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).

(E)xperimental study of the porosity and microstructure of self-compacting concrete (SCC) with binary and ternary mixes of fly ash and limestone filler

Self-compacting concrete (SCC) can soon be expected to replace conventional concrete due to its many advantages. Its main characteristics in the fresh state are achieved essentially by a higher volume of mortar (more ultrafine material) and a decrease of the coarse-aggregates. The use of over-large volumes of additions such as fly ash (FA) and/or limestone filler (LF) can substantially affect the concrete's pore structure and consequently its durability. In this context, an experimental programme was conducted to evaluate the effect on the concrete's porosity and microstructure of incorporating FA and LF in binary and ternary mixes of SCC. For this, a total of 11 SIX mixes were produced; 1 with cement only (C); 3 with C + FA in 30%, 60% and 70% substitution (fad); 3 with C + LF in 30%, 60% and 70% fad; 4 with C + FA + LF in combinations of 10-20%, 20-10%, 20-40% and 40-20% f(ad), respectively. The results enabled conclusions to be established regarding the SCC's durability, based on its permeability and the microstructure of its pore structure. The properties studied are strongly affected by the type and quantity of additions. The use of ternary mixes also proves to be extremely favourable, confirming the beneficial effect of the synergy between these additions. (C) 2015 Elsevier Ltd. All rights reserved.

Experimental study of the porosity and microstructure of self-compacting concrete (SCC) with binary and ternary mixes of fly ash and limestone filler

Abstract Self-compacting concrete (SCC) can soon be expected to replace conventional concrete due to its many advantages. Its main characteristics in the fresh state are achieved essentially by a higher volume of mortar (more ultrafine material) and a decrease of the coarse-aggregates. The use of over-large volumes of additions such as fly ash (FA) and/or limestone filler (LF) can substantially affect the concrete's pore structure and consequently its durability. In this context, an experimental programme was conducted to evaluate the effect on the concrete's porosity and microstructure of incorporating FA and LF in binary and ternary mixes of SCC. For this, a total of 11 SCC mixes were produced: 1 with cement only (C); 3 with C + FA in 30%, 60% and 70% substitution (fad); 3 with C + LF in 30%, 60% and 70% fad; 4 with C + FA + LF in combinations of 10-20%, 20-10%, 20-40% and 40-20% fad, respectively. The results enabled conclusions to be established regarding the SCC's durability, based on its permeability and the microstructure of its pore structure. The properties studied are strongly affected by the type and quantity of additions. The use of ternary mixes also proves to be extremely favourable, confirming the beneficial effect of the synergy between these additions. © 2015 Elsevier Ltd. All rights reserved.

Fresh-state properties of self-compacting mortar and concrete with combined use of limestone filler and fly ash

This paper presents the results of a study on the behaviour of self-compacting concrete (SCC) in the fresh and hardened states, produced with binary and ternary mixes of fly ash (FA) and limestone filler (LF), using the method proposed by Nepomuceno. His method determines the SCC composition parameters in the mortar phase (self-compacting mortar - SCM) easily and efficiently, whilst guaranteeing the SCC properties in both the fresh and hardened states. For this, 11 SCMs were studied: one with cement (C) only; three with FA at 30%, 60% and 70% C substitution; three with LF at 30%, 60% and 70% C substitution; four with FA + LF in combinations of 10-20%, 20-10%, 20-40% and 40-20% C substitution. Once the composition of these mortars was defined, 18 SCC mixes were produced: 14 binary SCC mixes were produced with the seven binary mortar mixes, and four ternary SCC mixes were produced with the four ternary mortar mixes. In addition to the methodology proposed by Nepomuceno, the combined use of FA and LF in ternary mixtures was tested. The results confirmed that the method could yield SCC with adequate properties in both the fresh and hardened states. It was also possible to determine the SCC composition parameters in the mortar phase (self-compacting mortar - SCM) that will guarantee the SCC properties in both the fresh and hardened states, as confirmed through the optimized behaviour of the SCC in the fresh state and the promising results in the hardened state (compressive strength). The potential demonstrated by the joint use of LF and FA through the synergetic interaction of both additions is emphasized.

Durability performance of self-compacting concrete (SCC) with binary and ternary mixes of fly ash and limestone filler

The basic objective of this work is to evaluate the durability of self-compacting concrete (SCC) produced in binary and ternary mixes using fly ash (FA) and limestone filler (LF) as partial replacement of cement. The main characteristics that set SCC apart from conventional concrete (fundamentally its fresh state behaviour) essentially depend on the greater or lesser content of various constituents, namely: greater mortar volume (more ultrafine material in the form of cement and mineral additions); proper control of the maximum size of the coarse aggregate; use of admixtures such as superplasticizers. Significant amounts of mineral additions are thus incorporated to partially replace cement, in order to improve the workability of the concrete. These mineral additions necessarily affect the concrete’s microstructure and its durability. Therefore, notwithstanding the many well-documented and acknowledged advantages of SCC, a better understanding its behaviour is still required, in particular when its composition includes significant amounts of mineral additions. An ambitious working plan was devised: first, the SCC’s microstructure was studied and characterized and afterwards the main transport and degradation mechanisms of the SCC produced were studied and characterized by means of SEM image analysis, chloride migration, electrical resistivity, and carbonation tests. It was then possible to draw conclusions about the SCC’s durability. The properties studied are strongly affected by the type and content of the additions. Also, the use of ternary mixes proved to be extremely favourable, confirming the expected beneficial effect of the synergy between LF and FA. © 2015 RILEM.

Durability performance of self-compacting concrete (SCC) with binary and ternary mixes of fly ash and limestone filler

The basic objective of this work is to evaluate the durability of self-compacting concrete (SCC) produced in binary and ternary mixes using fly ash (FA) and limestone filler (LF) as partial replacement of cement. The main characteristics that set SCC apart from conventional concrete (fundamentally its fresh state behaviour) essentially depend on the greater or lesser content of various constituents, namely: greater mortar volume (more ultrafine material in the form of cement and mineral additions); proper control of the maximum size of the coarse aggregate; use of admixtures such as superplasticizers. Significant amounts of mineral additions are thus incorporated to partially replace cement, in order to improve the workability of the concrete. These mineral additions necessarily affect the concrete's microstructure and its durability. Therefore, notwithstanding the many well-documented and acknowledged advantages of SCC, a better understanding its behaviour is still required, in particular when its composition includes significant amounts of mineral additions. An ambitious working plan was devised: first, the SCC's microstructure was studied and characterized and afterwards the main transport and degradation mechanisms of the SCC produced were studied and characterized by means of SEM image analysis, chloride migration, electrical resistivity, and carbonation tests. It was then possible to draw conclusions about the SCC's durability. The properties studied are strongly affected by the type and content of the additions. Also, the use of ternary mixes proved to be extremely favourable, confirming the expected beneficial effect of the synergy between LF and FA.

Experimental study of the mechanical properties and durability of self-compacting mortars with nano materials (SiO2 and TiO2)

Resumo: Cement, as well as the remaining constituents of self-compacting mortars, must be carefully selected, in order to obtain an adequate composition with a granular mix as compact as possible and a good performance in the fresh state (self-compacting effect) and the hardened state (mechanical and durability-related behavior). Therefore in this work the possibility of incorporating nano particles in self-compacting mortars was studied. Nano materials are very reactive due mostly to their high specific surface and show a great potential to improve the properties of these mortars, both in mechanical and durability terms. In this work two nano materials were used, nano silica (nano SiO2) in colloidal state and nano titanium (nano TiO2) in amorphous state, in two types of self-compacting mortars (ratio binder:sand of 1:1 and 1:2). The self-compacting mortar mixes have the same water/cement ratio and 30% of replacement of cement with fly ashes. The influence of nano materials nano-SiO2 and nano-TiO2 on the fresh and hardened state properties of these self-compacting mortars was studied. The results show that the use of nano materials in repair and rehabilitation mortars has significant potential but still needs to be optimized. (C) 2015 Elsevier Ltd. All rights reserved.

Sistema de fundações para postes de catenária com betão com pré-colocação de agregados (PAC)

Trabalho de Projecto de natureza científica para obtenção do grau de Mestre em Engenharia Civil

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.

Phase growth control in low temperature PLD Co: TiO2 films by pressure

This paper reports on the structural and optical properties of Co-doped TiO2 thin films grown onto (0001)Al2O3 substrates by non-reactive pulsed laser deposition (PLD) using argon as buffer gas. It is shown that by keeping constant the substrate temperature at as low as 310 degrees C and varying only the background gas pressure between 7 Pa and 70 Pa, it is possible to grow either epitaxial rutile or pure anatase thin films, as well as films with a mixture of both polymorphs. The optical band gaps of the films are red shifted in comparison with the values usually reported for undoped TiO2, which is consistent with n-type doping of the TiO2 matrix. Such band gap red shift brings the absorption edge of the Co-doped TiO2 films into the visible region, which might favour their photocatalytic activity. Furthermore, the band gap red shift depends on the films' phase composition, increasing with the increase of the Urbach energy for increasing rutile content. (C) 2012 Elsevier B.V. All rights reserved.

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.

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.

Structural and optical studies of Au doped titanium oxide films

Thin films of TiO2 were doped with Au by ion implantation and in situ during the deposition. The films were grown by reactive magnetron sputtering and deposited in silicon and glass substrates at a temperature around 150 degrees C. The undoped films were implanted with Au fiuences in the range of 5 x 10(15) Au/cm(2)-1 x 10(17) Au/cm(2) with a energy of 150 keV. At a fluence of 5 x 10(16) Au/cm(2) the formation of Au nanoclusters in the films is observed during the implantation at room temperature. The clustering process starts to occur during the implantation where XRD estimates the presence of 3-5 nm precipitates. After annealing in a reducing atmosphere, the small precipitates coalesce into larger ones following an Ostwald ripening mechanism. In situ XRD studies reveal that Au atoms start to coalesce at 350 degrees C, reaching the precipitates dimensions larger than 40 nm at 600 degrees C. Annealing above 700 degrees C promotes drastic changes in the Au profile of in situ doped films with the formation of two Au rich regions at the interface and surface respectively. The optical properties reveal the presence of a broad band centered at 550 nm related to the plasmon resonance of gold particles visible in AFM maps. (C) 2011 Elsevier B.V. All rights reserved.

Determination of airborne nanoparticles from welding operations

The aim of this study is to assess the levels of airborne ultrafine particles emitted in welding processes (tungsten inert gas [TIG], metal active gas [MAG] of carbon steel, and friction stir welding [FSW] of aluminum) in terms of deposited area in pulmonary alveolar tract using a nanoparticle surface area monitor (NSAM) analyzer. The obtained results showed the dependence of process parameters on emitted ultrafine particles and demonstrated the presence of ultrafine particles compared to background levels. Data indicated that the process that resulted in the lowest levels of alveolar deposited surface area (ADSA) was FSW, followed by TIG and MAG. However, all tested processes resulted in significant concentrations of ultrafine particles being deposited in humans lungs of exposed workers.

Formation of oriented nickel aggregates in rutile single crystals by Ni implantation

The magnetic and electrical properties of Ni implanted single crystalline TiO2 rutile were studied for nominal implanted fluences between 0.5 x 10(17) cm(-2) and 2.0 x 10(17) cm(-2) with 150 keV energy, corresponding to maximum atomic concentrations between 9 at% and 27 at% at 65 nm depth, in order to study the formation of metallic oriented aggregates. The results indicate that the as implanted crystals exhibit superparamagnetic behavior for the two higher fluences, which is attributed to the formation of nanosized nickel clusters with an average size related with the implanted concentration, while only paramagnetic behavior is observed for the lowest fluence. Annealing at 1073 K induces the aggregation of the implanted nickel and enhances the magnetization in all samples. The associated anisotropic behavior indicates preferred orientations of the nickel aggregates in the rutile lattice consistent with Rutherford backscattering spectrometry-channelling results. Electrical conductivity displays anisotropic behavior but no magnetoresistive effects were detected. (C) 2013 Elsevier B.V. All rights reserved.