Spectroscopic characterization of schiff base-copper complexes immobilized in smectite clays

Herein, the immobilization of some Schiff base-copper(II) complexes in smectite clays is described as a strategy for the heterogenization of homogeneous catalysts. The obtained materials were characterized by spectroscopic techniques, mostly UV/Vis, EPR, XANES and luminescence spectroscopy. SWy-2 and synthetic Laponite clays were used for the immobilization of two different complexes that have previously shown catalytic activity in the dismutation of superoxide radicals, and disproportionation of hydrogen peroxide. The obtained results indicated the occurrence of an intriguing intramolecular redox process involving copper and the imine ligand at the surface of the clays. These studies are supported by computational calculations.

Nanostructured thin films obtained by electrodeposition over a colloidal crystal template: applications in electrochemical devices

Colloidal particles have been used to template the electrosynthesis of several materials, such as semiconductors, metals and alloys. The method allows good control over the thickness of the resulting material by choosing the appropriate charge applied to the system, and it is able to produce high density deposited materials without shrinkage. These materials are a true model of the template structure and, due to the high surface areas obtained, are very promising for use in electrochemical applications. In the present work, the assembly of monodisperse polystyrene templates was conduced over gold, platinum and glassy carbon substrates in order to show the electrodeposition of an oxide, a conducting polymer and a hybrid inorganic-organic material with applications in the supercapacitor and sensor fields. The performances of the resulting nanostructured films have been compared with the analogue bulk material and the results achieved are depicted in this paper.

Nanochromics: old materials, new structures and architectures for high performance devices

Due to the development of nanoscience, the interest in electrochromism has increased and new assemblies of electrochromic materials at nanoscale leading to higher efficiencies and chromatic contrasts, low switching times and the possibility of color tuning have been developed. These advantages are reached due to the extensive surface area found in nanomaterials and the large amount of organic electrochromic molecules that can be easily attached onto inorganic nanoparticles, as TiO2 or SiO2. Moreover, the direct contact between electrolyte and nanomaterials produces high ionic transfer rates, leading to fast charge compensation, which is essential for high performance electrochromic electrodes. Recently, the layer-by-layer technique was presented as an interesting way to produce different architectures by the combination of both electrochromic nanoparticles and polymers. The present paper shows some of the newest insights into nanochromic science.

Radiocarbon geochronology of the sediments of the São Paulo Bight (southern Brazilian upper margin)

The aim of this work was to generate an inventory of the data on radiocarbon datings obtained from sediments of the São Paulo Bight (southern Brazilian upper margin) and to analyze the data in terms of Late Quaternary sedimentary processes and sedimentation rates. A total of 238 radiocarbon datings from materials collected using differents ampling procedures was considered for this work. The sedimentation rates varied from less than 2 to 68 cm.kyr-1. The highest sedimentation rate values were found in a low-energy (ría type) coastal system as well as in the upwelling zones of Santa Catarina and Cabo Frio. The lowest rates were found on the outer shelf and upper slopes. Our results confirm the strong dependency of the shelf currents, with an emphasis to the terrigenous input from the Río de La Plata outflow which is transported via the Brazilian Coastal Current, as well as of the coupled Brazil Current - Intermediate Western Boundary Current (BC-IWBC) dynamics on the sedimentary processes. At least three indicators ofthe paleo sea level were found at 12200 yr BP (conventional radiocarbon age) (103 meters below sea level - mbsl),8300-8800 cal yr BP (13 mbsl) and 7700-8100 cal yr BP (6 mbsl).

Study of calcium oxalate monohydrate of kidney stones by X-ray diffraction

X-ray powder diffraction was used to study the phase composition of human renal calculi. The stones were collected from 56 donors in Vitoria, Espirito Santo state, southeastern Brazil. An XRD phase quantification revealed that 61% of the studied renal stones were composed exclusively of calcium oxalate [34% formed only by calcium oxalate rnonohydrate (COM) and 27% presents both monohydrate and dihydratate calcium oxalate]. The 39% multi-composed calculi have various other phases such as uric acid and calcium phosphate. Rietveld refinement of XRD data of one apparent monophasic (COM) renal calculus revealed the presence of a small amount of hydroxyapatite. The presence of this second phase and the morphology of the stone (ellipsoidal) indicated that this calculus can be classified as non-papillary type and its nucleation process developed in closed kidney cavities. In order to show some advantages of the X-ray powder diffraction technique, a study of the phase transformation of monohydrate calcium oxalate into calcium carbonate (CaCO(3)) was carried out by annealing of a monophasic COM calculi at 200, 300, and 400 degrees C for 48 h in a N(2) gas atmosphere. The results of the XRD for the heat treated samples is ill good agreement with the thermogravimetric analysis found in the literature and shows that X-ray powder diffraction can be used as a suitable technique to study the composition and phase diagram of renal calculi. (C) 2008 International Centre for Diffraction Data.

Biomass Refinery as a Renewable Complement to the Petroleum Refinery

Biomass Refinery is a sequential of eleven thermochemical processes and one biological process with two initial basic treatments: prehydrolysis for lignocellulosics and low temperature conversion for biomass with medium-to-high content of lipids and proteins. The other ten processes are: effluent treatment plant, furfural plant, biodiesel plant, cellulignin dryer, calcination, fluidized bed boiler, authotermal reforming of cellulignin for syngas production, combined cycle of two-stroke low-speed engine or syngas turbine with fluidized bed boiler heat recovery, GTL technologies and ethanol from cellulose, prehydrolysate and syngas. Any kind of biomass such as wood, agricultural residues, municipal solid waste, seeds, cakes, sludges, excrements and used tires can be processed at the Biomass Refinery. Twelve basic products are generated such as cellulignin, animal feed, electric energy, fuels (ethanol, crude oil, biodiesel, char), petrochemical substitutes, some materials (ash, gypsum, fertilizers, silica, carbon black) and hydrogen. The technology is clean with recovery of energy and reuse of water, acid and effluents. Based on a holistic integration of various disciplines Biomass Refinery maximizes the simultaneous production of food, electric energy, liquid fuels and chemical products and some materials, achieving a competitive position with conventional and fossil fuel technologies, as well as payment capacity for biomass production. Biomass Refinery has a technical economical capability to complement the depletion of the conventional petroleum sources and to capture its GHGs resulting a biomass + petroleum ""green"" combination.

Template-based fluoroethylenepropylene piezoelectrets with tubular channels for transducer applications

We describe the concept, the fabrication, and the most relevant properties of a piezoelectric-polymer system: Two fluoroethylenepropylene (FEP) films with good electret properties are laminated around a specifically designed and prepared polytetrafluoroethylene (PTFE) template at 300 degrees C. After removing the PTFE template, a two-layer FEP film with open tubular channels is obtained. For electric charging, the two-layer FEP system is subjected to a high electric field. The resulting dielectric barrier discharges inside the tubular channels yield a ferroelectret with high piezoelectricity. d(33) coefficients of up to 160 pC/N have already been achieved on the ferroelectret films. After charging at suitable elevated temperatures, the piezoelectricity is stable at temperatures of at least 130 degrees C. Advantages of the transducer films include ease of fabrication at laboratory or industrial scales, a wide range of possible geometrical and processing parameters, straightforward control of the uniformity of the polymer system, flexibility, and versatility of the soft ferroelectrets, and a large potential for device applications e.g., in the areas of biomedicine, communications, production engineering, sensor systems, environmental monitoring, etc.

Brittle and ductile removal modes observed during diamond turning of carbon nanotube composites

Ultraprecision diamond turning was used to evaluate the surface integrity of a carbon nanotube (CNT) composite as a function of the cutting conditions and the percentage of CNT in the epoxy matrix. The effects of cutting conditions on the chip morphology and surface roughness were analysed. The results showed that an increase in the percentage of CNT may influence the mechanism of material removal and consequently improve the quality of the machined surface. When smaller quantities of CNT (0.02 and 0.07 wt %) are present in the matrix, microcracks form within the cutting grooves (perpendicular to the cutting direction). This indicates that the amount of CNT on the epoxy matrix may have a direct influence on the mechanical properties of these materials. Chips removed from the CNT composite samples were analysed by scanning electron microscopy in order to correlate the material removal mechanism and the surface generation process. The area average surface roughness Sa was influenced by the material removal mechanism (Sa ranging from 0.28 to 1.1 mu m).

Phase transformation and residual stress probed by Raman spectroscopy in diamond-turned single crystal silicon

Single-point diamond turning of monocrystalline semiconductors is an important field of research within brittle materials machining. Monocrystalline silicon samples with a (100) orientation have been diamond turned under different cutting conditions (feed rate and depth of cut). Micro-Raman spectroscopy and atomic force microscopy have been used to assess structural alterations and surface finish of the samples diamond turned under ductile and brittle modes. It was found that silicon undergoes a phase transformation when machined in the ductile mode. This phase transformation is evidenced by the creation of an amorphous surface layer after machining which has been probed by Raman scattering. Compressive residual stresses are estimated for the machined surface and it is observed that they decrease with an increase in the feed rate and depth of cut. This behaviour has been attributed to the formation of subsurface cracks when the feed rate is higher than or equal to 2.5 mu m/rev. The surface roughness was observed to vary with the feed rate and the depth of cut. An increase in the surface roughness was influenced by microcrack formation when the feed rate reached 5.0 mu m/rev. Furthermore, a high-pressure phase transformation induced by the tool/material interaction and responsible for the ductile response of this typical brittle material is discussed based upon the presented Raman spectra. The application of this machining technology finds use for a wide range of high quality components, for example the creation of a micrometre-range channel for microfluidic devices as well as microlenses used in the infrared spectrum range.

Analysis of the tip roundness effects on the micro- and macroindentation response of elastic-plastic materials

In this work, the effects of indenter tip roundness oil the load-depth indentation curves were analyzed using finite element modeling. The tip roundness level was Studied based on the ratio between tip radius and maximum penetration depth (R/h(max)), which varied from 0.02 to 1. The proportional Curvature constant (C), the exponent of depth during loading (alpha), the initial unloading slope (S), the correction factor (beta), the level of piling-up or sinking-in (h(c)/h(max)), and the ratio h(max)/h(f) are shown to be strongly influenced by the ratio R/h(max). The hardness (H) was found to be independent of R/h(max) in the range studied. The Oliver and Pharr method was successful in following the variation of h(c)/h(max) with the ratio R/h(max) through the variation of S with the ratio R/h(max). However, this work confirmed the differences between the hardness values calculated using the Oliver-Pharr method and those obtained directly from finite element calculations; differences which derive from the error in area calculation that Occurs when given combinations of indented material properties are present. The ratio of plastic work to total work (W(p)/W(t)) was found to be independent of the ratio R/h(max), which demonstrates that the methods for the Calculation of mechanical properties based on the *indentation energy are potentially not Susceptible to errors caused by tip roundness.

Analysis of the effects of conical indentation variables on the indentation response of elastic-plastic materials through factorial design of experiment

In this work, the effects of conical indentation variables on the load-depth indentation curves were analyzed using finite element modeling and dimensional analysis. A factorial design 2(6) was used with the aim of quantifying the effects of the mechanical properties of the indented material and of the indenter geometry. Analysis was based on the input variables Y/E, R/h(max), n, theta, E, and h(max). The dimensional variables E and h(max) were used such that each value of dimensionless Y/E was obtained with two different values of E and each value of dimensionless R/h(max) was obtained with two different h(max) values. A set of dimensionless functions was defined to analyze the effect of the input variables: Pi(1) = P(1)/Eh(2), Pi(2) = h(c)/h, Pi(3) = H/Y, Pi(4) = S/Eh(max), Pi(6) = h(max)/h(f) and Pi(7) = W(P)/W(T). These six functions were found to depend only on the dimensionless variables studied (Y/E, R/h(max), n, theta). Another dimension less function, Pi(5) = beta, was not well defined for most of the dimensionless variables and the only variable that provided a significant effect on beta was theta. However, beta showed a strong dependence on the fraction of the data selected to fit the unloading curve, which means that beta is especially Susceptible to the error in the Calculation of the initial unloading slope.

Using the ultrasound and instrumented indentation techniques to measure the elastic modulus of engineering materials

Currently, the acoustic and nanoindentation techniques are two of the most used techniques for material elastic modulus measurement. In this article fundamental principles and limitations of both techniques are shown and discussed. Last advances in nanoindentation technique are also reviewed. An experimental study in ceramic, metallic, composite and single crystals was also done. Results shown that ultrasonic technique is capable to provide results in agreement with those reported in literature. However, ultrasonic technique does not allow measuring the elastic modulus of some small samples and single crystals. On the other hand, the nanoindentation technique estimates the elastic modulus values in reasonable agreement with those measured by acoustic methods, particularly in amorphous materials, while in some policristaline materials some deviation from expected values was obtained.

Sliding wear of weld layers with application to cane mill shaft rebuilding

Three welding procedures used to rebuild worn shafts in sugar cane mills were analysed: two submerged arc welding processes and one flux cored arc welding (FCAW) process. Sliding wear tests were in accordance with ASTM G 77 standard, using rings of welding material, blocks of bronze SAE 67, and oil as lubricant. The worn surfaces of rings and blocks were analysed by scanning electron microscopy to determine the wear mechanisms. High contact pressure, high operating temperature, and low relative speed were applied in sliding wear tests to match the conditions in sugar cane mills. Transferred material and evidence of adhesive junctions were detected. Additionally, hardened fragments produced abrasive grooves on the worn surfaces. The welding deposits that presented strong adhesion on the worn surface showed higher mass loss than the materials that presented more abrasive characteristics. Plastic mechanical properties were measured and related to the mass loss. The tested materials presented similar hardness but different yield stress and hardening coefficient. A relationship between wear, strain hardening coefficient, and yield stress was found. The welding deposit that presented the highest hardening coefficient showed the highest mass loss, with evidence of severe adhesion on the worn surface.

NEAR INFRARED SPECTROSCOPY FOR ESTIMATING SUGARCANE BAGASSE CONTENT IN MEDIUM DENSITY FIBERBOARD

Medium density fiberboard (MDF) is an engineered wood product formed by breaking down selected lignin-cellulosic material residuals into fibers, combining it with wax and a resin binder, and then forming panels by applying high temperature and pressure. Because the raw material in the industrial process is ever-changing, the panel industry requires methods for monitoring the composition of their products. The aim of this study was to estimate the ratio of sugarcane (SC) bagasse to Eucalyptus wood in MDF panels using near infrared (NIR) spectroscopy. Principal component analysis (PCA) and partial least square (PLS) regressions were performed. MDF panels having different bagasse contents were easily distinguished from each other by the PCA of their NIR spectra with clearly different patterns of response. The PLS-R models for SC content of these MDF samples presented a strong coefficient of determination (0.96) between the NIR-predicted and Lab-determined values and a low standard error of prediction (similar to 1.5%) in the cross-validations. A key role of resins (adhesives), cellulose, and lignin for such PLS-R calibrations was shown. PLS-DA model correctly classified ninety-four percent of MDF samples by cross-validations and ninety-eight percent of the panels by independent test set. These NIR-based models can be useful to quickly estimate sugarcane bagasse vs. Eucalyptus wood content ratio in unknown MDF samples and to verify the quality of these engineered wood products in an online process.