Relation between photoluminescence emission and local order-disorder in the CaTiO3 lattice modifier

In this letter, the authors propose that photoluminescence emission in CaTiO3 is affected not only by disorder in the lattice former but also by structural disorder in the lattice modifier. Structural disorder was evaluated by Ti, Ca K-edge x-ray absorption near-edge structure experiments and by photoluminescence emission. The preedge feature of the Ca K edge was related to the intensity of photoluminescence emission. The results of the preedge feature of the Ca K-edge x-ray absorption near-edge structure confirm the presence of different Ca coordination numbers, namely, Ca-O-11 and Ca-O-12. (c) 2007 American Institute of Physics.

Sensitized thulium blue upconversion emission in Nd3+/Tm3+/Yb3+ triply doped lead and cadmium germanate glass excited around 800 nm

Bright blue upconversion emission by thulium ions in PbGeO3-PbF2-CdF2 glass triply doped with Nd3+-Tm3+-Yb3+ under diode laser excitation around 800 nm is reported. The results revealed that the Nd3+/Tm3+/Yb3+-codoped sample generated ten times more 475 nm blue upconversion fluorescence than the Yb3+-sensitized Tm3+-doped one, under the same excitation power. The upconversion process also showed a strong dependence upon the Yb3+ concentration. The results also indicated that the neodymium ions played a major role in the upconversion process by transfering the 800 nm excitation to thulium ions. The population of the Tm3+ ions (1)G(4) emitting level was accomplished through a multiion interaction involving ground-state absorption of pump photons around 800 nm by the Nd3+(I-4(9/2)-->H-2(9/2), F-4(5/2)) and Tm3+(H-3(6)-->F-3(4)) ions followed by energy-transfer processes involving the Nd3+-Yb3+(F-4(3/2), F-2(7/2)-->I-4(11/2), F-2(5/2)) and Yb3+-Tm3+(F-2(5/2), F-3(4)-->F-2(7/2), (1)G(4)) pairs. (C) 2003 American Institute of Physics.

Photoluminescence in amorphous zirconium titanate

Photoluminescence at room temperature was observed in amorphous zirconium titanate obtained from the polymeric precursor method. This was the first time in which PL was noticed in an amorphous compound made of two network formers. The PL spectra could be deconvoluted into two bands, whose center 1 was located from 540 nm to 552 nm and center 2 from 625 nm to 641 nm. The co-existence of fivefold and sixfold oxygen coordination of titanium and/or zirconium could be the origin of the radiative recombination of electron-hole pairs in amorphous ZT, which may be responsible for the emission of the photoluminescence.

Twentyfold blue upconversion emission enhancement through thermal effects in Pr3+/Yb3+-codoped fluoroindate glasses excited at 1.064 mu m

Infrared-to-visible upconversion emission enhancement through thermal effects in Yb3+-sensitized Pr3+-doped fluoroindate glasses excited at 1.064 mu m is investigated. A twentyfold increase in the 485 nm blue emission intensity as the sample temperature was varied from 20 to 260 degrees C was observed. The visible upconversion fluorescence enhancement is ascribed to the temperature dependent multiphonon-assisted anti-Stokes excitation of the ytterbium sensitizer and excited-state absorption of the praseodymium acceptor. A model based upon conventional rate equations considering a temperature dependent effective absorption cross section for the F-2(7/2)-->F-2(5/2) transition of the Yb3+ and (1)G(4)-->P-3(0) excited-state absorption of the Pr3+, agrees very well with the experimental results. (C) 2000 American Institute of Physics. [S0021-8979(00)08209-8].

Red-green-blue upconversion emission and energy-transfer between Tm3+ and Er3+ ions in tellurite glasses excited at 1.064 mu m

Red, green, and blue emission through frequency upconversion and energy-transfer processes in tellurite glasses doped with Tm3+ and Er3+ excited at 1.064 mum is investigated. The Tm3+/Er3+-codoped samples produced intense upconversion emission signals at around 480, 530, 550 and 660 nm. The 480 nm blue emission was originated from the (1)G(4)-->H-3(6) transition of the Tm3+ ions excited by a multiphoton stepwise phonon-assisted excited-state absorption process. The 5 30, 5 50 nm green and 660 mn red upconversion luminescences were identified as originating from the H-2(11/2), S-4(3/2) --> I-4(15/2) and F-4(9/2) --> I-4(15/2) transitions of the Er3+ ions, respectively, populated via efficient cross-relaxation processes and excited-state absorption. White light generation employing a single infrared excitation source is also examined. (C) 2003 Elsevier B.V. (USA). All rights reserved.

Detection of cracks in scratching tests in ceramic materials through acoustic emission

The mechanisms of material removal and the interactions among scratches performed in ceramic materials were investigated using acoustic emission signals, and scanning electron microscopy, in scratching experiments. Several testing conditions were used to produce different types of removing mechanism on a glass as well as on a polycrystalline alumina sample composed by heterogeneous grain size. It is known that the material removing process on a polycrystalline ceramic involves intergranular microfracture and grain dislodgement, unlike the chipping produced by the extension of lateral cracks in non-granular materials, such as glass. Distinct settings for velocities, loads, and two types of diamond indenter were tested. The material removal was carried out by three different methods of scratching: single passes, repeated overlapping passes, and parallel scratches. As a general result, there was a clear relationship between the acoustic emission signals and the damage intensity occurred in the material removal. More specifically, there were differences in the acoustic emission signal levels in the scratches made on the alumina and on the glass owing to the material removal mechanisms associated with the structure of these materials. A gradual increase in the acoustic emission levels was observed when the number of repeated passes was increased as a result of the damage accumulation process followed by severe material removal. It was also noticed that the acoustic emission signals were capable of reflecting the interactions between two parallel scratches.

On-line determination of Sb(III) and total Sb using baker's yeast immobilized on polyurethane foam and hydride generation inductively coupled plasma optical emission spectrometry

The yeast Saccharomyces cerevisiae was immobilized in cubes of polyurethane foam and the ability of this immobilized material to separate Sb(III) and Sb(V) was investigated. A method based on sequential determination of total Sb (after on-line reduction of Sb(V) to Sb(III) with thiourea) and Sb(Ill) (after on-line solid-liquid phase extraction) by hydride generation inductively coupled plasma optical emission spectrometry is proposed. A flow system assembled with solenoid valves was used to manage all stages of the process. The effects of pH, sample loading and elution flow rates on solid-liquid phase extraction of Sb(III) were evaluated. Also, the parameters related to online pre-reduction (reaction coil and flow rates) were optimized. Detection limits of 0.8 and 0.15 mu g L-1 were obtained for total Sb and Sb (III), respectively. The proposed method was applied to the analysis of river water and effluent samples. The results obtained for the determination of total Sb were in agreement with expected values, including the river water Standard Reference Material 1640 certified by the National Institute of Standards and Technology (NIST). Recoveries of Sb(III) and Sb(V) in spiked samples were between 81 19 and I I I 15% when 120 s of sample loading were used. (c) 2006 Elsevier B.V. All rights reserved.

Energy-transfer mechanisms and emission quantum yields in Eu3+-based siloxane-poly(oxyethylene) nanohybrids

We report the energy-transfer mechanisms and emission quantum yield measurements of sol-gel-derived Eu3+-based nanohybrids. The matrix of these materials, classified as diureasils and termed U(2000) and U(600), includes urea cross-links between a siliceous backbone and polyether-based segments of two molecular weights, 2000 and 600, respectively. These materials are full-color emitters in which the Eu3+ (5)Do --> F-7(0-4) lines merge with the broad green-blue emission of the nanoscopic matrix's backbone. The excitation spectra show the presence of a large broad band (similar to 27000-29000 cm(-1)) undoubtedly assigned to a ligand-to-metal charge-transfer state. Emission quantum yields range from 2% to 13.0% depending on the polymer molecular weight and Eu3+ concentration. Energy transfer between the hybrid hosts and the cations arises from two different and independent processes: the charge-transfer band and energy transfer from the hybrid's emitting centers. The activation of the latter mechanisms induces a decrease in the emission quantum yields (relative to undoped nanohybrids) and permits a fine-tuning of the emission chromaticity across the Comission Internacionalle d'Eclairage diagram, e.g., (x, y) color coordinates from (0.21, 0.24) to (0.39, 0.36). Moreover, that activation depends noticeably on the ion local coordination. For the diureasils with longer polymer chains, energy transfer occurs as the Eu3+ coordination involves the carbonyl-type oxygen atoms of the urea bridges, which are located near the hybrid's host emitting centers. on the contrary, in the U(600)-based diureasils, the Eu3+ ions are coordinated to the polymer chains, and therefore, the distance between the hybrid's emitting centers and the metal ions is large enough to allow efficient energy-transfer mechanisms.

Intense red upconversion emission in infrared excited holmium-doped PbGeO3-PbF2-CdF2 transparent glass ceramic

Intense red upconversion emission around 650 nm in PbGeO3-PbF2-CdF2 transparent glass ceramic containing beta-PbF2:Ho3+ nanocrystals, is presented. The holmium-doped vitroceramic samples were excited by a 980 nm diode laser source. The 650 nm upconversion signal was assigned to the F-5(5) --> I-5(8) transition of holmium ions. Very low intensity signals around 490 and 540 nm corresponding to the F-5(2,3) --> I-5(8) and S-4(2), F-5(4) --> I-5(8) transitions, respectively, were also detected. The upconversion excitation mechanism was achieved through a combination of stepwise phonon-assisted multiphoton absorption, cross-relaxation processes involving pairs of holmium ions, and excited-state absorption. Using a diode laser pump source around 850 nm green upconversion emission around 540 nm was the observed predominant signal. (C) 2004 Elsevier B.V. All rights reserved.

Effect of tannin levels in sorghum silage and concentrate supplementation on apparent digestibility and methane emission in beef cattle

This study evaluated the effect of diets containing sorghum silages with higher (HT) and lower-tannin (LT) concentrations supplemented with concentrate or urea on intake, digestibility, ruminal digestibility, methane emission and rumen parameters in beef cattle. Four treatments were distributed according to a 2 x 2 factorial arrangement in a duplicate 4 x 4 Latin square: LT sorghum silage + urea, LT sorghum silage + concentrate, HT sorghum silage + urea, and HT sorghum silage + concentrate. Total digestibility of the organic matter was higher when concentrate was included in the diet (0.749 and 0.753 in the LT and HT treatments, respectively). It was observed lower ruminal apparent digested matter of neutral detergent fiber in HT diets. There was no effect of tannin levels on digestibility and methane emission. The supplementation with concentrate in the LT diet decreased gas losses as a function of gross energy intake in comparison to the supplementation of the diet with urea. These results suggest the potential of concentrate supplementation to minimize energy loss as methane emission by ruminants and increase the efficiency of energy utilization. (c) 2006 Elsevier B.V. All rights reserved.

Highly intense violet-blue light emission at room temperature in structurally disordered SrZrO3 powders

Violet-blue photoluminescence was produced at room temperature in a structurally disordered SrZrO3 perovskite structure with a 350.7 nm excitation line. The intensity of this emission was higher than that of any other perovskites previously studied. The authors discuss the role of structural order-disorder that favors the self-trapping of electrons and charge transference, as well as a model to elucidate the mechanism that triggers photoluminescence. In this model the wide band model, the most important events occur before excitation. (c) 2007 American Institute of Physics.

Speciation analysis of Sn(II) and Sn(IV) using baker's yeast and inductively coupled plasma optical emission spectrometry

The use of Saccharomyces cerevisiae as a substrate to selectively retain Sn(II) and Sn(IV) has been investigated. Several factors affecting the retention of the analytes by yeast, such as pH, amount of biomass, temperature and time of contact were evaluated. Based on this study, a method for determination of Sn(II) and Sn(IV) combining inductively coupled plasma optical emission spectrometry (ICP OES) and solid phase extraction using Saccharomyces cerevisiae is proposed. The procedure consists of the selective retention of Sn(IV) by yeast at pH = 2.0 while Sn(II) remains in solution. Determination of tin in the solid phase was easily carried out by submitting a slurry of the yeast (0.5 g/40 mL) directly to ICP OES. The precision of the extraction procedure was characterized by an RSD lower than 4%. The detection limits of tin (3 sigma) in the solid phase and the liquid phase were 1.1 and 0.7 mu g L-1, respectively. The proposed approach was evaluated for determination of Sn(II) and Sn(IV) in spiked river water and real samples of industrial waste water (untreated and treated). For all samples, recoveries of spiked Sn(II) and Sn(IV) were between 85 and 112%.

Mechanisms behind blue, green, and red photoluminescence emissions in CaWO4 and CaMoO4 powders

A combined experimental and theoretical study was conducted to analyze the photoluminescence (PL) properties of ordered and disordered CaWO4 (CW) and CaMoO4 (CM) powders. Two mechanisms were found to be responsible for photoluminescence emission in CW and CM powders. The first one, in the disordered powders, was caused by oxygen complex vacancies [MO3 center dot V-O(x)], [MO3 center dot V-O(center dot)] and [MO3 center dot V-O(center dot center dot)], where M=W or Mo, which leads to additional levels in the band gap. The second mechanism, in ordered powders, was caused by an intrinsic slight distortion of the [WO4] or [MoO4] tetrahedral in the short range. (c) 2007 American Institute of Physics.

Determination of Cd(II) and Cd-metallothioneins in biological extracts using baker's yeast and inductively coupled plasma optical emission spectrometry

The use of Saccharomyces cerevisiae as a sorbent material to separate Cd(II) and Cd-metallothionein complex (Cd-MT) has been explored. Solid-liquid phase extractions were carried out in batch mode and the main parameters of the process (pH, temperature, time of incubation, amount of biomass and analyte) were evaluated. Under optimized conditions, the yeast quantitatively retain (94 +/- 5%) the Cd(II) while 97 +/- 2% of the Cd-MT remain in the supernatant. on base of the findings of this study, a simple method is proposed to determine Cd(II) and Cd-MT in cytosols extracted from mouse kidney and crab hepatopancreas. Inductively coupled plasma optical emission spectrometry was used to quantify the analytes in solid and liquid phase. Determination of Cd in the solid phase was carried out by introducing a slurry of the yeast (0.0625 g/10 mL) directly to the inductively coupled plasma optical emission spectrometer. Mixed standards solutions, which also have been submitted to the extraction procedure, were used to quantify the analytes in the samples. Thus, matrix effects due to nebulization of the slurry were overcame. Limits of detection (3 sigma) for Cd(II) and Cd-MT were 1.5 and 1.2 mu g L-1, respectively. Relative standard deviations of signals were 4.2% for measurements in the slurry of solid phase and 2.1% for measurements in the liquid phase. Recoveries of the analytes in cytosol samples were between 76 and 114%. The concentrations of Cd(II) (2.4 +/- 0.5 mu g L-1) and Cd-MT (3.0 +/- 0.5 mu g L-1) found by using the proposed approach were close to those found by tangential-flow ultrafiltration technique (2.6 +/- 0.7 mu g L-1 for Cd(II) and 3.7 +/- 1.7 mu g L-1 for Cd-MT).

Microwave synthesis of YAG : Eu by sol-gel methodology

Yttrium-aluminum oxides are interesting compounds and they have been extensively used as host for lasers and phosphors, due to their stable physical and chemical properties. The fabrication of yttrium-aluminum garnet (YAG) has been investigated thoroughly. Single-crystal YAG is expensive and to produce it a new way has been investigated. This process consists of modifying the methodology of reagents mixture and the process of heating them. The microwave irradiation is used to heat-treat the oxide mixture. The traditional synthesis of YAG powders occurs through the reaction of aluminum and yttrium powders at high temperatures. With this work we investigated the preparation of YAG by non-hydrolytic sol-gel route as an alternative methodology to obtain yttrium-aluminum matrix from inorganic precursors (yttrium and aluminum chloride). The preparation of the gel was carried out in an oven-dried glassware. The AlCl3, YCl3 and ethanol were reacted in reflux under argon atmosphere. Europium III chloride was added as a structural probe. The powder was dried and heat-treated in modified microwaves. The samples were pre-treated at 50 and 800 C during I h and then heated in microwaves for 30 s, 2 and 4 min. The formation process and structure of the powders were studied by means of X-ray diffraction (XRD), photoluminescence (PL) and transmission electronic microscopy (TEM). XRD presents only picks corresponding to the YAG phase and confirmed by TEM. PL date showed that the YAG phase was formed in 2 min with the samples pre-treated at 50 C. For the samples pretreated at 800 degrees C, the YAG phase appears in 30s. The excitation spectra present a maximum of 394 nm corresponding to the L-5(6) level and emission spectra of Eu III ion present bands characteristic transitions arising from the D-5(0) -> F-7(J) (J= 1, 2, 3, 4) monifolds excited at their maximum. The magnetic dipole D-5(0) -> F-7(1) transition presents more intensity than the electric dipole D-5(0) -> F-7(2) transition. This methodology showed efficiency in obtaining YAG phase. (c) 2006 Elsevier B.V. All rights reserved.