Conductivity variations of multi-walled carbon nanotubes oriented in liquid crystal cells

The control of carbon nanotubes conductivity is generating interest in several fields since it may be relevant for a number of applications. The self-organizing properties of liquid crystals may be used to impose alignment on dispersed carbon nanotubes,thus control-ling their conductivity and its anisotropy. This leads to a number of possible applications in photonic and electronic devices such as electrically controlled carbon nanotube switch- es and crossboards. In this work, cells of liquid crystals doped with multi-walled nanotubes have been prepared in different configurations. Their conductivity variations upon switching have been investigated. It turns out that conductivity evolution depends on the initial configuration (either homogeneous, homeotropic or in-plane switching), the cell thickness and the switching record. The control of these manufacturing paramenters allows the modulation of the electrical behavior of carbon nanotubes.

Produtos têxteis inteligentes incorporando filamentos compósitos com nanotubos de carbono

Programa Doutoral em Engenharia Têxtil.

Estudo da cinética de decomposição de compósitos nanoestruturados de poli (sulfeto de fenileno) reforçados com nanotubos de carbono

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Growth, modification and integration of carbon nanotubes into molecular electronics

Molecules are the smallest possible elements for electronic devices, with active elements for such devices typically a few Angstroms in footprint area. Owing to the possibility of producing ultrahigh density devices, tremendous effort has been invested in producing electronic junctions by using various types of molecules. The major issues for molecular electronics include (1) developing an effective scheme to connect molecules with the present micro- and nano-technology, (2) increasing the lifetime and stabilities of the devices, and (3) increasing their performance in comparison to the state-of-the-art devices. In this work, we attempt to use carbon nanotubes (CNTs) as the interconnecting nanoelectrodes between molecules and microelectrodes. The ultimate goal is to use two individual CNTs to sandwich molecules in a cross-bar configuration while having these CNTs connected with microelectrodes such that the junction displays the electronic character of the molecule chosen. We have successfully developed an effective scheme to connect molecules with CNTs, which is scalable to arrays of molecular electronic devices. To realize this far reaching goal, the following technical topics have been investigated. 1. Synthesis of multi-walled carbon nanotubes (MWCNTs) by thermal chemical vapor deposition (T-CVD) and plasma-enhanced chemical vapor deposition (PECVD) techniques (Chapter 3). We have evaluated the potential use of tubular and bamboo-like MWCNTs grown by T-CVD and PE-CVD in terms of their structural properties. 2. Horizontal dispersion of MWCNTs with and without surfactants, and the integration of MWCNTs to microelectrodes using deposition by dielectrophoresis (DEP) (Chapter 4). We have systematically studied the use of surfactant molecules to disperse and horizontally align MWCNTs on substrates. In addition, DEP is shown to produce impurityfree placement of MWCNTs, forming connections between microelectrodes. We demonstrate the deposition density is tunable by both AC field strength and AC field frequency. 3. Etching of MWCNTs for the impurity-free nanoelectrodes (Chapter 5). We show that the residual Ni catalyst on MWCNTs can be removed by acid etching; the tip removal and collapsing of tubes into pyramids enhances the stability of field emission from the tube arrays. The acid-etching process can be used to functionalize the MWCNTs, which was used to make our initial CNT-nanoelectrode glucose sensors. Finally, lessons learned trying to perform spectroscopic analysis of the functionalized MWCNTs were vital for designing our final devices. 4. Molecular junction design and electrochemical synthesis of biphenyl molecules on carbon microelectrodes for all-carbon molecular devices (Chapter 6). Utilizing the experience gained on the work done so far, our final device design is described. We demonstrate the capability of preparing patterned glassy carbon films to serve as the bottom electrode in the new geometry. However, the molecular switching behavior of biphenyl was not observed by scanning tunneling microscopy (STM), mercury drop or fabricated glassy carbon/biphenyl/MWCNT junctions. Either the density of these molecules is not optimum for effective integration of devices using MWCNTs as the nanoelectrodes, or an electroactive contaminant was reduced instead of the ionic biphenyl species. 5. Self-assembly of octadecanethiol (ODT) molecules on gold microelectrodes for functional molecular devices (Chapter 7). We have realized an effective scheme to produce Au/ODT/MWCNT junctions by spanning MWCNTs across ODT-functionalized microelectrodes. A percentage of the resulting junctions retain the expected character of an ODT monolayer. While the process is not yet optimized, our successful junctions show that molecular electronic devices can be fabricated using simple processes such as photolithography, self-assembled monolayers and dielectrophoresis.

Electrical and Thermal study of carbon nanotubes reinforced poly (phenylene sulfide) nanostructured composites

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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.

Modeling Carbon Nanotube Electrical Properties in CNT/Polymer Composites

In this work it is demonstrated that the capacitance between two cylinders increases with the rotation angle and it has a fundamental influence on the composite dielectric constant. The dielectric constant is lower for nematic materials than for isotropic ones and this can be attributed to the effect of the filler alignment in the capacitance. The effect of aspect ratio in the conductivity is also studied in this work. Finally, based on previous work and by comparing to results from the literature it is found that the electrical conductivity in this type of composites is due to hopping between nearest fillers resulting in a weak disorder regime that is similar to the single junction expression.

Carbon Nanotubes-Reinforced PET Nanocomposite by Melt-Compounding

Poly(ethylene terephthalate) (PET) nanocomposites with single-walled carbon nanotubes (SWNTs) have been prepared by a simple melt compounding method. With increasing concentration (0-3 wt %) of SWNTs, the mechanical and dynamic mechanical properties improved, corresponding to effective reinforcement. Melt rheological characterization indicated the effective entanglements provided by SWNTs in the melt state as well. Thermogravimetric analysis suggested no influence of SWNTs on the thermal stability of PET. Electrical conductivity measurements on the composite films pointed out that the melt compounded SWNTs can result in electrical percolation albeit at concentrations exceeding 2 wt %.

Nanostructured Composites Based on Carbon Nanotubes and Epoxy Resin for Use as Radar Absorbing Materials

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Multi-Walled Carbon Nanotubes and Poly(lactic acid) Nanocomposite Fibrous Membranes Prepared by Solution Blow Spinning

Nanocomposite fibers based on multi-walled carbon nanotubes (MWCNT) and poly(lactic acid) (PLA) were prepared by solution blow spinning (SBS). Fiber morphology was characterized by scanning electron microscopy (SEM) and optical microscopy (OM). Electrical, thermal, surface and crystalline properties of the spun fibers were evaluated, respectively, by conductivity measurements (4-point probe), thermogravimetric analyses (TGA), differential scanning calorimetry (DSC), contact angle and X-ray diffraction (XRD). OM analysis of the spun mats showed a poor dispersion of MWCNT in the matrix, however dispersion in solution was increased during spinning where droplets of PLA in solution loaded with MWCNT were pulled by the pressure drop at the nozzle, producing PLA fibers filled with MWCNT. Good electrical conductivity and hydrophobicity can be achieved at low carbon nanotube contents. When only 1 wt% MWCNT was added to low-crystalline PLA, surface conductivity of the composites increased from 5 x 10(-8) to 0.46 S/cm. Addition of MWCNT can slightly influence the degree of crystallinity of PLA fibers as studied by XRD and DSC. Thermogravimetric analyses showed that MWCNT loading can decrease the onset degradation temperature of the composites which was attributed to the catalytic effect of metallic residues in MWCNT. Moreover, it was demonstrated that hydrophilicity slightly increased with an increase in MWCNT content. These results show that solution blow spinning can also be used to produce nanocomposite fibers with many potential applications such as in sensors and biosensors.

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.

Development of functionalised multiwalled carbon nanotube/polyaniline composites for electrical applications

Combining intrinsically conducting polymers with carbon nanotubes (CNT) helps in creating composites with superior electrical and thermal characteristics. These composites are capable of replacing metals and semiconductors as they possess unique combination of electrical conductivity, flexibility, stretchability, softness and bio-compatibility. Their potential for use in various organic devices such as super capacitors, printable conductors, optoelectronic devices, sensors, actuators, electrochemical devices, electromagnetic interference shielding, field effect transistors, LEDs, thermoelectrics etc. makes them excellent substitutes for present day semiconductors.However, many of these potential applications have not been fully exploited because of various open–ended challenges. Composites meant for use in organic devices require highly stable conductivity for the longevity of the devices. CNT when incorporated at specific proportions, and with special methods contributes quite positively to this end.The increasing demand for energy and depleting fossil fuel reserves has broadened the scope for research into alternative energy sources. A unique and efficient method for harnessing energy is thermoelectric energy conversion method. Here, heat is converted directly into electricity using a class of materials known as thermoelectric materials. Though polymers have low electrical conductivity and thermo power, their low thermal conductivity favours use as a thermoelectric material. The thermally disconnected, but electrically connected carrier pathways in CNT/Polymer composites can satisfy the so-called “phonon-glass/electron-crystal” property required for thermoelectric materials. Strain sensing is commonly used for monitoring in engineering, medicine, space or ocean research. Polymeric composites are ideal candidates for the manufacture of strain sensors. Conducting elastomeric composites containing CNT are widely used for this application. These CNT/Polymer composites offer resistance change over a large strain range due to the low Young‟s modulus and higher elasticity. They are also capable of covering surfaces with arbitrary curvatures.Due to the high operating frequency and bandwidth of electronic equipments electromagnetic interference (EMI) has attained the tag of an „environmental pollutant‟, affecting other electronic devices as well as living organisms. Among the EMI shielding materials, polymer composites based on carbon nanotubes show great promise. High strength and stiffness, extremely high aspect ratio, and good electrical conductivity of CNT make it a filler of choice for shielding applications. A method for better dispersion, orientation and connectivity of the CNT in polymer matrix is required to enhance conductivity and EMI shielding. This thesis presents a detailed study on the synthesis of functionalised multiwalled carbon nanotube/polyaniline composites and their application in electronic devices. The major areas focused include DC conductivity retention at high temperature, thermoelectric, strain sensing and electromagnetic interference shielding properties, thermogravimetric, dynamic mechanical and tensile analysis in addition to structural and morphological studies.

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.

Mechanical, electrical and electro-mechanical properties of thermoplastic elastomer styrene–butadiene–styrene/multiwal carbon nanotubes composites

Composites of styrene–butadiene–styrene (SBS) block copolymer with multiwall carbon nanotubes were processed by solution casting to investigate the influence of filler content, the different ratios of styrene/butadiene in the copolymer and the architecture of the SBS matrix on the electrical, mechanical and electro-mechanical properties of the composites. It was found that filler content and elastomer matrix architecture influence the percolation threshold and consequently the overall composite electrical conductivity. Themechanical properties aremainly affected by the styrene and filler content. Hopping between nearest fillers is proposed as the main mechanism for the composite conduction. The variation of the electrical resistivity is linear with the deformation. This fact, together with the gauge factor values in the range of 2–18, results in appropriate composites to be used as (large) deformation sensors.

Mechanical, electrical and electro-mechanical properties of thermoplastic elastomer styrene–butadiene–styrene/multiwall carbon nanotubes composites

Composites of styrene–butadiene–styrene (SBS) block copolymer with multiwall carbon nanotubes were processed by solution casting to investigate the influence of filler content, the different ratios of styrene/butadiene in the copolymer and the architecture of the SBS matrix on the electrical, mechanical and electro-mechanical properties of the composites. It was found that filler content and elastomer matrix architecture influence the percolation threshold and consequently the overall composite electrical conductivity. The mechanical properties are mainly affected by the styrene and filler content. Hopping between nearest fillers is proposed as the main mechanism for the composite conduction. The variation of the electrical resistivity is linear with the deformation. This fact, together with the gauge factor values in the range of 2–18, results in appropriate composites to be used as (large) deformation sensors.