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The local binding and migration behavior of the proton defect in cubic yttria-stabilized zirconia (YSZ) is studied by first-principles calculations and muon-spin spectroscopy (μSR) measurements. The calculations are based on density-functional theory (DFT) supplemented with a hybrid-functional approach with the proton defect embedded in quasi-random supercells of 10.3 mol% yttria content, where the yttrium–zirconium substitutional defects are charge compensated by oxygen vacancies. Representative migration pathways for the proton comprising both transfer and bond reorientation modes are analysed and linked to the underlying microstructure of the YSZ lattice. The μSR data show the evolution of the diamagnetic fraction corresponding to the muon-isotope analogue with an activation energy of diffusion equal to 0.17 eV. Comparisons between the calculations and the experiment allow an assessment of the character of the short-range migration of the proton particle in cubic YSZ. [ABSTRACT FROM AUTHOR]

Thermography was used to study the propagation of fatigue cracks during cyclic loading of pre-cracked SAE keyhole polycarbonate specimens. A micro-bolometer infrared camera (FLIR A655sc) and a commercially available software program (DeltaTherm2) were employed. The stress intensity factors were determined using a hybrid thermoelastic stress analysis (TSA) technique. The crack growth rate was determined via thermography using two different approaches. The first approach used the output of the crack-tip position from the developed TSA algorithm and the number of cycles between data sets. The second approach used temperature measurement as a new way to determine da/dN (crack growth rate) directly. As a result, da/dN vs ΔK (stress intensity factor range) graphs were plotted and fitted using Paris’ law. A comparison between the resultant da/dN vs ΔK curves and results found in the literature, as well as curves from the finite element method (FEM) simulations showed good agreement. The conclusion was that thermography is a very powerful tool that can detect, measure and monitor fatigue cracks in polycarbonate. [ABSTRACT FROM AUTHOR]

Muonium, a positive muon and an electron, is often used as an experimentally accessible substitute for hydrogen in materials research. In semiconductors and insulators, a large amount of information on the hydrogen behavior is deduced from this analogy; however, it is seldom demonstrated that this procedure is justified. We show here, via a comparison of the hyperfine interactions, that in TiO2 muonium and hydrogen form the same configuration with the same basic electronic structure. A detailed description of the bonding characteristics of the muon to the Ti3+ polaron is presented. The special role of muon motion within the so-called oxygen channel in the rutile structure, which occurs at a lower temperature than for hydrogen, is emphasized. [ABSTRACT FROM AUTHOR]

We present a systematic study of isolated hydrogen in diverse forms of ZrO2 (zirconia), both undoped and stabilized in the cubic phase by additions of transition-metal oxides (Y2O3,Sc2O3, MgO, CaO). Hydrogen is modeled by using muonium as a pseudoisotope in muon-spin spectroscopy experiments. The muon study is also supplemented with first-principles calculations of the hydrogen states in scandia-stabilized zirconia by conventional density-functional theory (DFT) as well as a hybrid-functional approach which admixes a portion of exact exchange to the semilocal DFT exchange. The experimentally observable metastable states accessible by means of the muon implantation allowed us to probe two distinct hydrogen configurations predicted theoretically: an oxygen-bound configuration and a quasiatomic interstitial one with a large isotropic hyperfine constant. The neutral-oxygen-bound configuration is characterized by an electron spreading over the neighboring zirconium cations, forming a polaronic state with a vanishingly small hyperfine interaction at the muon. The atom-like interstitial muonium is observed also in all samples but with different fractions. The hyperfine interaction is isotropic in calcia-doped zirconia [Aiso=3.02(8) GHz], but slightly anisotropic in the nanograin yttria-doped zirconia [Aiso=2.1(1) GHz, D=0.13(2) GHz] probably due to muons stopping close to the interface regions between the nanograins in the latter case. [ABSTRACT FROM AUTHOR]

We present a systematic study of isolated hydrogen in α-TeO2 (paratellurite) by means of muon-spin spectroscopy measurements complemented by ab initio calculations based on density-functional theory (DFT). The observable metastable states accessible by means of the muon implantation allowed us to probe both the donor and the acceptor configurations of hydrogen, as well as to follow their dynamics. A shallow donor state with an ionization energy of 6 meV as well as a deep acceptor state are proposed, together with their atomic-level configurations and associated formation energies obtained from the DFT calculations. The latter show a tendency of interstitial hydrogen to bind strongly to bridging oxygen ions but also to coexist at sites deeper in the interior of the Te-O-Te rings with a more atomiclike character and a defect level in the gap. Atomlike interstitial muonium was observed; it has a hyperfine interaction of about 3.5 GHz. Charge and site changes with temperature are discussed. [ABSTRACT FROM AUTHOR]

The incorporation of interstitial hydrogen in yttria was studied by means of ab Initio calculations based on density-functional theory (DFT) and muonium spin polarization spectroscopy (μSR). The density-functional calculations, based on a semilocal functional within the GGA-PBE and a hybrid functional, uncovered multiple geometrical configurations for the neutral, H°, and the negatively charged, H~, states of hydrogen, thus demonstrating the existence of metastable minimum-energy sites. It was observed that the low-energy configurations for H° and H~ are similar: they prefer to relax in deep, interstitial sites, whereas the equilibrium configurations for the positively charged state, H+, were bond-type configurations with the hydrogen forming a covalent O-H bond with an Ο anion. For all neutral and negative configurations, localized defect levels were found inside the gap. Overall, the results for the formation energies obtained by the two different functionals are qualitatively similar; an amphoteric behavior was found for hydrogen after considering the lowest-energy structures for each charge state. The calculated acceptor transition level, obtained by the hybrid functional and seen near midgap, is consistent with μSR data from literature. The results are consistent with the present μSR data, where the observed diamagnetic signal is attributed to a donor-like muonium at the oxygen-bonded configurations and the paramagnetic signal to an acceptor-like deep muonium at the interstitial sites. [ABSTRACT FROM AUTHOR]

This study evaluated the use of natural coagulants (Moringa oleifera and chitosan) under different conditions with a mixed culture (C1 mixed culture). This culture was used for the biodegradation of hydrocarbons present in the effluent from fuel distribution terminals contaminated with diesel oil and gasoline. The biodegradation was evaluated by two central composite design (CCD) experiments: the first with varying concentrations of Moringa oleifera (MO), drying temperatures (TE) and seed drying times (TI); the second with varying concentrations of chitosan and the hydrochloric acid in which chitosan had been solubilized. The responses monitored in the CCD experiments included the sludge volume index (SVI), the turbidity removal (TR) and the specific rate of oxygen uptake (SOUR). Subsequently, the biodegradation was monitored in a sequencing batch reactor (SBR) under the optimal conditions obtained for each CCD experiment. The results indicated that the best coagulant was chitosan solubilized in 0.25 N HCl at a concentration of 50mg/L. Within five cycles with chitosan as a coagulant, the total organic carbon (TOC) removal increased from 77±1.0% to 82±0.5%, the volatile suspended solids (VSS) increased from 1.4±0.3 to 2.25±0.3 g/L and the total petroleum hydrocarbon (TPH) removal increased from 75±1.0% to 81±0.5%., (Copyright © 2012 Elsevier B.V. All rights reserved.)

This study evaluated the use of coagulants (ferric chloride and aluminium sulphate) and an anionic polyelectrolyte (polyacrylamide) in the settling of a mixed culture (C(1)), which was used for the biodegradation of hydrocarbons present in effluent of fuel distribution terminals contaminated with diesel oil and gasoline. In preliminary investigations conducted in jar tests, the optimal concentrations of coagulant were obtained for further studies. After preliminary tests, biodegradation was evaluated in a central composite design (CCD) with varying concentrations of ferric chloride and polyelectrolyte. Ferric chloride and polyelectrolyte concentrations ranged from 77.9 to 422.12 mg/L and 0.0 to 3.2mg/L, respectively. The responses monitored in CCD experiments included the sludge volume index (SVI), turbidity, and specific rate of oxygen uptake (SOUR), where values of 100mL/g, 840 nephelometric turbidity unit (NTU) and 58 mg O(2)/gh, respectively, were obtained. Subsequently, biodegradation was monitored in a sequencing batch reactor (SBR). The results indicated that within five cycles, total petroleum hydrocarbon (TPH) removal increased from 75 ± 1.0% to 79 ± 0.5%, while the volatile suspended solids (VSS) increased from 1300 to 2500 mg/L., (Copyright © 2010. Published by Elsevier B.V. All rights reserved.)

We examined the effects of aeration interval and agitation speed in an effort to optimize the biodegradation of effluent contaminated with diesel oil and gasoline. The biodegradation process employed a C(1) mixed culture and intermittent aeration. Optimization was performed using central composite design (CCD). The independent variables were aeration interval (X(1)) and agitation speed (X(2)) and the dependent variable was the degree of removal of total petroleum hydrocarbons (TPH). The optimum aeration interval (33h) and agitation speed (110rpm) resulted in TPH removal of 75.9% after 3 days. Five hydrocarbons classes were identified using gas chromatography: paraffins, isoparaffins, olefins, naphthenics, and aromatics. The following reductions were observed: 91.8% for the paraffins, 83.3% for the isoparaffins, 80.9% for the olefins, 39.3% for the naphthenics, and 80.9% for the aromatics. In comparative studies performed under constant aeration (CA), without aeration (WA), and intermittent aeration (IA) conditions, intermittent aeration resulted in the highest TPH removals, with 90% reduction after 22 days. Under the IA condition, the degradation percentages were 99.6% for the paraffins, 94% for the isoparaffins, 95.4% for the olefins, 70.8 for the naphthenics, and 83.4% for the aromatics.

We studied the effects of fuel concentration (diesel and gasoline), nitrogen concentration and culture type on the biodegradation of synthetic effluent similar to what was found at inland fuel distribution terminals. An experimental design with two levels and three variables (2(3)) was used. The mixed cultures used in this study were obtained from lake with a history of petroleum contamination and were named culture C(1) (collected from surface sediment) and C(2) (collected from a depth of approximately 30cm). Of the parameters studied, the ones that had the greatest influence on the removal of total petroleum hydrocarbons (TPH) were a nitrogen concentration of 550mg/L and a fuel concentration of 4% (v/v) in the presence of culture C(1). The biodegradability study showed a TPH removal of 90+/-2% over a process period of 49 days. Analysis using gas chromatography identified 16 hydrocarbons. The aromatic compounds did not degrade as readily as the other hydrocarbons that were identified.