Effects of Phonon Confinement on Anomalous Thermalization,Energy Transfer,and Upconversion in Ln3+‐Doped Gd2O3 Nanotubes

There is a growing interest in understanding how size‐dependent quantum confinement affects the photoluminescence efficiency, excited‐state dynamics, energy‐transfer and thermalization phenomena in nanophosphors. For lanthanide (Ln³⁺)‐doped nanocrystals, despite the localized 4f states, confinement effects are induced mostly via electron–phonon interactions. In particular, the anomalous thermalization reported so far for a handful of Ln³⁺‐doped nanocrystals has been rationalized by the absence of low‐frequency phonon modes. This nanoconfinement may further impact on the Ln³⁺ luminescence dynamics, such as phonon‐assisted energy transfer or upconversion processes. Here, intriguing and unprecedented anomalous thermalization in Gd₂O₃:Eu³⁺ and Gd₂O₃:Yb³⁺,Er³⁺ nanotubes, exhibiting up to one order of magnitude larger than previously reported for similar materials, is reported. This anomalous thermalization induces unexpected energy transfer from Eu³⁺ C₂ to S₆ crystallographic sites, at 11 K, and ²H_11/2 → ⁴I_15/2 Er³⁺ upconversion emission; it is interpreted on the basis of the discretization of the phonon density of states, easily tuned by varying the annealing temperature (923–1123 K) in the synthesis procedure, and/or the Ln³⁺ concentration (0.16–6.60%).     

Gate delay variability estimation method for parametric yield improvement in nanometer CMOS technology

In digital CMOS circuits, parametric yield improvement may be achieved by reducing the variability of performance and power consumption of individual cell instances. Such improvement of variation robustness can be attained by evaluating parameter variation impact at gate level. Statistical characterization of logic gates are usually obtained by computationally expensive electrical simulations. An efficient gate delay variability estimation method is proposed for variability-aware design. The proposed method has been applied to different topologies (transistor network arrangements) and CMOS gates, and it has been compared to Monte Carlo simulations for data validation, resulting in computation time savings.     

Anthocyanin composition and extractability in berry skin and wine of Vitis vinifera L. cv. Aglianico

BACKGROUND: The present article reports the anthocyanin content in the berry skin and wine of the Italian red grape cultivar Aglianico (clone VCR11 grafted onto 1103 Paulsen), one of the most ancient vines and famous for its deep‐red colour. Anthocyanins were extracted from frozen berry skin in an acidified methanol solution. The extraction mixtures, monitored for 120 h, were analysed by high‐performance liquid chromatography. RESULTS: The extraction from berry skin of delphinidin, petunidin and malvidin appeared to be a time‐independent process, whereas the concentration of peonidin increased linearly with time. Peonidin‐O‐acetyl‐glucoside was transferred from skin more slowly than petunidin‐O‐acetyl‐glucoside and malvidin‐O‐acetyl‐glucoside. The anthocyanin composition of the resulting wine showed that the total anthocyanin content was about one‐tenth of the corresponding berry skin content. The ratio acetyl/coumaroyl anthocyanins in the wine was sharply higher than the value in berry skin (0.85 and 0.10, respectively), indicating an enrichment of acetyl derivatives in the wine. CONCLUSION: Levels of single anthocyanins in wine were not always correlated with those detected in grapes, as they were affected by winemaking. The high values of some anthocyanins in Aglianico wine could ameliorate its quality, increasing the chromatic properties, aging stability and product acceptance. Copyright © 2011 Society of Chemical Industry     

Development of composites based on recycled polyethylene/sugarcane bagasse fibers

In this work, sugarcane bagasse fibers were used as filler in composites having recycled high‐density polyethylene (PEr) as matrix. Because of the poor interaction between fibers surface and the PEr, the surface of bagasse was chemically modified. This modification consists of washing with water at 80°C, a mercerization process using sodium hydroxide and acetylation reaction with acetic anhydride. The chemical modification was characterized by Fourier transform infrared–horizontal attenuated total reflectance (FTIR‐HATR) and ¹³C nuclear magnetic resonance spectroscopies (NMR), thermogravimetric analysis (TGA), and scanning electronic microscopy (SEM). The composites were prepared from modified and unmodified fibers into PEr matrix, containing 5, 10, and 20% (w/w) of fiber. The samples were processed by extrusion and molds were prepared by injection process in order to perform mechanical tests. These materials were analyzed by SEM, TGA, and the water uptake was evaluated. Also, their mechanical properties were analyzed. Morphological analysis indicated that the chemical modification of sugarcane bagasse increased the compatibility between matrix and reinforcement. Tensile, flexural, and impact tests showed that the mechanical properties of the composite were improved compared to PEr due to the presence of the fibers. POLYM. COMPOS., 35:768–774, 2014. © 2013 Society of Plastics Engineers     

Investigating the cutting phenomena in free-form milling using a ball-end cutting tool for die and mold manufacturing

This paper presents an investigation of nonplanar tool-workpiece interactions in free-form milling using a ball-end cutting tool, a technique that is widely applied in the manufacturing of dies and molds. The influence of the cutting speed on the cutting forces, surface quality of the workpiece, and chip formation was evaluated by considering the specific alterations of the contact between tool-surface along the cutting time. A trigonometric equation was developed for identifying the tool-workpiece contact along the toolpath and the point where the tool tip leaves the contact with the workpiece. The experimental validation was carried out in a machining center using a carbide ball-end cutting tool and a workpiece of AISI P20 steel. The experimental results demonstrated the negative effect of the engagement of the tool tip into the cut on machining performance. The length of this engagement depends on the tool and workpiece curvature radii and stock material. When the tool tip center is in the cut region, the material is removed by shearing together with plastic deformation. Such conditions increase the cutting force and surface roughness and lead to an unstable machining process, what was also confirmed by the chips collected.     

The uncapacitated hub location problem in networks under decentralized management

We propose a new hub location model defined by the minimization of costs. The main contribution of this work is to permit the analysis of a hub-and-spoke network operated under “decentralized management”. In this type of network, various transport companies act independently, and each makes its route choices according to its own criteria, which can include cost, time, frequency, security and other factors, including subjective ones. Therefore, due to the diversity of the various companies’ criteria, one can expect that between each origin–destination pair, a fraction of the flow will be carried through hubs and a fraction will be carried by the direct route. to resolve this problem, it becomes necessary to determine the probability that any network user will choose the hub route for each trip to be made (or for each load to be carried). We present an integer programming formulation, subject the new model to experiments with an intermodal general cargo network in Brazil and address questions regarding the solution of the problem in practice.     

Multi-Residue Determination of Pesticides in Açai Tropical Fruit (Euterpe oleracea) by Matrix Solid-Phase Dispersion Combined with Liquid Chromatography

An extraction method based on matrix solid phase dispersion was developed to determine bromuconazole, fenbuconazole, parathion-methyl, kresoxim-methyl, and teflubenzuron in açai using liquid chromatography with ultraviolet diode array detector. The best results were obtained using 1.0 g of açai, 3.0 g of neutral alumina as the dispersant sorbent, and cyclohexane/ethyl acetate (1:1, v/v, 20 mL) as an eluting solvent. The method was validated using açai samples fortified with pesticides at three concentration levels (0.25, 0.5, and 1.0 mg kg^?1). Average recoveries (seven replicates) ranged from 66 to 119 %, with relative standard deviations between 1.4 and 20 %. The detection and quantification limits for açai ranged from 0.02 to 0.05 mg kg^?1 and from 0.05 to 0.1 mg kg^?1, respectively.     

Failure analysis of a gear wheel of a marine azimuth thruster

A failure analysis of two helical gear wheels of a ducted azimuth thruster is presented. The research work consisted of a fracture examination of the material in order to determine the damage root causes. The samples for the failure analysis were obtained from two broken teeth of two helical gear wheels. An analysis through the scanning electron microscope (SEM) was carried out close to the crack initiation. It was found that the damage in the bevel gears were by the fatigue fracture mode. The SEM analysis showed that the gear teeth were under severe contact stress during the operation aggravated by an inappropriate lubricating. A possible misalignment between the pinions and the gear wheels teeth could also contribute for the premature failure.     

Effect of the root canal final rinse protocols on the debris and smear layer removal and on the push‐out strength of an epoxy‐based sealer

The aim of the present study was to evaluate the efficacy of QMiX, SmearClear, and 17% EDTA for the debris and smear layer removal from the root canal and its effects on the push‐out bond strength of an epoxy‐based sealer by scanning electron microscopy (SEM). Forty extracted human canines (n = 10) were assigned to the following final rinse protocols: G1‐distilled water (control), G2–17% EDTA, G3‐SmearClear, and G4‐QMiX. The specimens were submitted to a SEM analysis to evaluate the presence of debris and smear layer, respectively, in the apical or cervical segments. In sequence, forty extracted human maxillary canines with the root canals instrumented were divided into four groups (n = 10) similar to the SEM analysis study. After the filling with AH Plus, the roots were transversally sectioned to obtain dentinal slices. The specimens were submitted to a push‐out bond strength test using an electromechanical testing machine. The statistical analysis for the SEM and push‐out bond strength studies were performed using the Kruskal–Wallis and Dunn tests (α = 5%). There was no difference among the G2, G3, and G4 efficacy in removing the debris and smear layer (P > 0.05). The efficacy of these groups was superior to the control group. The push‐out bond strength values of G2, G3, and G4 were superior to the control group. The ability to remove the debris and smear layer by SmearClear and QMiX was as effective as the 17% EDTA. The final rinse with these solutions promoted similar push‐out bond strength values. Microsc. Res. Tech. 76:533–537, 2013. © 2013 Wiley Periodicals, Inc.