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.

Unstabilized rammed Earth: characterization of material collected from old constructions in South Portugal and comparison to normative requirements

Unstabilized rammed earth is a recyclable, economical, and eco-friendly building material, used in the past and still applied today. Traditionally, its use was based on a long empirical knowledge of the local materials. Because this knowledge was mostly lost or is no longer sufficient, in many countries normative documents have been produced to allow the assessment of rammed earth soils. With the aim of contributing for a refining of these normative requirements, this article presents a research work that included: (i) collection of Unstabilized rammed earth samples from six constructions in Portugal; (ii) a literature survey of normative and complementary documents to identify the most mentioned key-properties, the test procedures and the corresponding threshold limits; and (iii) a discussion of the test procedures and of the thresholds limits in the light of the experimental results. The analyzed properties are the particle size distribution, maximum particle size, plasticity, compaction, linear shrinkage, organic content, and salt content. The work highlights the advantages of taking into account the characteristics of existing constructions as a basis for the establishment and further refining of consistent threshold values. In particular, it shows that it is essential to adjust the requirements to the specificities of local materials.

Physical, chemical and mineralogical properties of fine recycled aggregates made from concrete waste

This paper assesses the physical, chemical and mineralogical characteristics of fine recycled aggregates obtained from crushed concrete waste, comparing them with two types of natural fine aggregates from different origins. A commercial concrete was jaw crushed, and the effect of different aperture sizes on the particle size distribution of the resulting aggregates was evaluated. The density and water absorption of the recycled aggregates was determined and a model for predicting water absorption over time is proposed. Both natural and recycled aggregates were characterized regarding bulk density and fines content. Recycled aggregates were additionally characterized by XRD, SEM/EDS and DTA/TG of individual size fractions. The results show that natural and recycled fine aggregates have very different characteristics. This should be considered in potential applications, both in terms of the limits for replacing amounts and of the rules and design criteria of the manufactured products. (C) 2015 Elsevier Ltd. All rights reserved.

Rheological behaviour of concrete made with fine recycled concrete aggregates - Influence of the superplasticizer

This paper evaluates the influence of two superplasticizers (SP) on the rheological behaviour of concrete made with fine recycled concrete aggregates (FRCA). Three families of concrete were tested: family CO made without SP, family Cl made with a regular superplasticizer and family C2 made with a high-performance superplasticizer. Five replacement ratios of natural sand by FRCA were tested: 0%, 10%, 30%, 50% and 100%. The coarse aggregates were natural gravels. Three criteria were established to design the concrete mixes' composition: keep the same particle size distribution curves, adjust the water/cement ratio to obtain a similar slump and no pre-saturation of the FRCA. All mixes had the same cement and SP content. The results show that the incorporation of FRCA significantly increased the shrinkage and creep deformation. The FRCA's effect was influenced by the curing age. The reference concrete made with natural sand stabilizes the creep deformation faster than the mixes made with FRCA. The incorporation of superplasticizer increased the shrinkage at early ages and decreased the shrinkage at 91 days of age. The regular superplasticizer did not improve the creep deformation while the high-performance superplasticizer highly improved this property. The incorporation of FRCA jeopardized the SP's effectiveness. This study demonstrated that to use FRCA and superplasticizer for concrete production it is necessary to take into account the different rheological behaviour of these mixes. (C) 2015 Elsevier Ltd. All rights reserved.

Unstabilised rammed earth: characterization of material collected from old constructions in South Portugal and comparison to normative requirements

International Journal of Architectural Heritage, 8: 185–212, 2014

Hygrothermal behaviour of earthen plasters for sustainable housing construction

A ready-mixed and several laboratory formulated mortars were produced and tested in fresh state and after hardening, simulating a masonry plaster for indoor application. All the mortars used a clayish earth from the same region and different compositions of aggregates, eventually including fibres and a phase change material. All the formulated mortars were composed by 1:3 volumetric proportions of earth and aggregate. Tests were developed for consistency, fresh bulk density, thermal conductivity, capillary absorption and drying, water vapour permeability and sorption-desorption. The use of PCM changed drastically the workability of the mortars and increased their capillary absorption. The use of fibres and variations on particle size distribution of the mixtures of sand that were used had no significant influence on tested properties. But particularly the good workability of these mortars and the high capacity of sorption and desorption was highlighted. With this capacity plasters made with these mortars are able to adsorb water vapour from indoor atmosphere when high levels of relative humidity exist and release water vapour when the indoor atmosphere became too dry. This fact makes them able to contribute passively for a healthier indoor environment. The technical, ecological and environmental advantages of the application of plasters with this type of mortars are emphasized, with the aim of contributing for an increased use for new or existent housing.

Modeling and simulation of population balances for particulate processes

This work focuses on the modeling and numerical approximations of population balance equations (PBEs) for the simulation of different phenomena occurring in process engineering. The population balance equation (PBE) is considered to be a statement of continuity. It tracks the change in particle size distribution as particles are born, die, grow or leave a given control volume. In the population balance models the one independent variable represents the time, the other(s) are property coordinate(s), e.g., the particle volume (size) in the present case. They typically describe the temporal evolution of the number density functions and have been used to model various processes such as granulation, crystallization, polymerization, emulsion and cell dynamics. The semi-discrete high resolution schemes are proposed for solving PBEs modeling one and two-dimensional batch crystallization models. The schemes are discrete in property coordinates but continuous in time. The resulting ordinary differential equations can be solved by any standard ODE solver. To improve the numerical accuracy of the schemes a moving mesh technique is introduced in both one and two-dimensional cases ...

Albuterol delivery in an in vitro pediatric ventilator lung model: comparison of jet, ultrasonic, and mesh nebulizers.

OBJECTIVE: : To determine the influence of nebulizer types and nebulization modes on bronchodilator delivery in a mechanically ventilated pediatric lung model. DESIGN: : In vitro, laboratory study. SETTING: : Research laboratory of a university hospital. INTERVENTIONS: : Using albuterol as a marker, three nebulizer types (jet nebulizer, ultrasonic nebulizer, and vibrating-mesh nebulizer) were tested in three nebulization modes in a nonhumidified bench model mimicking the ventilatory pattern of a 10-kg infant. The amounts of albuterol deposited on the inspiratory filters (inhaled drug) at the end of the endotracheal tube, on the expiratory filters, and remaining in the nebulizers or in the ventilator circuit were determined. Particle size distribution of the nebulizers was also measured. MEASUREMENTS AND MAIN RESULTS: : The inhaled drug was 2.8% ± 0.5% for the jet nebulizer, 10.5% ± 2.3% for the ultrasonic nebulizer, and 5.4% ± 2.7% for the vibrating-mesh nebulizer in intermittent nebulization during the inspiratory phase (p < 0.01). The most efficient nebulizer was the vibrating-mesh nebulizer in continuous nebulization (13.3% ± 4.6%, p < 0.01). Depending on the nebulizers, a variable but important part of albuterol was observed as remaining in the nebulizers (jet and ultrasonic nebulizers), or being expired or lost in the ventilator circuit (all nebulizers). Only small particles (range 2.39-2.70 µm) reached the end of the endotracheal tube. CONCLUSIONS: : Important differences between nebulizer types and nebulization modes were seen for albuterol deposition at the end of the endotracheal tube in an in vitro pediatric ventilator-lung model. New aerosol devices, such as ultrasonic and vibrating-mesh nebulizers, were more efficient than the jet nebulizer.

Design and evaluation of a solid sampler for the monitoring of airborne 1,6-hexamethylene diisocyanate (HDI) and its prepolymers in 2-component spray painting

An active, solvent-free solid sampler was developed for the collection of 1,6-hexamethylene diisocyanate (HDI) aerosol and prepolymers. The sampler was made of a filter impregnated with 1-(2-methoxyphenyl)piperazine contained in a filter holder. Interferences with HDI were observed when a set of cellulose acetate filters and a polystyrene filter holder were used; a glass fiber filter and polypropylene filter cassette gave better results. The applicability of the sampling and analytical procedure was validated with a test chamber, constructed for the dynamic generation of HDI aerosol and prepolymers in commercial two-component spray paints (Desmodur(R) N75) used in car refinishing. The particle size distribution, temporal stability, and spatial uniformity of the simulated aerosol were established in order to test the sample. The monitoring of aerosol concentrations was conducted with the solid sampler paired to the reference impinger technique (impinger flasks contained 10 mL of 0.5 mg/mL 1-(2-methoxyphenyl)piperazine in toluene) under a controlled atmosphere in the test chamber. Analyses of derivatized HDI and prepolymers were carried out by using high-performance liquid chromatography and ultraviolet detection. The correlation between the solvent-free and the impinger techniques appeared fairly good (Y = 0.979X - 0.161; R = 0.978), when the tests were conducted in the range of 0.1 to 10 times the threshold limit value (TLV) for HDI monomer and up to 60-mu-g/m3 (3 U.K. TLVs) for total -N = C = O groups.

Gold nanoparticles functionalized with gadolinium chelates as high-relaxivity MRI contrast agents

Water-dispersible gold nanoparticles functionalized with paramagnetic gadolinium have been fully characterized, and the NMRD profiles show very high relaxivities up to 1.5 T. Characterization using TEM images and dynamic light scattering indicate a particle size distribution from 2 to 15 nm. The gold cores of the nanoparticles do not contribute significantly to the overall magnetic moment.

A system to test the toxicity of brake wear particles

Fine particulate matter from traffic increases mortality and morbidity. An important source of traffic particles is brake wear. American studies reported cars to emit break wear particles at a rate of about 11mg/km to 20mg/km of driven distance. A German study estimated that break wear contributes about 12.5% to 21% of the total traffic particle emissions. The goal of this study was to build a system that allows the study of brake wear particle emissions during different braking behaviours of different car and brake types. The particles should be characterize in terms of size, number, metal, and elemental and organic carbon composition. In addition, the influence of different deceleration schemes on the particle composition and size distribution should be studied. Finally, this system should allow exposing human cell cultures to these particles. An exposure-box (0.25 cubic-m volume) was built that can be mounted around a car's braking system. This allows exposing cells to fresh brake wear particles. Concentrations of particle numbers, mass and surface, metals, and carbon compounds were quantified. Tests were conducted with A549 lung epithelial cells. Five different cars and two typical braking behaviours (full stop and normal deceleration) were tested. Particle number and size distribution was analysed for the first six minutes. In this time, two braking events occurred. Full stop produced significantly higher particle concentrations than normal deceleration (average of 23'000 vs. 10'400 #/cm3, p= 0.016). The particle number distribution was bi-modal with one peak at 60 to 100 nm (depending on the tested car and braking behaviour) and a second peak at 200 to 400 nm. Metal concentrations varied depending on the tested car type. Iron (range of 163 to 15'600 μg/m3) and Manganese (range of 0.9 to 135 μg/m3) were present in all samples, while Copper was absent in some samples (<6 to 1220 μg/m3). The overall "fleet" metal ratio was Fe:Cu:Mn = 128:14:1. Temperature and humidity varied little. A549-cells were successfully exposed in the various experimental settings and retained their viability. Culture supernatant was stored and cell culture samples were fixated to test for inflammatory response. Analysis of these samples is ongoing. The established system allowed testing brake wear particle emissions from real-world cars. The large variability of chemical composition and emitted amounts of brake wear particles between car models seems to be related to differences between brake pad compositions of different producers. Initial results suggest that the conditions inside the exposure box allow exposing human lung epithelial cells to freshly produced brake wear particles.

Leptonic secondary emission in a hadronic microquasar model

Context.It has been proposed that the origin of the very high-energy photons emitted from high-mass X-ray binaries with jet-like features, so-called microquasars (MQs), is related to hadronic interactions between relativistic protons in the jet and cold protons of the stellar wind. Leptonic secondary emission should be calculated in a complete hadronic model that includes the effects of pairs from charged pion decays inside the jets and the emission from pairs generated by gamma-ray absorption in the photosphere of the system. Aims.We aim at predicting the broadband spectrum from a general hadronic microquasar model, taking into account the emission from secondaries created by charged pion decay inside the jet. Methods.The particle energy distribution for secondary leptons injected along the jets is consistently derived taking the energy losses into account. The spectral energy distribution resulting from these leptons is calculated after assuming different values of the magnetic field inside the jets. We also compute the spectrum of the gamma-rays produced by neutral pion-decay and processed by electromagnetic cascades under the stellar photon field. Results.We show that the secondary emission can dominate the spectral energy distribution at low energies (~1 MeV). At high energies, the production spectrum can be significantly distorted by the effect of electromagnetic cascades. These effects are phase-dependent, and some variability modulated by the orbital period is predicted.

Estimation of water retention and availability in soils of Rio Grande do Sul

Dispersed information on water retention and availability in soils may be compiled in databases to generate pedotransfer functions. The objectives of this study were: to generate pedotransfer functions to estimate soil water retention based on easily measurable soil properties; to evaluate the efficiency of existing pedotransfer functions for different geographical regions for the estimation of water retention in soils of Rio Grande do Sul (RS); and to estimate plant-available water capacity based on soil particle-size distribution. Two databases were set up for soil properties, including water retention: one based on literature data (725 entries) and the other with soil data from an irrigation scheduling and management system (239 entries). From the literature database, pedotransfer functions were generated, nine pedofunctions available in the literature were evaluated and the plant-available water capacity was calculated. The coefficient of determination of some pedotransfer functions ranged from 0.56 to 0.66. Pedotransfer functions generated based on soils from other regions were not appropriate for estimating the water retention for RS soils. The plant-available water content varied with soil texture classes, from 0.089 kg kg-1 for the sand class to 0.191 kg kg-1 for the silty clay class. These variations were more related to sand and silt than to clay content. The soils with a greater silt/clay ratio, which were less weathered and with a greater quantity of smectite clay minerals, had high water retention and plant-available water capacity.

Aggregation of subtropical soil under liming: a study using laser diffraction

Laser diffraction (LD) provides detailed analysis of particle size distribution. Its application to testing the stability of soil aggregates can assist studies on the aggregation of soils with contrasting electrochemical properties. The objectives of the present work were: (a) to propose a protocol for using LD to study soil aggregation, (b) to study the aggregation of an Acrisol under the influence of different doses and forms of lime. Samples were collected in 2005 from a Brazilian Acrisol that in 1994 had received 0.0; 2.0; 8.5 and 17.0 Mg ha-1 of lime, left on the soil surface or incorporated. Aggregates from 4.76 to 8.00 mm diameters were studied using the traditional method proposed by Kemper & Chepil (1965), with wet sieving, while aggregates from 1.00 to 2.00 mm were studied using a CILAS® laser diffractometer that distinguishes particles ranging from 0.04 to 2,500.00 μm. LD readings were made after six consecutive pre-treatments, using agitation times, a chemical dispersion agent and ultrasound. Mean Weighted Diameter (MWD) and the Aggregate Stability Index (ASI) calculated, using the traditional method does not discriminate the treatments. However, LD is able to produce detailed data on soil aggregation, resulting in indexes of stability of aggregates that are linearly related to the doses of lime applied (MWD: R² = 0.986 and ASI: R² = 0.876). It may be concluded that electrochemical changes in the Brazilian Acrisol resulting from incorporated lime affect the stability of aggregates, increasing stability with increased doses of lime.

Structural changes in latosols of the cerrado region: II - soil compressive behavior and modeling of additional compaction

Currently in Brazil, as in other parts of the world, the concern is great with the increase of degraded agricultural soil, which is mostly related to the occurrence of soil compaction. Although soil texture is recognized as a very important component in the soil compressive behaviors, there are few studies that quantify its influence on the structural changes of Latosols in the Brazilian Cerrado region. This study aimed to evaluate structural changes and the compressive behavior of Latosols in Rio Verde, Goiás, through the modeling of additional soil compaction. The study was carried out using five Latosols with very different textures, under different soil compaction levels. Water retention and soil compression curves, and bearing capacity models were determined from undisturbed samples collected on the B horizons. Results indicated that clayey and very clayey Latosols were more susceptible to compression than medium-textured soils. Soil compression curves at density values associate with edaphic functions were used to determine the beneficial pressure (σ b) , i.e., pressure with optimal water retention, and critical pressure (σcrMAC), i.e., pressure with macroporosity below critical levels. These pressure values were higher than the preconsolidation pressure (σp), and therefore characterized as additional compaction. Based on the compressive behavior of these Latosols, it can be concluded that the combined preconsolidation pressure, beneficial pressure and critical pressure allow a better understanding of compression processes of Latosols.