POLYMER-NANOPARTICLE COMPOSITES FOR APPLICATIONS IN FLEXIBLE ELECTRONICS

The aim of this dissertation was to investigate flexible polymer-nanoparticle composites with unique magnetic and electrical properties. Toward this goal, two distinct projects were carried out. The first project explored the magneto-dielectric properties and morphology of flexible polymer-nanoparticle composites that possess high permeability (µ), high permittivity (ε) and minimal dielectric, and magnetic loss (tan δε, tan δµ). The main materials challenges were the synthesis of magnetic nanoparticle fillers displaying high saturation magnetization (Ms), limited coercivity, and their homogeneous dispersion in a polymeric matrix. Nanostructured magnetic fillers including polycrystalline iron core-shell nanoparticles, and constructively assembled superparamagnetic iron oxide nanoparticles were synthesized, and dispersed uniformly in an elastomer matrix to minimize conductive losses. The resulting composites have demonstrated promising permittivity (22.3), permeability (3), and sustained low dielectric (0.1), magnetic (0.4) loss for frequencies below 2 GHz. This study demonstrated nanocomposites with tunable magnetic resonance frequency, which can be used to develop compact and flexible radio frequency devices with high efficiency. The second project focused on fundamental research regarding methods for the design of highly conductive polymer-nanoparticle composites that can maintain high electrical conductivity under tensile strain exceeding 100%. We investigated a simple solution spraying method to fabricate stretchable conductors based on elastomeric block copolymer fibers and silver nanoparticles. Silver nanoparticles were assembled both in and around block copolymer fibers forming interconnected dual nanoparticle networks, resulting in both in-fiber conductive pathways and additional conductive pathways on the outer surface of the fibers. Stretchable composites with conductivity values reaching 9000 S/cm maintained 56% of their initial conductivity after 500 cycles at 100% strain. The developed manufacturing method in this research could pave the way towards direct deposition of flexible electronic devices on any shaped substrate. The electrical and electromechanical properties of these dual silver nanoparticle network composites make them promising materials for the future construction of stretchable circuitry for displays, solar cells, antennas, and strain and tactility sensors.

Characterization of sea water ageing effects on mechanical properties of carbon/epoxy composites for tidal turbine blades

In recent years, many tidal turbine projects have been developed using composites blades. Tidal turbine blades are subject to ocean forces and sea water aggressions, and the reliability of these components is crucial to the profitability of ocean energy recovery systems. The majority of tidal turbine developers have preferred carbon/epoxy blades, so there is a need to understand how prolonged immersion in the ocean affects these composites. In this study the long term behaviour of different carbon/epoxy composites has been studied using accelerated ageing tests. A significant reduction of composite strengths has been observed after saturation of water in the material. For longer immersions only small further changes in these properties occur. No significant changes have been observed for moduli nor for composite toughness. The effect of sea water ageing on damage thresholds and kinetics has been studied and modelled. After saturation, the damage threshold is modified while kinetics of damage development remain the same.

Structure dependencies for multiscale polymer composites using extrusion processes

Multiscale reinforcement, using carbon microfibers and multi-walled carbon nanotubes, of polymer matrix composites manufactured by twin-screw extrusion is investigated for enhanced mechanical and thermal properties with an emphasis on the use of a diverging flow in the die for fluid mechanical fiber manipulation. Using fillers at different length scales (microscale and nanoscale), synergistic combinations have been identified to produce distinct mechanical and thermal behavior. Fiber manipulation has been demonstrated experimentally and computationally, and has been shown to enhance thermal conductivity significantly. Finally, a new physics driven predictive model for thermal conductivity has been developed based on fiber orientation during flow, which is shown to successfully capture composite thermal conductivity.

Design of unique composites based on aromatic thermosetting copolyesters

Aromatic thermosetting copolyester (ATSP) has promise in high-temperature applications. It can be employed as a bulk polymer, as a coating and as a matrix for carbon fiber composites (ATSP/C composites). This work focuses on the applications of high performance ATSP/C composites. The morphology of the ATSP matrix in the presence of carbon fiber was studied. The effect of liquid crystalline character of starting oligomers used to prepare ATSP on the final crystal structure of the ATSP/C composite was evaluated. Matrices obtained by crosslinking of both liquid crystalline oligomers (ATSP2) and non-liquid crystalline oligomers (ATSP1) tend to crystallize in presence of carbon fibers. The crystallite size of ATSP2 is 4 times that of ATSP1. Composites made from ATSP2 yield tougher matrices compared to those made from ATSP1. Thus toughened matrices could be achieved without incorporating any additives by just changing the morphology of the final polymer. The flammability characteristics of ATSP were also studied. The limiting oxygen index (LOI) of bulk ATSP was found to be 40% whereas that of ATSP/C composites is estimated to be 85%. Thus, ATSP shows potential to be used as a flame resistant material, and also as an aerospace reentry shield. Mechanical properties of the ATSP/C composite were characterized. ATSP was observed to bond strongly with reinforcing carbon fibers. The tensile strength, modulus and shear modulus were comparable to those of conventionally used high temperature epoxy resins. ATSP shows a unique capability for healing of interlaminar cracks on application of heat and pressure, via the Interchain Transesterification Reaction (ITR). ITR can also be used for reduction in void volume and healing of microcracks. Thus, ATSP resin systems provide a unique intrinsic repair mechanism compared to any other thermosetting systems in use today. Preliminary studies on measurement of residual stresses for ATSP/C composites indicate that the stresses induced are much lower than that in epoxy/C composites. Thermal fatigue testing suggests that ATSP shows better resistance to microcracking compared to epoxy resins.

Experimental Modeling of Twin-Screw Extrusion Processes to Predict Properties of Extruded Composites

Twin-screw extrusion is used to compound fillers into a polymer matrix in order to improve the properties of the final product. The resultant properties of the composite are determined by the operating conditions used during extrusion processing. Changes in the operating conditions affect the physics of the melt flow, inducing unique composite properties. In the following work, the Residence Stress Distribution methodology has been applied to model both the stress behavior and the property response of a twin-screw compounding process as a function of the operating conditions. The compounding of a pigment into a polymer melt has been investigated to determine the effect of stress on the degree of mixing, which will affect the properties of the composite. In addition, the pharmaceutical properties resulting from the compounding of an active pharmaceutical ingredient are modeled as a function of the operating conditions, indicating the physical behavior inducing the property responses.

Natural fibers based composites - Technical and social issues

Brazil is the only country in South America to have an automotive supplier sector based on natural fibers. New opportunities are arising due to an increase demand by the car makers in applying natural fibers in their parts. Several crop fibers have been developed in Brazil. Among them can be listed caroa, piacava, pupunha, mutum and others of regional application. For the automotive industry, which requires large quantities with uniform quality, the alternatives are sisal (170,000 ton/yr), curaua (150 ton/yr in 2003), malva, 200 ton/yr; Brazil is the single largest producer country of sisal, and commercially, the only one in curaua. For South America, the alternatives are fique in Colombia, abaca in equator, flax in Argentina and curaua in Venezuela. It must be understood by the target countries of drugs, is that crop fiber can be an economic alternative to coca in the Andes region, therefore an instrument of land reform and drug reduction plantations. Several companies have a strong program of apply natural fibers based components in their products: Volkswagen do Brazil, DaimlerChrysler, General Motors do Brazil. Among their suppliers can be listed companies such Pematec (curaua), Toro (sisal, coir and jute), Incomer (sisal and jute), Ober (jute, curaua), Indaru (jute and sisal), Antolin (imported kenaf,) Tapetes Sao Carlos (sisal), Poematec (coir) and Art-Gore, with Woodstock'' wood and natural fibers). Figures about production and demand are discussed in the paper.

Diamond Surface Modification to Enhance Interfacial Thermal Conductivity in Al/Diamond Composites

Diamond/metal composites are very attractive materials for electronics because their excellent thermal properties make them suitable for use as heat sink elements in multifunctional electronic packaging systems. To enlarge the potential applications of these composites, current efforts are mainly focused on investigating different ways to improve the contact between metal and diamond. In the present work, a theoretical study has been carried out to determine the differences between the interfacial thermal conductance of aluminum/diamond and aluminum/graphite interfaces. Additionally, diamond particles were surface modified with oxygen to observe how it affects the quality of the diamond surface. The characterization of the surface of diamonds has been performed using different surface analysis techniques, especially x-ray photoelectron spectroscopy and temperature-programmed desorption.

Design of composites for thermal management: Aluminum reinforced with diamond-containing bimodal particle mixtures

A new design route is proposed in order to fabricate aluminum matrix diamond-containing composite materials with optimized values of thermal conductivity (TC) for thermal management applications. The proper size ratio and proportions of particulate diamond–diamond and diamond–SiC bimodal mixtures are selected based on calculations with predictive schemes, which combine two main issues: (i) the volume fraction of the packed particulate mixtures, and (ii) the influence of different types of particulates (with intrinsically different metal/reinforcement interfacial thermal conductances) on the overall thermal conductivity of the composite material. The calculated results are validated by comparison with measurements on composites fabricated by gas pressure infiltration of aluminum into preforms of selected compositions of particle mixtures. Despite the relatively low quality (low price) of the diamond particles used in this work, outstanding values of TC are encountered: a maximum of 770 W/m K for Al/diamond–diamond and values up to 690 W/m K for Al/diamond–SiC.

Effects of infiltration pressure on mechanical properties of Al–12Si/graphite composites for piston engines

In this work results for the flexural strength and the thermal properties of interpenetrated graphite preforms infiltrated with Al-12wt%Si are discussed and compared to those for packed graphite particles. To make this comparison relevant, graphite particles of four sizes in the range 15–124 μm, were obtained by grinding the graphite preform. Effects of the pressure applied to infiltrate the liquid alloy on composite properties were investigated. In spite of the largely different reinforcement volume fractions (90% in volume in the preform and around 50% in particle compacts) most properties are similar. Only the Coefficient of Thermal Expansion is 50% smaller in the preform composites. Thermal conductivity of the preform composites (slightly below 100 W/m K), may be increased by reducing the graphite content, alloying, or increasing the infiltration pressure. The strength of particle composites follows Griffith criterion if the defect size is identified with the particle diameter. On the other hand, the composites strength remains increasing up to unusually high values of the infiltration pressure. This is consistent with the drainage curves measured in this work. Mg and Ti additions are those that produce the most significant improvements in performance. Although extensive development work remains to be done, it may be concluded that both mechanical and thermal properties make these materials suitable for the fabrication of piston engines.