Conductive Polymer Composites

In recent years, nanotechnologies have led to the production of materials with new and sometimes unexpected qualities through the manipulation of nanoscale components. This research aimed primarily to the study of the correlation between hierarchical structures of hybrid organic-inorganic materials such as conductive polymer composites (CPCs). Using a bottom-up methodology, we could synthesize a wide range of inorganic nanometric materials with a high degree of homogeneity and purity, such as thiol capped metal nanoparticles, stoichiometric geomimetic chrysotile nanotubes and metal dioxide nanoparticles. It was also possible to produce inorganic systems formed from the interaction between the synthesized materials. These synthesized materials and others like multiwalled carbon nanotubes and grapheme oxide were used to produce conductive polymer composites. Electrospinning causes polymer fibers to become elongated using an electric field. This technique was used to produce fibers with a nanometric diameter of a polymer blend based on two different intrinsically conducting polymers polymers (ICPs): polyaniline (PANI) and poly(3-hexylthiophene) (P3HT). Using different materials as second phase in the initial electrospun polymer fibers caused significant changes to the material hierarchical structure, leading to the creation of CPCs with modified electrical properties. Further study of the properties of these new materials resulted in a better understanding of the electrical conductivity mechanisms in these electrospun materials.

Enhancing the thermomechanical behaviour of poly(phenylene sulphide) based composites via incorporation of covalently grafted carbon nanotubes

The thermal and thermomechanical properties of poly(phenylene sulphide) (PPS) based nanocomposites incorporating a polymer derivative covalently anchored onto single-walled carbon nanotubes (SWCNTs) were investigated. The grafted fillers acted as nucleating agents, increasing the crystallization temperature and degree of crystallinity of the matrix. They also enhanced its thermal stability, flame retardancy, glass transition (Tg) and heat deflection temperatures while reduced the coefficient of thermal expansion at temperatures below Tg. A strong rise in the thermal conductivity, Young?s modulus and tensile strength was found with increasing filler loading both in the glassy and rubbery states. All these outstanding improvements are ascribed to strong matrix-filler interfacial interactions combined with a compatibilization effect that results in very homogeneous SWCNT dispersion. The results herein offer useful insights towards the development of engineering thermoplastic/CNT nanocomposites for high-temperature applications.

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.

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.

Enhancement of the Electrochemical Performance of SWCNT dispersed in a Silica Sol-gel Matrix by Reactive Insertion of a Conducting Polymer

The electroassisted encapsulation of Single-Walled Carbon Nanotubes was performed into silica matrices (SWCNT@SiO2). This material was used as the host for the potentiostatic growth of polyaniline (PANI) to yield a hybrid nanocomposite electrode, which was then characterized by both electrochemical and imaging techniques. The electrochemical properties of the SWCNT@SiO2-PANI composite material were tested against inorganic (Fe3+/Fe2+) and organic (dopamine) redox probes. It was observed that the electron transfer constants for the electrochemical reactions increased significantly when a dispersion of either SWCNT or PANI was carried out inside of the SiO2 matrix. However, the best results were obtained when polyaniline was grown through the pores of the SWCNT@SiO2 material. The enhanced reversibility of the redox reactions was ascribed to the synergy between the two electrocatalytic components (SWCNTs and PANI) of the composite material.

Electrocatalytic oxidation of ascorbic acid on mesostructured SiO2-conducting polymer composites

The conducting self-doping copolymer poly(aniline-co-ABA) preserves its redox activity at pH values as high as 7. This observation was the starting point to synthesize an organic–inorganic hybrid composite able to electrochemically oxidize ascorbic acid molecules at that pH. The inorganic part of the catalytic element was an ordered mesoporous electrodeposit of SiO2, which has been used as the template for the electrochemical insertion of the self-doping copolymer. The oxidation of ascorbate ions at a fixed potential on this composite was studied by means of the kinetic model proposed by Bartlett and Wallace (2001). It was observed that the effective kinetic constant KME increased significantly but, simultaneously, k′ME remained almost constant when the composite was employed as the electrocatalytic substrate. These results were interpreted in the light of two combinations of kinetic constants, which strongly suggested that the increase in KME should be ascribed to the improvement in electronic conductivity of the copolymer induced by the highly ordered silica template.

The Problem Sensitization Robotic Complex Drilling and Milling of Sandwich Shells of Polymer Composites

In clause is given robotic a complex for drilling and milling sandwich shells from polymeric composites. The machining of polymeric composite materials has technological problems. At drilling sandwich shells there is a probability of destruction of a drill from hit of the tool in a partition. The system sensibilization robotic complex for increase of reliability of work of the cutting tool of the small size is offered.

A new approach to the synthesis of nanocrystal conjugated polymer composites

A novel one pot process has been developed for the preparation of PbS nanocrystals in the conjugated polymer poly 2-methoxy,5-(2 ethyl-hexyloxy-p-phenylenevinylene) (MEH-PPV). Current techniques for making such composite materials rely upon synthesizing the nanocrystals and conducting polymer separately, and subsequently mixing them. This multi-step technique has two serious drawbacks: templating surfactant must be removed before mixing, and co-solvent incompatibility causes aggregation. In our method, we eliminate the need for an initial surfactant by using the conducting polymer to terminate and template nanocrystal growth. Additionally, the final product is soluble in a single solvent. We present materials analysis which shows PbS nanocrystals can be grown directly in a conducting polymer, the resulting composite is highly ordered and nanocrystal size can be controlled.

Polyethylene multiwalled carbon nanotube composites

Polyethylene (PE) multiwalled carbon nanotubes (MWCNTs) with weight fractions ranging from 0.1 to 10 wt% were prepared by melt blending using a mini-twin screw extruder. The morphology and degree of dispersion of the MWCNTs in the PE matrix at different length scales was investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and wide-angle X-ray diffraction (WAXD). Both individual and agglomerations of MWCNTs were evident. An up-shift of 17 cm(-1) for the G band and the evolution of a shoulder to this peak were obtained in the Raman spectra of the nanocomposites, probably due to compressive forces exerted on the MWCNTs by PE chains and indicating intercalation of PE into the MWCNT bundles. The electrical conductivity and linear viscoelastic behaviour of these nanocomposites were investigated. A percolation threshold of about 7.5 wt% was obtained and the electrical conductivity of PE was increased significantly, by 16 orders of magnitude, from 10(-20) to 10(-4) S/cm. The storage modulus (G') versus frequency curves approached a plateau above the percolation threshold with the formation of an interconnected nanotube structure, indicative of 'pseudo-solid-like' behaviour. The ultimate tensile strength and elongation at break of the nanocomposites decreased with addition of MWCNTs. The diminution of mechanical proper-ties of the nanocomposites, though concomitant with a significant increase in electrical conductivity, implies the mechanism for mechanical reinforcement for PE/MWCNT composites is filler-matrix interfacial interactions and not filler percolation. The temperature of crystallisation (T.) and fraction of PE that was crystalline (F-c) were modified by incorporating MWCNTs. The thermal decomposition temperature of PE was enhanced by 20 K on addition of 10 wt% MWCNT. (c) 2005 Elsevier Ltd. All rights reserved.

Energy transfer dynamics of nanocrystal-polymer composites

Steady-state and time-resolved photoluminescence spectroscopy are used to examine the photoluminescent properties of nanocrystal-polymer composites consisting of colloidal PbS nanocrystals blended with poly(2-methoxy-5(2-ethylhexyloxy)-p-phenylene vinylene). Quenching of the emission from the conjugated polymer due to the PbS nanocrystals is observed along with band edge emission from the ligand capped PbS nanocrystals. A decrease in the photoluminescence lifetime of MEH-PPV is also observed in the thin film nanocrystal-polymer composite materials. Photoluminescence excitation spectroscopy of the PbS nanocrystal emission from the composite shows features attributed to MEH-PPV providing evidence of a Forster transfer process.

Carrier transport in PbS nanocrystal conducting polymer composites

In this letter we report the carrier mobilities in an inorganic nanocrystal: conducting polymer composite. The composite material in question (lead sulphide nanocrystals in the conducting polymer poly [2-methoxy-5-(2(')-ethyl-hexyloxy)-p-phenylene vinylene] (MEH-PPV) was made using a single-pot, surfactant-free synthesis. Mobilties were measured using time of flight techniques. We have found that the inclusion of PbS nanocrystals in MEH-PPV both balances and markedly increases the hole and electron mobilities-the hole mobility is increased by a factor of similar to 10(5) and the electron mobility increased by similar to 10(7) under an applied bias of 5 kV cm(-1). These results explain why dramatic improvements in electrical conductivity and photovoltaic performance are seen in devices fabricated from these composites.

Nanotube-polymer composites for ultrafast photonics

Polymer composites are one of the most attractive near-term means to exploit the unique properties of carbon nanotubes and graphene. This is particularly true for composites aimed at electronics and photonics, where a number of promising applications have already been demonstrated. One such example is nanotube-based saturable absorbers. These can be used as all-optical switches, optical amplifier noise suppressors, or mode-lockers to generate ultrashort laser pulses. Here, we review various aspects of fabrication, characterization, device implementation and operation of nanotube-polymer composites to be used in photonic applications. We also summarize recent results on graphene-based saturable absorbers for ultrafast lasers.

Synthesis and evaluation of nanoparticle-polymer composites

This thesis describes the synthesis of functionalised polymeric material by variety of free-radical mediated polymerisation techniques including dispersion emulsion, seeded emulsion, suspension and bulk polymerisation reactions. Organic fluorophores and nanoparticles such as quantum dots were incorporated within polymeric materials, in particular, thiol-functionalised polymer microspheres, which were fluorescently labelled either during synthesis or by covalent attachment post synthesis. The resultant fluorescent polymeric conjugates were then assessed for their utility in biological systems as an analytical tool for cells or biological structures. Quantum dot labelled, thiol-functionalised microspheres were assessed for their utility in the visualisation and tracking of red blood cells. Determination of the possible internalisation of fluorescent microspheres into red blood cells was required before successful tracking of red blood cells could take place. Initial work appeared to indicate the presence of fluorescent microspheres inside red blood cells by the process of beadfection. A range of parameters were also investigated in order to optimise beadfection. Thiol-functionalised microspheres labelled successfully with organic fluorophores were used to image the tear film of the eye. A description of problems encountered with the covalent attachment of hydrophilic, thiol-reactive fluorescent dyes to a variety of modified polymer microspheres is also included in this section. Results indicated large microspheres were particularly useful when tracking the movement of fluid along the tear meniscus. Functional bulk polymers were synthesised for assessment of their interaction with titanium dioxide nanoparticles. Thiol-functionalised polymethyl methacrylate and spincoated thiouronium-functionalised polystyrene appeared to facilitate the attachment of titanium dioxide nanoparticles. Interaction assays included the use of XPS analysis and processes such as centrifugation. Attempts to synthesise 4-vinyl catechol, a compound containing hydroxyl moieties with potential for coordination with titanium dioxide nanoparticles, were also carried out using 3,4-dihydroxybenzaldehyde as the starting material.

Computational modeling of biodegradable starch based polymer composites

Purpose. The goal of this study is to improve the favorable molecular interactions between starch and PPC by addition of grafting monomers MA and ROM as compatibilizers, which would advance the mechanical properties of starch/PPC composites. ^ Methodology. DFT and semi-empirical methods based calculations were performed on three systems: (a) starch/PPC, (b) starch/PPC-MA, and (c) starch-ROM/PPC. Theoretical computations involved the determination of optimal geometries, binding-energies and vibrational frequencies of the blended polymers. ^ Findings. Calculations performed on five starch/PPC composites revealed hydrogen bond formation as the driving force behind stable composite formation, also confirmed by the negative relative energies of the composites indicating the existence of binding forces between the constituent co-polymers. The interaction between starch and PPC is also confirmed by the computed decrease in stretching CO and OH group frequencies participating in hydrogen bond formation, which agree qualitatively with the experimental values. ^ A three-step mechanism of grafting MA on PPC was proposed to improve the compatibility of PPC with starch. Nine types of 'blends' produced by covalent bond formation between starch and MA-grafted PPC were found to be energetically stable, with blends involving MA grafted at the 'B' and 'C' positions of PPC indicating a binding-energy increase of 6.8 and 6.2 kcal/mol, respectively, as compared to the non-grafted starch/PPC composites. A similar increase in binding-energies was also observed for three types of 'composites' formed by hydrogen bond formation between starch and MA-grafted PPC. ^ Next, grafting of ROM on starch and subsequent blend formation with PPC was studied. All four types of blends formed by the reaction of ROM-grafted starch with PPC were found to be more energetically stable as compared to the starch/PPC composite and starch/PPC-MA composites and blends. A blend of PPC and ROM grafted at the ' a&d12; ' position on amylose exhibited a maximal increase of 17.1 kcal/mol as compared with the starch/PPC-MA blend. ^ Conclusions. ROM was found to be a more effective compatibilizer in improving the favorable interactions between starch and PPC as compared to MA. The ' a&d12; ' position was found to be the most favorable attachment point of ROM to amylose for stable blend formation with PPC.^