An eco-friendly way to fire retardant flexible polyurethane foam: layer-by-layer assembly of fully bio-based substances

The objective of the present study is to develop fully renewable and environmentally benign techniques for improving the fire safety of flexible polyurethane foams (PUFs). A multilayered coating made from cationic chitosan (CS) and anionic alginate (AL) was deposited on PUFs through layer-by-layer assembly. This coating system exhibits a slight influence on the thermal stability of PUF, but significantly improves the char formation during combustion. Cone calorimetry reveals that 10 CS-AL bilayers (only 5.7% of the foams weight) lead to a 66% and 11% reduction in peak heat release rate and total heat release, respectively, compared with those of the uncoated control. The notable decreased fire hazards of PUF are attributed to the CS-AL coatings being beneficial to form an insulating protective layer on the surface of burning materials that inhibits the oxygen and heat permeation and slows down the flammable gases in the vapor phase, and thereby improves the flame resistance. This water-based, environmentally benign natural coating will stimulate further efforts in improving fire safety for a variety of polymer substrates.

Stability and mechanical evaluation of bovine pericardium cross-linked with polyurethane prepolymer in aqueous medium

The present study investigates the potential use of non-catalyzed water-soluble blocked polyurethane prepolymer (PUP) as a bifunctional cross-linker for collagenous scaffolds. The effect of concentration (5, 10, 15 and 20%), time (4, 6, 12 and 24 h), medium volume (50, 100, 200 and 300%) and pH (7.4, 8.2, 9 and 10) over stability, microstructure and tensile mechanical behavior of acellular pericardial matrix was studied. The cross-linking index increased up to 81% while the denaturation temperature increased up to 12 °C after PUP crosslinking. PUP-treated scaffold resisted the collagenase degradation (0.167 ± 0.14 mmol/g of liberated amine groups vs. 598 ± 60 mmol/g for non-cross-linked matrix). The collagen fiber network was coated with PUP while viscoelastic properties were altered after cross-linking. The treatment of the pericardial scaffold with PUP allows (i) different densities of cross-linking depending of the process parameters and (ii) tensile properties similar to glutaraldehyde method.

Graphene foam functionalized with electrodeposited nickel hydroxide for energy applications

The need of new systems for the storage and conversion of renewable energy sources is fueling the research in supercapacitors. In this work, we propose a low temperature route for the synthesis of electrodes for these supercapacitors: electrodeposition of a transition metal hydroxide–Ni(OH)2 on a graphene foam. This electrode combines the superior mechanical and electrical properties of graphene, the large specific surface area of the foam and the large pseudocapacitance of Ni(OH)2. We report a specific capacitance up to 900 F/g as well as specific power and energy comparable to active carbon electrodes. These electrodes are potential candidates for their use in energy applications.

Properties of aluminium nodules foamed with concentrated solar energy

Commercial aluminium foam filled structures and sandwich panels are available for structural applications. As alternative to these materials, small granular foamed pieces are proposed to fill structures as well as sandwich panels. On the present work, foam precursors are obtained by Powder Metallurgy (PM) route, using natural calcium carbonate as foaming agent instead of titanium hydride. Extruded precursor bars were cut into small pieces (around 4.5 mm long and 5mm in diameter). Foaming treatment was carried out on two different ways: electrical preheated furnace and by solar furnace. Foamed nodules presented a low cell size, density e.g. 0.67 g/cm3 to 0.88 g/cm3 and a height/diameter ratio between 0.72 and 0.84 as a function of precursor size. These properties depend on the foaming particle size, foaming cycle and precursor dimensions. Carbonate precursors are easily foamed by concentrated solar energy, due to the lower risk of cell collapse than with hydride precursors, resulting from cell stabilization by oxide skin formation into cells and a low degree of foamed nodules bonding.

Multi-criteria selection of structural adhesives to bond ABS parts obtained by rapid prototyping

One of the most used methods in rapidprototyping is Fused Deposition Modeling (FDM), which provides components with a reasonable strength in plastic materials such as ABS and has a low environmental impact. However, the FDM process exhibits low levels of surface finishing, difficulty in getting complex and/or small geometries and low consistency in “slim” elements of the parts. Furthermore, “cantilever” elements need large material structures to be supported. The solution of these deficiencies requires a comprehensive review of the three-dimensional part design to enhance advantages and performances of FDM and reduce their constraints. As a key feature of this redesign a novel method of construction by assembling parts with structuraladhesive joints is proposed. These adhesive joints should be designed specifically to fit the plastic substrate and the FDM manufacturing technology. To achieve this, the most suitable structuraladhesiveselection is firstly required. Therefore, the present work analyzes five different families of adhesives (cyanoacrylate, polyurethane, epoxy, acrylic and silicone), and, by means of the application of technical multi-criteria decision analysis based on the analytic hierarchy process (AHP), to select the structuraladhesive that better conjugates mechanical benefits and adaptation to the FDM manufacturing process

Desarrollo, análisis y caracterización de procesos de soldeo térmico de espumas de aluminio

Uno de los retos actuales aún pendiente de lograr trabajando con espumas de aluminio, es el desarrollo de métodos de unión fácilmente reproducibles a nivel industrial que permitan la unión de espumas de aluminio entre sí o con otros componentes tipo pletinas, para así poder fabricar piezas de mayor tamaño o con formas complejas, a la vez que se conserven las propiedades y características principales de las espumas de aluminio, tanto en la zona principal de unión o cordón, como en la interfase y zona afectada térmicamente, que se encuentran anexa. Los actuales procesos de unión más utilizados con espumas de aluminio, se basan principalmente en adhesivos y uniones mecánicas. Estas soluciones a priori válidas, añaden problemas técnicos a determinadas aplicaciones de las espumas que frenan la completa integración de estos materiales en un entorno de fabricación flexible y global. Por esta razón, los actuales procesos de producción de las espumas de aluminio se restringen a determinadas ofertas hechas a la medida del cliente, no pudiendo atender por falta de soluciones, a una gran parte del potencial mercado de estos materiales. En el presente trabajo de investigación se han desarrollado y caracterizado diferentes métodos de unión de espumas de aluminio, en configuración a tope y de espumas de aluminio con pletinas en configuración a solape, basados en procesos por soldeo térmico. One of the current challenges even pending of being achieved working with aluminium foams, is the development of easily reproducible methods at industrial level that allow the joint of aluminium foams between them or with other elements as for example aluminium plates for making bigger pieces or with more complex forms, remaining simultaneously in the weld bead the properties and main characteristics of aluminium foam, so much in the joint area or interface, since in the affected closer thermal zone. Currently, the most used joint processes for applying to aluminium foams are based mainly on adhesives and mechanical joins. These solutions initially valid, add technical problems to certain aluminium foams applications, which stop the complete integration of these materials in a more flexible and global manufacture environment. For this reason, current aluminium foam manufacturing processes are restricted to certain offers done to a specific customer requirement, not being able to attend for lack of available solutions, to a great potential market of these materials. In the present work, different joint methods between aluminium foams and between aluminium foams and plates for butt and lap configurations have been developed and characterized based on thermal welding processes.

Estudio del comportamiento mecánico de las espumas pulvimetalúrgicas de aluminio

Con este trabajo se pretende determinar la relación entre las características físicas y mecánicas y la estructura para espumas de aluminio de Al12Si y AA6061 obtenidas por pulvimetalurgia utilizando probetas prismáticas de dimensiones diecisiete por diecisiete por sesenta milímetros. De su estudio mecánico y de análisis de imagen se concluye que las probetas cuyas propiedades físicas y mecánicas están moderadamente por encima de la media poseen mayor número de poros medianos y paredes de poro más gruesas. Por el contrario, las propiedades resultan inferiores cuando se presentan estructuras con un mayor número de poros medianos. Aquellas espumas con estructuras obtenidas por una espumación incompleta presentan una menor porosidad y por ello mayores densidades. En aquellos casos donde la estructura presenta una elevada presencia de poros grandes, sus propiedades mecánicas disminuyen. ABSTRACT With this work we are trying to determine the relation between physical and mechanical characteristics and its structure, for Al12Si and AA6061 aluminium foams, obtained by podwer metallurgy. Aluminium foam samples with dimensions of seventeen per seventeen per sixty millimeters were used. After its mechanical and image analysis study, we conclude that samples whose physical and mechanical properties are moderately over the average, they have a major proportion of medium pores and thicker pore walls. Otherwise, properties result to be inferior when a major number of medium pores structures are presented. Those foam structures obtained with an incomplete foaming process show a lower porosity, and so higher densities. Also, properties decrease in those cases in which the structure presents a high presence of big pores.

Degradation in seawater of structural adhesives for hybrid fibre-metal laminated materials

The adhesives used for applications in marine environments are subject to particular chemical conditions, which are mainly characterised by an elevated chlorine ion content and intermittent wetting/drying cycles, among others.These conditions can limit the use of adhesives due to the degradation processes that they experience. In this work, the chemical degradation of two different polymers, polyurethane and vinylester, was studied in natural seawater under immersion for different periods of time.The diffusion coefficients and concentration profiles of water throughout the thickness of the adhesiveswere obtained.Microstructural changes in the polymer due to the action of water were observed by SEM, and the chemical degradation of the polymer was monitored with the Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The degradation of the mechanical properties of the adhesive was determined by creep tests withMixed Cantilever Beam (MCB) specimens at different temperatures. After 180 days of immersion of the specimens, it was concluded that the J-integral value (depending on the strain) implies a loss of stiffness of 51% and a decrease in the failure load of 59% for the adhesive tested.

Mode II fracture energy in the adhesive bonding of dissimilar substrates: carbon fibre composite to aluminium joints

The end-notched flexure (ENF) test calculates the value of mode II fracture energy in adhesive bonding between the substrates of same nature. Traditional methods of calculating fracture energy in the ENF test are not suitable in cases where the thickness of the adhesive is non-negligible compared with adherent thicknesses. To address this issue, a specific methodology for calculating mode II fracture energy has been proposed in this paper. To illustrate the applicability of the proposed method, the fracture energy was calculated by the ENF test for adhesive bonds between aluminium and a composite material, which considered two different types of adhesive (epoxy and polyurethane) and various surface treatments. The proposed calculation model provides higher values of fracture energy than those obtained from the simplified models that consider the adhesive thickness to be zero, supporting the conclusion that the calculation of mode II fracture energy for adhesives with non-negligible thickness relative to their adherents should be based on mathematical models, such as the method proposed in this paper, that incorporate the influence of this thickness.

MRI and Bidimensional relaxometry sequences for macro and microstructure assessment in food models.

Physico-chemical and organoleptic characteristics of food depend largely on the microscopic level distribution of gases and water, and connectivity and mobility through the pores. Microstructural characterization of food can be accomplished by Magnetic Resonance Imaging (MRI) and Nuclear Magnetic Spectroscopy (NMR) combined with the application of methods of dissemination and multidimensional relaxometry. In this work, funded by the EC Project InsideFood, several artificial food models, based on foams and gels were studied using MRI and 2D relaxometry. Two different kinds of foams were used: a sugarless and a sugar foam. Then, a half of a syringe was filled with the sugarless foam and the other half with the sugar foam. Then, MRI and NMR experiments were performed and the sample evolution was observed along 3 days in order to quantify macrostructural changes through proton density images and microstructural ones using T1T2 maps, using an inversion CPMG sequence. On the proton density images it may be seen that after 16 hours it was possible to differentiate the macrostructural changes, as the apparition of free water due to a syneresis phenomenon. On the interface it can be seen a brighter area after 16 hours, due to the occurrence of free water. Moreover, thanks to the bidimensional relaxometry (T1-T2) it was possible to differentiate among microscopic changes. Differences between the pores size can be observed as well as the microstructure evolution after 30.5 hours, as a consequence differences are shown on free water redistribution through larger pores and capillarity phenomena between both foams.

Diseño y comportamiento de uniones estructurales mecánicas y adhesivas. Condiciones superficiales y operacionales

Las uniones estructurales mecánicas y adhesivas requieren la combinación de un número importante de parámetros para la obtención de la continuidad estructural que exigen las condiciones de diseño. Las características de las uniones presentan importantes variaciones, ligadas a las condiciones de ejecución, tanto en uniones mecánicas como especialmente en uniones adhesivas y mixtas (unión mecánica y adhesiva, también conocidas como uniones híbridas). Las propiedades mecánicas de las uniones adhesivas dependen de la naturaleza y propiedades de los adhesivos y también de muchos otros parámetros que influyen directamente en el comportamiento de estas uniones. Algunos de los parámetros más significativos son: el acabado superficial de los materiales, área y espesor de la capa adhesiva, diseño adecuado, secuencia de aplicación, propiedades químicas de la superficie y preparación de los sustratos antes de aplicar el adhesivo. Los mecanismos de adhesión son complejos. En general, cada unión adhesiva solo puede explicarse considerando la actuación conjunta de varios mecanismos de adhesión. No existen adhesivos universales para un determinado material o aplicación, por lo que cada pareja sustrato-adhesivo requiere un particular estudio y el comportamiento obtenido puede variar, significativamente, de uno a otro caso. El fallo de una junta adhesiva depende del mecanismo cohesión-adhesión, ligado a la secuencia y modo de ejecución de los parámetros operacionales utilizados en la unión. En aplicaciones estructurales existen un número muy elevado de sistemas de unión y de posibles sustratos. En este trabajo se han seleccionado cuatro adhesivos diferentes (cianoacrilato, epoxi, poliuretano y silano modificado) y dos procesos de unión mecánica (remachado y clinchado). Estas uniones se han aplicado sobre chapas de acero al carbono en diferentes estados superficiales (chapa blanca, galvanizada y prepintada). Los parámetros operacionales analizados han sido: preparación superficial, espesor del adhesivo, secuencia de aplicación y aplicación de presión durante el curado. Se han analizado tanto las uniones individuales como las uniones híbridas (unión adhesiva y unión mecánica). La combinación de procesos de unión, sustratos y parámetros operacionales ha dado lugar a la preparación y ensayo de más de mil muestras. Pues, debido a la dispersión de resultados característica de las uniones adhesivas, para cada condición analizada se han ensayado seis probetas. Los resultados obtenidos han sido: El espesor de adhesivo utilizado es una variable muy importante en los adhesivos flexibles, donde cuanto menor es el espesor del adhesivo mayor es la resistencia mecánica a cortadura de la unión. Sin embargo en los adhesivos rígidos su influencia es mucho menor. La naturaleza de la superficie es fundamental para una buena adherencia del adhesivo al substrato, que repercute en la resistencia mecánica de la unión. La superficie que mejor adherencia presenta es la prepintada, especialmente cuando existe una alta compatibilidad entre la pintura y el adhesivo. La superficie que peor adherencia tiene es la galvanizada. La secuencia de aplicación ha sido un parámetro significativo en las uniones híbridas, donde los mejores resultados se han obtenido cuando se aplicaba primero el adhesivo y la unión mecánica se realizaba antes del curado del adhesivo. La aplicación de presión durante el curado se ha mostrado un parámetro significativo en los adhesivos con poca capacidad para el relleno de la junta. En los otros casos su influencia ha sido poco relevante. El comportamiento de las uniones estructurales mecánicas y adhesivas en cuanto a la resistencia mecánica de la unión puede variar mucho en función del diseño de dicha unión. La resistencia mecánica puede ser tan grande que falle antes el substrato que la unión. Las mejores resistencias se consiguen diseñando las uniones con adhesivo cianoacrilato, eligiendo adecuadamente las condiciones superficiales y operacionales, por ejemplo chapa blanca aplicando una presión durante el curado de la unión. La utilización de uniones mixtas aumenta muy poco o nada la resistencia mecánica, pero a cambio proporciona una baja dispersión de resultados, siendo destacable para la superficie galvanizada, que es la que presenta peor reproducibilidad cuando se realizan uniones sólo con adhesivo. Las uniones mixtas conducen a un aumento de la deformación antes de la rotura. Los adhesivos dan rotura frágil y las uniones mecánicas rotura dúctil. La unión mixta proporciona ductilidad a la unión. Las uniones mixtas también pueden dar rotura frágil, esto sucede cuando la resistencia del adhesivo es tres veces superior a la resistencia de la unión mecánica. Las uniones híbridas mejoran la rigidez de la junta, sobre todo se aprecia un aumento importante en las uniones mixtas realizadas con adhesivos flexibles, pudiendo decirse que para todos los adhesivos la rigidez de la unión híbrida es superior. ABSTRACT The mechanical and adhesive structural joints require the combination of a large number of parameters to obtain the structural continuity required for the design conditions. The characteristics of the junctions have important variations, linked to performance conditions, in mechanical joints as particular in mixed adhesive joints (mechanical and adhesive joints, also known as hybrid joints). The mechanical properties of the adhesive joints depend of the nature and properties of adhesives and also of many other parameters that directly influence in the behavior of these joints. Some of the most significant parameters are: the surface finished of the material, area and thickness of the adhesive layer, suitable design, and application sequence, chemical properties of the surface and preparation of the substrate before applying the adhesive. Adhesion mechanisms are complex. In general, each adhesive joint can only be explained by considering the combined action of several adhesions mechanisms. There aren’t universal adhesives for a given material or application, so that each pair substrate-adhesive requires a particular study and the behavior obtained can vary significantly from one to another case. The failure of an adhesive joint depends on the cohesion-adhesion mechanism, linked to the sequence and manner of execution of the operational parameters used in the joint. In the structural applications, there are a very high number of joining systems and possible substrates. In this work we have selected four different adhesives (cyanoacrylate, epoxy, polyurethane and silano modified) and two mechanical joining processes (riveting and clinching). These joints were applied on carbon steel with different types of surfaces (white sheet, galvanized and pre-painted). The operational parameters analyzed were: surface preparation, thickness of adhesive, application sequence and application of pressure during curing. We have analyzed individual joints both as hybrid joints (adhesive joint and mechanical joint). The combination of joining processes, substrates and operational parameters has resulted in the preparation and testing of over a thousand specimens. Then, due to the spread of results characteristic of adhesive joints, for each condition analyzed we have tested six samples. The results have been: The thickness of adhesive used is an important variable in the flexible adhesives, where the lower the adhesive thickness greater the shear strength of the joint. However in rigid adhesives is lower influence. The nature of the surface is essential for good adherence of the adhesive to the substrate, which affects the shear strength of the joint. The surface has better adherence is preprinted, especially when there is a high compatibility between the paint and the adhesive. The surface which has poor adherence is the galvanized. The sequence of application has been a significant parameter in the hybrid junctions, where the best results are obtained when applying first the adhesive and the mechanical joint is performed before cured of the adhesive. The application of pressure during curing has shown a significant parameter in the adhesives with little capacity for filler the joint. In other cases their influence has been less relevant. The behavior of structural mechanical and adhesive joints in the shear strength of the joint can vary greatly depending on the design of such a joint. The shear strength may be so large that the substrate fails before the joint. The best shear strengths are achieved by designing the junctions with cyanoacrylate adhesive, by selecting appropriately the surface and operating conditions, for example by white sheet applying a pressure during curing of the joint. The use of hybrid joints no increase shear strength, but instead provides a low dispersion of results, being remarkable for the galvanized surface, which is the having worst reproducibility when performed bonded joints. The hybrid joints leading to increased deformation before rupture. The joints witch adhesives give brittle fracture and the mechanics joints give ductile fracture. Hybrid joint provides ductility at the joint. Hybrid joint can also give brittle fracture, this happens when the shear strength of the adhesive is three times the shear strength of the mechanical joint. The hybrid joints improve stiffness of joint, especially seen a significant increase in hybrid joints bonding with flexible adhesives, can be said that for all the adhesives, the hybrid junction stiffness is higher.

Sistema de protección contra incendios de un parque de almacenamiento de líquidos petrolíferos

Los procesos relacionados con el almacenamiento y manipulación de productos petrolíferos, conllevan siempre determinados riesgos de incendio que dependen básicamente de las propiedades físicas y químicas de los productos, y hacen indispensable la adopción de importantes medidas de seguridad contra incendios. Esto es debido a que las consecuencias previsibles en caso de la producción y expansión del incendio son tan graves que aconsejan la instalación de medios más potentes de lucha contra incendios, que los simples extintores manuales. En base a ello, el presente proyecto pretende definir y desarrollar una propuesta de diseño del sistema de protección contra incendios en la zona de almacenamiento de una planta de almacenamiento de líquidos petrolíferos. La planta almacena Gasóleo, Gasolina y Queroseno de Aviación en ocho tanques atmosféricos de techo fijo situados en un único cubeto de retención. Se desarrolla un extenso estudio de los requisitos normativos para este tipo de casos, y en consecuencia, se calcula y clasifica el nivel de riesgo intrínseco de incendio en la zona estudiada, a partir de su carga de fuego ponderada y corregida. Además, se muestra la distribución de los tanques en el cubeto, basada en el cálculo de las distancias de seguridad entre cada uno de ellos y con el exterior. A partir de ello, el proyecto se centra en el cálculo de los valores de descarga de agua de refrigeración, requeridos en las boquillas de agua pulverizada e hidrantes exteriores de alrededor de la zona de riesgo; de espuma física para hidrocarburos, en las cámaras de espuma de la parte superior de la envolvente de los tanques, y en los monitores auxiliares de descarga de espuma, de la zona del cubeto de retención. Los objetivos, métodos y bases de cálculo se recogen en la memoria del proyecto. Además se incluye, la planificación temporal con MS Project, de la implementación del proyecto; la elección de los equipos que componen los sistemas, el presupuesto asociado y los planos de distribución de la planta y del flujo de tuberías propuesto. ABSTRACT Fire protection units and equipment are necessary on processes and operations related to storage and handling of petroleum products, because of their flammable and combustible properties. In case a hazard of fire from petroleum products is materialized, huge consequences are to be expected. To reduce losses, facilities should be equipped with appropriate protection. Based on that, this project seeks to define and develop the fire protection system design for a petroleum liquids storage installation. The plant stores Gasoil, Gasoline, and aviation Kerosene in eight fixed roof atmospheric tanks. A complete study of the fire protection regulations is carried out and, as a result, the studied area’s risk level is determined from its fire load density. The calculation of the minimum shell-to-shell spacing of adjacent aboveground storage tanks and external equipment, is also determined for a correct distribution of tanks in the bunded area. Assuming that, the design includes calculations of required discharge of water for spray nozzles and hydrants, and required discharge of foam from foam chambers and foam monitors. Objectives, methodology and calculation basis are presented on the project technical report; which also includes project scheduling with MS. Project software, the selection of system components and equipment, related budget and lay out of installation and piping.

Corrosión inducida por contaminantes hidrosolubles en la intercara metal/pintura

El objetivo principal de este trabajo es profundizar en el conocimiento del fenómeno de la corrosión subpelicular inducida por contaminantes hidrosolubles en la intercara metal/pintura. La contaminación salina del substrato es una situación común en la práctica: la superficie metálica suele estar expuesta a atmósferas contaminadas antes de ser recubierta, limpieza previa del metal con abrasivos contaminados, etc. La eliminación total de estos contaminantes resulta muy difícil de conseguir incluso con las técnicas más sofisticadas de limpieza. Esta investigación se centra en la determinación del efecto de la naturaleza del contaminante y la naturaleza y espesor del recubrimiento en el proceso de corrosión subpelicular del acero. En la investigación se utilizaron dos barnices de naturaleza diferente: poliuretano y vinílico; y se aplicaron a tres espesores diferentes. Los contaminantes empleados en este trabajo fueron: NaCl, NH4C1, CaCl2, Na2S04, (NH4)2S04, NaN03, NH4N03, Ca(N03)2. Los ensayos se realizaron en una cámara de condensación de humedad permanente. Los tiempos de exposición fueron 100, 300 y 600 horas. La velocidad de corrosión se evaluó gravimétricamente, mediante la técnica de pérdida de peso. Se realizaron estudios de permeabilidad al oxígeno y al agua de películas libres de substrato, evaluación de la velocidad de corrosión de probetas sin pintar inmersas en soluciones salinas de los contaminantes seleccionados, conductividad de dichas soluciones salinas, solubilidad del oxígeno en las soluciones salinas, adherencia en seco y en húmedo a diferentes tiempos de exposición. Se aporta evidencia respecto al control ejercido en el proceso corrosivo por el oxígeno que permea a través de la película, mientras que la permeación de agua controla la pérdida de adherencia del recubrimiento. Ambas permeabilidades dependen de la naturaleza del recubrimiento y de su espesor. Se ha investigado la influencia de la naturaleza del contaminante en la intercara metal/pintura. La naturaleza del catión parece quedar enmascarada por el efecto definitivo del anión. La concentración salina ejerce asimismo un efecto importante en la corrosión subpelicular. ABSTRACT The main aim of this work is to study in depth the knowledge of underfilm corrosión induced by hydrosoluble contaminants at the metal/paint Ínterface. The saline contamination of the substrate is a common situation in practice: metallic surfaces use to be exposed to polluted atmospheres, previous cleaning of the metal with contaminated abrasives, etc. Total elimination of these contaminants is hard to obtain even with modern cleaning techniques. This research is focused in determining the effect of contaminant nature, coating nature and its thickness on the steel underfilm corrosión process. In this work we used two varnishes with different nature: polyurethane and vinyl; they were applied in three different thicknesses. The saline contaminants employed were: NaCl, NH4C1, CaCl2, Na2S04, (NH4)2S04, NaN03, NH4N03/ Ca(N03)2. The tests were carried out in a condensation humidity chamber. The period of exposure were 100, 300 and 600 hours. Corrosión rate was assessed by weight loss. Simultaneously, studies on oxygen and water permeability of free films, assessing on corrosión rate of uncoated samples immersed in saline solutions of the selected contaminants, conductivity of these solutions, oxygen solubility in saline solutions, wet and dry adhesión of the polyurethane varnish at different periods of exposure, were carried out. There is clear evidence about control on corrosión process of oxygen that passes through the coating, while the passing of water controls the loss of adhesión of the coating. Both, water and oxygen permeation, depend on the nature and thickness of the coating. It has been researched the inf luence of the nature of contaminant at the metal/paint interface. The nature of the catión seems to be "masked" by the definitive effect of the nature of anión. The saline concentration also exerts an important effect on underfilm corrosión.

Ca-amendement and tillage: medium term synergies for improving key soil properties of acid soils. Soil and tillage research, 134: 195-206

Ca-amendments are routinely applied to improve acid soils, whilst no-tillage (NT) has been widely recommended in soils where traditional tillage (TT) has led to losses of organic matter. However, the potential interactions between the two treatments are only partially known. Our study was conducted on an annual forage crop agrosystem with a degraded Palexerult soil located in SW Spain, in order to assess if the combination of NT plus a Ca-amendment provides additional benefits to those of their separate use. To this end we analysed the effects of four different combinations of tillage and Ca-amendment on selected key soil properties, focusing on their relationships. The experimental design was a split-plot with four replicates. The main factor was tillage (NT versus TT) and the second factor was the application or not of a Ca-amendment, consisting of a mixture of sugar foam (SF) and red gypsum (RG). Soil samples were collected from 3 soil layers down to 50 cm after four years of treatment (2009). The use of the Ca-amendment improved pH and Al-toxicity down to 25 cm and increased exchangeable Ca2+ down to 50 cm, even under NT due to the combined effect of SF and RG. Both NT and the Ca-amendment had a beneficial effect on total organic carbon (TOC), especially on particulate organic carbon (POC), in the 0–5 cm layer, with the highest contents observed when both practices were combined. Unlike NT, the Ca-amendment failed to improve soil aggregation in spite of the carbon supplied. This carbon was not protected within the stable aggregates in the medium term, making it more susceptible to mineralization. We suggest that the fraction of Al extracted by oxalate from solid phase (AlOxa-Cu-K) and the glomalin-related soil proteins (GRSPs) are involved in the accumulation of carbon within water stable aggregates, probably through the formation of non-toxic stable Al-OM compounds, including those formed with GRSPs. NT alone decreased AlK in the 0–5 cm soil layer, possibly by increasing POC, TOC and GRSPs, which were observed to play a role in reducing Al toxicity. From our findings, the combination of NT and Ca-amendment appears to be the best management practice to improve chemical and physical characteristics of acid soils degraded by tillage.

Evaluación teórico experimental de la influencia de espumas de relleno metálicas como elementos de absorción de energía en perfiles tubulares de pequeño espesor. Su aplicación a vehículos para el transporte colectivo de personas

Los accidentes con implicación de autocares en los que se producen vuelcos ponen de manifiesto la especial agresividad de los mismos, como lo confirman las estadísticas. Como medida para mejorar la seguridad de los Vehículos de Grandes Dimensiones para el Transporte de Pasajeros (V.G.D.T.P.) frente a vuelco fue aprobado por las Naciones Unidas el Reglamento Nº 66 de Ginebra. Este reglamento establece los requisitos mínimos que las estructuras de los vehículos de grandes dimensiones deben cumplir con respecto a vuelco. El reglamento 66 ha supuesto un paso adelante muy importante en relación con la seguridad de los autocares, puesto que especifica por primera vez requerimientos estructurales a este tipo de vehículos, y en general ha supuesto una mejora del vehículo . Por otro lado, a consecuencia de la obligatoriedad de instalación de cinturones de seguridad, existe una unión entre pasajeros y vehículo, pero como no se trata de una unión rígida, hay que contemplar el porcentaje de la masa de los ocupantes que influye en la absorción de energía de la estructura. Además la retención de los ocupantes con cinturones de seguridad influye en la energía a absorber por la estructura del vehículo en dos aspectos, por un lado aumenta la masa del vehículo y en el otro se incrementa la altura el centro de gravedad. Esta situación a conducido a elaborar por parte de las Naciones Unidas la revisión 01 del Reglamento 66, en el que se considera que el 50 % de la masa total de los pasajeros posee una unión rígida con la estructura del vehículo, y por lo tanto debe ser tenida en cuenta si el vehículo posee sistemas de retención. En la situación actual, con limitaciones de peso del vehículo y peso por eje, los elementos de confort, seguridad y espacio para maleteros contribuyen a aumentar el peso del vehículo. Esto unido a la dificultad de introducción de cambios radicales en la concepción actual de fabricación de este tipo de vehículos por suponer unas pérdidas importantes para los fabricantes existentes, tanto en su conocimiento del producto como en su metodología de proceso, conlleva la necesidad cada vez más agobiante de analizar y evaluar otras alternativas estructurales que sin suponer grandes revoluciones a los productos actualmente en fabricación los complementen permitiendo adaptarse a los nuevos requerimientos en seguridad. Recientes desarrollos en la relación costo-beneficio de los procesos para la producción de materiales celulares metálicos de baja densidad, tales como las espumas metálicas, los posiciona como una alternativa de especial interés para la aplicación como elementos de absorción de energía para reforzar estructuras. El relleno con espumas metálicas puede ser más eficiente en términos de optimización de peso comparado con el aumento de espesor de los perfiles estructurales, dado que la absorción de energía se produce en una fracción relativamente pequeña de los perfiles, en las denominadas rótulas plásticas. La aplicación de espumas de relleno metálicas en estructuras de vehículos se está empezando a emplear en determinadas zonas de los vehículos de turismo, siendo totalmente novedosa cualquier intento de aplicación en estructuras de autobuses y autocares. Conforme a lo expuesto, y con el objeto de resolver estos problemas, se ha elaborado el presente trabajo de tesis doctoral, cuyos objetivos son: -Desarrollar un modelo matemático, que permita simular el ensayo de vuelco, considerando la influencia de los ocupantes retenidos con cinturones de seguridad para evaluar su influencia en la absorción de energía de la estructura. -Validar el modelo matemático de vuelco de la estructura mediante ensayos de secciones representativas de la estructura del vehículo y mediante el ensayo de un vehículo completo. -Realizar un estudio de las propiedades de las espumas metálicas que permitan incorporarlas como elemento de absorción de energía en el relleno de componentes de la superestructura de autobuses y autocares. -Desarrollar un modelo matemático para evaluar el aporte del relleno de espuma metálica en la absorción de energía ante solicitaciones por flexión estática y dinámica en componentes de la superestructura de autobuses o autocares. -Realizar un programa de ensayos a flexión estáticos y dinámicos para validar el modelo matemático del aporte del relleno de espuma metálica sobre componentes de la superestructura de autobuses y autocares. . -Incorporar al modelo matemático de vuelco de la estructura, los resultados obtenidos sobre componentes con relleno de espuma metálica, para evaluar el aporte en la absorción de energía. -Validar el modelo de vuelco de la estructura del autobús o autocar con relleno de espuma metálica, mediante ensayos de secciones de carrocería. ABSTRACT Accidents involving buses in which rollovers occur reveal the special aggressiveness thereof, as the statistics prove. As a measure to improve the safety of large vehicles for the transport of passengers to rollover, Regulation 66 of Geneva was approved by the United Nations. This regulation establishes the minimum requirements that structures of large vehicles must comply with respect to rollovers. The regulation 66 has been a major step forward in relation to the safety of coaches, since it specifies structural requirements to such vehicles and has been an improvement for the vehicle. In turn, as a result of compulsory installation of safety belts, there is contact between passengers and vehicle, but as it is not a rigid connection we must contemplate the percentage of the mass of the occupants that impacts on the energy absorption of the structure. Thus, the passengers’ restraining modifies the energy to absorb by the vehicle in two different aspects: On the one hand, it increases the vehicle weight and on the other the height of the center of gravity. This circumstance has taken the United Nations to elaborate Revision 01 of Regulation 66, in which it is considered that the 50 percent of passengers’ mass has a rigid joint together with the vehicle structure and, therefore, the passengers’ mass mentioned above should be highly considered if the vehicle has seat belts. In the present situation, in which limitations in vehicle weight and weight in axles are stricter, elements of comfort, safety and space for baggage are contributing to increase the weight of the vehicle. This coupled with the difficulty of introducing radical changes in the current conception of manufacturing such vehicles pose significant losses for existing manufacturers, both in product knowledge and process methodology, entails the overwhelming need to analyze and evaluate other structural alternatives without assuming relevant modifications on the products manufactured currently allowing them to adapt to the new safety requirements. Recent developments in cost-benefit processes for the production of metallic foams of low density, such as metal foams, place them as an alternative of special interest to be used as energy absorbers to strengthen structures. The filling with metal foams can be more efficient in terms of weight optimization compared with increasing thickness of the structural beams, since the energy absorption occurs in a relatively small fraction of the beams, called plastic hinges. The application of metal filling foams in vehicle structures is beginning to be used in certain areas of passenger cars, being an innovative opportunity in structures for application in buses and coaches. According to the mentioned before, and in order to come forward with a solution, this doctoral thesis has been prepared and its objectives are: - Develop a mathematical model to simulate the rollover test, considering the influence of the occupants held with seat belts to assess their influence on energy absorption structure. - Validate the mathematical model of the structure rollover by testing representative sections of the vehicle structure and by testing a complete vehicle. - Conduct a study of the properties of metal foams as possible incorporation of energy absorbing element in the filler component of the superstructure of buses and coaches. - Elaborate a mathematical model to assess the contribution of the metal foam filling in absorbing energy for static and dynamic bending loads on the components of buses or coaches superstructure. - Conduct a static and dynamic bending test program to validate the mathematical model of contribution of metal foam filling on components of the superstructure of buses and coaches bending. - To incorporate into the mathematical model of structure rollover, the results obtained on components filled with metal foam, to evaluate the contribution to the energy absorption. - Validate the rollover model structure of the bus or coach filled with metal foam through tests of bay sections. The objectives in this thesis have been achieved successfully. The contribution calculation model with metal foam filling in the vehicle structure has revealed that the filling with metal foam is more efficient than increasing thickness of the beams, as demonstrated in the experimental validation of bay sections.