Templated synthesis of carbon materials mediated by porous clay heterostructures

Mesoporous carbon materials were prepared through template method approach using porous clay heterostructures (PCHs) as matrix and furfuryl alcohol as carbon precursor. Three PCHs prepared using amines with 8, 10 and 12 carbon atoms were used. The effect of several impregnation-polymerization cycles of the carbon precursor, the carbonization temperature and the need of a previous surface alumination were evaluated. The presence of two porosity domains was identified in all the carbon materials. These two domains comprise pores resulting from the carbonization of the polymer film formed in the inner structure of the PCH (domain I) and larger pores created by the clay particles aggregation (domain II). The predominance of the porosity associated to domain I or II can be achieved by choosing a specific amine to prepare the PCH matrix. Carbonization at 700 C led to the highest development of pores of domain I. In general, the second impregnation-polymerization cycle of furfuryl alcohol resulted in a small decrease of both types of porosity domains. Furthermore the previous acidification of the surface to create acidic sites proved to be unnecessary. The results showed the potential of PCHs as matrices to tailor the textural properties of carbons prepared by template mediated synthesis.

Implementação e validação do método de determinação de metais e fósforo por ICP-OES (inductively coupled plasma-optical emission spectometry) em biodiesel

O objectivo do presente trabalho foi desenvolver, implementar e validar métodos de determinação de teor de cálcio (Ca), magnésio (Mg), sódio (Na), potássio (K) e fósforo (P) em biodiesel, por ICP-OES. Este método permitiu efectuar o controlo de qualidade do biodiesel, com a vantagem de proporcionar uma análise multi-elementar, reflectindo-se numa diminuição do tempo de análise. Uma vez que o biodiesel é uma das principais fontes de energia renovável e alternativa ao diesel convencional, este tipo de análises revela-se extremamente útil para a sua caracterização. De acordo com a análise quantitativa e qualitativa e após a validação dos respectivos ensaios, apresentam-se, na Tabela 1 as condições optimizadas para cada elemento em estudo. As condições de trabalho do ICP-OES foram escolhidas tendo em conta as características do elemento em estudo, o tipo de equipamento utilizado para a sua análise, e de modo a obter a melhor razão sinal/intensidade de fundo. Para a validação dos ensaios foram efectuados ensaios de recuperação, determinados limites de detecção e quantificação, ensaios de repetibilidade e reprodutibilidade, e verificação das curvas de calibração. Na tabela 2 apresentam-se os comprimentos de onda escolhidos (livres de interferências) e respectivos limites de detecção e quantificação dos elementos analisados por ICP-OES, na posição radial e radial atenuado.

Síntese e fotosensibilização de nanotubos de titanatos

Nesta tese é descrita a preparação de nanotubos de titanatos (TNT) via síntese hidrotérmica alcalina, usando uma nova metodologia que evita a utilização de TiO2 cristalino como precursor. Foi estudada a influência da substituição sódio/protão na estrutura, morfologia e propriedades ópticas dos materiais preparados. Os resultados mostraram que a substituição Na+ → H+ resulta numa redução na distância intercamadas dos TNTs, tendo sido medidos valores entre 1.13±0.03 nm e 0.70±0.02 nm para aquele parâmetro. O comportamento óptico dos TNTs foi estudado na região UV-vis, estimando-se um hiato óptico de energia 3.27±0.03 eV para a amostra com maior teor de sódio enquanto que para a amostra protonada foi determinado um valor de 2.81±0.02 eV. Estes valores mostram que a troca iónica Na+ → H+ teve influência no desvio da banda de absorção dos TNTs para a região do visível próximo. A actividade fotocatalítica dos TNTs na degradação do corante rodamina 6G (R6G) foi posteriormente estudada. Verificou-se que, apesar de a amostra com maior teor de sódio ter sido a que exibiu maior capacidade para adsorver o R6G, foi a amostra protonada que apresentou a actividade catalítica mais elevada na fotodegradação deste corante. Numa segunda fase, e com o objectivo de preparar novos materiais nanoestruturados fotosensíveis, procedeu-se à decoração dos TNTs protonados com semicondutores (SC) nanocristalinos usando um método novo. Para o efeito os TNTs foram decorados com nanocristalites de ZnS, CdS e Bi2S3. Foi estudada a influência do tipo de semicondutor na estrutura, morfologia e propriedades ópticas dos SC/TNTs obtidos. Verificou-se que, para qualquer dos semicondutores usados no processo de decoração, a estrutura dos TNTs é preservada e não ocorre segregação do SC. Verificou-se ainda que a morfologia dos nanocompósitos preparados depende fortemente da natureza do semicondutor. No que respeita ao comportamento óptico destes materiais, foram determinados hiatos ópticos de energia 3.67±0.03 eV, 2.47±0.03 eV e 1.35±0.01 eV para as amostras ZnS/TNT, CdS/TNT e Bi2S3/TNT, respectivamente. Estes resultados mostram que através do processo de decoração de TNTs com semicondutores podem ser preparados materiais nanocompósitos inovadores, com propriedades ópticas novas e/ou pré-definidas numa gama alargada do espectro electromagnético.

Nanocrystalline p-layer for a-Si:H p-i-n solar cells and photodiodes

We report on structural, electronic, and optical properties of boron-doped, hydrogenated nanocrystalline silicon (nc-Si:H) thin films deposited by plasma-enhanced chemical vapor deposition (PECVD) at a substrate temperature of 150 degrees C. Film properties were studied as a function of trimethylboron-to-silane ratio and film thickness. The absorption loss of 25% at a wavelength of 400 nm was measured for the 20 nm thick films on glass and glass/ZnO:Al substrates. By employing the p(+) nc-Si:H as a window layer, complete p-i-n structures were fabricated and characterized. Low leakage current and enhanced sensitivity in the UV/blue range were achieved by incorporating an a-SiC:H buffer between the p- and i-layers.

A two terminal optical signal and image processing p-i-n/p-i-n image and colour sensor

A two terminal optically addressed image processing device based on two stacked sensing/switching p-i-n a-SiC:H diodes is presented. The charge packets are injected optically into the p-i-n sensing photodiode and confined at the illuminated regions changing locally the electrical field profile across the p-i-n switching diode. A red scanner is used for charge readout. The various design parameters and addressing architecture trade-offs are discussed. The influence on the transfer functions of an a-SiC:H sensing absorber optimized for red transmittance and blue collection or of a floating anode in between is analysed. Results show that the thin a-SiC:H sensing absorber confines the readout to the switching diode and filters the light allowing full colour detection at two appropriated voltages. When the floating anode is used the spectral response broadens, allowing B&W image recognition with improved light-to-dark sensitivity. A physical model supports the image and colour recognition process.

ITO/SiOx/Si optical sensor with internal gain

A visible/near-infrared optical sensor based on an ITO/SiOx/n-Si structure with internal gain is presented. This surface-barrier structure was fabricated by a low-temperature processing technique. The interface properties and carder transport were investigated from dark current-voltage and capacitance-voltage characteristics. Examination of the multiplication properties was performed under different light excitation and reverse bias conditions. The spectral and pulse response characteristics are analysed. The current amplification mechanism is interpreted by the control of electron current by the space charge of photogenerated holes near the SiOx/Si interface. The optical sensor output characteristics and some possible device applications are presented.

Optical confinement and colour separation in a double colour laser scanned photodiode (D/CLSP)

Large area n-i-p-n-i-p a-SiC:H heterostructures are used as sensing element in a double colour laser scanned photodiode image sensor (D/CLSP). This work aims to clarify possible improvements, physical limits and performance of CLSP image sensor when used as non-pixel image reader. Here, the image capture device and the scanning reader are optimized and the effects of the sensor structure on the output characteristics discussed. The role of the design of the sensing element, the doped layer composition and thickness, the read-out parameters (applied voltage and scanner frequency) on the image acquisition and the colour detection process are analysed. A physical model is presented and supported by a numerical simulation of the output characteristics of the sensor.

Optical confinement and colour separation in a double colour laser scanned photodiode (D/CLSP)

Large area n-i-p-n-i-p a-SiC:H heterostructures are used as sensing element in a Double Color Laser Scanned Photodiode image sensor (D/CLSP). This work aims to clarify possible improvements, physical limits and performance of CLSP image sensor when used as non-pixel image reader. Here, the image capture device and the scanning reader are optimized and the effects of the sensor structure on the output characteristics discussed. The role of the design of the sensing element, the doped layer composition and thickness, the read-out parameters (applied voltage and scanner frequency) on the image acquisition and the color detection process are analyzed. A physical model is presented and supported by a numerical simulation of the output characteristics of the sensor.

Optical demultiplexer device operating in the visible spectrum

In this paper, we present results on the use of multilayered a-SiC:H heterostructures as a device for wavelength-division demultiplexing of optical signals. These devices are useful in optical communications applications that use the wavelength division multiplexing technique to encode multiple signals into the same transmission medium. The device is composed of two stacked p-i-n photodiodes, both optimized for the selective collection of photo generated carriers. Band gap engineering was used to adjust the photogeneration and recombination rate profiles of the intrinsic absorber regions of each photodiode to short and long wavelength absorption in the visible spectrum. The photocurrent signal using different input optical channels was analyzed at reverse and forward bias and under steady state illumination. A demux algorithm based on the voltage controlled sensitivity of the device was proposed and tested. An electrical model of the WDM device is presented and supported by the solution of the respective circuit equations.

Optical properties and transport in PLD-GaN

We present structural, optical and transport data on GaN samples grown by hybrid, two-step low temperature pulsed laser deposition. The band gap of samples with good crystallinity has been deduced from optical spectra. Large below gap band tails were observed. In samples with the lowest crystalline quality the PL spectra are quite dependent on spot laser incidence. The most intense PL lines can be attributed to excitons bounded to stacking faults. When the crystalline quality of the samples is increased the ubiquitous yellow emission band can be detected following a quenching process described by a similar activation energy to that one found in MOCVD grown samples. The samples with the highest quality present, besides the yellow band, show a large near band edge emission which peaked at 3.47 eV and could be observed up to room temperature. The large width of the NBE is attributed to effect of a wide distribution of band tail states on the excitons. Photoconductivity data supports this interpretation.

Production of surfactants from bio-materials

Este trabalho foi desenvolvido no âmbito de um projecto europeu, BIOPRODUCTION, tendo em vista o desenvolvimento de dois tipos de biomaterias funcionais: ésteres de açúcares com ácidos gordos (SFAE) e metacrilatos funcionais. A síntese laboratorial do biosurfactante SFAE foi efectuada utilizando como matérias-primas diferentes sacáridos, nomeadamente sacarose, glucose e melaço de cana-de-açúcar (mistura de polissacáridos), e ésteres metílicos de ácidos gordos (FAME) de óleos vegetais, tais como colza e coco. Esta síntese é constituída por dois passos: acilação dos açúcares com anidrido acético, e transesterificação do açúcar acilado com FAME, utilizando triflatos de lantanídeos como catalisador. Diferentes estequiometrias foram testadas, bem como diferentes processos de modo a evitar a degradação dos açúcares. Foram efectuados testes preliminares de emulsão e calculou-se, empiricamente, o respectivo HLB. Procedeu-se à caracterização do produto através de FTIR e RMN e também à optimização iterativa do processo de síntese. A modificação, à escala laboratorial, de metacrilatos de metilo (MMA) realizou-se recorrendo à sua transesterificação com polióis convencionais. Efectuaram-se testes de reticulação do produto com diferentes catalisadores e iniciadores para posterior aplicação em revestimentos de borracha. Por fim, para ambos os produtos serão necessários estudos adicionais de caracterização, nomeadamente tensão superficial para os biosurfactantes e propriedades mecânicas para polímeros modificados com MMA.

: SiC Multilayer Photonic Structures with Self Optical Bias Amplification

Characteristics of tunable wavelength pi'n/pin filters based on a-SiC:H multilayered stacked cells are studied both experimental and theoretically. Results show that the device combines the demultiplexing operation with the simultaneous photodetection and self amplification of the signal. An algorithm to decode the multiplex signal is established. A capacitive active band-pass filter model is presented and supported by an electrical simulation of the state variable filter circuit. Experimental and simulated results show that the device acts as a state variable filter. It combines the properties of active high-pass and low-pass filter sections into a capacitive active band-pass filter using a changing photo capacitance to control the power delivered to the load.

Incorporation of niobium in SAPO-11 materials: Synthesis and characterization

The present work concerns a new synthesis approach to prepare niobium based SAPO materials with AEL structure and the characterization ofNb species incorporated within the inorganic matrixes. The SAPO-11 materials were synthesized with or without the help of a small amine, methylamine (MA) as co-template, while Nb was added directly during the preparation of the initial gel. Structural, textural and acidic properties of the different supports were evaluated by XRD, TPR, UV-Vis spectroscopy, pyridine adsorption followed by IR spectroscopy and thermal analyses. Pure and well crystalline Nb based SAPO-11 materials were obtained, either with or without MA, using in the initial gel a low Si content of about 0.6. Increasing the Si content of the gel up to 0.9 led to an important decrease of the samples crystallinity. Niobium was found to incorporate the AEL pores support as small Nb2O5 oxide particles and also as extra framework cationic species (Nb5+), compensating the negative charges from the matrix and generating new Lewis acid sites. (C) 2011 Elsevier Inc. All rights reserved.

Mass spectrometry improvement on an high current ion implanter

The development of accurate mass spectrometry, enabling the identification of all the ions extracted from the ion source in a high current implanter is described. The spectrometry system uses two signals (x-y graphic), one proportional to the magnetic field (x-axes), taken from the high-voltage potential with an optic fiber system, and the other proportional to the beam current intensity (y-axes), taken from a beam-stop. The ion beam mass register in a mass spectrum of all the elements magnetically analyzed with the same radius and defined by a pair of analyzing slits as a function of their beam intensity is presented. The developed system uses a PC to control the displaying of the extracted beam mass spectrum, and also recording of all data acquired for posterior analysis. The operator uses a LabView code that enables the interfacing between an I/O board and the ion implanter. The experimental results from an ion implantation experiment are shown. (C) 2011 Elsevier B.V. All rights reserved.

Multilayer Architectures Based on a-SiC:H Material: Tunable Wavelength Filters in Optical Processing Devices

The characteristics of tunable wavelength filters based on a-SiC:H multilayered stacked pin cells are studied both theoretically and experimentally. The optical transducers were produced by PECVD and tested for a proper fine tuning of the cyan and yellow fluorescent proteins emission. The active device consists of a p-i'(a-SiC:H)-n/p-i(a-Si:H)-n heterostructures sandwiched between two transparent contacts. Experimental data on spectral response analysis, current-voltage characteristics and color and transmission rate discrimination are reported. Cyan and yellow fluorescent input channels were transmitted together, each one with a specific transmission rate and different intensities. The multiplexed optical signal was analyzed by reading out, under positive and negative applied voltages, the generated photocurrents. Results show that the optimized optical transducer has the capability of combining the transient fluorescent signals onto a single output signal without losing any specificity (color and intensity). It acts as a voltage controlled optical filter: when the applied voltages are chosen appropriately the transducer can select separately the cyan and yellow channel emissions (wavelength and frequency) and also to quantify their relative intensities. A theoretical analysis supported by a numerical simulation is presented.