Magnetic properties of Co-doped TiO(2) anatase nanopowders

This letter reports on the magnetic properties of Ti(1-x)Co(x)O(2) anatase phase nanopowders with different Co contents. It is shown that oxygen vacancies play an important role in promoting long-range ferromagnetic order in the material studied in addition to the transition-metal doping. Furthermore, the results allow ruling out the premise of a strict connection between Co clustering and the ferromagnetism observed in the Co:TiO(2) anatase system.

Synthesis of titanate nanostructures using amorphous precursor material and their adsorption/photocatalytic properties

This article reports on a new and swift hydrothermal chemical route to prepare titanate nanostructures (TNS) avoiding the use of crystalline TiO2 as starting material. The synthesis approach uses a commercial solution of TiCl3 as titanium source to prepare an amorphous precursor, circumventing the use of hazardous chemical compounds. The influence of the reaction temperature and dwell autoclave time on the structure and morphology of the synthesised materials was studied. Homogeneous titanate nanotubes with a high length/diameter aspect ratio were synthesised at 160 degrees C and 24 h. A band gap of 3.06 +/- 0.03 eV was determined for the TNS samples prepared in these experimental conditions. This value is red shifted by 0.14 eV compared to the band gap value usually reported for the TiO2 anatase. Moreover, such samples show better adsorption capacity and photocatalytic performance on the dye rhodamine 6G (R6G) photodegradation process than TiO2 nanoparticles. A 98% reduction of the R6G concentration was achieved after 45 min of irradiation of a 10 ppm dye aqueous solution and 1 g L-1 of TNS catalyst.

alpha-Co(OH)(2)/carbon nanofoam composite as electrochemical capacitor electrode operating at 2 V in aqueous medium

In this work, alpha-Co(OH)(2) is electrodeposited onto carbon nanofoam forming a composite electrode operating in a potential window of 2 V in aqueous medium. Prior to electrodeposition, the carbon nanofoam substrate is subjected to a functionalization process, which leads to an increase of about 40% in its specific capacitance value. Formation of cobalt hydroxide clusters onto the functionalized carbon nanofoam by pulse electrodeposition further enhances the specific capacitance of the electrode. The combination of these factors with an enlarged working potential window, results in a material with specific capacitance close to 300 F g(-1) at current density of 1 A g(-1), considering the total mass loading of the composite. This suggests the potential application of the prepared composites in high energy density electrochemical supercapacitors. (c) 2015 Elsevier B.V. All rights reserved.

Influence of the substrate on structure and magnetic properties of Co-N thin films

Cubic cobalt nitride films were grown onto different single crystalline substrates Al2O3 (0 0 0 1) and (1 1 View the MathML source 0), MgO (1 0 0) and (1 1 0) and TiO2 (1 0 0) and (1 1 0). The films display low atomic densities compared with the bulk material, are ferromagnetic and have metallic electrical conductivity. X-ray diffraction and X-ray absorption fine structure confirm the cubic structure of the films and with RBS results indicate that samples are not homogeneous at the microscopic scale, coexisting Co4+xN nitride with nitrogen rich regions. The magnetization of the films decreases with increase of the nitrogen content, variation that is shown to be due to the decrease of the cobalt density, and not to a decrease of the magnetic moment per cobalt ion. The films are crystalline with a nitrogen deficient stoichiometry and epitaxial with orientation determined by the substrate.

Synthesis of titanate nanofibers co-sensitized with ZnS and Bi2S3 nanocrystallites and their application on pollutants removal

The synthesis of nanocomposite materials combining titanate nanofibers (TNF) with nanocrystalline ZnS and Bi2S3 semiconductors is described in this work. The TNF were produced via hydrothermal synthesis and sensitized with the semiconductor nanoparticles, through a single-source precursor decomposition method. ZnS and Bi2S3 nanoparticles were successfully grown onto the TNF's surface and Bi2S3-ZnS/TNF nanocomposite materials with different layouts. The samples' photocatalytic performance was first evaluated through the production of the hydroxyl radical using terephthalic acid as probe molecule. All the tested samples show photocatalytic ability for the production of this oxidizing species. Afterwards, the samples were investigated for the removal of methylene blue. The nanocomposite materials with best adsorption ability were the ZnS/TNF and Bi2S3ZnS/TNF. The dye removal was systematically studied, and the most promising results were obtained considering a sequential combination of an adsorption-photocatalytic degradation process using the Bi2S3ZnS/TNF powder as a highly adsorbent and photocatalyst material. (C) 2015 Elsevier Ltd. All rights reserved.

Influência da longevidade da solução de Verhoeff na intensidade/especificidade das fibras elásticas, em material biológico de origem suína

As fibras elásticas são responsáveis pela elasticidade e flexibilidade dos tecidos. A técnica de Verhoeff é o método mais utilizado para demonstrar a presença destas fibras, corando-as de preto. A solução de Verhoeff é exclusivamente utilizada de um modo extemporâneo, no entanto, pela revisão da literatura verificou-se que a mesma poderia ter uma maior durabilidade. O presente estudo tem como principal objectivo determinar a longevidade da solução de Verhoeff. Utilizou-se material biológico de origem suína,fixado em formol neutro tamponado a 10% e incluído em parafina. Foi avaliado um total de 33 lâminas segundo critérios de intensidade e especificidade. Os resultados obtidos provam que o tempo tem influência sobre a referida solução, levando à perda de intensidade de coloração, não se tendo registado alterações significativas a nível de especificidade. Concluiu-se que a solução de Verhoeff pode não ser uma solução descartável, encontrando-se em perfeitas condições de utilização até às 48h de repouso.

Ash deposition during the co-firing of bituminous coal with pine sawdust and olive stones in a laboratory furnace

This article describes an experimental study on ash deposition during the co-firing of bituminous coal with pine sawdust and olive stones in a laboratory furnace. The main objective of this study was to relate the ash deposit rates with the type of biomass burned and its thermal percentage in the blend. The thermal percentage of biomass in the blend was varied between 10% and 50% for both sawdust and olive stones. For comparison purposes, tests have also been performed using only coal or only biomass. During the tests, deposits were collected with the aid of an air-cooled deposition probe placed far from the flame region, where the mean gas temperature was around 640 degrees C. A number of deposit samples were subsequently analyzed on a scanning electron microscope equipped with an energy dispersive X-ray detector. Results indicate that blending sawdust with coal decreases the deposition rate as compared with the firing of unblended coal due to both the sawdust low ash content and its low alkalis content. The co-firing of coal and sawdust yields deposits with high levels of silicon and aluminium which indicates the presence of ashes with high fusion temperature and, thus, with less capacity to adhere to the surfaces. In contrast, in the co-firing of coal with olive stones the deposition rate increases as compared with the firing of unblended coal and the deposits produced present high levels of potassium, which tend to increase their stickiness.

Hydroisomerization of n-decane over SAPO-11 catalysts synthesized with methylamine as co-template

The present work deals with preliminary studies concerning a new synthesis approach to prepare SAPO materials with AEL structure and evaluate their catalytic behavior in the hydroisomerization of long paraffins. The new SAPO-11 catalysts were synthesized with the help of a small amine (methylamine, MA) added during the preparation of the initial gel. As MA incorporates into the structure of the final materials, it contributes, together with DPA (dipropylamine), to an increase in Si incorporation as isolated species, which results in Bronsted acid sites. Thus, this new and original synthesis strategy allows to obtain materials with enhanced Bronsted acidity when compared with free MA materials. The catalysts were tested in n-decane hydroisomerization (n-decane was used as a model molecule) and confirmed the effect of MA on the acidic properties of the catalysts. The samples synthesized with MA present a higher number of acid sites that increase the catalytic conversion but have a negative effect in the isomerization selectivity, i.e. a more significant amount of cracking products is formed.

Avaliação da exposição de crianças a material particulado em suspensão

Este trabalho teve como principal objectivo caracterizar a exposição de crianças a partículas atmosféricas e aos elementos químicos que as constituem. Pretendeu-se também determinar as fontes e processos que afectam os níveis e composição das partículas em suspensão no ar ambiente e no interior de salas de aula de escolas do 1º ciclo localizadas no centro de Lisboa. Os efeitos das partículas atmosféricas na saúde humana manifestam-se sobretudo ao nível do aparelho respiratório, dependendo da sua composição química, e principalmente da sua dimensão. As partículas inaláveis (PM10) podem depositar-se nas unidades funcionais do sistema respiratório. O PM2,5 podem atingir os alvéolos pulmonares e penetrar no sistema circulatório. As crianças são um dos principais grupos de risco, visto que os seus órgãos e tecidos ainda estão em desenvolvimento, ficando mais susceptíveis à exposição de partículas. A recolha de material particulado foi realizada no ar ambiente recorrendo a um colector PARTISOL e no interior e exterior das escolas usando amostradores GENT. A concentração total de partículas em suspensão foi determinada por gravimetria. A caracterização química da matéria particulada foi efectuada por Análise por Activação com Neutrões (INAA) para a determinação da concentração dos elementos e por Cromatografia Iónica para a quantificação de iões solúveis em água. Em 2007, a concentração média anual de PM2,5 no Centro de Lisboa foi de 18µg/m3. Através da Análise de Componentes Principais e Regressão Multilinear verificou-se que a massa das partículas da fracção fina resulta essencialmente da produção de aerossóis secundários (35%) de uma fonte de cálcio (28%) e da emissão de poluentes por veículos motorizados (23%). No interior das escolas verificou-se que as concentrações de partículas são mais elevadas comparativamente com o ambiente exterior, principalmente no PM2,5-10 (74µg/m3). A ressuspensão de partículas causada pelas actividades desempenhadas no interior das salas e a suspensão de poeiras do solo transportada pelas crianças, são as principais causas apontadas. O Ca é o elemento maioritário no interior das escolas. Os resultados obtidos neste trabalho não excederam os limites estabelecidos pela Legislação Portuguesa.

Riscos da co-incineração ou co-incineração dos riscos? Análise das controvérsias sobre resíduos industriais perigosos

A co-incineração constitui um método de tratamento de resíduos industriais, introduzido em diversos países e proposto também em Portugal, como alternativa à construção de centrais de incineração “dedicada”. A co-incineração consiste na queima de resíduos, incluindo resíduos industriais perigosos, em fornos de fábricas cimenteiras, onde são utilizados como combustível. Motivos de ordem ambiental, assim como de ordem económica, têm sido invocados em defesa do recurso a esse método como parte de estratégias de gestão dos resíduos industriais.

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.

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).

KrP laser CVD of chromium oxide by photodissociation of Cr(CO)(6)

This work reports on the synthesis of chromium oxide thin films prepared by photodissociation of Cr(CO)(6) in an oxidizing atmosphere, using a pulsed UV laser (KrF, lambda = 248 nm). The experimental conditions, which should enable the synthesis of CrO2, are discussed and results on the deposition of CrxOy films on Al2O3 (0001) substrates are presented.

Fabrication of Three-Dimensional Dendritic Ni-Co Films By Electrodeposition on Stainless Steel Substrates

Co-deposition of nickel and cobalt was carried out on austenitic stainless steel (AISI 304) substrates by imposing a square waveform current in the cathodic region. The innovative procedure applied in this work allows creating a stable, fully developed, and open porous three-dimensional (3D) dendritic structure, which can be used as electrode for redox supercapacitors. This study investigates in detail the influence of the applied current density on the morphology, mass, and chemical composition of the deposited Ni-Co films and the resulting 3D porous network dendritic structure. The morphology and the physicochemical composition were studied by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (W). The electrochemical behavior of the materials was evaluated by cyclic voltammetry (CV). The results highlight the mechanism involved in the coelectrodeposition process and how the lower limit current density tailors the film composition and morphology, as well as its electrochemical activity.