Adding value [valorization] to tannery fleshings: part II – effect of protein hydrolysates on leather dyeing

The tanning industry generates a high quantity of solid wastes. Therefore, there is a need to create valorization [added value] options for these wastes. The main objective of the present work was to study the effect of protein hydrolysates (HP) prepared from fleshings on leather dyeing. During previous studies it was found that the application of HP products, obtained from fleshings, in leather retannage intensified the colour of crust leather. In this work the CIELAB colour system was used to evaluate the effect of HP on retannage processes. The main conclusions of this study were: (i) HP can be used instead of a dicyanodiamide resin (Fortan DC) if the colour parameters of the standard procedure are to be maintained, and (ii) the replacement of an acrylic resin (Fortan A40) by glutaraldehyde-modified HP (GHP) results in a darker skin, and can therefore be interesting for the reduction of the quantity of dye used.

Complex evolution of a multi-particle system

This paper studies a discrete dynamical system of interacting particles that evolve by interacting among them. The computational model is an abstraction of the natural world, and real systems can range from the huge cosmological scale down to the scale of biological cell, or even molecules. Different conditions for the system evolution are tested. The emerging patterns are analysed by means of fractal dimension and entropy measures. It is observed that the population of particles evolves towards geometrical objects with a fractal nature. Moreover, the time signature of the entropy can be interpreted at the light of complex dynamical systems.

Dynamical behaviour of multi-particle large-scale systems

Collective behaviours can be observed in both natural and man-made systems composed of a large number of elemental subsystems. Typically, each elemental subsystem has its own dynamics but, whenever interaction between individuals occurs, the individual behaviours tend to be relaxed, and collective behaviours emerge. In this paper, the collective behaviour of a large-scale system composed of several coupled elemental particles is analysed. The dynamics of the particles are governed by the same type of equations but having different parameter values and initial conditions. Coupling between particles is based on statistical feedback, which means that each particle is affected by the average behaviour of its neighbours. It is shown that the global system may unveil several types of collective behaviours, corresponding to partial synchronisation, characterised by the existence of several clusters of synchronised subsystems, and global synchronisation between particles, where all the elemental particles synchronise completely.

Task-based occupational exposure assessment and particle number concentration: two important data resources to perform risk assessment for occupational exposure to particles

Environment monitoring has an important role in occupational exposure assessment. However, due to several factors is done with insufficient frequency and normally don´t give the necessary information to choose the most adequate safety measures to avoid or control exposure. Identifying all the tasks developed in each workplace and conducting a task-based exposure assessment help to refine the exposure characterization and reduce assessment errors. A task-based assessment can provide also a better evaluation of exposure variability, instead of assessing personal exposures using continuous 8-hour time weighted average measurements. Health effects related with exposure to particles have mainly been investigated with mass-measuring instruments or gravimetric analysis. However, more recently, there are some studies that support that size distribution and particle number concentration may have advantages over particle mass concentration for assessing the health effects of airborne particles. Several exposure assessments were performed in different occupational settings (bakery, grill house, cork industry and horse stable) and were applied these two resources: task-based exposure assessment and particle number concentration by size. The results showed interesting results: task-based approach applied permitted to identify the tasks with higher exposure to the smaller particles (0.3 μm) in the different occupational settings. The data obtained allow more concrete and effective risk assessment and the identification of priorities for safety investments.

Surface morphology and phase transformations of femtosecond laser-processed saphire

The morphological and structural modifications induced in sapphire by surface treatment with femtosecond laser radiation were studied. Single-crystal sapphire wafers cut parallel to the (0 1 2) planes were treated with 560 fs, 1030 nm wavelength laser radiation using wide ranges of pulse energy and repetition rate. Self-ordered periodic structures with an average spatial periodicity of similar to 300 nm were observed for fluences slightly higher than the ablation threshold. For higher fluences the interaction was more disruptive and extensive fracture, exfoliation, and ejection of ablation debris occurred. Four types of particles were found in the ablation debris: (a) spherical nanoparticles about 50 nm in diameter; (b) composite particles between 150 and 400 nm in size; (c) rounded resolidified particles about 100-500 nm in size; and (d) angular particles presenting a lamellar structure and deformation twins. The study of those particles by selected area electron diffraction showed that the spherical nanoparticles and the composite particles are amorphous, while the resolidified droplets and the angular particles, present a crystalline a-alumina structure, the same of the original material. Taking into consideration the existing ablation theories, it is proposed that the spherical nanoparticles are directly emitted from the surface in the ablation plume, while resolidified droplets are emitted as a result of the ablation process, in the liquid phase, in the low intensity regime, and by exfoliation, in the high intensity regime. Nanoparticle clusters are formed by nanoparticle coalescence in the cooling ablation plume. (C) 2013 Elsevier B.V. All rights reserved.

Role of abrasive material on micro-abrasion wear tests

Micro-abrasion wear tests with ball-cratering configuration are widely used. Sources of variability are already studied by different authors and conditions for testing are parameterized by BS EN 1071-6: 2007 standard which refers silicon carbide as abrasive. However, the use of other abrasives is possible and allowed. In this work, ball-cratering wear tests were performed using four different abrasive particles of three dissimilar materials: diamond, alumina and silicon carbide. Tests were carried out under the same conditions on a steel plate provided with TiB2 hard coating. For each abrasive, five different test durations were used allowing understanding the initial wear phenomena. Composition and shape of abrasive particles were investigated by SEM and EDS. Scar areas were observed by optical and electronic microscopy in order to understand the wear effects caused by each of them. Scar geometry and grooves were analyzed and compared. Wear coefficient was calculated for each situation. It was observed that diamond particles produce well-defined and circular wear scars. Different silicon carbide particles presented dissimilar results as consequence of distinct particle shape and size distribution.

Determiation 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.

Exposure to airborne ultrafine particles from cooking in portuguese homes

Cooking was found to be a main source of submicrometer and ultrafine aerosols from gas combustion in stoves. Therefore, this study consisted of the determination of the alveolar deposited surface area due to aerosols resulting from common domestic cooking activities (boiling fish, vegetables, or pasta, and frying hamburgers and eggs). The concentration of ultrafine particles during the cooking events significantly increased from a baseline of 42.7 mu m(2)/cm(3) (increased to 72.9 mu m(2)/cm(3) due to gas burning) to a maximum of 890.3 mu m(2)/cm(3) measured during fish boiling in water, and a maximum of 4500 mu m(2)/cm(3) during meat frying. This clearly shows that a domestic activity such as cooking can lead to exposures as high as those of occupational exposure activities.

Monitoring exposure to airborne ultrafine particles in Lisbon, Portugal

The aim of this study is to contribute to the assessment of exposure levels of ultrafine particles (UFP) in the urban environment of Lisbon, Portugal, due to automobile traffic, by monitoring lung-deposited alveolar surface area (resulting from exposure to UFP) in a major avenue leading to the town centre during late Spring, as well as in indoor buildings facing it. This study revealed differentiated patterns for week days and weekends, consistent with PM2.5 and PM10 patterns currently monitored by air quality stations in Lisbon. The observed ultrafine particulate levels could be directly related with the fluxes of automobile traffic. During a typical week, UFP alveolar deposited surface area varied between 35.0 and 89.2 mu m(2)/cm(3), which is comparable with levels reported for other towns such in Germany and United States. The measured values allowed the determination of the number of UFP per cm(3), which are comparable to levels reported for Madrid and Brisbane. In what concerns outdoor/indoor levels, we observed higher levels (32-63%) outdoor, which is somewhat lower than levels observed in houses in Ontario.

Micro-abrasion wear behaviour of TiAlCrSiN nanostructured coatings

The injection process of glass fibres reinforced plastics promotes the moulds surface degradation by erosion. In order to improve its wear resistance, several kinds of PVD thin hard coatings were used. It is well-known that nanostructures present a better compromise between hardness and toughness. Indeed, when the coating is constituted by a large number of ultra-thin different layers, cracks and interface troubles tend to decrease. However, it is not clear that these nanostructures present a better wear behaviour in erosion processes. In order to study its wear behaviour, a sputtered PVD nanostructured TiAlCrSiN coating was used. The substrate and film surfaces topography were analyzed by profilometry and atomic force microscopy techniques. Film adhesion to the substrate was evaluated by scratch tests. The surface hardness was measured with a Vickers micro-hardness tester. The wear resistance was evaluated by micro-abrasion with a rotating ball tribometer tests. Slurry of SiC particles in distilled water was used in order to provoke the surface abrasion. Different duration tests were performed in order to analyze the wear evolution. After these tests, the wear mechanisms developed were analyzed by scanning electron microscopy. Wear craters were measured and the wear rate was calculated and discussed. With the same purpose, coated inserts were mounted in an injection mould working with a 30% glass fibres reinforced polypropylene. After 45 000 cycles no relevant wear was registered.

Biofunctional composite coating architectures based on polycaprolactone and nanohydroxyapatite for controlled corrosion activity and enhanced biocompatibility of magnesium AZ31 alloy

In this work a biofunctional composite coating architecture for controlled corrosion activity and enhanced cellular adhesion of AZ31 Mg alloys is proposed. The composite coating consists of a polycaprolactone (PCL) matrix modified with nanohydroxyapatite (HA) applied over a nanometric layer of polyetherimide (PEI). The protective properties of the coating were studied by electrochemical impedance spectroscopy (EIS), a non-disturbing technique, and the coating morphology was investigated by field emission scanning electron microscopy (FE-SEM). The results show that the composite coating protects the AZ31 substrate. The barrier properties of the coating can be optimized by changing the PCL concentration. The presence of nanohydroxyapatite particles influences the coating morphology and decreases the corrosion resistance. The biocompatibility was assessed by studying the response of osteoblastic cells on coated samples through resazurin assay, confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). The results show that the polycaprolactone to hydroxyapatite ratio affects the cell behavior and that the presence of hydroxyapatite induces high osteoblastic differentiation. (C) 2014 Elsevier B.V. All rights reserved.

Generalization of Wertheim's theory for the assembly of various types of rings

We generalize Wertheim's first order perturbation theory to account for the effect in the thermodynamics of the self-assembly of rings characterized by two energy scales. The theory is applied to a lattice model of patchy particles and tested against Monte Carlo simulations on a fcc lattice. These particles have 2 patches of type A and 10 patches of type B, which may form bonds AA or AB that decrease the energy by epsilon(AA) and by epsilon(AB) = r epsilon(AA), respectively. The angle theta between the 2 A-patches on each particle is fixed at 601, 90 degrees or 120 degrees. For values of r below 1/2 and above a threshold r(th)(theta) the models exhibit a phase diagram with two critical points. Both theory and simulation predict that rth increases when theta decreases. We show that the mechanism that prevents phase separation for models with decreasing values of theta is related to the formation of loops containing AB bonds. Moreover, we show that by including the free energy of B-rings ( loops containing one AB bond), the theory describes the trends observed in the simulation results, but that for the lowest values of theta, the theoretical description deteriorates due to the increasing number of loops containing more than one AB bond.

Preliminary study on the production of functionally graded materials by friction stir processing

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia Mecânica

Pozzolanic activity of oil-refining catalyst: evaluation by electron and atomic microscopy

The reuse of waste fluid catalytic cracking (FCC) catalyst as partial surrogate for cement can reduce the environmental impact of both the oil-refinery and cement production industries [1,2]. FCC catalysts can be considered as pozzolanic materials since in the presence of water they tend to chemically react with calcium hydroxide to produce compounds possessing cementitious properties [3,4]. In addition, partial replacement of cement with FCC catalysts can enhance the performance of pastes and mortars, namely by improving their compressive strength [5,6]. In the present work the reaction of waste FCC catalyst with Ca(OH)2 has been investigated after a curing time of 28 days by scanning electron microscopy (SEM) with electron backscattered signal (BSE) combined with X-ray energy dispersive spectroscopy (EDS) carried out with a JEOL JSM 7001F instrument operated at 15 kV coupled to an INCA pentaFetx3 Oxford spectrometer. The polished cross-sections of FCC particles embedded in resin have also been evaluated by atomic force microscopy (AFM) in contact mode (CM) using a NanoSurf EasyScan 2 instrument. The SEM/EDS results revealed that an inward migration of Ca occurred during the reaction. A weaker outward migration of Si and Al was also apparent (Fig. 1). The migration of Ca was not homogeneous and tended to follow high-diffusivity paths within the porous waste FCC catalyst particles. The present study suggests that the porosity of waste FCC catalysts is key for the migration/reaction of Ca from the surrounding matrix, playing an important role in the pozzolanic activity of the system. The topography images and surface roughness parameters obtained by atomic force microscopy can be used to infer the local porosity in waste FCC catalyst particles (Fig. 2).

Magma flow pattern in dykes of the Azores revealed by ansiotropy of magnetic susceptibility

The localization of magma melting areas at the lithosphere bottom in extensional volcanic domains is poorly understood. Large polygenetic volcanoes of long duration and their associated magma chambers suggest that melting at depth may be focused at specific points within the mantle. To validate the hypothesis that the magma feeding a mafic crust, comes from permanent localized crustal reservoirs, it is necessary to map the fossilized magma flow within the crustal planar intrusions. Using the AMS, we obtain magmatic flow vectors from 34 alkaline basaltic dykes from São Jorge, São Miguel and Santa Maria islands in the Azores Archipelago, a hot-spot related triple junction. The dykes contain titanomagnetite showing a wide spectrum of solid solution ranging from Ti-rich to Ti-poor compositions with vestiges of maghemitization. Most of the dykes exhibit a normal magnetic fabric. The orientation of the magnetic lineation k1 axis is more variable than that of the k3 axis, which is generally well grouped. The dykes of São Jorge and São Miguel show a predominance of subhorizontal magmatic flows. In Santa Maria the deduced flow pattern is less systematic changing from subhorizontal in the southern part of the island to oblique in north. These results suggest that the ascent of magma beneath the islands of Azores is predominantly over localized melting sources and then collected within shallow magma chambers. According to this concept, dykes in the upper levels of the crust propagate laterally away from these magma chambers thus feeding the lava flows observed at the surface.