Bifurcation diagrams for polymer blends with diffuse interfaces in confined and adaptive geometries

Dynamics of binary mixtures such as polymer blends, and fluids near the critical point, is described by the model-H, which couples momentum transport and diffusion of the components [1]. We present an extended version of the model-H that allows to study the combined effect of phase separation in a polymer blend and surface structuring of the film itself [2]. We apply it to analyze the stability of vertically stratified base states on extended films of polymer blends and show that convective transport leads to new mechanisms of instability as compared to the simpler diffusive case described by the Cahn- Hilliard model [3, 4]. We carry out this analysis for realistic parameters of polymer blends used in experimental setups such as PS/PVME. However, geometrically more complicated states involving lateral structuring, strong deflections of the free surface, oblique diffuse interfaces, checkerboard modes, or droplets of a component above of the other are possible at critical composition solving the Cahn Hilliard equation in the static limit for rectangular domains [5, 6] or with deformable free surfaces [6]. We extend these results for off-critical compositions, since balanced overall composition in experiments are unusual. In particular, we study steady nonlinear solutions of the Cahn-Hilliard equation for bidimensional layers with fixed geometry and deformable free surface. Furthermore we distinguished the cases with and without energetic bias at the free surface. We present bifurcation diagrams for off-critical films of polymer blends with free surfaces, showing their free energy, and the L2-norms of surface deflection and the concentration field, as a function of lateral domain size and mean composition. Simultaneously, we look at spatial dependent profiles of the height and concentration. To treat the problem of films with arbitrary surface deflections our calculations are based on minimizing the free energy functional at given composition and geometric constraints using a variational approach based on the Cahn-Hilliard equation. The problem is solved numerically using the finite element method (FEM).

Confined crystallization of nanolayered poly(ethylene terephthalate) using X-ray diffraction methods

The development of crystalline lamellae in ultra-thin layers of poly(ethylene terephthalate) PET confined between polycarbonate (PC) layers in an alternating assembly is investigated as a function of layer thickness by means of X-ray diffraction methods. Isothermal crystallization from the glassy state is in-situ followed by means of small-angle X-ray diffraction. It is found that the reduced size of the PET layers influences the lamellar nanostructure and induces a preferential lamellar orientation. Two lamellar populations, flat-on and edge-on, are found to coexist in a wide range of crystallization temperatures (Tc = 117–150 °C) and within layer thicknesses down to 35 nm. Flat-on lamellae appear at a reduced crystallization rate with respect to bulk PET giving rise to crystals of similar dimensions separated by larger amorphous regions. In addition, a narrower distribution of lamellar orientations develops when the layer thickness is reduced or the crystallization temperature is raised. In case of edge-on lamellae, crystallization conditions also influence the development of lamellar orientation; however, the latter is little affected by the reduced size of the layers. Results suggest that flat-on lamellae arise as a consequence of spatial confinement and edge-on lamellae could be generated due to the interactions with the PC interface. En este trabajo se investiga mediante difracción de rayos X a ángulos bajos (SAXS) y a ángulos altos (WAXS), la cristalización de láminas delgadas de Polietilén tereftalato (PET) confinadas entre láminas de Policarbonato (PC), tomando como referencia PET sin confinar. El espesor de las capas de PET varía entre 35nm y 115 nm. Se realizaron medidas de difracción a tres temperaturas de cristalización (117ºC, 132ºC y 150ºC) encontrándose que el reducido espesor de las capas de PET influye en la estructura lamelar que se desarrolla, induciendo una orientación preferente de las láminas. Se integró la intensidad difractada alrededor del máximo en SAXS para obtener una representación de la intensidad en función del ángulo acimutal. Mediante análisis de mínimos cuadrados se separó la curva experimental obtenida en tres contribuciones diferentes: una función Gausiana que describe la distribución de las orientaciones de las lamelas, una función lorenziana asociada a los máximos meridionales (asociados a las interfases PET-PC) y un background constante. Por otra parte la cantidad de material cristalizado se estimó asumiendo que la intensidad del background en el barrido acimutal, una vez restado el background del primer difractograma (sin máximos en SAXS) se asocia con la contribución del material isotrópico que resta en la muestra cristalizada. Se observa la coexistencia de dos poblaciones de lamelas: flat-on y edge-on. A medida que el espesor de las láminas de PET disminuye la población de las lamelas flat-on experimenta los siguientes cambios: 1) la distribución de orientación se estrecha, 2) la fracción de material cristalizado orientado aumenta, 3) la cinética de cristalización se ralentiza y 4) el largo espaciado aumenta es decir las regiones amorfas entre lamelas aumentan su tamaño. Parece demostrarse que es en las primeras etapas del crecimiento lamelar cuando la restricción espacial fuerza a las lamelas a esta orientación tipo flat-on frente a la orientación edge-on.

Microindentation Characterization of Polymers and Polymer Based Nanocomposites

El objetivo de los diferentes grupos integrantes de está red es diseñar, preparar y caracterizar novedosos materiales basados en polipropileno de alto valor añadido, preferentemente reciclables o biodegradables, optimizando el consumo energético en su preparación y procesamiento.

Polymer-solvent interaction parameters of SBS rubbers by inverse gas chromatography measurements

The solubility parameters of two SBS commercial rubbers with different structures (lineal and radial), and with slightly different styrene content have been determined by inverse gas chromatography technique. The Flory–Huggins interaction parameters of several polymer–solvent mixtures have also been calculated. The influence of the polymer composition, the solvent molecular weight and the temperature over these parameters have been discussed; besides, these parameters have been compared with previous ones, obtained by intrinsic viscosity measurements. From the Flory–Huggins interaction parameters, the infinite dilution activity coefficients of the solvents have been calculated and fitted to the well-known NRTL model. These NRTL binary interaction parameters have a great importance in modelling the separation steps in the process of obtaining the rubber.

Diseño y fabricación de dispositivos basados en cristal líquido polimérico

Esta tesis se centra en el estudio y desarrollo de dispositivos de aplicación basados en cristal líquido polimérico. Las propiedades de los cristales líquidos los hacen interesantes para su uso en el desarrollo de dispositivos de seguridad para autenticación de productos y marcas, y detección y prevención de falsificaciones. Asimismo, pueden ser muy útiles para fabricar dispositivos basados en CLs dispersos en polímero, los cuales tienen a su vez múltiples aplicaciones. La orientación de las moléculas de cristal líquido y la birrefringencia son las dos características principales que afectan a las propiedades de estos dispositivos. Un dispositivo de cristal líquido estándar consiste en un sándwich formado por dos sustratos de vidrio transparente, dotados con electrodo de ITO (Indium Tin Oxide) en su superficie interna, que confinan el cristal líquido en su interior. En la primera parte de esta tesis se describen las características más importantes que describen una célula de cristal líquido. Esta introducción básica en necesaria para la correcta comprensión de los capítulos posteriores en los que se detalla el desarrollo concreto de los dispositivos desarrollados en la investigación llevada a cabo. Por ejemplo, en el caso de los dispositivos de seguridad se han eliminado los sustratos de vidrio (en la última fase de su desarrollo) para conseguir dispositivos flexibles. En la segunda parte de la tesis se incluye la descripción completa de los dispositivos fabricados, así como de los protocolos de fabricación seguidos y diseñados específicamente para ello. También se detallan en esta parte los resultados obtenidos, así como las propiedades ópticas y electroópticas en cada caso, y el/los equipos de caracterización utilizados. Utilizando cristal líquido nemático y colorante dicroico, se han desarrollado dispositivos que contienen múltiples imágenes latentes en cada cara del mismo. Utilizando distintas técnicas de alineamiento se consigue crear cualquier tipo de motivo latente, ya sean símbolos sencillos, figuras, logotipos o incluso imágenes con escala de gris. Cuanto más complejo es el dispositivo, mayor es la dificultad para reproducirlo en una eventual falsificación. Para visualizar e identificar los motivos es necesario emplear luz polarizada, por ejemplo, con la ayuda de un sencillo polarizador lineal. Dependiendo de si el polarizador está colocado delante del dispositivo o detrás del él, se mostrarán las imágenes generadas en una u otra cara. Este efecto es posible gracias al colorante dicroico añadido al CL, a la orientación inducida sobre las moléculas, y a la estructura de twist utilizada en los dispositivos. En realidad, para ver el efecto de los dispositivos no es necesario el uso de un polarizador, basta con el reflejo de una superficie dielétrica (percialmente polarizado), o la luz emitida por la pantalla de dispositivos de consumo comunes como un televisor LCD, un monitor de ordenador o un “smartphone”. Por otro lado, utilizando una mezcla entre un CL nemático polimérico y un CL nemático no polimérico es posible fabricar dispositivos LCPC (Liquid Crystal Polymer Composite) con propiedades electroópticas muy interesantes, que funcionan a tensiones de conmutación bajas. El CL polimérico conforma una estructura de red en el interior del sándwich que mantiene confinado al CL nemático en pequeños microdominios. Se han fabricado dispositivos LCPC con conmutación inversa utilizando tanto alineamiento homogéneo como homeotrópico. Debido a que tanto la estructura de CL polimérico como el CL nemático que rellena los microdominios están orientados en una misma dirección de alineamiento preinducida, la luz dispersada por el dispositivo se encuentra polarizada. La dirección de polarización coincide con la dirección de alineamiento. La innovación aportada por esta investigación: un nuevo dispositivo LCPC inverso de respuesta ultrarápida y polarizada basado en la mezcla de dos CL nemáticos y, un dispositivo de seguridad y autenticación, patentado internacionalmente, basado en CL nemáticos dopados con colorante dicroico. Abstract This thesis is centered on the availability to use polymerizable liquid crystals to develop non-display application LC devices. Liquid crystal properties make them useful for the development of security devices in applications of authentication and detection of fakes, and also to achieve polymer dispersed LC devices to be used for different applications that will be studied here. Induced orientation of liquid crystal molecules and birefringence are the two main properties used in these devices. A standard liquid crystal device is a sandwich consisting of two parallel glass substrates carrying a thin transparent ITO (Indium‐Tin‐Oxide) electrode on their inner surfaces with the liquid crystal in the middle. The first part of this thesis will describe the most important parameters describing a liquid crystal cell. This basis is necessary for the understanding of later chapters where models of the liquid crystal devices will be discussed and developed. In the case of security devices the standard structure of an LC device has been modified by eliminating the glass substrates in order to achieve plastic and flexible devices. The second part of the thesis includes a detailed description of the devices achieved and the manufacturing protocols that have been developed ad-hoc. The optical and electrooptical properties and the characterization equipment are described here as well. Employing nematic liquid crystal and dichroic colorants, we have developed devices that show, with the aid of a polarizer, multiple images on each side of the device. By different alignment techniques it is possible to create any kind of symbols, drawings or motifs with a grayscale; the more complex the created device is, the more difficult is to fake it. To identify the motifs it is necessary to use polarized light. Depending on whether the polarizer is located in front of the LC cell or behind it, different motifs from one or the other substrate are shown. The effect arises from the dopant color dye added to the liquid crystal, the induced orientation and the twist structure. In practice, a grazing reflection on a dielectric surface is polarized enough to see the effect. Any LC flat panel display (LCD TV, computer, mobile phone) can obviously be used as backlight as well. On the other hand, by using a mixture of polymerizable and non-polymerizable nematics liquid crystals it is also possible to achieve LCPC (Liquid Crystal Polymer Composite) devices that show really interesting electrooptical characteristics using low switching voltages. Polymerizable LC creates a hollow structure inside the sandwich glass cell that keep nematics liquid crystal confined creating microdomains. Homogeneous and homeotropic alignments have been used to develop inverse switching mode LCPCs. Due to the double LC oriented structure, the outgoing scattered light from these devices is already polarized. The polarization axis coincides with LC molecules director, the alignment direction promoted. The novelties derived from the investigation presented here, new ultrafast inverse LCPC with polarized outgoing scattered light based on oriented nematic LC mixture, and an internationally patented security and authentication device based on nematics (doped with dichroic dye) oriented polymerizable LC.

New inorganic nanotube polymer nanocomposites: Improved thermal, mechanical and tribological properties in isotactic polypropylene incorporating INT-MoS2.

Environmentally friendly molybdenum disulfide (INT-MoS2) inorganic nanotubes were introduced into an isotactic polypropylene (iPP) polymer matrix to generate novel nanocomposite materials through an advantageous melt-processing route. The effects of INT-MoS2 content on the thermal, mechanical and tribological properties were investigated. The incorporation of INT-MoS2 generates notable performance enhancements through reinforcement effects, highly efficient nucleation activity and excellent lubricating ability in comparison with other nanoparticle fillers such as nanoclays, carbon nanotubes, silicon nitrides and halloysite nanotubes. It was shown that these INT-MoS2 nanocomposites can provide an effective balance between performance, cost effectiveness and processability, and should be of some interest in the area of multifunctional polymer nanocomposite materials.

X-Ray Diffraction, Calorimetric and Dielectric Relaxation Study of the Amorphous and Smectic States of a Main Chain Liquid Crystalline Polymer

Los polímeros cristales líquidos (LCP) son sistemas complejos que forman mesofases que presentan orden orientacional y polímeros amorfos. Con frecuencia, el estado amorfo isotrópico no puede ser estudiado debido a la rápida formación de mesofases. En este trabajo se ha sintetizado y estudiado un nuevo LCP: poli(trietilenglicol metil p, p '-bibenzoato), PTEMeB. Este polímero presenta una formación de mesofase bastante lenta haciendo posible estudiar de forma independiente tanto los estados amorfo y de cristal líquidos. La estructura y las transiciones de fase del PTEMeB han sido investigados por calorimetría (DSC), con MAXS / WAXS con temperatura variable que emplean radiación de sincrotrón y con difracción de rayos X. Estos estudios han mostrado la existencia de dos transiciones vítreas, relacionadas con las fases amorfa y cristal líquido. Se ha realizado un estudio de relajación dieléctrica en amplios intervalos de temperatura y presión. Se ha encontrado que la transición vítrea dinámica de la fase amorfa es más lenta que la del cristal líquido. El estudio de la relajación ? nos ha permitido seguir la formación isoterma de la mesofase a presión atmosférica. Además, con el estudio el comportamiento dinámico a alta presión se ha encontrado que se produce la formación rápida de la mesofase inducida por cambios bruscos de presión. Liquid crystalline polymers (LCPs) are complex systems that include features of both orientationally ordered mesophases and amorphous polymers. Frequently, the isotropic amorphous state cannot be studied due to the rapid mesophase formation. Here, a new main chain LCP, poly(triethyleneglycol methyl p,p'-bibenzoate), PTEMeB, has been synthesized. It shows a rather slow mesophase formation making possible to study independently both the amorphous and the liquid crystalline states. The structure and phase transitions of PTEMeB have been investigated by calorimetry, variable-temperature MAXS/WAXS employing synchrotron radiation, and X-ray diffraction in oriented fibers. These experiments have pointed out the presence of two glass transitions, related to the amorphous or to the liquid crystal phases. Additionally, the mesophase seems to be a coexistence of orthogonal and tilted smectic phases. A dielectric relaxation study of PTEMeB over broad ranges of temperature and pressure has been performed. The dynamic glass transition turns out to be slower for the amorphous state than for the liquid crystal. Monitoring of the α relaxation has allowed us to follow the isothermal mesophase formation at atmospheric pressure. Additionally, the dynamical behavior at high pressures has pointed out the fast formation of the mesophase induced by sudden pressure changes.

Modelización de los Procesos de Cristalización en Poliolefinas

“Por lo tanto, la cristalización de polímeros se supone, y en las teorías se describe a menudo, como un proceso de múltiples pasos con muchos aspectos físico-químicos y estructurales influyendo en él. Debido a la propia estructura de la cadena, es fácil entender que un proceso que es termodinámicamente forzado a aumentar su ordenamiento local, se vea obstaculizado geométricamente y, por tanto, no puede conducirse a un estado de equilibrio final. Como resultado, se forman habitualmente estructuras de no equilibrio con diferentes características dependiendo de la temperatura, presión, cizallamiento y otros parámetros físico-químicos del sistema”. Estas palabras, pronunciadas recientemente por el profesor Bernhard Wunderlich, uno de los mas relevantes fisico-quimicos que han abordado en las ultimas décadas el estudio del estado físico de las macromoléculas, adelantan lo que de alguna manera se explicita en esta memoria y constituyen el “leitmotiv” de este trabajo de tesis. El mecanismo de la cristalización de polímeros esta aun bajo debate en la comunidad de la física de polímeros y la mayoría de los abordajes experimentales se explican a través de la teoría LH. Esta teoría clásica debida a Lauritzen y Hoffman (LH), y que es una generalización de la teoría de cristalización de una molécula pequeña desde la fase de vapor, describe satisfactoriamente muchas observaciones experimentales aunque esta lejos de explicar el complejo fenómeno de la cristalización de polímeros. De hecho, la formulación original de esta teoría en el National Bureau of Standards, a comienzos de la década de los 70, sufrió varias reformulaciones importantes a lo largo de la década de los 80, buscando su adaptación a los hallazgos experimentales. Así nació el régimen III de cristalización que posibilita la creacion de nichos moleculares en la superficie y que dio pie al paradigma ofrecido por Sadler y col., para justificar los experimentos que se obtenian por “scattering” de neutrones y otras técnicas como la técnica de “droplets” o enfriamiento rapido. Por encima de todo, el gran éxito de la teoría radica en que explica la dependencia inversa entre el tamaño del plegado molecular y el subenfriamiento, definido este ultimo como el intervalo de temperatura que media entre la temperatura de equilibrio y la temperatura de cristalización. El problema concreto que aborda esta tesis es el estudio de los procesos de ordenamiento de poliolefinas con distinto grado de ramificacion mediante simulaciones numéricas. Los copolimeros estudiados en esta tesis se consideran materiales modelo de gran homogeneidad molecular desde el punto de vista de la distribución de tamaños y de ramificaciones en la cadena polimérica. Se eligieron estas poliolefinas debido al gran interes experimental en conocer el cambio en las propiedades fisicas de los materiales dependiendo del tipo y cantidad de comonomero utilizado. Además, son modelos sobre los que existen una ingente cantidad de información experimental, que es algo que preocupa siempre al crear una realidad virtual como es la simulación. La experiencia en el grupo Biophym es que los resultados de simulación deben de tener siempre un correlato mas o menos próximo experimental y ese argumento se maneja a lo largo de esta memoria. Empíricamente, se conoce muy bien que las propiedades físicas de las poliolefinas, en suma dependen del tipo y de la cantidad de ramificaciones que presenta el material polimérico. Sin embargo, tal como se ha explicado no existen modelos teóricos adecuados que expliquen los mecanismos subyacentes de los efectos de las ramas. La memoria de este trabajo es amplia por la complejidad del tema. Se inicia con una extensa introducción sobre los conceptos básicos de una macromolecula que son relevantes para entender el contenido del resto de la memoria. Se definen los conceptos de macromolecula flexible, distribuciones y momentos, y su comportamiento en disolución y fundido con los correspondientes parametros caracteristicos. Se pone especial énfasis en el concepto de “entanglement” o enmaranamiento por considerarse clave a la hora de tratar macromoléculas con una longitud superior a la longitud critica de enmaranamiento. Finaliza esta introducción con una reseña sobre el estado del arte en la simulación de los procesos de cristalización. En un segundo capitulo del trabajo se expone detalladamente la metodología usada en cada grupo de casos. En el primer capitulo de resultados, se discuten los estudios de simulación en disolución diluida para sistemas lineales y ramificados de cadena única. Este caso mas simple depende claramente del potencial de torsión elegido tal como se discute a lo largo del texto. La formación de los núcleos “babys” propuestos por Muthukumar parece que son consecuencia del potencial de torsión, ya que este facilita los estados de torsión mas estables. Así que se propone el análisis de otros potenciales que son igualmente utilizados y los resultados obtenidos sobre la cristalización, discutidos en consecuencia. Seguidamente, en un segundo capitulo de resultados se estudian moleculas de alcanos de cadena larga lineales y ramificados en un fundido por simulaciones atomisticas como un modelo de polietileno. Los resultados atomisticos pese a ser de gran detalle no logran captar en su totalidad los efectos experimentales que se observan en los fundidos subenfriados en su etapa previa al estado ordenado. Por esta razon se discuten en los capítulos 3 y 4 de resultados sistemas de cadenas cortas y largas utilizando dos modelos de grano grueso (CG-PVA y CG-PE). El modelo CG-PE se desarrollo durante la tesis. El uso de modelos de grano grueso garantiza una mayor eficiencia computacional con respecto a los modelos atomísticos y son suficientes para mostrar los fenómenos a la escala relevante para la cristalización. En todos estos estudios mencionados se sigue la evolución de los procesos de ordenamiento y de fusión en simulaciones de relajación isoterma y no isoterma. Como resultado de los modelos de simulación, se han evaluado distintas propiedades fisicas como la longitud de segmento ordenado, la cristalinidad, temperaturas de fusion/cristalizacion, etc., lo que permite una comparación con los resultados experimentales. Se demuestra claramente que los sistemas ramificados retrasan y dificultan el orden de la cadena polimérica y por tanto, las regiones cristalinas ordenadas decrecen al crecer las ramas. Como una conclusión general parece mostrarse una tendencia a la formación de estructuras localmente ordenadas que crecen como bloques para completar el espacio de cristalización que puede alcanzarse a una temperatura y a una escala de tiempo determinada. Finalmente hay que señalar que los efectos observados, estan en concordancia con otros resultados tanto teoricos/simulacion como experimentales discutidos a lo largo de esta memoria. Su resumen se muestra en un capitulo de conclusiones y líneas futuras de investigación que se abren como consecuencia de esta memoria. Hay que mencionar que el ritmo de investigación se ha acentuado notablemente en el ultimo ano de trabajo, en parte debido a las ventajas notables obtenidas por el uso de la metodología de grano grueso que pese a ser muy importante para esta memoria no repercute fácilmente en trabajos publicables. Todo ello justifica que gran parte de los resultados esten en fase de publicación. Abstract “Polymer crystallization is therefore assumed, and in theories often described, to be a multi step process with many influencing aspects. Because of the chain structure, it is easy to understand that a process which is thermodynamically forced to increase local ordering but is geometrically hindered cannot proceed into a final equilibrium state. As a result, nonequilibrium structures with different characteristics are usually formed, which depend on temperature, pressure, shearing and other parameters”. These words, recently written by Professor Bernhard Wunderlich, one of the most prominent researchers in polymer physics, put somehow in value the "leitmotiv "of this thesis. The crystallization mechanism of polymers is still under debate in the physics community and most of the experimental findings are still explained by invoking the LH theory. This classical theory, which was initially formulated by Lauritzen and Hoffman (LH), is indeed a generalization of the crystallization theory for small molecules from the vapor phase. Even though it describes satisfactorily many experimental observations, it is far from explaining the complex phenomenon of polymer crystallization. This theory was firstly devised in the early 70s at the National Bureau of Standards. It was successively reformulated along the 80s to fit the experimental findings. Thus, the crystallization regime III was introduced into the theory in order to explain the results found in neutron scattering, droplet or quenching experiments. This concept defines the roughness of the crystallization surface leading to the paradigm proposed by Sadler et al. The great success of this theory is the ability to explain the inverse dependence of the molecular folding size on the supercooling, the latter defined as the temperature interval between the equilibrium temperature and the crystallization temperature. The main scope of this thesis is the study of ordering processes in polyolefins with different degree of branching by using computer simulations. The copolymers studied along this work are considered materials of high molecular homogeneity, from the point of view of both size and branching distributions of the polymer chain. These polyolefins were selected due to the great interest to understand their structure– property relationships. It is important to note that there is a vast amount of experimental data concerning these materials, which is essential to create a virtual reality as is the simulation. The Biophym research group has a wide experience in the correlation between simulation data and experimental results, being this idea highly alive along this work. Empirically, it is well-known that the physical properties of the polyolefins depend on the type and amount of branches presented in the polymeric material. However, there are not suitable models to explain the underlying mechanisms associated to branching. This report is extensive due to the complexity of the topic under study. It begins with a general introduction to the basics concepts of macromolecular physics. This chapter is relevant to understand the content of the present document. Some concepts are defined along this section, among others the flexibility of macromolecules, size distributions and moments, and the behavior in solution and melt along with their corresponding characteristic parameters. Special emphasis is placed on the concept of "entanglement" which is a key item when dealing with macromolecules having a molecular size greater than the critical entanglement length. The introduction finishes with a review of the state of art on the simulation of crystallization processes. The second chapter of the thesis describes, in detail, the computational methodology used in each study. In the first results section, we discuss the simulation studies in dilute solution for linear and short chain branched single chain models. The simplest case is clearly dependent on the selected torsion potential as it is discussed throughout the text. For example, the formation of baby nuclei proposed by Mutukhumar seems to result from the effects of the torsion potential. Thus, we propose the analysis of other torsion potentials that are also used by other research groups. The results obtained on crystallization processes are accordingly discussed. Then, in a second results section, we study linear and branched long-chain alkane molecules in a melt by atomistic simulations as a polyethylene-like model. In spite of the great detail given by atomistic simulations, they are not able to fully capture the experimental facts observed in supercooled melts, in particular the pre-ordered states. For this reason, we discuss short and long chains systems using two coarse-grained models (CG-PVA and CG-PE) in section 3 and 4 of chapter 2. The CG-PE model was developed during the thesis. The use of coarse-grained models ensures greater computational efficiency with respect to atomistic models and is enough to show the relevant scale phenomena for crystallization. In all the analysis we follow the evolution of the ordering and melting processes by both isothermal and non isothermal simulations. During this thesis we have obtained different physical properties such as stem length, crystallinity, melting/crystallization temperatures, and so on. We show that branches in the chains cause a delay in the crystallization and hinder the ordering of the polymer chain. Therefore, crystalline regions decrease in size as branching increases. As a general conclusion, it seems that there is a tendency in the macromolecular systems to form ordered structures, which can grown locally as blocks, occupying the crystallization space at a given temperature and time scale. Finally it should be noted that the observed effects are consistent with both, other theoretical/simulation and experimental results. The summary is provided in the conclusions chapter along with future research lines that open as result of this report. It should be mentioned that the research work has speeded up markedly in the last year, in part because of the remarkable benefits obtained by the use of coarse-grained methodology that despite being very important for this thesis work, is not easily publishable by itself. All this justify that most of the results are still in the publication phase.

Opportunities and challenges in the use of inorganic fullerene-like nanoparticles to produce advanced polymer nanocomposites

Polymer/inorganic nanoparticle nanocomposites have garnered considerable academic and industrial interest over recent decades in the development of advanced materials for a wide range of applications. In this respect, the dispersion of so-called inorganic fullerene-like (IF) nanoparticles, e.g., tungsten disulfide (IF-WS2) or molybdenum disulfide (IF-MoS2), into polymeric matrices is emerging as a new strategy. The surprising properties of these layered metal dichalcogenides such as high impact resistance and superior tribological behavior, attributed to their nanoscale size and hollow quasi-spherical shape, open up a wide variety of opportunities for applications of these inorganic compounds. The present work presents a detailed overview on research in the area of IF-based polymer nanocomposites, with special emphasis on the use of IF-WS2 nanoparticles as environmentally friendly reinforcing fillers. The incorporation of IF particles has been shown to be efficient for improving thermal, mechanical and tribological properties of various thermoplastic polymers, such as polypropylene, nylon-6, poly(phenylene sulfide), poly(ether ether ketone), where nanocomposites were fabricated by simple melt-processing routes without the need for modifiers or surfactants. This new family of nanocomposites exhibits similar or enhanced performance when compared with nanocomposites that incorporate carbon nanotubes, carbon nanofibers or nanoclays, but are substantially more cost-effective, efficient and environmentally satisfactory. Most recently, innovative approaches have been described that exploit synergistic effects to produce new materials with enhanced properties, including the combined use of micro- and nanoparticles such as IF-WS2/nucleating agent or IF-WS2/carbon fiber, as well as dual nanoparticle systems such as SWCNT/IF-WS2 where each nanoparticle has different characteristics. The structure–property relationships of these nanocomposites are discussed and potential applications proposed ranging from medicine to the aerospace, automotive and electronics industries.

Microstructure and mechanical properties at high temperature of SiC-matrix by electrophoretic deposition and polymer infiltration and pyrolysis process

The EFDA-ITER programme for materials wants to develop new structural materials for future nuclear magnetic fusion reactors. In this context, special attention must be paid in the development of new composite materials that could support the hard working conditions of the nuclear fusion reactors: high temperature, high stresses, and high radiation.

Real time monitoring of click chemistry self-healing in polymer composites

A photo-healable rubber composite based on effective and fast thiol-alkyne click chemistry as a selfhealing agent prestored in glass capillaries is reported. The click reaction and its effect on the mechanical properties of the composite are monitored in real time by dynamic mechanical analysis, showing that the successful bleeding of healing agents to the crack areas and the effective photoinitiated click reaction result in a 30% storage modulus increase after only 5 min of UV light exposure. X-ray tomography confirms capillary-driven bleeding of reactants to the damaged areas. The effect of storing the click chemistry reactants in separate capillaries is also studied, and results show the importance of stoichiometry in achieving a significant level of repair of the composite. No reactant degradation or premature chemical reaction is observed over time in samples stored in the absence of UV radiation; they are able to undergo the self-healing reaction even one month after preparation.

Robust fabrication of electrospun-like polymer mats to direct cell bahaviour

Currently, cell culture systems that include nanoscale topography are widely used in order to provide cells additional cues closer to the in vivo environment, seeking to mimic the natural extracellular matrix. Electrospinning is one of the most common techniques to produce nano fiber mats. However, since many sensitive parameters play an important role in the process, a lack of reproducibility is a major drawback. Here we present a simple and robust methodology to prepare reproducible electrospun-like samples. It consists of a polydimethylsiloxane mold reproducing the fiber pattern to solvent-cast a polymer solution and obtain the final sample. To validate this methodology, poly(L-lactic) acid (PLLA) samples were obtained and, after characterisation, bioactivity and ability to direct cell response were assessed. C2C12 myoblasts developed focal adhesions on the electrospun-like fibers and, when cultured under myogenic differentiation conditions, similar differentiation levels to electrospun PLLA fibers were obtained.

Polarization properties of polymer-based photonic crystal fibers

Selectively filled photonic crystal fibers with polydimethylsiloxane (PDMS), a silicon-type material, have been studied. Is has been demonstrated that polarization properties of these hybrid devices and the properties of the guided light in relation with the temperature changes, finding that the state of polarization (SOP) change with the increasing temperature but remains constant for a wide spectrum of wavelengths for a determinate temperature.

Hierarchical and hybrid polymer nanocomposites based on carbon nanotubes and inorganic fullerene type nanoparticles

The influence of singlewalled carbon nanotubes (SWCNT) and inorganic fullerenelike tungsten disulfide nanoparticles (IFWS2) on the morphology and thermal, mechanical and electrical performance of multifunctional fibrereinforced polymer composites has been investigated. Significant improvements were observed in stiffness, strength and toughness in poly (ether ether ketone) (PEEK) / (SWCNT) / glass fibre (GF) laminates when a compatibilizer was used for wrapping the CNTs. Hybrid poly(phenylene sulphide) (PPS)/IFWS2/ carbon fibre (CF) reinforced polymer composites showed improved mechanical and tribological properties attributed to a synergetic effect between the IF nanoparticles and CF.

Thermoplastic Polymer Nanocomposites Based on Inorganic Fullerene-like Nanoparticles and Inorganic Nanotubes

Using inorganic fullerene-like (IF) nanoparticles and inorganic nanotubes (INT) in organic-inorganic hybrid composite, materials provide the potential for improving thermal, mechanical, and tribological properties of conventional composites. The processing of such high-performance hybrid thermoplastic polymer nanocomposites is achieved via melt-blending without the aid of any modifier or compatibilizing agent. The incorporation of small quantities (0.1-4 wt.%) of IF/INTs (tungsten disulfide, IF-WS2 or molybdenum disulfide, MoS2) generates notable performance enhancements through reinforcement effects and excellent lubricating ability in comparison with promising carbon nanotubes or other inorganic nanoscale fillers. It was shown that these IF/INT nanocomposites can provide an effective balance between performance, cost effectiveness, and processability, which is of significant importance for extending the practical applications of diverse hierarchical thermoplastic-based composites.