Propriedades físicas e químicas de solos incubados com resíduo alcalino da indústria de celulose

A indústria de celulose e papel descarta toneladas de resíduos com composição química variada. Certos resíduos estão sendo utilizados por produtores rurais para correção da acidez do solo, pois apresentam hidróxido em sua composição. Contudo, nenhum critério é adotado para quantificar a dose a ser utilizada, bem como para sua reaplicação, o que pode acarretar problemas de dispersão da argila, redução da estabilidade dos agregados e desbalanço de nutrientes, comprometendo, dessa forma, propriedades físicas e químicas dos solos. O objetivo deste estudo foi avaliar as propriedades físicas e químicas de dois solos incubados com resíduo alcalino (dregs) da indústria de celulose. Foram utilizadas amostras da camada superficial de um Latossolo Bruno distrófico e de um Cambissolo Húmico alumínico incubadas com doses de resíduo alcalino equivalentes a 0, 12, 25, 35 e 50 % de carbonato de cálcio necessário para elevar o pH da camada de 0-20 cm para 6,0. Foram analisados: a estabilidade de agregados, argila dispersa em água, cátions trocáveis, pH e o ponto de efeito salino nulo (PESN). O resíduo alcalino reduziu o teor e a saturação por alumínio e aumentou o pH e os teores de cálcio, magnésio, potássio e sódio trocáveis. Aumentou o potencial elétrico negativo de ambos os solos, mas reduziu o grau de floculação da argila apenas do Cambissolo Húmico alumínico. Nesse solo, o grau de floculação foi negativamente relacionado com o potencial elétrico negativo (r = -0,93**). A redução do grau de floculação da argila se deve, provavelmente, à maior repulsão das partículas que apresentam carga variável com o pH. A estabilidade dos agregados não foi alterada pela adição do resíduo alcalino.

Influência da adição de um resíduo alcalino da indústria de papel e celulose na lixiviação de cátions em um solo ácido

Os subprodutos alcalinos gerados nas indústrias de papel e celulose podem ser utilizados como corretivos da acidez do solo. Entretanto, eles possuem pouco Mg e médio teor de Na e, por isso, podem afetar negativamente a biodisponibilidade de alguns nutrientes, assim como alguns atributos do solo. Antes de recomendá-los, portanto, é importante avaliar seus efeitos. Este trabalho teve por objetivo quantificar a composição química do solo e a mobilidade vertical de cátions decorrente de formas de aplicação de um desses resíduos em relação ao calcário dolomítico. O experimento foi realizado em laboratório, sobre um Cambissolo Húmico, entre 2005 e 2006, utilizando-se colunas de lixiviação (30 x 10 cm de diâmetro). Os tratamentos consistiram de um fatorial 4 x 2 x 2, incluindo dois valores prévios de pH do solo com uma testemunha cada, dois corretivos de acidez (subproduto industrial ou calcário dolomítico) e dois métodos de aplicação (superficial ou incorporado). Foram realizadas 10 percolações, espaçadas em intervalos de sete dias, num volume de 300 mL de água destilada por semana, totalizando o equivalente a 380 mm de chuva. A incorporação do resíduo industrial ao solo causou a lixiviação de 60 % do Na adicionado, porém essa perda diminuiu para 12 % quando o corretivo foi aplicado sobre a superfície. O resíduo alcalino não ocasionou lixiviação de Ca, Mg ou K, e o calcário dolomítico lixiviou apenas 2,4 % do Ca e 7,2 % do Mg adicionados, comprovando a baixa mobilidade vertical desses cátions quando aplicados por meio de produtos alcalinos a solos com carga variável. A elevação prévia do pH diminuiu substancialmente a lixiviação dos cátions em decorrência do aumento das cargas elétricas negativas no solo. Nas condições pluviométricas da região Sul do Brasil, o Na adicionado pelo resíduo industrial lixiviará da camada arável em menos de um ano após sua aplicação e, portanto, não deverá prejudicar os atributos químicos e físicos do solo.

Low-loss rib waveguides containing Si nanocrystals embedded in SiO2

We report on the study and modeling of the structural and optical properties of rib-loaded waveguides working in the 600-900-nm spectral range. A Si nanocrystal (Si-nc) rich SiO2 layer with nominal Si excess ranging from 10% to 20% was produced by quadrupole ion implantation of Si into thermal SiO2 formed on a silicon substrate. Si-ncs were precipitated by annealing at 1100°C, forming a 0.4-um-thick core layer in the waveguide. The Si content, the Si-nc density and size, the Si-nc emission, and the active layer effective refractive index were determined by dedicated experiments using x-ray photoelectron spectroscopy, Raman spectroscopy, energy-filtered transmission electron microscopy, photoluminescence and m-lines spectroscopy. Rib-loaded waveguides were fabricated by photolithographic and reactive ion etching processes, with patterned rib widths ranging from 1¿to¿8¿¿m. Light propagation in the waveguide was observed and losses of 11dB/cm at 633 and 780 nm were measured, modeled and interpreted.

Optical-geometrical effects on the photoluminescence spectra of Si nanocrystals embedded in SiO2

We demonstrate that thickness, optical constants, and details of the multilayer stack, together with the detection setting, strongly influence the photoluminescence spectra of Si nanocrystals embedded in SiO2. Due to multiple reflections of the visible light against the opaque silicon substrate, an interference pattern is built inside the oxide layer, which is responsible for the modifications in the measured spectra. This interference effect is complicated by the depth dependence of (i) the intensity of the excitation laser and (ii) the concentration of the emitting nanocrystals. These variations can give rise to apparent features in the recorded spectra, such as peak shifts, satellite shoulders, and even splittings, which can be mistaken as intrinsic material features. Thus, they can give rise to an erroneous attribution of optical bands or estimate of the average particle size, while they are only optical-geometrical artifacts. We have analyzed these effects as a function of material composition (Si excess fraction) and thickness, and also evaluated how the geometry of the detection setup affects the measurements. To correct the experimental photoluminescence spectra and extract the true spectral shape of the emission from Si nanocrystals, we have developed an algorithm based on a modulation function, which depends on both the multilayer sequence and the experimental configuration. This procedure can be easily extended to other heterogeneous systems.

Conduction mechanisms and charge storage in Si-nanocrystals metal-oxide-semiconductor memory devices studied with conducting atomic force microscopy

In this work, we demonstrate that conductive atomic force microscopy (C-AFM) is a very powerful tool to investigate, at the nanoscale, metal-oxide-semiconductor structures with silicon nanocrystals (Si-nc) embedded in the gate oxide as memory devices. The high lateral resolution of this technique allows us to study extremely small areas ( ~ 300nm2) and, therefore, the electrical properties of a reduced number of Si-nc. C-AFM experiments have demonstrated that Si-nc enhance the gate oxide electrical conduction due to trap-assisted tunneling. On the other hand, Si-nc can act as trapping centers. The amount of charge stored in Si-nc has been estimated through the change induced in the barrier height measured from the I-V characteristics. The results show that only ~ 20% of the Si-nc are charged, demonstrating that the electrical behavior at the nanoscale is consistent with the macroscopic characterization.

Linear and nonlinear optical properties of Si nanocrystals in SiO2 deposited by plasma-enhanced chemical-vapor deposition

Linear and nonlinear optical properties of silicon suboxide SiOx films deposited by plasma-enhanced chemical-vapor deposition have been studied for different Si excesses up to 24¿at.¿%. The layers have been fully characterized with respect to their atomic composition and the structure of the Si precipitates. Linear refractive index and extinction coefficient have been determined in the whole visible range, enabling to estimate the optical bandgap as a function of the Si nanocrystal size. Nonlinear optical properties have been evaluated by the z-scan technique for two different excitations: at 0.80¿eV in the nanosecond regime and at 1.50¿eV in the femtosecond regime. Under nanosecond excitation conditions, the nonlinear process is ruled by thermal effects, showing large values of both nonlinear refractive index (n2 ~ ¿10¿8¿cm2/W) and nonlinear absorption coefficient (ß ~ 10¿6¿cm/W). Under femtosecond excitation conditions, a smaller nonlinear refractive index is found (n2 ~ 10¿12¿cm2/W), typical of nonlinearities arising from electronic response. The contribution per nanocrystal to the electronic third-order nonlinear susceptibility increases as the size of the Si nanoparticles is reduced, due to the appearance of electronic transitions between discrete levels induced by quantum confinement.

Silicon nanocrystals as an enabling material for silicon Ppotonics

Silicon nanocrystals (Si-nc) is an enabling material for silicon photonics, which is no longer an emerging field of research but an available technology with the first commercial products available on the market. In this paper, properties and applications of Si-nc in silicon photonics are reviewed. After a brief history of silicon photonics, the limitations of silicon as a light emitter are discussed and the strategies to overcome them are briefly treated, with particular attention to the recent achievements. Emphasis is given to the visible optical gain properties of Si-nc and to its sensitization effect on Er ions to achieve infrared light amplification. The state of the art of Si-nc applied in a few photonic components is reviewed and discussed. The possibility to exploit Si-nc for solar cells is also presented. in addition, nonlinear optical effects, which enable fast all-optical switches, are described.

Direct modulation of electroluminescence from silicon nanocrystals beyond radiative recombination rates

We propose a light emitting transistor based on silicon nanocrystals provided with 200 Mbits/ s built-in modulation. Suppression of electroluminescence from silicon nanocrystals embedded into the gate oxide of a field effect transistor is achieved by fast Auger quenching. In this process, a modulating drain signal causes heating of carriers in the channel and facilitates the charge injection into the nanocrystals. This excess of charge enables fast nonradiative processes that are used to obtain 100% modulation depths at modulating voltages of 1 V.

Influence of average size and interface passivation on the spectral emission of Si nanocrystals embedded in SiO2

The correlation between the structural (average size and density) and optoelectronic properties [band gap and photoluminescence (PL)] of Si nanocrystals embedded in SiO2 is among the essential factors in understanding their emission mechanism. This correlation has been difficult to establish in the past due to the lack of reliable methods for measuring the size distribution of nanocrystals from electron microscopy, mainly because of the insufficient contrast between Si and SiO2. With this aim, we have recently developed a successful method for imaging Si nanocrystals in SiO2 matrices. This is done by using high-resolution electron microscopy in conjunction with conventional electron microscopy in dark field conditions. Then, by varying the time of annealing in a large time scale we have been able to track the nucleation, pure growth, and ripening stages of the nanocrystal population. The nucleation and pure growth stages are almost completed after a few minutes of annealing time at 1100°C in N2 and afterward the ensemble undergoes an asymptotic ripening process. In contrast, the PL intensity steadily increases and reaches saturation after 3-4 h of annealing at 1100°C. Forming gas postannealing considerably enhances the PL intensity but only for samples annealed previously in less time than that needed for PL saturation. The effects of forming gas are reversible and do not modify the spectral shape of the PL emission. The PL intensity shows at all times an inverse correlation with the amount of Pb paramagnetic centers at the Si-SiO2 nanocrystal-matrix interfaces, which have been measured by electron spin resonance. Consequently, the Pb centers or other centers associated with them are interfacial nonradiative channels for recombination and the emission yield largely depends on the interface passivation. We have correlated as well the average size of the nanocrystals with their optical band gap and PL emission energy. The band gap and emission energy shift to the blue as the nanocrystal size shrinks, in agreement with models based on quantum confinement. As a main result, we have found that the Stokes shift is independent of the average size of nanocrystals and has a constant value of 0.26±0.03 eV, which is almost twice the energy of the Si¿O vibration. This finding suggests that among the possible channels for radiative recombination, the dominant one for Si nanocrystals embedded in SiO2 is a fundamental transition spatially located at the Si¿SiO2 interface with the assistance of a local Si-O vibration.

Calagem superficial com resíduo alcalino da indústria de papel e celulose em um solo altamente tamponado

Solos dos planaltos subtropicais do Brasil são pobres em nutrientes e têm alta necessidade de calagem, o que encarece e pode limitar a correção da acidez. O objetivo deste estudo foi avaliar modificações químicas e físicas de um Cambissolo Húmico alumínico e a resposta da cultura do trigo ao resíduo alcalino da indústria de papel e celulose (Dregs) em comparação com um corretivo convencional. Os tratamentos foram doses de resíduo (Res) de 25, 50 e 100 % da recomendação indicada pelo método SMP, visando elevar o pH para 6,0, que correspondem a 2.625, 5.250 e 10.500 kg ha-1, respectivamente. Essas doses se comparam a 50 e 100 % SMP de calcário dolomítico (Cal), e correspondem a 5.600 e 11.200 kg ha-1, respectivamente, além do solo sem correção (testemunha, sem resíduo e, ou, corretivo). O delineamento experimental foi em blocos ao acaso, com quatro repetições. Os corretivos foram aplicados superficialmente em duas épocas: primeira metade em junho de 2004 e o restante em junho de 2006, em uma área de campo nativo pastejado, sem revolvimento do solo. As amostras de solo foram coletadas nas camadas de 0 a 5, 5 a 10, e 10 a 15 cm para caracterização química e física do solo. Em 2006, foram avaliados os teores foliares de nutrientes e a produtividade de grãos de trigo. A aplicação superficial do resíduo alcalino melhorou os atributos químicos do solo, principalmente na camada superficial, com aumento do pH e dos teores de Ca e Mg, da relação molar entre Ca e Mg e do teor de Na, sem, entretanto, atingir o valor crítico de saturação da CTC por Na. A calagem superficial com resíduo ou calcário reduziu linearmente o grau de floculação das argilas na camada superficial do solo. Os teores de nutrientes nas plantas e a produtividade de grãos foram semelhantes entre os tratamentos com calcário ou resíduo, com respostas crescentes às doses dos corretivos.

Nonparabolicity and dielectric effects on addition energy spectra of spherical nanocrystals

An extension of the spin density functional theory simultaneously accounting for dielectric mismatch between neighboring materials and nonparabolicity corrections originating from interactions between conduction and valence bands is presented. This method is employed to calculate ground state and addition energy spectra of homogeneous and multishell spherical quantum dots. Our calculations reveal that corrections become especially relevant when they come into play simultaneously in strong regimes of spatial confinement.

Características anatômicas para produção de celulose do lenho de reação de árvores inclinadas de eucalipto

O objetivo deste trabalho foi avaliar as características anatômicas para produção de celulose dos lenhos normal e de reação (de tração e oposto), do clone de Eucalyptus grandis x Eucalyptus urophylla, com fuste inclinado por ação de ventos. As árvores foram agrupadas em quatro faixas de inclinação, que variaram de 0 a 50º. Foram analisadas as características anatômicas dos elementos de vasos e das fibras no sentido longitudinal do tronco, nos lados superior e inferior à inclinação, nos lenhos de tração e oposto, respectivamente. A frequência e o diâmetro tangencial dos vasos, bem como as dimensões das fibras e os seus respectivos índices de qualidade, foram influenciados pela inclinação. Nos lenhos de tração e oposto, os vasos apresentaram diâmetro reduzido e aumento da frequência. Observou-se diferença no comprimento das fibras, entre os lenhos de tração, oposto e normal, com influência nos índices de qualidade de fibra. A grande variabilidade na dimensão das fibras e dos vasos no lenho de reação contribui para reduzir a qualidade da madeira dos fustes inclinados, para obtenção de polpa celulósica.

Tailoring the surface density of silicon nanocrystals embedded in SiOx single layers

In this article, we explore the possibility of modifying the silicon nanocrystal areal density in SiOx single layers, while keeping constant their size. For this purpose, a set of SiOx monolayers with controlled thickness between two thick SiO2 layers has been fabricated, for four different compositions (x=1, 1.25, 1.5, or 1.75). The structural properties of the SiO x single layers have been analyzed by transmission electron microscopy (TEM) in planar view geometry. Energy-filtered TEM images revealed an almost constant Si-cluster size and a slight increase in the cluster areal density as the silicon content increases in the layers, while high resolution TEM images show that the size of the Si crystalline precipitates largely decreases as the SiO x stoichiometry approaches that of SiO2. The crystalline fraction was evaluated by combining the results from both techniques, finding a crystallinity reduction from 75% to 40%, for x = 1 and 1.75, respectively. Complementary photoluminescence measurements corroborate the precipitation of Si-nanocrystals with excellent emission properties for layers with the largest amount of excess silicon. The integrated emission from the nanoaggregates perfectly scales with their crystalline state, with no detectable emission for crystalline fractions below 40%. The combination of the structural and luminescence observations suggests that small Si precipitates are submitted to a higher compressive local stress applied by the SiO2 matrix that could inhibit the phase separation and, in turn, promotes the creation of nonradiative paths.

Remediação de efluentes derivados da indústria de papel e celulose: tratamento biológico e fotocatalítico

The contribution of the industrial activities to the environmental contamination phenomena is evident. Great efforts are dedicated to the establishment of methodologies which permits an adequate treatment of the produced effluents, as a manner of minimizing the environmental impact of these wastes. The methodologies based on photocatalytic processes are very promise alternatives, because permits degradation of a great number of chemical substances of high toxic potential, without the use of other chemicals. The present work is an overview about the principal environmental aspects related with the paper and cellulose industry and the main alternatives employed for the reduction of environmental impact produced for its residues. The principal results of the photocatalytic treatment of this kind of effluents using metallic semiconductors is also showed.