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.

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.

Diseño e implementación de un canal de movilidad para tecnologías Polymer

Durante el siglo XXI hemos sido testigos de cambios con una gran trascendencia en el campo de las tecnologías tanto a nivel de hardware como software, aunque uno de los más notables ha sido el cambio del paradigma de la distribución del software, donde la instalación de herramientas de escritorio queda relegada a un segundo plano y toman fuerza las aplicaciones que consumen servicios web o que, simplemente, son aplicaciones web, que no requieren de un proceso de instalación y siempre que tengamos una conexión a internet activa podremos acceder a nuestra aplicación y datos, sin importar desde donde nos conectemos. Gracias a este cambio, últimamente han proliferado distintas tecnologías para la creación de aplicaciones web, entre estas encontramos los componentes web basados en tecnología Polymer como herramienta para el desarrollo de aplicaciones modulares y componentes reutilizables en distintos sitios web, modificando y añadiendo funcionalidad a las etiquetas de HTML, de esta manera una vez desarrollado un componente, volver a utilizarlo es realizar un trabajo de unos cuantos segundo añadiendo la etiqueta necesaria en nuestro código HTML, esta ventaja es la principal característica de Polymer. En paralelo al desarrollo de tecnologías web, y gracias a su masificación, se han generado herramientas y frameworks a través de los cuales se pueden desarrollar aplicaciones para dispositivos móviles mediante tecnologías web, esto beneficia directamente a los ecosistemas de desarrolladores, herramientas, frameworks y aplicaciones ya que los hace más amplios y accesibles a todo aquel que sea capaz de programar una aplicación web basada en HTML, CSS y Javascript. El objetivo de este trabajo es generar un canal de movilidad definiendo una metodología eficaz para portar las ventajas de los componentes web de Polymer a entornos móviles, conservando su capacidad de ser reutilizados de manera sencilla y sin perder, dentro de lo posible, la usabilidad de los mismos teniendo en cuenta las particularidades de los dispositivos móviles, esto se realizará mediante pruebas de usabilidad para posteriormente validar la metodología generada aplicándola a un caso real.---ABSTRACT---During 21st century we have witness the important changes in technologies field, involving both hardware and software level, but one of the most relevant ones has been the software distribution paradigm change, where desktop tools has lost their importance to benefit web services or just web applications, among which the web components are included. Web components are based on Polymer technology as its main tool for developing modular applications and reusable components in different web sites, adding and modifying functionality to HTML tags. So, when a components is developed, reusing it is possible just adding its correspondant tag inour HTML code. This is the main Polymer feature. As web technologies grow, different tools and frameworks has been created. They can be used to develop applications for web devices though web technologies, which is a benefit for developer, tools, frameworks and applications ecosystems, in such a way this new tools make them wider and more accessible for every one able to develop web applications with HTML, CSS and Javascript languages. The goal of this work is to generate a mobility channel defining an efficient methodology to carry the Polymer web components advantages to mobile environments, keeping their features of being reused in an easy way and without losing, when possible, their usability being aware the special features of mobile devices. This work will be evaluated through usability tests to validate then the generated methodology applying it to a real case.

Non contact inspection of the fatigue damage state of carbon fiber reinforced polymer by optical surface roughness measurements

This work presents the evaluation of a new non-contact technique to assess the fatigue damage state of CFRP structures by measuring surface roughness parameters. Surface roughness and stiffness degradation have been measured in CFRP coupons cycled with constant amplitude loads, and a Pearson?s correlation of 0.79 was obtained between both variables. Results suggest that changes on the surface roughness measured in strategic zones of components made of the evaluated CFRP, could be indicative of the level of damage due to fatigue loads. This methodology could be useful for other FRP due to similarities in the fatigue damage process.

Bio-based polymer nanocomposites based on nylon 11 and WS2 inorganic nanotubes

Tungsten disulphide nanotubes (INT-WS2) have been successfully dispersed in a bio-based polyamide matrix (nylon 11) by conventional melt processing. The effect of INT-WS2 content on the morphology, thermal stability, crystallization behaviour and dynamic mechanical properties is investigated. The results indicate that these inorganic nanotubes can be efficiently incorporated into the bio-based polymer matrix without the need for modifiers or surfactants. Additionally, it is found that the non-isothermal crystallization behaviour of nylon 11/INT-WS2 depends on both the cooling rate and INT-WS2 concentration. In particular, crystallization kinetics results demonstrate that the nucleating activity of INTs plays a dominant role in accelerating the crystallization of nylon 11. This fact leads to the appearance of the more-disordered phase at higher temperature. More significantly, it was shown that these INT-WS2 nanocomposites can facilitate a good processability and cost efficiency, and will be of interest for many eco-friendly and medical applications.

Highly sensitive biological and chemical sensors based on reversible fluorescence quenching in a conjugated polymer

The fluorescence of a polyanionic conjugated polymer can be quenched by extremely low concentrations of cationic electron acceptors in aqueous solutions. We report a greater than million-fold amplification of the sensitivity to fluorescence quenching compared with corresponding “molecular excited states.” Using a combination of steady-state and ultrafast spectroscopy, we have established that the dramatic quenching results from weak complex formation [polymer(−)/quencher(+)], followed by ultrafast electron transfer from excitations on the entire polymer chain to the quencher, with a time constant of 650 fs. Because of the weak complex formation, the quenching can be selectively reversed by using a quencher-recognition diad. We have constructed such a diad and demonstrate that the fluorescence is fully recovered on binding between the recognition site and a specific analyte protein. In both solutions and thin films, this reversible fluorescence quenching provides the basis for a new class of highly sensitive biological and chemical sensors.

Stimulation of neurite outgrowth using an electrically conducting polymer

Damage to peripheral nerves often cannot be repaired by the juxtaposition of the severed nerve ends. Surgeons have typically used autologous nerve grafts, which have several drawbacks including the need for multiple surgical procedures and loss of function at the donor site. As an alternative, the use of nerve guidance channels to bridge the gap between severed nerve ends is being explored. In this paper, the electrically conductive polymer—oxidized polypyrrole (PP)—has been evaluated for use as a substrate to enhance nerve cell interactions in culture as a first step toward potentially using such polymers to stimulate in vivo nerve regeneration. Image analysis demonstrates that PC-12 cells and primary chicken sciatic nerve explants attached and extended neurites equally well on both PP films and tissue culture polystyrene in the absence of electrical stimulation. In contrast, PC-12 cells interacted poorly with indium tin oxide (ITO), poly(l-lactic acid) (PLA), and poly(lactic acid-co-glycolic acid) surfaces. However, PC-12 cells cultured on PP films and subjected to an electrical stimulus through the film showed a significant increase in neurite lengths compared with ones that were not subjected to electrical stimulation through the film and tissue culture polystyrene controls. The median neurite length for PC-12 cells grown on PP and subjected to an electrical stimulus was 18.14 μm (n = 5643) compared with 9.5 μm (n = 4440) for controls. Furthermore, animal implantation studies reveal that PP invokes little adverse tissue response compared with poly(lactic acid-co-glycolic acid).

A Polymer Model for the Structural Organization of Chromatin Loops and Minibands in Interphase Chromosomes

A quantitative model of interphase chromosome higher-order structure is presented based on the isochore model of the genome and results obtained in the field of copolymer research. G1 chromosomes are approximated in the model as multiblock copolymers of the 30-nm chromatin fiber, which alternately contain two types of 0.5- to 1-Mbp blocks (R and G minibands) differing in GC content and DNA-bound proteins. A G1 chromosome forms a single-chain string of loop clusters (micelles), with each loop ∼1–2 Mbp in size. The number of ∼20 loops per micelle was estimated from the dependence of geometrical versus genomic distances between two points on a G1 chromosome. The greater degree of chromatin extension in R versus G minibands and a difference in the replication time for these minibands (early S phase for R versus late S phase for G) are explained in this model as a result of the location of R minibands at micelle cores and G minibands at loop apices. The estimated number of micelles per nucleus is close to the observed number of replication clusters at the onset of S phase. A relationship between chromosomal and nuclear sizes for several types of higher eukaryotic cells (insects, plants, and mammals) is well described through the micelle structure of interphase chromosomes. For yeast cells, this relationship is described by a linear coil configuration of chromosomes.

Polymer Models of Meiotic and Mitotic Chromosomes

Polymers tied together by constraints exhibit an internal pressure; this idea is used to analyze physical properties of the bottle-brush–like chromosomes of meiotic prophase that consist of polymer-like flexible chromatin loops, attached to a central axis. Using a minimal number of experimental parameters, semiquantitative predictions are made for the bending rigidity, radius, and axial tension of such brushes, and the repulsion acting between brushes whose bristles are forced to overlap. The retraction of lampbrush loops when the nascent transcripts are stripped away, the oval shape of diplotene bivalents between chiasmata, and the rigidity of pachytene chromosomes are all manifestations of chromatin pressure. This two-phase (chromatin plus buffer) picture that suffices for meiotic chromosomes has to be supplemented by a third constituent, a chromatin glue to understand mitotic chromosomes, and explain how condensation can drive the resolution of entanglements. This process resembles a thermal annealing in that a parameter (the affinity of the glue for chromatin and/or the affinity of the chromatin for buffer) has to be tuned to achieve optimal results. Mechanical measurements to characterize this protein–chromatin matrix are proposed. Finally, the propensity for even slightly chemically dissimilar polymers to phase separate (cluster like with like) can explain the apparent segregation of the chromatin into A+T- and G+C-rich regions revealed by chromosome banding.

Shape anisotropy of a single random-walk polymer

Random walks have been used to describe a wide variety of systems ranging from cell colonies to polymers. Sixty-five years ago, Kuhn [Kuhn, W. (1934) Kolloid-Z. 68, 2–11] made the prediction, backed later by computer simulations, that the overall shape of a random-walk polymer is aspherical, yet no experimental work has directly tested Kuhn's general idea and subsequent computer simulations. By using fluorescence microscopy, we monitored the conformation of individual, long, random-walk polymers (fluorescently labeled DNA molecules) at equilibrium. We found that a polymer most frequently adopts highly extended, nonfractal structures with a strongly anisotropic shape. The ensemble-average ratio of the lengths of the long and short axes of the best-fit ellipse of the polymer was much larger than unity.

Brownian flocculation of polymer colloids in the presence of a secondary minimum

Most analyses of Brownian flocculation apply to conditions where London–van der Waals attractive forces cause particles to be strongly bound in a deep interparticle potential well. In this paper, results are reported that show the interaction between primary- and secondary-minimum flocculation when the interparticle potential curve reflects both attractive and electrostatic repulsive forces. The process is highly time-dependent because of transfer of particles from secondary- to primary-minimum flocculation. Essential features of the analysis are corroborated by experiments with 0.80-μm polystyrene spheres suspended in aqueous solutions of NaCl over a range of ionic strengths. In all cases, experiments were restricted to the initial stage of coagulation, where singlets and doublets predominate.

A chemically diverse conducting polymer-based "electronic nose".

We describe a method for generating a variety of chemically diverse broadly responsive low-power vapor sensors. The chemical polymerization of pyrrole in the presence of plasticizers has yielded conducting organic polymer films whose resistivities are sensitive to the identity and concentration of various vapors in air. An array of such sensing elements produced a chemically reversible diagnostic pattern of electrical resistance changes upon exposure to different odorants. Principal component analysis has demonstrated that such sensors can identify and quantify different airborne organic solvents and can yield information on the components of gas mixtures.

Activation of polymer blend carbon nanofibres by alkaline hydroxides and their hydrogen storage performances

In the present work we study the hydroxide activation (NaOH and KOH) of phenol-formaldehyde resin derived CNFs prepared by a polymer blend technique to prepare highly porous activated carbon nanofibres (ACNFs). Morphology and textural characteristics of these ACNFs were studied and their hydrogen storage capacities at 77 K (at 0.1 MPa and at high pressures up to 4 MPa) were assessed, and compared, with reported capacities of other porous carbon materials. Phenol-formaldehyde resin derived carbon fibres were successfully activated with these two alkaline hydroxides rendering highly microporous ACNFs with reasonable good activation process yields up to 47 wt.% compared to 7 wt.% yields from steam activation for similar surface areas of 1500 m2/g or higher. These nano-sized activated carbons present interesting H2 storage capacities at 77 K which are comparable, or even higher, to other high quality microporous carbon materials. This observation is due, in part, to their nano-sized diameters allowing to enhance their packing densities to 0.71 g/cm3 and hence their resulting hydrogen storage capacities.

Polymer-supported l-prolinol-based catalysts for the enantioselective addition of dialkylzinc reagents to N-(diphenylphosphinyl)imines

l-Prolinol-based ligands anchored to Merrifield or Wang-type resins have been shown to form efficient catalysts for the enantioselective addition of dialkylzinc reagents to N-(diphenylphosphinyl)imines. The enantioselectivity achieved with the polymeric catalyst (ee up to 88%) is slightly lower than the one obtained with the homogeneous ligand N-benzyl-l-prolinol, but the polymer-supported ligand presents the advantage of its recyclability: it can be recovered and used in up to six consecutive catalytic cycles with only a slight decrease in the enantiomeric excess. The phosphinamides obtained as addition products can be transformed into the corresponding enantiomerically enriched α-branched primary amines under mild acidic conditions.