This thesis presents the investigation of the liquid crystal (LC) - particle suspensions. Particles from nano- to micro-size, spherical to two-dimensional shapes, with different functionality are dispersed into nematic and smectic phases. The aim is to create ordered nanoparticle (NP) assemblies and thereby modify the common properties of the liquid crystal, such as dielectric anisotropy and electro-optical, revealing any interaction between particles and LC properties. It is found that for concentrations (>0.5vol%), the ferroelectric NPs have increased the sensitivity of the nematic liquid crystal to the electric field through electro-optical responses, which is seen by an enhancement in the dielectric anisotropy. This could be induced by the coupling of the electrical dipole moments in the spherical NPs with the LC director field. The electro-optical properties of the chiral smectic (SmC*) phase (tilt angle Θ, switching time τ_s and spontaneous polarisation P_s) are found to be independent of the concentration and sizes of the doped NPs. The relaxation frequency f_R of the Goldstone mode is faster in the ferroelectric NPs suspensions of 2.0vol% compared to the paraelectric NPs. In the graphene oxide (GO) - nematic LC (5CB) suspensions, the small GO sizes of mean size 560 nm are more easily dispersible than larger flakes of 2.8 micro metre mean size. As the GO concentration is increased, each of the threshold voltage and splay elastic constant dramatically increases, reaching saturation at ≈1.0wt%. The field driven switching-on time is practically not affected, while the purely elastically driven switching-off time is strongly sped-up. Interestingly, thermotropic and lyotropic LC phases are exhibited in the GO-5CB suspensions when heating the thermotropic liquid crystal into its isotropic phase. The isotropic phase of 5CB acts as a solvent for the GO particles, forming a lyotropic nematic phase with largely reduced birefringence. It is found that the nematic to isotropic phase transition is shifted toward higher temperature for the GO-5CB system compared to the BaTiO3-5CB system. Dispersions of different sizes of GO flakes are prepared in isotropic and nematic fluid media. The dielectric relaxation behaviour of GO-dispersions was examined for a wide temperature range (25-60 ℃) and frequency range (100 Hz-2 MHz). The mixtures containing GO flakes were found to exhibit varying dielectric relaxation processes, depending on the size of the flakes and the elastic properties of the dispersant fluid. The relaxation frequencies in the isotropic media were lower compared to the nematic medium. Relaxation frequencies (~10 kHz) are observed in the GO-isotropic media, which are reduced as the size of the GO flakes are decreased, are anticipated to be inherited from GO flakes. However, the fast relaxations (~100 kHz) that are observed in the nematic suspensions could imply strongly slowed down molecular relaxation modes of the nematogenic molecules. Finally, the phase diagram of lyotropic LC as a function of the lateral dimensions of the GO flakes, their concentration, geometrical confinement configuration and solvent polarity was investigated. Polarising optical microscopy was used to determine isotropic-biphasic-nematic phase evolution. The confinement volume and geometry of the sample relative to the GO size are shown to be vital to the observation of the lyotropic phase. GO LCs have the potential for a range of applications from display technologies to conductive fibres. The confinement related LC phase transition is critical toward their applications. It is also found that the stability of the LC phase is higher for the solvent of higher dielectric constant.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-06-02T20:23:35Z No. of bitstreams: 1 RitaSousaCarvalho.pdf: 1881186 bytes, checksum: 0d50276b7867c21064584927762057dc (MD5) / Made available in DSpace on 2017-06-02T20:23:35Z (GMT). No. of bitstreams: 1 RitaSousaCarvalho.pdf: 1881186 bytes, checksum: 0d50276b7867c21064584927762057dc (MD5) Previous issue date: 2016-07-29 / A novel and selective electrochemical sensor for the determination of the butylated hydroxyanisole (BHA) and tert-butylhydroquinone (TBHQ) antioxidants employing the differential pulse voltammetry (DPV) was developed. In this sense, a glassy carbon electrode (GCE) modified with a copper tetrasulfonated phthatocyanine (CuTSPc) adsorbed on reduced graphene oxide (rGO) showed excellent response for the TBHQ and BHA oxidation with a decrease in the overpotentials about 130mV vs Ag/AgCl and anodic peak currents about 4 times higher than the observed responsesat an electrode unmodified. The increase of the oxidation reaction rates for TBHQ and BHA was attributed to the efficient electron transfer between the studied species and the immobilized materials on surface of the GCE.The materials rGO, CuTSPc and rGO/CuTSPc were characterized by Fourier transform infrared spectroscopy (FTIR) and the analytical response of the sensor for the analytes was studied by cyclic voltammetry (CV) and linear scan voltammetry (LSV) techniques. After optimization of the experimental parameters, the analytical curves for determination of BHA and TBHQ by DPV technique demonstrated an excellent linear response from 0.1 to 500µmol L-1 with detection limit of 0.045 µmol L-1 for TBHQ and 0.036 µmol L-1 for BHA. Finally, the proposed method was successfully applied in the simultaneous determination of BHA and TBHQ in six biodiesel samples, and the results obtained were found to be similar to those obtained using the HPLC method with agreement at 95 % confidence level. The addition and recovery studies have shown that the proposed method has good accuracy with recovery values between 99.5 and 100.5 % forTBHQ and 99.1 and 100.2 for BHA. / Um novo e seletivo sensor eletroquímico para a determinação dos antioxidantes butilato de hidroxianisol (BHA) e terc-bultil-hidroquinona (TBHQ) empregando a Voltametria de Pulso Diferencial (VPD) foi desenvolvido. Neste sentido, um eletrodo de carbono vítreo (ECV) modificado coma ftalocianina tetrassulfonada de cobre (CuTSPc) adsorvida sobre óxido de grafeno reduzido (OGr) mostrou uma excelente resposta para as oxidações de TBHQ e BHA com uma diminuição nos sobrepotenciais cerca de 130 mV vs Ag/AgCl e correntes de pico anódicas cerca de 4 vezes maiores do que as respostas observadasem um eletrodo não modificado. O aumento nas velocidades das reações de oxidação de TBHQ e BHA foi atribuído à eficiente transferência de elétrons entre as espécies estudadas e os materiais imobilizados na superfície do ECV. Os materiais OGr, CuTSPc e OGr/CuTSPc foram caracterizados por espectroscopia no infravermelho com transformada de Fourrier (FTIR) e a resposta analítica do sensor para os analitos foi estudada pelas técnicas voltametria cíclica (VC) e voltametria de varredura linear (VVL). Após a otimização dos parâmetros experimentais e operacionais, as curvas analíticas para a determinação individual e simultânea de BHA e TBHQ, pela técnica VPD, demonstraram uma excelente resposta linear de 0,1 a 500 µmol L-1 com limite de detecção de 0,045 µmol L-1 para TBHQ e 0,036 µmol L-1 para BHA. Finalmente, o sensor proposto foi utilizado com sucesso para a determinação TBHQ e BHA em seis amostras de biodiesel e os resultados foram similares aos obtidos pelo método HPLC com um nível de concordância de 95 %. Os estudos de adição e recuperação mostraram que o método proposto apresenta boa exatidão com valores de recuperação entre 99,5 e 100,5% para TBHQ e 99,1 e 100,2 para BHA.

Dentre as formas alotrópicas do carbono, o grafeno merece destaque. Este material consiste de uma monocamada atômica de carbono sp2 disposta em uma rede bidimensional cristalina hexagonal tipo favo de mel. Uma das formas de se obter o grafeno é pela esfoliação química, que consiste da oxigenação do grafite policristalino em um ambiente altamente oxigenado, formando um produto intermediário chamado de grafeno oxidado (GO). Por este método, gera-se um produto altamente estável e solúvel em água, podendo ser utilizado na construção de filmes ultrafinos. Uma das aplicações possíveis do grafeno oxidado é em sensores e biossensores, área de aplicações de novos materiais que viabilizem o diagnostico rápido, preciso, seletivo e de baixo custo, principalmente os do tipo, point-of-care. O grafeno é um forte candidato, nessa área, devido a sua alta performace e seu baixo custo de processamento. Neste trabalho, a técnica de automontagem eletrostatic layer-by-layer (ELBL) foi utilizada na construção de filmes de grafeno oxidado, juntamente com o policátion dendritico poli(amido amina) geração 4 (PAMAM-G4) em uma plataforma potenciométrica, utilizando um amplificador de instrumentação comercial AD620 como transdutor em um sensor de pH para caracterização da sensibilidade do dispositivo. Diversas técnicas espectroscópicas, óticas e morfológicas foram utilizadas para caracterizar a esfoliação química do grafite e dos filmes automontados. Através destas caracterizações mostrou-se que a esfoliação ocorreu satisfatoriamente concordando com resultados já existentes na literatura. A construção dos filmes ultrafinos ocorreu pela rápida adsorção do GO em camadas alternadas de PAMAM-G4, e o monitoramento do crescimento dos filmes foi realizado utilizando espectroscopia no UV-Vis, onde o crescimento é linear a partir da décima camada. Por microscopia de força atômica, mostrou-se que a adsorção das folhas de grafeno se dá primeiramente pelas folhas de menor número de camada (1 e 2 camadas) de GO e para camadas de número superior tem-se uma morfologia totalmente diferente da primeira. Por espectroscopia no infravermelho, mostrou-se a interação entre os dois polieletrólitos, onde há formação de ligações do tipo cross-linking entre as camadas. Medidas de potenciometria indicam a sensibilidade máxima em torno de 57 mV/pH em um substrato de ouro( sensibilidade Nerstiana), o que evidencia a sua aplicabilidade em sensoriamento e também a sua aplicação em biossensores. / Among the allotropic forms of carbon, graphene deserves special attention. This material consists of one atomic monolayer of sp2 carbon arranged in a two-dimensional hexagonal lattice type, namely \"honeycomb\". One common method to obtain graphene is -=by chemical exfoliation, which consists of oxygenation of polycrystalline graphite in a highly oxygenated medium, forming an intermediate product namely graphene oxide (GO). This method generates a highly stable and water soluble GO that can be used in the fabrication of ultrathin films. Graphene is a strong candidate for sensing, due to its high performance and low cost processing. In this dissertation, GO was obtained via chemical routs and processed in the form of ultrathin films in conjunction with polyamidoamine dendrimer (PAMAM G4) in a layered fashion using the Electrostatic Layer-by-Layer (ELBL). The GO/PAMAM films were deposited on potentiometric platforms and used as pH sensors using a commercial amplifier AD620 instrumentation as the detection technique. GO and the LbL films were characterized via spectroscopic, optical and morphological techniques. Film growth was monitored via UV-Vis spectroscopy and revealed a linear adsorption up to the tenth GO/PAMAM bilayer. AFM analyses revealed that graphene sheets containing 1 or 2 layers occurred adsorbed first on the substrates. Potentiometric measurements indicated a maximum sensitivity of ca. 57 mV/pH for GO/PAMAM films deposited on gold substrates (Nernstian Sensitivity), which demonstrates the applicability of the films in sensing and biosensing.

The efficacy of dispersed reduced graphene oxide (rGO) as a nucleation site for the growth of mesophase in an isotropic pitch was investigated and quantified in this study. Concentrations of rGO were systematically tested in an isotropic petroleum and coal-tar pitch during thermal treatments and compared to pitch without rGO. The mesophase content of each thermally treated pitch was quantified by polarized light point counting. Further characterization of softening temperature and insolubles were quantified. Additionally, the pitches with and without rGO were melt spun, graphitized, and tensile tested to determine the effects of rGO on graphitized fiber mechanical properties and fiber morphology.

Photophysical, electronic, and compositional properties of single-walled carbon nanotubes (SWCNTs) and bulk nanotube samples were investigated together with graphene oxide photoluminescence. First, we studied the effect of external electric fields on SWCNT photoluminescence. Fields of up to 10 7 V/m caused dramatic, reversible decreases in emission intensity. Quenching efficiency was proportional to the projection of the field on the SWCNT axis, and showed inverse correlation with optical band gap. The magnitude of the effect was experimentally related to exciton binding energy, as consistent with a proposed field-induced exciton dissociation model. Further, the electronic composition of various SWCNT samples was studied. A new method was developed to measure the fraction of semiconducting nanotubes in as- grown or processed samples. SWCNT number densities were compared in images from near-IR photoluminescence (semiconducting species) and AFM (all species) to compute the semiconducting fraction. The results provide important information about SWCNT sample compositions that can guide controlled growth methods and help calibrate bulk characterization techniques. The nature of absorption backgrounds in SWCNT samples was also studied. A number of extrinsic perturbations such as extensive ultrasonication, sidewall functionalization, amorphous carbon impurities, and SWCNT aggregation were applied and their background contributions quantified. Spectral congestion backgrounds from overlapping absorption bands were assessed with spectral modeling. Unlike semiconducting nanotubes, metallic SWCNTs gave broad intrinsic absorption backgrounds. The shape of the metallic background component and its absorptivity coefficient were determined. These results can be used to minimize and evaluate SWCNT absorption backgrounds. Length dependence of SWCNT optical properties was investigated. Samples were dispersed by ultrasonication or shear processing, and then length-fractionated by gel electrophoresis or controlled ultrasonication shortening. Fractions from both methods showed no significant absorbance variations with SWCNT length. The photoluminescence intensity increased linearly with length, and the relative quantum yield gradually increased, approaching a limiting value. Finally, a strong pH dependence of graphene oxide photoluminescence was observed. Sharp and structured excitation/emission features resembling the spectra of molecular fluorophores were obtained in basic conditions. Based on the observed pH-dependence and quantum calculations, these spectral features were assigned to quasi-molecular fluorophores formed by the electronic coupling of oxygen-containing addends with nearby graphene carbon atoms.

With the progress of technology, large capacity and scalable are required for the future. Recent years, the physical limit is approached and a next-generation memory is needed in the future. In addition, non- volatile memory occupies more than 96% in the memory market, and RRAM has great advantages such as simple structure, high scalable, low operation voltage, high operation speed, high endurance and retention. That is the reason RRAM is the candidate in the next generation. In this experiment, multi-sputtering was used to deposit Zr:SiO 2 and Pt on TiN bottom electrode. The sandwich structure was metal/insulator/metal (MIM). With the different dielectric constant material, a different electrical field will be produced. And then I-V measurement and materials analysis were used to investigate the characteristic of the RRAM. At first, a forming process is required to the RRAM. The device was swept from negative to positive voltage and obtained the conduction mechanism from curve fitting. The different dielectric constant materials were used to fabricate the RRAM. High and low dielectric materials were HfO 2 and BN, respectively. The electric field distribution is centralized in low dielectric material so the electrons will drift to the direction of electric field. Hence, the Vset will be centralized and more stable. We also fabricated a Zr:SiO 2 /C:SiO 2 RRAM as an high K and low K material. The current fitting results that a hopping conduction occurs in low resistive state (LRS) and high resistive state (HRS). Both from Raman spectrum and FT-IR spectrum, a graphene oxide was existed in the C:SiO 2 thin film. While the filament was form, the tip of the filament will approach the graphene oxide because of the point effect. Hence, the resistance switching will happen in the grapheme oxide and set voltage will be more stable and lower the operated current. Next, an ICP treatment was used in order to "burn" the carbon in SiO 2 . The purpose is to make an extremely low K material and ignore the effect of the existence of carbon. From the FT-IR spectrum, the carbon signals were disappeared after the ICP oxygen plasma treatment. In the I-V fitting diagram, space char limit results in the high voltage region. The electrical field simulation was an auxiliary tool which shows a strong electrical field occurs in the extremely low K area. While the electrons flow through the conduction path, they will be confined in the porous area. The operation current will decrease because of the limited conduction area.

Various solution-processed methods have been employed in this work. For the synthesis of graphene, a chemical exfoliation method has been used to generate large graphene flakes in the solution phase. In addition, chemical or electro polymerization has been used for synthesizing polyanthracene, which tends to form graphene nanoribbon through cyclodehydrogenation. For the device fabrication, graphene oxide (GO) thin films were deposited from solution phase on the vapor-silanzed aminosilane surface to make semiconducting active layer or conducting electrodes. Gold nanoparticles (AuNPs) were selectively self-assembled from solution phase to pattern nanowires.

Following the first report on electronic transport measurements of graphene, an atom-thick carbon material, many scientists have devoted effort to understand its fundamental properties. In this work, the mechanical properties of graphene-based materials, including monolayer graphene oxide and chemical vapor deposition (CVD) grown graphene, were determined using membrane structures. Furthermore, a membrane structure was used to demonstrate thermoacoustic sound generation from monolayer graphene. In order to realize the mechanical characterization, reproducible methods to fabricate graphene membranes were developed using dry and wet transfer techniques. A novel dry transfer technique produced graphene-sealed microchambers without trapping liquid inside. An improved wet transfer technique enabled the transfer of graphene onto perforated substrates. Monolayer graphene oxide was mechanically tested using scanning atomic force microscopy (AFM) combined with finite element analysis of the data. The mechanical deformation was measured by scanning AFM tips over the suspended graphene oxide membranes. The Young’s modulus of the membranes was obtained by analyzing the deformation using finite element analysis together with a mapping technique. In addition, membranes with 2 and 3 layers of graphene oxide were identified using transmission electron microscopy and mechanically characterized. Moreover, these same methods were used for measuring mechanical properties of ultra-thin amorphous carbon membranes. Bulge tests, which apply uniform pressure on the suspended membrane, revealed the mechanical behavior of polycrystalline graphene grown on copper foils by chemical vapor deposition. In particular, the effect of grain boundaries on the elastic properties of polycrystalline graphene was studied by correlating its Young’s modulus with the density of grain boundaries within the membranes. It was observed that a large number of grain boundaries softened the graphene membranes. Graphene, along with monolayer hexagonal boron nitride, is the ultimate limit of thin materials. Thus, it is an ideal candidate as a thermoacoustic sound source because of its low heat capacity per unit area. The work presented here provides the first demonstration of thermoacoustic sound generation from large-area monolayer graphene. A fundamental understanding of the influence of the underlying substrates was achieved by comparing the acoustic performance of graphene membranes on various patterned substrates with different porosities. / text

Graphene, the first two-dimensional crystal ever found, is a material that has attracted fervent and sustained interest from condensed matter researchers from around the world. It has a unique and unprecedented band structure in a bulk material: the bands near the Fermi level are linear, leading to massless charge carriers that propagate at the speed of light. However, graphene does not possess a band gap, and as such, it cannot be used to process information in any electronic device that uses digital logic. Graphene is oxidized when several different basic functional groups like hydroxyls, carboxyls, and epoxides bond to the hexagonal carbon basal plane to make graphene oxide (GO). The result is a nonstoichiometric and highly disordered system that, according to the results shown in this thesis, consists of zones of densely-packed functional groups interspersed between zones of relatively small functional group concentration. This has been confirmed by DFT calculations presented here, which is the first time that a successful simulation of the GO density of states has been compared to X-ray data. Contrary to many assumptions in the literature, many of the features in the density of states of GO are due not to carbon sites bonded to functional groups, but are due to nearby non-functionalized carbon sites. The band gap of graphene oxide is principally controlled by oxidation level. Reduction, followed by heating, will regenerate the near-Fermi states and close the band gap significantly as has been seen by others. However, heating non-reduced graphene oxide can also result in a much-reduced band gap, which occurs because intercalated water can react with the heated GO sample to remove functional groups by creation and eventual expulsion of carbon dioxide. The band gap of GO is further complicated by stacking effects if it is multilayered, because residual pi-conjugated states in neighboring planes interact. The two major types of stacking in graphite are AA-stacking and AB-stacking. AA-stacking interactions cause the pi * resonance to broaden and push states to lower energy, which means that AA-stacking determines the width of the gap in highly oxidized samples. However, direct oxidation of graphene is not the only way that one alter the electronic structure of GO. Other results presented here also show that non-covalent functionalization of graphene oxide by amorphous solid water is a powerful, reversible way to dramatically change the GO electronic structure.

This project was basically exploratory in the electrical properties of carbon nanotube (CNT) based materials. The direct current (DC) conductivity of CNT/polymer composites was computed by using equivalent circuit method and a three dimensional (3-D) numerical continuum model with the consideration of tunneling conduction. The effects of the potential barrier of polymer and the tortousity of CNTs on the conductivity were analyzed. It was found that both of percolation threshold and DC conductivity can be strongly affected by the potential barrier and the tortousity. The influence of contact resistance on DC conductivity was also computed, and the results revealed that contact resistance and tunneling resistance had significant influences on the conductivity, but did not affect the percolation threshold. The microstructure-dependent alternating current (AC) properties of CNT/polymer composites were investigated using the 3-D numerical continuum model. It was found that AC conductivity and critical frequency of CNT/polymer composites can be enhanced by increasing the curl ratio of CNTs. In the mid-range CNT mass fraction, with increasing curl ratio of CNTs, AC conductivity, interestingly, became frequency-dependent in low frequency range, which cannot be explained by reference to the percolation theory. A proper interpretation was given based on the linear circuit theory. It was also found that the critical frequency can also be affected by the size of CNT cluster. Series numerical formulas were derived by using a numerical capacitively and resistively junction model. In particular, this work introduced an equivalent resistor-capacitor (RC) circuit with simple definitions of the values of contact resistance and average mutual capacitance for CNT/polymer nanocomposites. Theoretical results were in good agreement with experimental data, and successfully predicted the effect of morphology on the AC properties of CNT/polymer composites. DC and AC conductivities of multi-walled carbon nanotube (MWCNT)/graphene oxide (GO) hybrid films were measured for selected MWCNT mass fractions of 10%, 33.3%, 50%, 66.7%, and 83.3% using four-probe method. The experimental results were fitted using scaling law, and relatively high percolation threshold was found. This high percolation threshold was understood in terms of the potential energy and intrinsic ripples and warping in the freestanding graphene sheets. The capacitance of these hybrid films were measured using the voltmeter-ammeter-wattmeter test circuit with different voltages and heat treatments. The MWCNT/GO film showed relatively high specific capacitance (0.192F/cm3 for the mass fraction of 83.3%) and power factor compared to conventional dielectric capacitors. Both of measured capacitance and power factor can be enhanced by increasing testing voltages. The capacitance of MWCNT/GO films rapidly decreased after heat treatments above 160 ℃. This decrease was caused by redox reaction in the GO sheets. The capacitive behaviour of MWCNT/GO hybrid films was also interpreted by using the equivalent circuit model. Single-walled carbon nanotube (SWCNT) and SWCNT/Poly(vinyl alcohol) (PVA) films were used to form a piezoresistive strain sensor. Both of static and dynamic strain sensing behaviours of SWCNT and SWCNT/PVA films were measured. It was found that the sensitivities of these films decreased with increasing their thicknesses. The SWCNT film with a thickness of 1900 nm and SWCNT/PVA film exhibited viscoelastic sensing behaviour, because van der Waals attraction force allowed axial slippages of the smooth surface of nanotubes. A numerical model was derived based on the dynamic strain sensing behaviour. This model could be useful for designing CNT strain sensors. Finally, thermoelectric power (TEP) of deformed SWCNT films with various thicknesses was measured. It was observed that positive TEP of SWCNT films increased with increasing stain above the critical point. The experimental results were fitted by using a numerical model in terms of a variation of Nordheim-Gorter relation and fluctuation induced tunneling (FIT) model. From the numerical model, it was found that the increase of TEP above the critical strain resulted from the positive term of the contribution from the barrier region, and the effect of barrier regions decreases with increasing the thickness of the film.