White Light and Multicolor Emission Tuning in Triply Doped Yb3+/Tm3+/Er3+ Novel Fluoro-phosphate Transparent Glass-ceramics

New Yb3+, Er3+ and Tm3+ doped fluoro-phosphate glasses belonging to the system NaPO3–YF3–BaF2–CaF2 and containing up to 10 wt% of rare-earth ion fluorides were prepared and characterized by differential scanning calorimetry, absorption spectroscopy and up-conversion emission spectroscopy under excitation with a 975 nm laser diode. Transparent and homogeneous glass-ceramics have been reproducibly obtained with a view to manage the red, green and blue emission bands and generate white light. X-ray diffraction as well as electron microscopy techniques have confirmed the formation of fluorite-type cubic nanocrystals at the beginning of the crystallization process while complex nanocrystalline phases are formed after a longer heat-treatment. The prepared glass-ceramics exhibit high optical transparency even after 170 h of thermal treatment. An improvement of up-conversion emission intensity – from 10 to 160 times larger – was measured in the glass-ceramics when compared to the parent glass, suggesting an important incorporation of the rare-earth ions into the crystalline phase(s). The involved mechanisms and lifetime were described in detail as a function of heat-treatment time. Finally, a large range of designable color rendering (from orange to turquoise through white) can be observed in these materials by controlling the laser excitation power and the crystallization rate.

Al3+ environments in nanostructured ZnAl2O4 and their effects on the luminescence properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Excitation mechanisms and effects of dopant concentration in Gd2O2S : Tb3+ phosphor

Gadolinium oxysulfide powders doped with different Tb3+ concentrations were prepared from sulfur vaporization on rare earths' basic carbonate precursors. Single-phase Gd2O2S samples were obtained, with Tb3+ doping up to 9 at%. The study of the excitation mechanisms revealed that the Tb3+ emission might occur after the direct Tb3+ excitation either by energy transfer from Gd3+ or from the phosphor host. The characteristic terbium emission lines were observed, resulting from the radiative decay from D-5(3) or D-5(4), to F-7(j) levels. The cross-relaxation phenomenon was observed and its effects on the materials emission color were discussed based on the CIE diagram. By using time-resolved spectroscopy, D-5(3) -> F-7(J) and D-5(4) -> F-7(J) transitions were separated. (c) 2007 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.

Spectral redistribution of waveguided emission in BEH-PPV films

We report on spectral redistribution of the photoluminescence (PL) emission from the edge of thin-film planar waveguides of the conjugated polymer BEH-PPV [Poly(2,5-bis(2'-ethyl-hexyl)-1,4-phenylenevinylene] induced by self-absorption in the polymer film. The PL spectra present drastic changes and displace to longer wavelengths with increasing self-absorption. We observe an enhancement of the absolute PL intensity at longer wavelengths, which was interpreted as due to re-emission of self-absorbed photons. The significant efficiency for the PL re-emission suggests the use of self-absorption as a mechanism for tuning the emission into the near infrared.

Al-based anodic oxide films structure observation using field emission gun scanning electron microscopy

In the present work, the anodic oxide films of Al, Al-Cu 4.5% and Al-Si 6.5% alloys are formed using direct and pulse current. In the case of Al-Cu and Al-Si alloys, the electrolyte used contains sulfuric acid and oxalic acid, meanwhile for Al the electrolyte contains sulfuric acid only. Al-Cu alloy was submitted to a heat treatment in order to decrease the effect of inter metallic phase theta upon the anodic film structure. Fractured samples were observed using a field emission gun scanning electron microscope JSM-6330F at (LME)/Brazilian Synchrotron Light Laboratory (LNLS), Campinas, SP, Brazil. The oxide film images enable evaluation of the pore size and form with a resolution similar to the transmission electron microscope (TEM) resolution. It is also observed that the anodizing process using pulse current produces an irregular structure of pore walls, and by direct cur-rent it is produced a rectilinear pore wall. (c) 2005 Elsevier B.V. All rights reserved.

Spatial variability of soil CO2 emission in a sugarcane area characterized by secondary information

Soil CO2 emission (FCO2) is governed by the inherent properties of the soil, such as bulk density (BD). Mapping of FCO2 allows the evaluation and identification of areas with different accumulation potential of carbon. However, FCO2 mapping over larger areas is not feasible due to the period required for evaluation. This study aimed to assess the quality of FCO2 spatial estimates using values of BD as secondary information. FCO2 and BD were evaluated on a regular sampling grid of 60 m × 60 m comprising 141 points, which was established on a sugarcane area. Four scenarios were defined according to the proportion of the number of sampling points of FCO2 to those of BD. For these scenarios, 67 (F67), 87 (F87), 107 (F107) and 127 (F127) FCO2 sampling points were used in addition to 127 BD sampling points used as supplementary information. The use of additional information from the BD provided an increase in the accuracy of the estimates only in the F107, F67 and F87 scenarios, respectively. The F87 scenario, with the approximate ratio between the FCO2 and BD of 1.00:1.50, presented the best relative improvement in the quality of estimates, thereby indicating that the BD should be sampled at a density 1.5 time greater than that applied for the FCO2. This procedure avoided problems related to the high temporal variability associated with FCO2, which enabled the mapping of this variable to be elaborated in large areas.

Soil CO2 emission as related to incorporation of sugarcane crop residues and aggregate breaking after rotary tiller

O preparo do solo é um dos processos que aceleram a decomposição da matéria orgânica, transferindo carbono para atmosfera, principalmente na forma de CO2. Neste trabalho, investigou-se o efeito do preparo com enxada rotativa sobre as emissões de CO2 do solo durante 02 semanas após o preparo do solo, incluindo-se a presença de resíduos vegetais sobre a superfície. As emissões foram avaliadas por 15 dias após preparo em 3 parcelas: 1) sem preparo e sem palha superficial (SPs); 2) preparo com enxada rotativa sem a presença de palha na superfície (ERs), e 3) preparo com enxada rotativa com a presença de palha superficial (ERc). As emissões provenientes da ERc foram superiores às demais (0,777 g CO2 m-2 h-1), sendo as menores emissões registradas na parcela SPs (0,414 g CO2 m-2 h-1). As emissões totais indicaram que a diferença de C-CO2 emitida à atmosfera corresponde a 3% do total de carbono adicional presente na palha, na parcela ERc, quando comparado à parcela ERs. O aumento da emissão da parcela SPs para ERs foi acompanhado de uma modificação na distribuição do tamanho de agregados, especialmente aqueles com diâmetro médio inferior a 2 mm. O aumento da emissão da parcela ERs para ERc esteve relacionado a uma diminuição da massa de palha na superfície, com fragmentação e incorporação da mesma no interior do solo. Quando se analisa a correlação linear entre emissão de CO2 versus temperatura e umidade do solo, somente a emissão da ERc foi significativamente correlacionada (p<0,05) à umidade do solo.

Soil CO2 emission estimated by different interpolation techniques

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Fractal dimension and anisotropy of soil CO2 emission in a mechanically harvested sugarcane production area

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Temporal variability of soil CO2 emission after conventional and reduced tillage described by an exponential decay in time model

A quantificação do impacto das práticas de preparo sobre as perdas de carbono do solo é dependente da habilidade de se descrever a variabilidade temporal da emissão de CO2 do solo após preparo. Tem sido sugerido que as grandes quantidades de CO2 emitido após o preparo do solo podem servir como um indicador das modificações nos estoques de carbono do solo em longo termo. Neste trabalho é apresentado um modelo de duas partes baseado na temperatura e na umidade do solo e que inclui um termo exponencial decrescente do tempo que é eficiente no ajuste das emissões intermediárias após preparo: arado de disco seguido de uma passagem com a grade niveladora (convencional) e escarificador de arrasto seguido da passagem com rolo destorroador (reduzido). As emissões após o preparo do solo são descritas utilizando-se estimativa não linear com um coeficiente de determinação (R²) tão alto quanto 0.98 após preparo reduzido. Os resultados indicam que nas previsões da emissão de CO2 após o preparo do solo é importante considerar um termo exponencial decrescente no tempo após preparo.

Soil CO2 emission and its relation to soil properties in sugarcane areas under Slash-and-burn and Green harvest

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Spatial variability of soil CO2 emission in different topographic positions

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Soil CO2 emission of sugarcane fields as affected by topography

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Temporal analysis of the reduction in gas emission in areas of mechanically-harvested sugarcane using satellite imagery

The primary objective of this study was to estimate the amount of gas not emitted into the air in areas cultivated with sugarcane (Saccharum officinarum) that were mechanically harvested. Satellite images CBERS-2/CCD, from 08-13-2004, 08-14-2005, 08-15-2006 and 08-16-2007, of northwestern São Paulo State were processed using the Geographic Information System (GIS)-IDRISI 15.0. Areas of interest (the mechanically-harvested sugarcane fields) were identified and quantified based on the spectral response of the bands studied. Based on these data, the amount of gas that was not emitted was evaluated, according to the estimate equation proposed by the Intergovernmental Panel on Climate Change (IPCC). The results of 396.65 km(2) (5.91% for 2004); 447.56 km(2) (6.67% for 2005); 511.54 km(2) (7.62% in 2006); and 474.60 km(2) (7.07% for 2007), calculated from a total area of 6,710.89 km(2) with sugarcane, showed a significant increase of mechanical harvesting in the study area and a reduction of gas emissions of more than 300,000 t yr(-1).