A method to determine volatile contaminants in polyethylene terephthalate (PET) packages by HDC-GC-FID and its application to post-consumer materials

A simple and low cost method to determine volatile contaminants in post-consumer recycled PET flakes was developed and validated by Headspace Dynamic Concentration and Gas Chromatography-Flame Ionization Detection (HDC-GC-FID). The analytical parameters evaluated by using surrogates include: correlation coefficient, detection limit, quantification limit, accuracy, intra-assay precision, and inter-assay precision. In order to compare the efficiency of the proposed method to recognized automated techniques, post-consumer PET packaging samples collected in Brazil were used. GC-MS was used to confirm the identity of the substances identified in the PET packaging. Some of the identified contaminants were estimated in the post-consumer material at concentrations higher than 220 ng.g-1. The findings in this work corroborate data available in the scientific literature pointing out the suitability of the proposed analytical method.

Evaluation of recycled tiles and OSB ceiling materials in closed broiler house prototypes

This study aimed at evaluating the thermal performance of a modular ceiling system for poultry houses. The reduced- and distorted-scale prototypes used ceiling modules made of reforested wood and were covered with recycled long-life package tiles. The following parameters were measured for 21 days: tile internal surface temperature (ST), globe temperature and humidity index (WBGT), and radiant heat load (RHL). Measurements were made at times of highest heat load (11:00 am, 13:00 pm, and 03:00 pm). Collected data were analyzed by "R" statistics software. Means were compared by multiple comparison test (Tukey) and linear regression was performed, both at 5% significance level. The results showed that the prototype with the ceiling was more efficient to reduce internal tile surface temperature; however, this was not sufficient to provide a comfortable environment for broilers during the growout. Therefore, other techniques to provide proper cooling are required in addition to the ceiling.

Effect of therapeutic dose X rays on mechanical and chemical properties of esthetic dental materials

The aim of this study was to investigate the influence of therapeutic dose X rays on the microhardness (MH) and degree of conversion (DC) of two different esthetic restorative dental materials. The materials were photo-activated with a LED light-curing unit using three cure-times: 5, 20 and 40 seconds. The photo-activation was carried out in two distinct periods: before and after irradiation with doses of 5, 35 and 70 Gy, from a 6 MV X rays beam. In accordance with the methodology used, it was conclude that a therapeutic dose does not have a detrimental effect on the photoinitiator molecules, because the photo-activation occurred after they were irradiated. When the irradiation was applied before photo-activation, the materials showed MH improvement, but when photo-activation was performed after irradiation, there was less improvement. However, there was no correlation between MH and DC. Thus, a therapeutic dose applied to cured material can promote linking and breaking of chain bonds in a non-linear way.

Técnica de bombeio e prova para medidas de absorção de estado excitado e de emissão estimulada, em materiais sólidos dopados com íons terras raras

Rare earth ion doped solid state materials are the most important active media of near-infrared and visible lasers and other photonic devices. In these ions, the occurrence of Excited State Absorptions (ESA), from long lived electronic levels, is commonplace. Since ESA can deeply affect the efficiencies of the rare earth emissions, evaluation of these transitions cross sections is of greatest importance in predicting the potential applications of a given material. In this paper a detailed description of the pump-probe technique for ESA measurements is presented, with a review of several examples of applications in Nd3+, Tm3+ and Er3+ doped materials.

Analyzing the n→π* Electronic Transition of Formaldehyde in Water. A Sequential Monte Carlo/Time-Dependent Density Functional Theory

The n→π* absorption transition of formaldehyde in water is analyzed using combined and sequential classical Monte Carlo (MC) simulations and quantum mechanics (QM) calculations. MC simulations generate the liquid solute-solvent structures for subsequent QM calculations. Using time-dependent density functional theory in a localized set of gaussian basis functions (TD-DFT/6-311++G(d,p)) calculations are made on statistically relevant configurations to obtain the average solvatochromic shift. All results presented here use the electrostatic embedding of the solvent. The statistically converged average result obtained of 2300 cm-1 is compared to previous theoretical results available. Analysis is made of the effective dipole moment of the hydrogen-bonded shell and how it could be held responsible for the polarization of the solvent molecules in the outer solvation shells.

Electronic conduction and electrocatalysis by supramolecular tetraruthenated copper porphyrazine films

A new tetraruthenated copper(II)-tetra(3,4-pyridyl)porphyrazine species, [CuTRPyPz]4+, has been synthesized and fully characterized by means of analytical, spectroscopic and electrochemical techniques. This À-conjugated system contrasts with the related meso-tetrapyridylporphyrins by exhibiting strong electronic interaction between the coordinated peripheral complexes and the central ring. Based on favorable À-stacking and electrostatic interactions, layer-by-layer assembled films were successfully generated from the appropriate combination of [CuTRPyPz]4+ with copper(II)-tetrasulfonated phtalocyanine, [CuTSPc]4-. Their conducting and electrocatalytic properties were investigated by means of impedance spectroscopy and rotating disc voltammetry, exhibiting metallic behavior near the Ru(III/II) redox potential, as well as enhanced catalytic activity for the oxidation of nitrite and sulphite ions.

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.

Energy absorbed by electronic body protectors from kicks in a taekwondo competition

Objective: Although some scientific information on electronic body protectors in taekwondo is available, no research has been done to assess the impact of kicks in a competitive situation. The purpose of this study, then, was to assess the energy absorbed by these protectors from kicks performed in an actual taekwondo competition. Methods: Subjects consisted of junior (14-17 years) and senior (>= 18 years) male taekwondo-in, who participated in an open tournament. Data on the energy imparted by valid kicks in Joules (1) were collected from a public visual electronic monitor. Results: Energy was higher for the seniors: 264.31 +/- 56.63 J versus 224.38 +/- 48.23 J for the juniors (eta(2) = 0.121). The seniors scored lower in percent impact but the effect was trivial: 123.46 +/- 24.77% versus 136.70 +/- 26.33% (eta(2) = 0.087). Conclusions: The difference between senior and junior taekwondo-in in absolute energy generated was small, while the difference in relative energy impact was trivial in favour of the junior taekwondo athletes.

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.

Modified Steels for Cold-Forming U-Bolts Used In Leaf Springs Systems

In this work, a low alloy steel and a fabrication process were developed to produce U-Bolts for commercial vehicles. Thus, initially five types of no-heat treated steel were developed with different additions of chrome, nickel, and silicon to produce strain hardening effect during cold-forming processing of the U-Bolts, assuring the required mechanical properties. The new materials exhibited a fine perlite and ferrite microstructure due to aluminum and vanadium additions, well known as grain size refiners. The mechanical properties were evaluated in a servo-hydraulic test machine system-MTS 810 according to ASTM A370-03; E739 and E08m-00 standards. The microstructure and fractography analyses of the cold-formed steels were performed by using optical and scanning electronic microscope techniques. To evaluate the performance of the steels and the production process, fatigue tests were carried out under load control (tensile-tensile), R = 0.1 and f = 30 Hz. The Weibull statistic methodology was used for the analysis of the fatigue results. At the end of this work the 0.21% chrome content steel, Alloy 2, presented the best fatigue performance.

Evaluation technique for determining wheel performance in the grinding of aerospace materials

Nickel-based super alloys are used in a variety of applications in which high-temperature strength and resistance to creep, corrosion, and oxidation are required, such as in aircraft gas turbines, combustion chambers, and automotive engine valves. The properties that make these materials suitable for these applications also make them difficult to grind. Grinding systems for such materials are often built around vitrified cBN (cubic boron nitride) wheels to realize maximum productivity and minimum cost per part. Conditions that yield the most economical combination of stock removal rate and wheel wear are key to the successful implementation of the grinding system. Identifying the transition point for excessive wheel wear is important. The aim of this study is to compare the performance of different cBN wheels when grinding difficult-to-grind (DTG) materials by determining the 'wheel wear characteristic curve', which correlates the G-ratio to the calculated tangential force per abrasive grain. With the proposed methodology, a threshold force per grit above which the wheel wear rate increases rapidly can be quickly identified. A comparison of performance for two abrasive product formulations in the grinding of three materials is presented. The obtained results can be applied for the development of grinding applications for DTG materials.

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.

Electronic properties and hyperfine fields of nickel-related complexes in diamond

We carried out a first-principles investigation on the microscopic properties of nickel-related defect centers in diamond. Several configurations, involving substitutional and interstitial nickel impurities, have been considered either in isolated configurations or forming complexes with other defects, such as vacancies and boron and nitrogen dopants. The results, in terms of spin, symmetry, and hyperfine fields, were compared with the available experimental data on electrically active centers in synthetic diamond. Several microscopic models, previously proposed to explain those data, have been confirmed by this investigation, while some models could be discarded. We also provided insights into the microscopic structure of several of those centers.