The surface chemistry of leaching coal fly ash

The utilization of coal fly ash in the construction and non-construction areas has seen a rapid growth in the last decade. As production outweighs the utilization of fly ash, its disposal as a dilute or dense slurry is still practiced in coal fired power stations. In this review the surface chemistry of leaching coal fly ash is presented to highlight the role of mass transfer in providing resistance and consequently delayed leaching of elements, when fly ash is disposed or used for value addition. (C) 2002 Elsevier Science B.V. All rights reserved.

HPLC measurement of harderoporphyrin in the harderian glands of rodents as a biomarker for sub-lethal or chronic arsenic exposure

An improved HPLC method has been established for the measurement of harderoporphyrin (HP) in the harderian gland of rats and mice. Groups of female Wistar rats were given a single oral dose of sodium arsenite at 0, 0.5 or 5.0 mg As(III)/kg body weight, or a slurry of arsenic-contaminated soil at equivalent dose rates and the animals were sacrificed 96 h after dosing. A group of C57BL/6J female mice were chronically exposed to drinking water containing 500 mug As(V)/I of sodium arsenate ad libitum for over 2 years. Porphyrins were measured in the harderian glands of rats and mice. Our results suggest that HP and the alteration of the porphyrin profile in the harderian glands of rodents is a highly sensitive biomarker for both single sub-lethal and chronic arsenic exposure. (C) 2002 Elsevier Science Ireland Ltd. All rights reserved.

Variables affecting the fine grinding of minerals using stirred mills

Base metal resources are becoming more fine-grained and refractory and minerals separation processes require these ores to be milled to increasingly finer sizes. To cope with very fine grinding to below a P-80 of approximately 15 mum stirred milling technology has been adopted from other industries Neither this technology, nor the basic concepts of fine grinding, are well understood by the minerals processing industry. Laboratory studies were therefore carried out in order to investigate fine milling using different types of stirred mills. The variables analysed were stirrer speed, grinding media type and size, slurry solids content as well as the feed and product size. The results of the testwork have shown that all of these variables affect the grinding efficiency. The ratio of media size to material size was found to be of particular significance. The results were also analysed using the stress intensity approach and the optimum stress intensity ranges for the most efficient grinding were determined. Application of the results for process optimisation in the industrial size units is also discussed in this paper. (C) 2003 Elsevier Science Ltd. All rights reserved.

Catalytic combustion of toluene on Pt zeolite coated cordierite foams

The catalytic properties of Pt based cordierite foam catalysts have been evaluated in catalytic combustion of toluene (800 ppm in air). The catalysts contain identical Pt content (0.1%) which was introduced by three different ways: Pt ion exchange on MFI zeolite and then coating on the foam; Pt ion exchange after zeolite coating and finally Pt directly wet impregnated on the cordierite foam. The catalytic behaviour of Pt foam based catalysts was compared with that of PtMFI zeolite under powder form. Pt exchanged MFI supported on the cordierite foams present an improvement of activity for toluene combustion of about 50 degrees C on the light off temperature (T-50%). The enhanced performance of the structured catalysts is due not only to the open structure of foams and homogeneous thin layers catalyst deposited on their cell walls, but also to the fact that the size and location of Pt particles present in MFI zeolite are changed during the dipping step. Indeed, as prepared Pt samples and those used in the preparation of the slurry were observed by transmission electron microscopy revealing that the chemical interaction of PtMFI zeolite with the binder and detergent, both present in the slurry, leads to an increase of Pt particles size which were found to migrate from internal pores to the external surface of zeolite crystallites thereby increasing catalytic activity. (C) 2011 Elsevier B.V. All rights reserved.

TiB2 nanostructured coating for GFRP injection moulds

In the injection moulding of polypropylene reinforced with hard glass fibres, die materials are commonly subjected to severe abrasive wear. In order to improve its wear resistance, an unbalanced magnetron sputtering PVD compositional monolayered coating has been produced. The film was composed by a nanostructured TiB2 monolayer. Microstructure characterization and thickness evaluation were conducted by scanning electron microscopy (SEM). Film topography and roughness were accessed by SEM and Atomic Force Microscopy (AFM). The phase analyse was investigated by X-ray diffraction (XRD), using Cu Kalpha radiation. Scratch tests were conducted in order to study the film adhesion to the substrate. Load-Displacement curves (nanoindentation analysis) allowed measuring the film hardness and Young's modulus. A ball-cratering tribometer was used to determine the micro-abrasion laboratorial wear resistance, under different tests conditions, using SiC particles in distilled water slurry. At the end of these tests, the worn surfaces were analyzed by SEM and Energy Dispersive X-ray Spectroscopy (EDS) in order to compare these results with some other coatings already tested in the same conditions. To test the practical wear resistance, 135000 injection cycles were done in a plastic injection industrial mould. Coated samples were put on the plastic feed canal, after a turbulent zone. In these tests, a 30% (wt) glass fibres reinforced polypropylene was used. Worn sample surfaces were analyzed by SEM after 45.000 and 90.000 cycles. Image analyses were made in order to evaluate the damage increases and to observe the wear mechanisms involved.

Adhesion and wear behaviour of NCD coatings on Si3N4 by micro-abrasion tests

Nanocrystalline diamond (NCD) coatings offer an excellent alternative for tribological applications, preserving most of the intrinsic mechanical properties of polycrystalline CVD diamond and adding to it an extreme surface smoothness. Silicon nitride (Si3N4) ceramics are reported to guarantee high adhesion levels to CVD microcrystalline diamond coatings, but the NCD adhesion to Si3N4 is not yet well established. Micro-abrasion tests are appropriate for evaluating the abrasive wear resistance of a given surface, but they also provide information on thin film/substrate interfacial resistance, i.e., film adhesion. In this study, a comparison is made between the behaviour of NCD films deposited by hot-filament chemical vapour deposition (HFCVD) and microwave plasma assisted chemical vapour deposition (MPCVD) techniques. Silicon nitride (Si3N4) ceramic discs were selected as substrates. The NCD depositions by HFCVD and MPCVD were carried out using H2–CH4 and H2–CH4–N2 gas mixtures, respectively. An adequate set of growth parameters was chosen for each CVD technique, resulting in NCD films having a final thickness of 5 m. A micro-abrasion tribometer was used, with 3 m diamond grit as the abrasive slurry element. Experiments were carried out at a constant rotational speed (80 r.p.m.) and by varying the applied load in the range of 0.25–0.75 N. The wear rate for MPCVD NCD (3.7±0.8 × 10−5 m3N−1m−1) is compatible with those reported for microcrystalline CVD diamond. The HFCVD films displayed poorer adhesion to the Si3N4 ceramic substrates than the MPCVD ones. However, the HFCVD films show better wear resistance as a result of their higher crystallinity according to the UV Raman data, despite evidencing premature adhesion failure.

Influence of the abrasive particles size in the micro-abrasion wear tests of TiAlSiN thin coatings

Ball rotating micro-abrasion tribometers are commonly used to carry out wear tests on thin hard coatings. In these tests, different kinds of abrasives were used, as alumina (Al2O3), silicon carbide (SiC) or diamond. In each kind of abrasive, several particle sizes can be used. Some studies were developed in order to evaluate the influence of the abrasive particle shape in the micro-abrasion process. Nevertheless, the particle size was not well correlated with the material removed amount and wear mechanisms. In this work, slurry of SiC abrasive in distilled water was used, with three different particles size. Initial surface topography was accessed by atomic force microscopy (AFM). Coating hardness measurements were performed with a micro-hardness tester. In order to evaluate the wear behaviour, a TiAlSiN thin hard film was used. The micro-abrasion tests were carried out with some different durations. The abrasive effect of the SiC particles was observed by scanning electron microscopy (SEM) both in the films (hard material) as in the substrate (soft material), after coating perforation. Wear grooves and removed material rate were compared and discussed.

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.

Edifício do Terminal de Cruzeiros do Porto de Leixões: Acompanhamento dos trabalhos de Fundações e Estruturas de Suporte.

Infraestrutura com mais de um século de história, o Porto de Leixões encontra-se em fase de renovação com a criação de um emblemático Edifício de Terminal de Cruzeiros. Obra de arquitetura arrojada, o edifício é implantado em condições geológico-geotécnicas adversas e na convivência com o efeito da água do mar e das respetivas marés. O presente relatório é relativo a um Estágio realizado na obra numa fase de execução dos trabalhos de fundações e de contenções periféricas (ensecadeira). Apresentam-se as soluções sugeridas em projeto, as soluções apresentadas inicialmente pelo construtor e as alternativas a estas, propostas já durante a obra. Descrevem-se as diferentes soluções, identificando os equipamentos, recursos humanos e procedimentos envolvidos. Comparam-se os respetivos rendimentos e custos. Apresenta-se o Plano de Instrumentação e de Monitorização implementado em obra. Descreve-se em pormenor o trabalho realizado pelo estagiário, em obra, no decurso do estágio.

Wear of PEEK-Ti6Al4V systems under micro-abrasion and linear sliding conditions

Dissertação de mestrado integrado em Engenharia Biomédica

Optimization of low-cost nutritional supplementation for lignocellulosic ethanol fermentation

[Excerpt] Bioethanol from lignocellulosic materials (LCM), also called second generation bioethanol, is considered a promising alternative to first generation bioethanol. An efficient production process of lignocellulosic bioethanol involves an effective pretreatment of LCM to improve the accessibility of cellulose and thus enhance the enzymatic saccharification. One interesting approach is to use the whole slurry from treatment, since allows economical and industrial benefits: washing steps are avoided, water consumption is lower and the sugars from liquid phase can be used, increasing ethanol concentration [1]. However, during the pretreatment step some compounds (such as furans, phenolic compounds and weak acids) are produced. These compounds have an inhibitory effect on the microorganisms used for hydrolysate fermentation [2]. To overcome this, the use of a robust industrial strain together with agro-industrial by-products as nutritional supplementation was proposed to increase the ethanol productivities and yields. (...)

The appraisal of anaerobic digestion in Ireland to develop improved designs and operational practice

Mesophilic Anaerobic Digestion treating sewage sludge was investigated at five full-scale sewage treatment plants in Ireland. The anaerobic digestion plants are compared and evaluated in terms of design, equipment, operation, monitoring and management. All digesters are cylindrical, gas mixed and heated Continuously Stirred Tank Reactors (CSTR), varying in size from 130m3 to 800m3. Heat exchanger systems heat all digesters. Three plants reported difficulties with the heating systems ranging from blockages to insufficient insulation and design. Exchangers were modified and replaced within one year of operation at two plants. All but one plant had Combined Heat and Power (CHP) systems installed. Parameter monitoring is a problem at all plants mainly due to a lack of staff and knowledge. The plant operators consider pH and temperature the most important parameters to be measured in terms of successful monitoring of an anaerobic digester. The short time taken and the ease at which pH and temperature can be measured may favour these parameters. Three laboratory scale pilot anaerobic digesters were operated using a variety of feeds over at 144-day period. Two of the pilots were unmixed and the third was mechanically mixed. As expected the unmixed reactors removed more COD by retention of solids in the digesters but also produced greater quantities of biogas than the mixed digester, especially when low solids feed such as whey was used. The mixed digester broke down more solids due to the superior contact between the substrate and the biomass. All three reactors showed good performance results for whey and sewage solids. Scum formation occurred giving operational problems for mixed and unmixed reactors when cattle slurry was used as the main feed source. The pilot test was also used to investigate which parameters were the best indicators of process instability. These trials clearly indicated that total Volatile Fatty Acid (VFA) concentrations was the best parameter to show signs of early process imbalance, while methane composition in the biogas was good to indicate possible nutrient deficiencies in the feed and oxygen shocks. pH was found to be a good process parameter only if the wastewater being treated produced low bicarbonate alkalinities during treatment.

A nutrient balance model for typical Irish farming systems

The twin objectives of the work described were to construct nutrient balance models (NBM) for a range of Irish animal production systems and to evaluate their potential as a means of estimating the nutrient composition of farm wastes. The NBM has three components. The first is the intake of nutrients in the animal's diet. The second is retention or the nutrients the animal retains for the production of milk, meat or eggs. The third is the balance or the difference between the nutrient intake and retention. Data on the intake levels and their nutrient value for dairy cows, beef cattle, pigs and poultry systems were assembled. Literature searches and interviews with National experts were the primary sources of information. NBMs were then constructed for each production system. Summary tables of the nutrient values for the common diet constituents used in Irish animal production systems, the nutrient composition of the animal products and the NBMs (nutrient intake, retention and excretion) for a range of production systems were assembled. These represent the first comprehensive data set of this type for Irish animal production systems. There was generally good agreement between the derived NBMs values and those published in the literature. The NBMs were validated on a number of farms. Data on animal numbers, fertiliser use, concentrates inputs and production output were recorded on seven farms. Using the data a nutrient input/output balance was constructed for each farm. This was compared with the NBM estimate of the farm nutrient balance. The results showed good agreement between the measured balance and the NBM estimate particularly for the pig and poultry farms. However, the validation emphasised the inherent risks associated with NBMs. The average values used for feed intake and production parameters in the NEMs may result in the under or over estimate of actual nutrient balances on individual farms where these variables are substantially different. On the grassland farms there was a poor correlation between the input/output estimate and the NBM. This possibly results from the omission of the soil's contribution to the nutrient balance. However, the results indicate that the NBMs developed are a potentially useful tool for estimating nutrient balances. They also will serve to highlight the significant fraction of the nutrient inputs into farming systems that are retained on the farm. The potential of the NBM as a means of estimating the nutrient composition of farm wastes was evaluated on two farms. Feed intake and composition, animal production, slurry production was monitored during the indoor winter feeding period. Slurry samples were taken for analysis. The appropriates NBMs were used to estimate the nutrient balance for each farm. The nutrient content of the slurry produced was calculated. There was a good agreement between the NBM estimate and the measured values. This preliminary evaluation suggests that the NBM has a potential to provide the farmer with a simple means of estimating the nutrient value of his slurry.

Alternativas tecnológicas para la recuperación y valorización del nitrógeno presente en los residuos orgánicos

La conciencia de los problemas asociados a la gestión de los residuos orgánicos y el interés por las oportunidades de su recuperación y valorización han ido tomando importancia en los últimos años, tanto en el campo de las deyecciones ganaderas como en el sector de las aguas residuales. Consecuentemente, las combinaciones tecnológicas que permitan cerrar los ciclos de los nutrientes y la recuperación energética han adquirido mayor importancia en la investigación así como en las nuevas normativas sectoriales. En este contexto se sitúa el trabajo realizado durante el periodo becado (octubre 2010 - noviembre 2011). En una primera etapa de estudio bibliográfico se identificaron i) el aumento de la eficiencia en el uso del nitrógeno en la agricultura y en la ganadería, ii) la reutilización del nitrógeno en los mismos ecosistemas agrícolas y iii) el tratamiento de las deyecciones para redistribuir el nitrógeno a zonas con poca disponibilidad, como las tres direcciones principales hacia las cuales se está focalizando el interés del sector agrícola. Se puso en marcha una planta piloto de stripping y absorción para estudiar la posibilidad de recuperar y valorizar el amoniaco presente en los purines en forma de solución amoniacal para la industria de fertilizantes. Los resultados obtenidos evidenciaron el rol fundamental de las características iníciales del substrato en el rendimiento global del proceso. En particular, elevados contenidos en materia orgánica resultaron en bajas eficiencias y en elevadas contaminaciones del producto obtenido. Finalmente, considerando sus potenciales ventajas tanto en la gestión de los residuos ganaderos como de las aguas residuales y focalizándose en las perdidas de nitrógeno se estudió un sistema descentralizado de separación de orina instalado en un centro de investigación. Los resultados preliminares permitieron caracterizar los principales procesos que ocurren en el sistema e identificar las posibles líneas futuras de investigación.

La cascarilla cerámica y su uso innovador

The ceramic shell is a material mainly used for making foundry molds. This research demonstrates that ceramic shell can be used for making sculptures with exceptional definition in its finish. The research has identified a number of advantages of the material to meet the challenges of an artist during the making of a sculpture. The research has been developed in six stages: In the first stage data were collected from the chaff as the process material. This was the starting point for research. In the second stage, we have set the appropriate composition of the slurry, both in percentage and type of binder, and firing curve. To this end, we evaluated the application characteristics, thickness, drying, mechanical strength, the reduction coefficient and porosity. In the third stage it was observed that the husk is suitable for all types of materials acting as support. It was also found that the slurry can be used with various sculptural processes: modeling, molding using silicone or plaster mold, shuttering, with internal metal frame, and so on. In addition, we have established methods to repair and modify the husk by hand and power tools. In the fourth stage we have found ways to modify the surface of the husk with other minerals that affect the structure: introduction of filing of copper, bronze and iron in the slurry ceramics, different staining procedure in hot or cold, by enamel slip, and so on. In the fifth stage sculptures were made using the methods established in the previous stages, to verify this hypothesis. The sixth stage, which is annexed, contains a new method to process the ceramic shell as a mold in casting that emerged from the proven methods in the investigation.