Análisis de los modelos de comportamiento de vigas de hormigón armado reforzadas a cortante con polímeros armados con fibras (frp). Validación y calibración experimental

Los polímeros armados con fibras (FRP) se utilizan en refuerzos de estructuras de hormigón debido sobre todo a sus excelentes propiedades mecánicas, su resistencia a la corrosión y a su ligereza que se traduce en facilidad y ahorro en el transporte, puesta en obra y aplicación, la cual se realiza de forma muy rápida, con pocos operarios y utilizando medios auxiliares ligeros, minimizándose las interrupciones del uso de la estructura y las molestias a los usuarios. Las razones presentadas anteriormente, han despertado un gran inter´es por parte de diferentes grupos de investigación a nivel mundial y que actualmente se encuentran desarrollando nuevas técnicas de aplicación y métodos de cálculo. Sin embargo, las investigaciones realizadas hasta la fecha, muestran un procedimiento bien definido y aceptado en lo referente al cálculo a flexión, lo cual no ocurre con el refuerzo a cortante y aunque se ha demostrado que el refuerzo con FRP es un sistema eficaz para incrementar la capacidad ´ultima frente a esfuerzos cortantes, también se pone de manifiesto la necesidad de más estudios experimentales y teóricos para avanzar en el entendimiento de los mecanismos involucrados para este tipo de refuerzo y establecer un procedimiento de diseño apropiado que maximice las excelentes propiedades de este material. Los modelos que explican el comportamiento del refuerzo a cortante de elementos de hormigón armado son complejos y sin transposición directa a fórmulas ingenieriles. Las normas actualmente en vigor, generalmente, establecen empíricamente la capacidad cortante como la suma de las capacidades del hormigón y el refuerzo transversal de acero. Cuando un elemento es reforzado externamente con FRP, los modelos son evidentemente aun más complejos. Las guías y recomendaciones existentes proponen calcular la capacidad del elemento añadiendo la resistencia aportada por el refuerzo externo de FRP a la ya dada por el hormigón y acero transversal. Sin embargo, la idoneidad de este acercamiento es cuestionable puesto que no tiene en cuenta una posible interacción entre refuerzos. Con base en lo anterior se da origen al tema objeto de este trabajo, el cual está orientado al estudio a cortante de elementos de hormigón armado (HA), reforzados externamente con material compuesto de tejido unidireccional de fibra de carbono y resina epoxi. Inicialmente se hace una completa revisión del estado actual del conocimiento de la resistencia a cortante en elementos de hormigón armado con y sin refuerzo externo de FRP, prestando especial atención en los mecanismos actuantes estudiados hasta la fecha. La bibliografía consultada ha sido exhaustiva y actualizada lo que ha permitido el estudio de los modelos propuestos más importantes, tanto para la descripción del fenómeno de adherencia entre hormigón-FRP como de la valoración del aporte al cortante total hecho por el FRP, a través de sendas bases de datos de ensayos de pull-out y de vigas de hormigón armado ensayadas a cortante. Con base en todo lo anterior, se expusieron los mecanismos actuantes en el aporte a cortante hecho por el FRP en elementos de hormigón armado y la forma como las principales guías de cálculo existentes hasta la fecha los abordan. De igual forma se define un modelo de resistencia de esfuerzos para el FRP y se proponen dos modelos para el cálculo de las tensiones o deformaciones efectivas, de los cuales uno esta basado en el modelo de adherencia propuesto por Oller (2005) y el otro en una regresión multivariante para los mecanismos expuestos. Como complemento del estudio de los trabajos encontrados en la literatura, se lleva acabo un programa experimental que, además de aportar más registros a la exigua base de datos existentes, aporte mayor luz a los puntos que se consideran están deficientemente resueltos. Dentro de este programa se realizaron 32 ensayos sobre 16 vigas de 4.5 m de longitud (dos ensayos por viga), reforzadas a cortante con tejido unidireccional de CFRP. Finalmente, estos estudios han permitido proponer modificaciones a las formulaciones existentes en los códigos y guías en vigor. Abstract Its excellent mechanical properties, as well as its corrosion resistance and light weight, which make it easy to apply and inexpensive to ship to the worksite, are the basis of the extended use of fiber reinforced polymer (FRP) as external strengthening for structures. FRP strengthening is a rapid operation calling for only limited labor and lightweight ancillary equipment, all of which minimizes both the interruption of facility usage and user inconvenience. These advantages have aroused considerable interest in civil engineering science and technology and have led to countless applications the world over. Research studies on the shear strength of FRP-strengthened members have been much fewer in number and more controversial than the research on flexural strengthening, for which a more or less standardized and generally accepted procedure has been established. The research conducted and a host of applications around the world have shown that FRP strengthening is an effective technique for raising ultimate shear strength, but it has also revealed a need for further experimental and theoretical research to advance in the understanding of the mechanisms involved and establish suitable design procedures that optimize the excellent properties of this material The models that explain reinforced concrete (RC) shear strength behavior are complex and cannot be directly transposed to engineering formulas. The standards presently in place generally establish shear capacity empirically as the sum of the capacities of the concrete and the passive reinforcement. When members are externally strengthened with FRP, the models are obviously even more complex. The existing guides and recommendations propose calculating capacity by adding the external strength provided by the FRP to the contributions of the concrete and passive reinforcement. The suitability of this approach is questionable, however, because it fails to consider the interaction between passive reinforcement and external strengthening. The subject of this work is based in above, which is focused on externally shear strengthening for reinforced concrete members with unidirectional carbon fiber sheets bonded with epoxy resin. v Initially a thorough literature review on shear of reinforced concrete beams with and without external FRP strengthening was performed, paying special attention to the acting mechanisms studied to date, which allowed the study of the most important models both to describe the bond phenomenon as well as calculating the FRP shear contribution, through separate databases of pull-out tests and shear tests on reinforced concrete beams externally strengthened with FRP. Based on above, they were exposed the acting mechanisms in a FRP shear strengthening on reinforced concrete beams and how guidelines deal the topic. The same way, it is defined a FRP stress strength model and two more models are proposed for calculating the effective stress, one of these is based on the Oller (2005) bond model and another one is the data best fit, taking into account most of the acting mechanisms. To complement the theoretical part we develop an experimental program that, in addition to providing more records to the meager existing database provide greater understanding to the points considered poorly resolved. The test program included 32 tests of 16 beams (2 per beam) of 4.5 m long, shear strengthened with FRP, externally. Finally, modifications to the existing codes and guidelines are proposed.

Bonding shear strength in timber and GFRP glued with epoxy adhesives

The bonding quality of epoxy glued timber and glass fibre reinforced polymers (GFRP) was evaluated by means of compression loading shear test. Three timber species (Radiata pine, Laricio pine and Oak) and two kinds of GFRP (plates and rods made with polyester resin reinforced with mat and roving glass fibre) were glued and tested using three epoxy formulations. The increase in shear strength with age after the setting of epoxy formulations and the effect of surface roughness on timber and GRP gluing (the planing of the surface of timber and the previous sanding of GRP) were studied. It can be concluded that the mechanical properties of these products make them suitable for use in the reinforcement of deteriorated timber structures, and that a rough timber surface is preferable to a planed one, while the previous sanding of GRP surfaces is not advantageous.

Effect of adhesive thickness and concrete strength on FRP-Concrete Bonds

The use of fiber-reinforced polymer (FRP) composites for strengthening, repairing, or rehabilitating concrete structures has become more and more popular in the last 10 years. Irrespective of the type of strengthening used, design is conditioned, among others, by concrete-composite bond failure, normally attributed to stress at the interface between these two materials. Single shear, double shear, and notched beam tests are the bond tests most commonly used by the scientific community to estimate bond strength, effective length, and the bond stress-slip relationship. The present paper discusses the effect of concrete strength and adhesive thickness on the results of beam tests, which reproduce debonding conditions around bending cracks much more accurately. The bond stress-slip relationship was analyzed in a cross section near the inner edge, where stress was observed to concentrate. The ultimate load and the bond stress-slip relationship were visibly affected by concrete strength. Adhesive thickness, in turn, was found to have no significant impact on low-strength concrete but a somewhat greater effect on higher strength materials.

Experimental and numerical analysis of concrete Slabs subjected to Blast

This paper summarizes the research activities focused on the behaviour of concrete and concrete structures subjected to blast loading carried out by the Department of Materials Science of the Technical University of Madrid (PUM). These activities comprise the design and construction of a test bench that allows for testing up to four planar concrete specimens with one single explosion, the study of the performance of different protection concepts for concrete structures and, finally, the development of a numerical model for the simulation of concrete structural elements subjected to blast. Up to date 6 different types of concrete have been studied, from plain normal strength concrete, to high strength concrete, including also fibre reinforced concretes with different types of fibres. The numerical model is based on the Cohesive Crack Model approach, and has been developed for the LSDYNA finite element code through a user programmed subroutine. Despite its simplicity, the model is able to predict the failure patterns of the concrete slabs tested with a high level of accuracy

Identification of intermediate debonding damage in FRP-plated RC beams based on multi-objective particle swarm optimization without updated baseline model

Fiber reinforced polymer composites (FRP) have found widespread usage in the repair and strengthening of concrete structures. FRP composites exhibit high strength-to-weight ratio, corrosion resistance, and are convenient to use in repair applications. Externally bonded FRP flexural strengthening of concrete beams is the most extended application of this technique. A common cause of failure in such members is associated with intermediate crack-induced debonding (IC debonding) of the FRP substrate from the concrete in an abrupt manner. Continuous monitoring of the concrete?FRP interface is essential to pre- vent IC debonding. Objective condition assessment and performance evaluation are challenging activities since they require some type of monitoring to track the response over a period of time. In this paper, a multi-objective model updating method integrated in the context of structural health monitoring is demonstrated as promising technology for the safety and reliability of this kind of strengthening technique. The proposed method, solved by a multi-objective extension of the particle swarm optimization method, is based on strain measurements under controlled loading. The use of permanently installed fiber Bragg grating (FBG) sensors embedded into the FRP-concrete interface or bonded onto the FRP strip together with the proposed methodology results in an automated method able to operate in an unsupervised mode.

Beam Spectral Element with FRP Debonding

The behaviour of the interface between the FRP and the concrete is the key factor controlling debonding failures in FRP-strengthened RC structures. This defect can cause reductions in static strength, structural integrity and the change in the dynamic behavior of the structure. The adverse effect on the dynamic behavior of the defects can be utilized as an effective means for identifying and assessing both the location and size of debonding at its earliest stages. The presence of debonding changes the structural dynamic characteristics and might be traced in modal parameters, dynamic strain and wave patterns etc. Detection of minor local defects, as those origin of a future debonding, requires working at high frequencies so that the wavelength of the excited is small and sensitive enough to detect local damage. The development of a spectral element method gives a large potential in high-frequency structural modeling. In contrast to the conventional finite element, since inertial properties are modeled exactly few elements are necessary to capture very accurate solutions at the highest frequencies in large regions. A wide variety of spectral elements have been developed for structural members over finite and semi-infinite regions. The objective of this paper is to develop a Spectral Finite Element Model to efficiently capture the behavior of intermediate debonding of a FRP strengthened RC beam during wave-based diagnostics.

Methodology based on FBG sensors for monitoring of FRP-strengthened beams

Advanced composite materials are increasingly used in the strengthening of reinforced concrete (RC) structures. The use of externally bonded strips made of fibre-reinforced plastics (FRP) as strengthening method has gained widespread acceptance in recent years since it has many advantages over the traditional techniques. However, unfortunately, this strengthening method is often associated with a brittle and sudden failure caused by some form of FRP bond failure, originated at the termination of the FRP material or at intermediate areas in the vicinity of flexural cracks in the RC beam. Up to date, little effort in the early prediction of the debonding in its initial instants even though this effect is not noticeable by simple visual observation. An early detection of this phenomenon might help in taking actions to prevent future catastrophes. Fibre-optic Bragg grating (FBG) sensors are able to measure strains locally with high resolution and accuracy. Furthermore, as their physical size is extremely small compared with other strain measuring components, it enables to be embedded at the concrete-FRP interface for determining the strain distribution without influencing the mechanical properties of the host materials. This paper shows the development of a debonding identification methodology based on strains experimentally measured. For, it a simplified model is implemented to simulate the behaviour of FRP-strengthened reinforced concrete beams. This model is taken as a basis to. develop an model updating procedure able to detect minor debonding at the concrete-FRP interface from experimental strains obtained by using FBG sensors embedded at the interface

Fatiga en CFRP: Caracterización y Método Óptico para la Estimación del Daño

El desarrollo de nuevas estructuras aeroespaciales optimizadas, utilizan materiales compuestos, para los componentes críticos y subsistemas, principalmente polímeros reforzados con fibra de carbono (CFRP). Un conocimiento profundo del estado de daño por fatiga de estructuras de CFRP avanzado, es esencial para predecir la vida residual y optimizar los intervalos de inspección estructural, reparaciones y/o sustitución de componentes. Las técnicas actuales se basan principalmente en la medición de cargas estructurales a lo largo de la vida útil de la estructura mediante galgas extensométricas eléctricas. Con esos datos, se estima la vida a fatiga utilizando modelos de acumulación de daño. En la presente tesis, se evalúa la metodología convencional para la estimación de la vida a fatiga de un CFRP aeronáutico. Esta metodología está basada en la regla de acumulación de daño lineal de Palmgren-Miner, y es aplicada para determinar la vida a fatiga de estructuras sometidas a cargas de amplitud variable. Se ha realizado una campaña de ensayos con cargas de amplitud constante para caracterizar un CFRP aeronáutico a fatiga, obteniendo las curvas clásicas S-N, en diferentes relaciones de esfuerzo. Se determinaron los diagramas de vida constante, (CLD), también conocidos como diagramas de Goodman, utilizando redes neuronales artificiales debido a la ausencia de modelos coherentes para materiales compuestos. Se ha caracterizado la degradación de la rigidez debido al daño por fatiga. Se ha ensayado un segundo grupo de probetas con secuencias estandarizadas de cargas de amplitud variable, para obtener la vida a fatiga y la degradación de rigidez en condiciones realistas. Las cargas aplicadas son representativas de misiones de aviones de combate (Falstaff), y de aviones de transporte (Twist). La vida a fatiga de las probetas cicladas con cargas de amplitud variable, se comparó con el índice de daño teórico calculado en base a la regla de acumulación de daño lineal convencional. Los resultados obtenidos muestran predicciones no conservativas. Esta tesis también presenta el estudio y desarrollo, de una nueva técnica de no contacto para evaluar el estado de daño por fatiga de estructuras de CFRP por medio de cambios de los parámetros de rugosidad. La rugosidad superficial se puede medir fácilmente en campo con métodos sin contacto, mediante técnicas ópticas tales como speckle y perfilómetros ópticos. En el presente estudio, se han medido parámetros de rugosidad superficial, y el factor de irregularidad de la superficie, a lo largo de la vida de las probetas cicladas con cargas de amplitud constante y variable, Se ha obtenido una buena tendencia de ajuste al correlacionar la magnitud de la rugosidad y el factor de irregularidad de la superficie con la degradación de la rigidez de las probetas fatigadas. Estos resultados sugieren que los cambios en la rugosidad superficial medida en zonas estratégicas de componentes y estructuras hechas de CFRP, podrían ser indicativas del nivel de daño interno debido a cargas de fatiga. Los resultados también sugieren que el método es independiente del tipo de carga de fatiga que ha causado el daño. Esto último hace que esta técnica de medición sea aplicable como inspección para una amplia gama de estructuras de materiales compuestos, desde tanques presurizados con cargas de amplitud constante, estructuras aeronáuticas como alas y colas de aeronaves cicladas con cargas de amplitud variable, hasta aplicaciones industriales como automoción, entre otros. ABSTRACT New optimized aerospace structures use composite materials, mainly carbon fiber reinforced polymer composite (CFRP), for critical components and subsystems. A strong knowledge of the fatigue state of highly advanced (CFRP) structures is essential to predict the residual life and optimize intervals of structural inspection, repairs, and/or replacements. Current techniques are based mostly on measurement of structural loads throughout the service life by electric strain gauge sensors. These sensors are affected by extreme environmental conditions and by fatigue loads in such a way that the sensors and their systems require exhaustive maintenance throughout system life. In the present thesis, the conventional methodology based on linear damage accumulation rules, applied to determine the fatigue life of structures subjected to variable amplitude loads was evaluated for an aeronautical CFRP. A test program with constant amplitude loads has been performed to obtain the classical S-N curves at different stress ratios. Constant life diagrams, CLDs, where determined by means of Artificial Neural Networks due to the absence of consistent models for composites. The stiffness degradation due to fatigue damage has been characterized for coupons under cyclic tensile loads. A second group of coupons have been tested until failure with a standardized sequence of variable amplitude loads, representative of missions for combat aircraft (Falstaff), and representative of commercial flights (Twist), to obtain the fatigue life and the stiffness degradation under realistic conditions. The fatigue life of the coupons cycled with variable amplitude loads were compared to the theoretical damage index calculated based on the conventional linear damage accumulation rule. The obtained results show non-conservative predictions. This thesis also presents the evaluation of a new non-contact technique to evaluate the fatigue damage state of CFRP structures by means of measuring roughness parameters to evaluate changes in the surface topography. Surface roughness can be measured easily on field with non-contact methods by optical techniques such as speckle and optical perfilometers. In the present study, surface roughness parameters, and the surface irregularity factor, have been measured along the life of the coupons cycled with constant and variable amplitude loads of different magnitude. A good agreement has been obtained when correlating the magnitude of the roughness and the surface irregularity factor with the stiffness degradation. These results suggest that the changes on the surface roughness measured in strategic zones of components and structures made of CFRP, could be indicative of the level of internal damage due to fatigue loads. The results also suggest that the method is independent of the type of fatigue load that have caused the damage. It makes this measurement technique applicable for a wide range of inspections of composite materials structures, from pressurized tanks with constant amplitude loads, to variable amplitude loaded aeronautical structures like wings and empennages, up to automotive and other industrial applications.

Optical sensing of the fatigue damage state of CFRP under realistic aeronautical load sequences

We present an optical sensing methodology to estimate the fatigue damage state of structures made of carbon fiber reinforced polymer (CFRP), by measuring variations on the surface roughness. Variable amplitude loads (VAL), which represent realistic loads during aeronautical missions of fighter aircraft (FALSTAFF) have been applied to coupons until failure. Stiffness degradation and surface roughness variations have been measured during the life of the coupons obtaining a Pearson correlation of 0.75 between both variables. The data were compared with a previous study for Constant Amplitude Load (CAL) obtaining similar results. Conclusions suggest that the surface roughness measured in strategic zones is a useful technique for structural health monitoring of CFRP structures, and that it is independent of the type of load applied. Surface roughness can be measured in the field by optical techniques such as speckle, confocal perfilometers and interferometry, among others.

Curing, defects and mechanical performance of fiber-reinforced composites

Tradicionalmente, la fabricación de materiales compuestos de altas prestaciones se lleva a cabo en autoclave mediante la consolidación de preimpregnados a través de la aplicación simultánea de altas presiones y temperatura. Las elevadas presiones empleadas en autoclave reducen la porosidad de los componentes garantizando unas buenas propiedades mecánicas. Sin embargo, este sistema de fabricación conlleva tiempos de producción largos y grandes inversiones en equipamiento lo que restringe su aplicación a otros sectores alejados del sector aeronáutico. Este hecho ha generado una creciente demanda de sistemas de fabricación alternativos al autoclave. Aunque estos sistemas son capaces de reducir los tiempos de producción y el gasto energético, por lo general, dan lugar a materiales con menores prestaciones mecánicas debido a que se reduce la compactación del material al aplicar presiones mas bajas y, por tanto, la fracción volumétrica de fibras, y disminuye el control de la porosidad durante el proceso. Los modelos numéricos existentes permiten conocer los fundamentos de los mecanismos de crecimiento de poros durante la fabricación de materiales compuestos de matriz polimérica mediante autoclave. Dichos modelos analizan el comportamiento de pequeños poros esféricos embebidos en una resina viscosa. Su validez no ha sido probada, sin embargo, para la morfología típica observada en materiales compuestos fabricados fuera de autoclave, consistente en poros cilíndricos y alargados embebidos en resina y rodeados de fibras continuas. Por otro lado, aunque existe una clara evidencia experimental del efecto pernicioso de la porosidad en las prestaciones mecánicas de los materiales compuestos, no existe información detallada sobre la influencia de las condiciones de procesado en la forma, fracción volumétrica y distribución espacial de los poros en los materiales compuestos. Las técnicas de análisis convencionales para la caracterización microestructural de los materiales compuestos proporcionan información en dos dimensiones (2D) (microscopía óptica y electrónica, radiografía de rayos X, ultrasonidos, emisión acústica) y sólo algunas son adecuadas para el análisis de la porosidad. En esta tesis, se ha analizado el efecto de ciclo de curado en el desarrollo de los poros durante la consolidación de preimpregnados Hexply AS4/8552 a bajas presiones mediante moldeo por compresión, en paneles unidireccionales y multiaxiales utilizando tres ciclos de curado diferentes. Dichos ciclos fueron cuidadosamente diseñados de acuerdo a la caracterización térmica y reológica de los preimpregnados. La fracción volumétrica de poros, su forma y distribución espacial se analizaron en detalle mediante tomografía de rayos X. Esta técnica no destructiva ha demostrado su capacidad para analizar la microestructura de materiales compuestos. Se observó, que la porosidad depende en gran medida de la evolución de la viscosidad dinámica a lo largo del ciclo y que la mayoría de la porosidad inicial procedía del aire atrapado durante el apilamiento de las láminas de preimpregnado. En el caso de los laminados multiaxiales, la porosidad también se vio afectada por la secuencia de apilamiento. En general, los poros tenían forma cilíndrica y se estaban orientados en la dirección de las fibras. Además, la proyección de la población de poros a lo largo de la dirección de la fibra reveló la existencia de una estructura celular de un diámetro aproximado de 1 mm. Las paredes de las celdas correspondían con regiones con mayor densidad de fibra mientras que los poros se concentraban en el interior de las celdas. Esta distribución de la porosidad es el resultado de una consolidación no homogenea. Toda esta información es crítica a la hora de optimizar las condiciones de procesado y proporcionar datos de partida para desarrollar herramientas de simulación de los procesos de fabricación de materiales compuestos fuera de autoclave. Adicionalmente, se determinaron ciertas propiedades mecánicas dependientes de la matriz termoestable con objeto de establecer la relación entre condiciones de procesado y las prestaciones mecánicas. En el caso de los laminados unidireccionales, la resistencia interlaminar depende de la porosidad para fracciones volumétricas de poros superiores 1%. Las mismas tendencias se observaron en el caso de GIIc mientras GIc no se vio afectada por la porosidad. En el caso de los laminados multiaxiales se evaluó la influencia de la porosidad en la resistencia a compresión, la resistencia a impacto a baja velocidad y la resistencia a copresión después de impacto. La resistencia a compresión se redujo con el contenido en poros, pero éste no influyó significativamente en la resistencia a compresión despues de impacto ya que quedó enmascarada por otros factores como la secuencia de apilamiento o la magnitud del daño generado tras el impacto. Finalmente, el efecto de las condiciones de fabricación en el proceso de compactación mediante moldeo por compresión en laminados unidireccionales fue simulado mediante el método de los elementos finitos en una primera aproximación para simular la fabricación de materiales compuestos fuera de autoclave. Los parámetros del modelo se obtuvieron mediante experimentos térmicos y reológicos del preimpregnado Hexply AS4/8552. Los resultados obtenidos en la predicción de la reducción de espesor durante el proceso de consolidación concordaron razonablemente con los resultados experimentales. Manufacturing of high performance polymer-matrix composites is normally carried out by means of autoclave using prepreg tapes stacked and consolidated under the simultaneous application of pressure and temperature. High autoclave pressures reduce the porosity in the laminate and ensure excellent mechanical properties. However, this manufacturing route is expensive in terms of capital investment and processing time, hindering its application in many industrial sectors. This fact has driven the demand of alternative out-of-autoclave processing routes. These techniques claim to produce composite parts faster and at lower cost but the mechanical performance is also reduced due to the lower fiber content and to the higher porosity. Corrient numerical models are able to simulate the mechanisms of void growth in polymer-matrix composites processed in autoclave. However these models are restricted to small spherical voids surrounded by a viscous resin. Their validity is not proved for long cylindrical voids in a viscous matrix surrounded by aligned fibers, the standard morphology observed in out-of-autoclave composites. In addition, there is an experimental evidence of the detrimental effect of voids on the mechanical performance of composites but, there is detailed information regarding the influence of curing conditions on the actual volume fraction, shape and spatial distribution of voids within the laminate. The standard techniques of microstructural characterization of composites (optical or electron microscopy, X-ray radiography, ultrasonics) provide information in two dimensions and are not always suitable to determine the porosity or void population. Moreover, they can not provide 3D information. The effect of curing cycle on the development of voids during consolidation of AS4/8552 prepregs at low pressure by compression molding was studied in unidirectional and multiaxial panels. They were manufactured using three different curing cycles carefully designed following the rheological and thermal analysis of the raw prepregs. The void volume fraction, shape and spatial distribution were analyzed in detail by means of X-ray computed microtomography, which has demonstrated its potential for analyzing the microstructural features of composites. It was demonstrated that the final void volume fraction depended on the evolution of the dynamic viscosity throughout the cycle. Most of the initial voids were the result of air entrapment and wrinkles created during lay-up. Differences in the final void volume fraction depended on the processing conditions for unidirectional and multiaxial panels. Voids were rod-like shaped and were oriented parallel to the fibers and concentrated in channels along the fiber orientation. X-ray computer tomography analysis of voids along the fiber direction showed a cellular structure with an approximate cell diameter of 1 mm. The cell walls were fiber-rich regions and porosity was localized at the center of the cells. This porosity distribution within the laminate was the result of inhomogeneous consolidation. This information is critical to optimize processing parameters and to provide inputs for virtual testing and virtual processing tools. In addition, the matrix-controlled mechanical properties of the panels were measured in order to establish the relationship between processing conditions and mechanical performance. The interlaminar shear strength (ILSS) and the interlaminar toughness (GIc and GIIc) were selected to evaluate the effect of porosity on the mechanical performance of unidirectional panels. The ILSS was strongly affected by the porosity when the void contents was higher than 1%. The same trends were observed in the case of GIIc while GIc was insensitive to the void volume fraction. Additionally, the mechanical performance of multiaxial panels in compression, low velocity impact and compression after impact (CAI) was measured to address the effect of processing conditions. The compressive strength decreased with porosity and ply-clustering. However, the porosity did not influence the impact resistance and the coompression after impact strength because the effect of porosity was masked by other factors as the damage due to impact or the laminate lay-up. Finally, the effect of the processing conditions on the compaction behavior of unidirectional AS4/8552 panels manufactured by compression moulding was simulated using the finite element method, as a first approximation to more complex and accurate models for out-of autoclave curing and consolidation of composite laminates. The model parameters were obtained from rheological and thermo-mechanical experiments carried out in raw prepreg samples. The predictions of the thickness change during consolidation were in reasonable agreement with the experimental results.

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.

Tuning the properties of carbon fiber-reinforced poly (phenylene sulphide) laminates via incorporation of inorganic fullerene-like WS2 nanoparticles

Novel carbon fiber (CF)-reinforced poly(phenylene sulphide) (PPS) laminates incorporating inorganic fullerene-like tungsten disulfide (IF-WS2) nanoparticles were prepared via melt-blending and hot-press processing. The influence of the IF-WS2 on the morphology, thermal, mechanical and tribological properties of PPS/CF composites was investigated. Efficient nanoparticle dispersion within the matrix was attained without using surfactants. A progressive rise in thermal stability was found with increasing IF-WS2 loading, as revealed by thermogravimetric analysis. The addition of low nanoparticle contents retarded the crystallization of the matrix, whereas concentrations equal or higher than 1.0 wt% increased both the crystallization temperature and degree of crystallinity compared to those of PPS/CF. Mechanical tests indicated that with only 1.0 wt% IF-WS2 the flexural modulus and strength of PPS/CF improved by 17 and 14%, respectively, without loss in toughness, ascribed to a synergistic effect between the two fillers. A significant enhancement in the storage modulus and glass transition temperature was also observed. Moreover, the wear rate and coefficient of friction strongly decreased, attributed to the lubricant role of the IF-WS2 combined with their reinforcing effect. These inorganic nanoparticles show great potential to improve the mechanical and tribological properties of conventional thermoplastic/CF composites for structural applications.

Mechanical and thermal behaviour of isotactic polypropylene reinforced with inorganic fullerene-like WS2 nanoparticles: Effect of filler loading and temperature

The thermal and mechanical behaviour of isotactic polypropylene (iPP) nanocomposites reinforced with different loadings of inorganic fullerene-like tungsten disulfide (IF-WS2) nanoparticles was investigated. The IF-WS2 noticeably enhanced the polymer stiffness and strength, ascribed to their uniform dispersion, the formation of a large nanoparticle?matrix interface combined with a nucleating effect on iPP crystallization. Their reinforcement effect was more pronounced at high temperatures. However, a drop in ductility and toughness was found at higher IF-WS2 concentrations. The tensile behaviour of the nanocomposites was extremely sensitive to the strain rate and temperature, and their yield strength was properly described by the Eyring s equation. The activation energy increased while the activation volume decreased with increasing nanoparticle loading, indicating a reduction in polymer chain motion. The nanoparticles improved the thermomechanical properties of iPP: raised the glass transition and heat deflection temperatures while decreased the coefficient of thermal expansion. The nanocomposites also displayed superior flame retardancy with longer ignition time and reduced peak heat release rate. Further, a gradual rise in thermal conductivity was found with increasing IF-WS2 loading both in the glassy and rubbery states. The results presented herein highlight the benefits and high potential of using IF-nanoparticles for enhancing the thermomechanical properties of thermoplastic polymers compared to other nanoscale fillers.

Polymer interaction with macroscopic carbon nanotube fibres and fabrication of nanostructured composites

El ensamblado de nanotubos de carbono (CNT) como una fibra macroscópica en la cual están orientados preferentemente paralelos entre sí y al eje de la fibra, ha dado como resultado un nuevo tipo de fibra de altas prestaciones derivadas de la explotación eficiente de las propiedades axiales de los CNTs, y que tiene un gran número de aplicaciones potenciales. Fibras continuas de CNTs se produjeron en el Instituto IMDEA Materiales mediante el proceso de hilado directo durante la reacción de síntesis por deposición química de vapores. Uno de los objetivos de esta tesis es el estudio de la estructura de estas fibras mediante técnicas del estado del arte de difracción de rayos X de sincrotrón y la elaboración de un modelo estructural de dicho material. Mediciones texturales de adsorción de gases, análisis de micrografías de electrones y dispersión de rayos X de ángulo alto y bajo (WAXS/SAXS) indican que el material tiene una estructura mesoporosa con una distribución de tamaño de poros ancha derivada del amplio rango de separaciones entre manojos de CNTs, así como una superficie específica de 170m2/g. Los valores de dimensión fractal obtenidos mediante SAXS y análisis Barrett-Joyner-Halenda (BJH) de mediciones texturales coinciden en 2.4 y 2.5, respectivamente, resaltando el carácter de red de la estructura de dichas fibras. La estructura mesoporosa y tipo hilo de las fibra de CNT es accesible a la infiltración de moléculas externas (líquidos o polímeros). En este trabajo se estudian los cambios en la estructura multiescala de las fibras de CNTs al interactuar con líquidos y polímeros. Los efectos de la densificación en la estructura de fibras secas de CNT son estudiados mediante WAXS/SAXS. El tratamiento de densificación junta los manojos de la fibra (los poros disminuyen de tamaño), resultando en un incremento de la densidad de la fibra. Sin embargo, los dominios estructurales correspondientes a la transferencia de esfuerzo mecánica y carga eléctrica en los nanotubos no son afectados durante este proceso de densificación; como consecuencia no se produce un efecto sustancial en las propiedades mecánicas y eléctricas. Mediciones de SAXS and fibra de CNT antes y después de infiltración de líquidos confirman la penetración de una gran cantidad de líquidos que llena los poros internos de la fibra pero no se intercalan entre capas de nanotubos adyacentes. La infiltración de cadenas poliméricas de bajo peso molecular tiende a expandir los manojos en la fibra e incrementar el ángulo de apertura de los poros. Los resultados de SAXS indican que la estructura interna de la fibra en términos de la organización de las capas de tubos y su orientación no es afectada cuando las muestras consisten en fibras infiltradas con polímeros de alto peso molecular. La cristalización de varios polímeros semicristalinos es acelerada por la presencia de fibras de CNTs alineados y produce el crecimiento de una capa transcristalina normal a la superficie de la fibra. Esto es observado directamente mediante microscopía óptica polarizada, y detectado mediante calorimetría DSC. Las lamelas en la capa transcristalina tienen orientación de la cadena polimérica paralela a la fibra y por lo tanto a los nanotubos, de acuerdo con los patrones de WAXS. Esta orientación preferencial se sugiere como parte de la fuerza impulsora en la nucleación. La nucleación del dominio cristalino polimérico en la superficie de los CNT no es epitaxial. Ocurre sin haber correspondencia entre las estructuras cristalinas del polímero y los nanotubos. Estas observaciones contribuyen a la compresión del fenómeno de nucleación en CNTs y otros nanocarbonos, y sientan las bases para el desarrollo de composites poliméricos de gran escala basados en fibra larga de CNTs alineados. ABSTRACT The assembly of carbon nanotubes into a macroscopic fibre material where they are preferentially aligned parallel to each other and to the fibre axis has resulted in a new class of high-performance fibres, which efficiently exploits the axial properties of the building blocks and has numerous applications. Long, continuous CNT fibres were produced in IMDEA Materials Institute by direct fibre spinning from a chemical vapour deposition reaction. These fibres have a complex hierarchical structure covering multiple length scales. One objective of this thesis is to reveal this structure by means of state-of-the-art techniques such as synchrotron X-ray diffraction, and to build a model to link the fibre structural elements. Texture and gas absorption measurements, using electron microscopy, wide angle and small angle X-ray scattering (WAXS/SAXS), and pore size distribution analysis by Barrett-Joyner-Halenda (BJH), indicate that the material has a mesoporous structure with a wide pore size distribution arising from the range of fibre bundle separation, and a high surface area _170m2/g. Fractal dimension values of 2.4_2.5 obtained from the SAXS and BJH measurements highlight the network structure of the fibre. Mesoporous and yarn-like structure of CNT fibres make them accessible to the infiltration of foreign molecules (liquid or polymer). This work studies multiscale structural changes when CNT fibres interact with liquids and polymers. The effects of densification on the structure of dry CNT fibres were measured by WAXS/SAXS. The densification treatment brings the fibre bundles closer (pores become smaller), leading to an increase in fibre density. However, structural domains made of the load and charge carrying nanotubes are not affected; consequently, it has no substantial effect on mechanical and electrical properties. SAXS measurements on the CNT fibres before and after liquid infiltration imply that most liquids are able to fill the internal pores but not to intercalate between nanotubes. Successful infiltration of low molecular weight polymer chains tends to expand the fibre bundles and increases the pore-opening angle. SAXS results indicate that the inner structure of the fibre, in terms of the nanotube layer arrangement and the fibre alignment, are not largely affected when infiltrated with polymers of relatively high molecular weight. The crystallisation of a variety of semicrystalline polymers is accelerated by the presence of aligned fibres of CNTs and results in the growth of a transcrystalline layer perpendicular to the fibre surface. This can be observed directly under polarised optical microscope, and detected by the exothermic peaks during differential scanning calorimetry. The discussion on the driving forces for the enhanced nucleation points out the preferential chain orientation of polymer lamella with the chain axis parallel to the fibre and thus to the nanotubes, which is confirmed by two-dimensional WAXS patterns. A non-epitaxial polymer crystal growth habit at the CNT-polymer interface is proposed, which is independent of lattice matching between the polymer and nanotubes. These findings contribute to the discussion on polymer nucleation on CNTs and other nanocarbons, and their implication for the development of large polymer composites based on long and aligned fibres of CNTs.