samples without holes to validate the method employed for the study of the strength of silicon drilled wafers.

Metal transfer mapping for FCAW process by using near-infrared filming

In the Flux Cored Arc Welding (FCAW) process, the transfer of filler metal (metal transfer modes) to the base material to accomplish the weld bead determines the weld quality and therefore studies of such phenomena is demanded. Thus, in this work, the metal transfer through the FCAW process is investigated by filming the phenomena with the assist of near infrared visualization. During the literature survey, it was found that this technic has not been used so far for analyzing the FCAW process. It must be pointed out that the radiation emitted from the weld arc, fumes and particles (spattering) in this process represent a barrier for these studies based in the process visualization. The monitoring of metal transfer for FCAW process was carried out within the operational envelope of voltage and wire feed speed with the electrode E71T-1 (1.2 mm diameter) and Ar+25%CO2 as a shielding gas. A local developed near infrared filming with frame rate of 300 Hz was employed for metal transfer visualization in order to contribute to a better understanding of this process and evaluating characteristics of metal transfer, unlike previous studies, which used shadowgraph technique. It can clearly be seen how the droplet is created and transferred in this process and also identify the different modes of metal transfer by changing the parameters of voltage and wire feed speed in metal transfer maps. The final result of this study is the metal transfer mode maps, which establish suitable conditions and provide the basis for developing arc control strategies for the FCAW process.

A geometric study of liquid retention in open-cell metal foams

Open-cell metal foams show promise as an emerging novel material for heat exchanger applications. The high surface-area-to-volume ratio suggests increased compactness and decrease in weight of heat exchanger designs. However, the metal foam structure appears conducive to condensate retention, which would degenerate heat transfer performance. This research investigates the condensate retention behavior of aluminum open-cell metal foams through the use of static dip tests and geometrical classification via X-ray Micro-Computed Tomography. Aluminum open-cell metal foam samples of 5, 10, 20, and 40 pores per inch (PPI), all having a void fraction greater than 90%, were included in this investigation. In order to model the condensate retention behavior of metal foams, a clearer understanding of the geometry was required. After exploring the ideal geometries presented in the open literature, X-ray Micro-Computed Tomography was employed to classify the actual geometry of the metal foam samples. The images obtained were analyzed using specialized software from which geometric information including strut length and pore shapes were extracted. The results discerned a high variability in ligament length, as well as features supporting the ideal geometry known as the Weaire-Phelan unit cell. The static dip tests consisted of submerging the metal foam samples in a liquid, then allowing gravity-induced drainage until steady-state was reached and the liquid remaining in the metal foam sample was measured. Three different liquids, water, ethylene glycol, and 91% isopropyl alcohol, were employed. The behaviors of untreated samples were compared to samples subjected to a Beomite surface treatment process, and no significant differences in retention behavior were discovered. The dip test results revealed two distinct regions of condensate retention, each holding approximately half of the total liquid retained by the sample. As expected, condensate retention increased as the pores sizes decreased. A model based on surface tension was developed to predict the condensate retention in the metal foam samples and verified using a regular mesh. Applying the model to both the ideal and actual metal foam geometries showed good agreement with the dip test results in this study.

Stability of hydrotalcites formed from Bayer refinery environmental control processes

Bauxite refinery residues (red mud) are derived from the Bayer process by the digestion of crushed bauxite in concentrated sodium hydroxide at elevated temperatures and pressures. This slurry residue, if untreated, is unsuitable for discharge directly into the environment and is usually stored in tailing dams. The liquid portion has the potential for discharge, but requires pre-treatment before this can occur. The seawater neutralisation treatment facilitates a significant reduction in pH and dissolved metal concentrations, through the precipitation of hydrotalcite-like compounds and some other Mg, Ca, and Al hydroxide and carbonate minerals. The hydrotalcite-like compounds, precipitated during seawater neutralisation, also remove a range of transition metals, oxy-anions and other anionic species through a combination of intercalation and adsorption reactions: smaller anions are intercalated into the hydrotalcite matrix, while larger molecules are adsorbed on the particle surfaces. A phenomenon known as ‘reversion’ can occur if the seawater neutralisation process is not properly controlled. Reversion causes an increase in the pH and dissolved impurity levels of the neutralised effluent, rendering it unsuitable for discharge. It is believed that slow dissolution of components of the red mud residue and compounds formed during the neutralisation process are responsible for reversion. This investigation looked at characterising natural hydrotalcite (Mg6Al2(OH)16(CO3)∙4H2O) and ‘Bayer’ hydrotalcite (synthesised using the seawater neutralisation process) using a variety of techniques including X-ray diffraction, infrared and Raman spectroscopy, and thermogravimetric analysis. This investigation showed that Bayer hydrotalcite is comprised of a mixture of 3:1 and 4:1 hydrotalcite structures and exhibited similar chemical characteristic to the 4:1 synthetic hydrotalcite. Hydrotalcite formed from the seawater neutralisation of Bauxite refinery residues has been found not to cause reversion. Other components in red mud were investigated to determine the cause of reversion and this investigation found three components that contributed to reversion: 1) tricalcium aluminate, 2) hydrocalumite and 3) calcium hydroxide. Increasing the amount of magnesium in the neutralisation process has been found to be successful in reducing reversion.

Premonolayer oxidation of nanostructured gold : an important factor influencing electrocatalytic activity

The study of the electrodeposition of polycrystalline gold in aqueous solution is important from the viewpoint that in electrocatalysis applications ill-defined micro- and nanostructured surfaces are often employed. In this work, the morphology of gold was controlled by the electrodeposition potential and the introduction of Pb(CH3COO)2•3H2O into the plating solution to give either smooth or nanostructured gold crystallites or large dendritic structures which have been characterized by scanning electron microscopy (SEM). The latter structures were achieved through a novel in situ galvanic replacement of lead with AuCl4−(aq) during the course of gold electrodeposition. The electrochemical behavior of electrodeposited gold in the double layer region was studied in acidic and alkaline media and related to electrocatalytic performance for the oxidation of hydrogen peroxide and methanol. It was found that electrodeposited gold is a significantly better electrocatalyst than a polished gold electrode; however, performance is highly dependent on the chosen deposition parameters. The fabrication of a deposit with highly active surface states, comparable to those achieved at severely disrupted metal surfaces through thermal and electrochemical methods, does not result in the most effective electrocatalyst. This is due to significant premonolayer oxidation that occurs in the double layer region of the electrodeposited gold. In particular, in alkaline solution, where gold usually shows the most electrocatalytic activity, these active surface states may be overoxidized and inhibit the electrocatalytic reaction. However, the activity and morphology of an electrodeposited film can be tailored whereby electrodeposited gold that exhibits nanostructure within the crystallites on the surface demonstrated enhanced electrocatalytic activity compared to smaller smooth gold crystallites and larger dendritic structures in potential regions well within the double layer region.

Synthesis and Spectroscopic Investigations of Complexes of Lanthanide Nitrates with N-(4-Hethyl-2-Pyridyl)-Acetamide

New complexes of Lanthanide nitrates with N-(4-methyl-2-pyridyl)-acetamide (4-me-aapH) of the general formulae. [Ln(4-me-aapH)2] [NO3] (where Ln=La=La-Yb and Y)have been synthesized and haracterised by chemical analysis, molar conductivity and physical methods such as infrared, 13C NMR an electronic spectra in the visible region. Molar conductance and infrared data point to the presence to the coordinated nitrates groups. Infrared and 13C NMR data have been interpreted in terms of the coordination of the legand to the metal ion through the oxygen of the secondary amide and nitrogen of the hetrocyclic ring, in a bidentate fashion. Coordination number of ten seems probable for the complexes.