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.

Factores de riesgo para el desarrollo psicomotor en lactantes nacidos en óptimas condiciones biológicas

OBJECTIVO: Evaluar el efecto de factores de riesgo para el desarrollo infantil en niños, de nivel socioeconómico bajo, nacidos en óptimas condiciones biológicas pero expuestos a condiciones sociales adversas. METODOLOGÍA: Lactantes de ambos sexos em número de 788, fueron exhaustivamente estudiados en términos de: alimentación, crecimiento, ambiente físico y psicosocial. Se controlaron prospectivamente hasta los 12 meses de edad, momento en que se evaluó el desarrollo mental (MDI) y motor (PDI) a través de la escala de Bayley. A partir de las variables medidas se identificó 18 factores de riesgo, los que fueron dicotomizados (bajo y alto riesgo). RESULTADOS: Lactancia materna, temperamento del niño, inteligencia materna y estimulación en el hogar se asocian consistentemente con MDI y PDI. Luego de ajustar por covariables, la estimulación en el hogar persiste como factor significativo en la explicación de la variabilidad del MDI y PDI, en tanto que el sexo del niño se consolida como factor condicionante del desarrollo motor. El efecto acumulado de 7 o más factores de riesgo se asocia con una disminución significativa de los puntajes de desarrollo. La combinación de categorías de riesgo de temperamento infantil, inteligencia materna, rol del padre y estimulación en el hogar alcanza mejor predicción del desarrollo infantil que otras combinaciones puestas a prueba en este estudio. CONCLUSIONE: Se concluye que, aún en niños biológicamente indemnes, el desarrollo psicomotor se afecta negativamente ante la presencia de condiciones ambientales adversas que actúan simultáneamente.

Ecologia de mosquitos (Diptera: Culicidae) em áreas do Parque Nacional da Serra da Bocaina, Brasil.I - Distribuição por habitat

OBJETIVO: Estabelecer a influência exercida por três diferentes biótopos em áreas do Parque Nacional da Serra da Bocaina (PNSB) sobre a fauna local de mosquitos. MÉTODOS: Foram realizadas capturas mensais em ambiente silvestre e domiciliar, em isca humana, durante três diferentes períodos do dia, pelo período de 24 meses consecutivos, de janeiro de 1991 a dezembro de 1992. RESULTADOS: Foram capturados 11.808 espécimes adultos, pertencentes a 28 espécies. Ru. reversa e An. cruzii foram predominantes, respectivamente 52,5% e 17,9% do total de mosquitos. Ru. reversa representou 59,4% do total de espécimes no ambiente de mata fechada, seguida por Ru. frontosa com 10,5% e An. cruzii com 9,9%. No ambiente formado por campos de altitude e matas de galeria, o An. cruzii predominou com 48,1%, seguido por Ru. reversa com 28,1%. No ambiente modificado pelo homem, o An. cruzii predominou com 73,7% dos espécimes. Coquillettidia chrysonotum foi a única que se apresentou preferencialmente nesse biótopo: 14,9% no intra, 19,4% no peri e 65,7% no extradomicílio. An. cruzii e Ru. reversa foram constantes em todos os ambientes ao longo do ano. CONCLUSÕES: Com exceção de Cq. chrysonotum, com preferência pelo ambiente modificado pelo homem, os mosquitos apresentam hábitos assinantrópicos no PNSB. An. cruzii, embora assinantrópico, se aproxima e adentra o domicílio para realizar a hematofagia. A presença do Ae. serratus no extra e peridomicílio reforça a importância epidemiológica como vetora potencial de arboviroses. Os Sabethini apresentaram-se exclusivamente silvestres.

Hábito alimentar de Triatoma vitticeps no Estado do Rio de Janeiro, Brasil

OBJETIVO: O estudo do hábito alimentar dos triatomíneos tem contribuído para o conhecimento da sua biologia no habitat natural. Triatoma vitticeps, espécie que vem invadindo freqüentemente o domicílio apresentando-se infectado por T. cruzi, foi analisado sob esse aspecto, possibilitando conhecer a situação epidemiológica da área. MÉTODOS: De fevereiro de 1989 a abril de 1993, 122 espécimes de T. vitticeps foram capturados em duas áreas da localidade de Triunfo, 2° Distrito do Município de Santa Maria Madalena (RJ). Os insetos foram dissecados para a retirada do conteúdo estomacal. Os anti-soros utilizados foram: homem, vaca, cavalo, cão, porco, tatu, gambá, roedor e ave. RESULTADOS: Do total analisado, 79 estavam positivos e 43 negativos para os anti-soros testados: tatu (30,3%) > homem e porco (13,1%) > ave e cão (11,5%) > cavalo (5,7%) > gambá (4,9%) > roedor (4,1%) > boi (3,3%). As fontes alimentares identificadas variaram de 1 a 4 e 6: 0 - 25,41%; 1 - 45,08%; 2 - 10,66%; 3 - 6,56%; 4 - 1,64% e 6 - 0,82%. Quanto à infecção por T. cruzi, 74 espécimes (65,54%) estavam positivos, 39 (34,51%) negativos e 9 não foram examinados. CONCLUSÕES: Os resultados caracterizam o hábito silvestre de T. vitticeps e a tripanosomíase como uma enzootia. A vigilância epidemiológica se faz necessária para o acompanhamento do comportamento dessa espécie.

Ferromagnetic order in aged Co-doped TiO2 anatase nanopowders

Oxide based diluted magnetic semiconductor (DMS) materials have been a subject of increasing interest due to reports of room temperature ferromagnetism in several systems and their potential use in the development of spintronic devices. However, concerns on the stability of the magnetic properties of different DMS systems have been raised. Their magnetic moment is often unstable, vanishing with a characteristic decay time of weeks or months, which precludes the development of real applications. This paper reports on the ferromagnetic properties of two-year-aged Ti1-xCoxO2-δ reduced anatase nanopowders with different Co contents (0.03≤x≤0.10). Aged samples retain rather high values of magnetization, remanence and coercivity which provide strong evidence for a quite preserved long-range ferromagnetic order. In what concern Co segregation, some degree of metastability of the diluted Co doped anatase structure could be inferred in the case of the sample with the higher Co content.

Cr2O3 thin films grown at room temperature by low pressure laser chemical vapour deposition

Chromia (Cr2O3) has been extensively explored for the purpose of developing widespread industrial applications, owing to the convergence of a variety of mechanical, physical and chemical properties in one single oxide material. Various methods have been used for large area synthesis of Cr2O3 films. However, for selective area growth and growth on thermally sensitive materials, laser-assisted chemical vapour deposition (LCVD) can be applied advantageously. Here we report on the growth of single layers of pure Cr2O3 onto sapphire substrates at room temperature by low pressure photolytic LCVD, using UV laser radiation and Cr(CO)(6) as chromium precursor. The feasibility of the LCVD technique to access selective area deposition of chromia thin films is demonstrated. Best results were obtained for a laser fluence of 120 mJ cm(-2) and a partial pressure ratio of O-2 to Cr(CO)(6) of 1.0. Samples grown with these experimental parameters are polycrystalline and their microstructure is characterised by a high density of particles whose size follows a lognormal distribution. Deposition rates of 0.1 nm s(-1) and mean particle sizes of 1.85 mu m were measured for these films. (C) 2011 Elsevier B.V. All rights reserved.

Coexistence of Universal and Topological Anomalous Hall Effects in Metal CrO2 Thin Films in the Dirty Limit

The scaling exponent of 1.6 between anomalous Hall and longitudinal conductivity, characteristic of the universal Hall mechanism in dirty-metal ferromagnets, emerges from a series of CrO2 films as we systematically increase structural disorder. Magnetic disorder in CrO2 increases with temperature and this drives a separate topological Hall mechanism. We find that these terms are controlled discretely by structural and magnetic defect populations, and their coexistence leads to apparent divergence from exponent 1.6, suggesting that the universal term is more prevalent than previously realized.

A new chemical route to synthesise TM-doped (TM = Co, Fe) TiO2 nanoparticles

Since the discovery of ferromagnetism well above room temperature in the Co-doped TiO2 system, diluted magnetic semiconductors based on TiO2 doped with transition metals have generated great interest because of their potential use in the development of spintronic devices. The purpose of this paper is to report on a new and swift chemical route to synthesise highly stable anatase single-phase Co- and Fe-doped TiO2 nanoparticles, with dopant concentrations of up to 10 at.-% and grain sizes that range between 20 and 30 nm. Complementary structural, microstructural and chemical analyses of the different nanopowders synthesised strongly support the hypothesis that a homogeneous distribution of the dopant element in the substitutional sites of the anatase structure has been achieved. Moreover, UV/Vis diffuse reflectance spectra of powder samples show redshifts to lower energies and decreasing bandgap energies with increasing Co or Fe concentration, which is consistent with n-type doping of the TiO2 anatase matrix. Films of Co-doped TiO2 were successfully deposited onto Si (100) substrates by the dip-coating method, with suspensions of Ti1-xCOxO2 nanoparticles in ethylene glycol. ((C)Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

Comparing a current-carrying circular wire with polygons of equal perimeter: Magnetic field versus magnetic flux

We compare the magnetic field at the centre and the self-magnetic flux through a current-carrying circular loop, with those obtained for current-carrying polygons with the same perimeter. As the magnetic field diverges at the position of the wires, we compare the self-fluxes utilizing several regularization procedures. The calculation is best performed utilizing the vector potential, thus highlighting its usefulness in practical applications. Our analysis answers some of the intuition challenges students face when they encounter a related simple textbook example. These results can be applied directly to the determination of mutual inductances in a variety of situations.

CVD of CrO(2): Towards a lower temperature deposition process

The deposition of highly oriented a-axis CrO(2) films onto Al(2)O(3)(0001) by atmospheric pressure (AP)CVD at temperatures as low as 330 C is reported. Deposition rates strongly depend on the substrate temperature, whereas for film surface microstructures the dependence is mainly on film thickness. For the experimental conditions used in this work, CrO(2) growth kinetics are dominated by a surface reaction mechanism with an apparent activation energy of (121.0 +/- 4.3) kJ mol(-1). The magnitude and temperature dependence of the saturation magnetization, up to room temperature, is consistent with bulk measurements.

CVD of CrO2 thin films: Influence of the deposition parameters on their structural and magnetic properties

This work reports on the synthesis of CrO2 thin films by atmospheric pressure CVD using chromium trioxide (CrO3) and oxygen. Highly oriented (100) CrO2 films containing highly oriented (0001) Cr2O3 were grown onto Al2O3(0001) substrates. Films display a sharp magnetic transition at 375 K and a saturation magnetization of 1.92 mu(B)/f.u., close to the bulk value of 2 mu(B)/f.u. for the CrO2.

Influence of growth temperature and carrier flux on the structure and transport properties of highly oriented CrO2 on Al2O3 (0001)

In this work we report on the structure and magnetic and electrical transport properties of CrO2 films deposited onto (0001) sapphire by atmospheric pressure (AP)CVD from a CrO3 precursor. Films are grown within a broad range of deposition temperatures, from 320 to 410 degrees C, and oxygen carrier gas flow rates of 50-500 seem, showing that it is viable to grow highly oriented a-axis CrO2 films at temperatures as low as 330 degrees C i.e., 60-70 degrees C lower than is reported in published data for the same chemical system. Depending on the experimental conditions, growth kinetic regimes dominated either by surface reaction or by mass-transport mechanisms are identified. The growth of a Cr2O3 interfacial layer as an intrinsic feature of the deposition process is studied and discussed. Films synthesized at 330 degrees C keep the same high quality magnetic and transport properties as those deposited at higher temperatures.

KrF pulsed laser deposition of chromium oxide thin films from Cr8O21 targets

Chromium oxides, CrxOy, are of great interest due to the wide variety of their technological applications. Among them, CrO2 has been extensively investigated in recent years because it is an attractive compound for use in spintronic heterostructures. However, its synthesis at low temperatures has been a difficult task due to the metastable nature of this oxide. This is indeed essential to ensure interface quality and the ability to coat thermal-sensitive materials such as those envisaged in spintronic devices. Pulsed Laser Deposition (PLD) is a technique that has the potential to meet the requirements stated above. In this work, we describe our efforts to grow chromium oxide thin films by PLD from Cr8O21 targets, using a KrF excimer laser. The as-deposited films were investigated by X-ray diffraction and Rutherford backscattering spectrometry. Structural and chemical composition studies showed that the films consist of a mixture of amorphous chromium oxides exhibiting different stoichiometries depending on the processing parameters, where nanocrystals of mainly Cr2O3 are dispersed. The analyses do not exclude the possibility of co-deposition of Cr2O3 and a low fraction of CrO2.

Laser-assisted deposition of thin films from photoexcited vapour phases

Laser-assisted chemical vapour deposition (LCVD) has been extensively studied in the last two decades. A vast range of applications encompass various areas such as microelectronics, micromechanics, microelectromechanics and integrated optics, and a variety of metals, semiconductors and insulators have been grown by LCVD. In this article, we review briefly the LCVD process and present two case studies of thin film deposition related to laser thermal excitation (e.g., boron carbide) and non-thermal excitation (e.g., CrO(2)) of the gas phase.

The spin polarization of CrO2 revisited

Here, we use Andreev reflection spectroscopy to study the spin polarization of high quality CrO2 films. We study the spin polarization as a function of growth temperature, resulting in grain size and electrical resistivity. In these films low temperature growth appears to be a necessary but not sufficient condition to guarantee the observation of high spin polarization, and this is only observed in conjunction with suppressed superconducting gap values and anomalously low interface properties. We suggest that this combination of observations is a manifestation of the long range spin triplet proximity effect. (C) 2007 American Institute of Physics.