Organic coatings are widely used to lower the corrosion rate of metallic structures. However, penetration of water, oxygen and corrosive ions through pores present in the coating results in corrosion initiation and propagation once these species reach the metal substrate. Considering the need for systems that offer active protection with self-healing functionality, composite coatings containing polyaniline (PANI) conducting polymer are proposed in this study. In the first phase of my work, PANI was synthesized by various methods and characterized. The rapid mixing synthesis method was chosen for the rest of this study, providing PANI with high electrical conductivity, molecular structure of emeraldine salt, and morphology of spherical nanoparticles. PANIs doped with phosphoric and methane sulfonic acid revealed hydrophilic nature, and I showed that by incorporating a long-chain alkylphosphonic acid a hydrophobic PANI could be prepared. The second phase of my project was dedicated to making homogenous dispersions of PANI in a UV-curable resin based on polyester acrylate (PEA). Interfacial energy studies revealed the highest affinity of PEA to PANI doped with phosphoric acid (PANI-PA), and no attractive or long-range repulsive forces were measured between the PANI-PA surfaces in PEA.This is ideal for making conductive composites as, along withno aggregation tendency, the PANI-PA particles might come close enough to form an electrically connected network. Highly stable PEA/PANI-PA dispersions were prepared by pretreatment of PANI-PA in acetone followed by mixing in PEA in small portions under pearl-milling. The third phase of my project dealt with kinetics of the free radical polymerization that was utilized to cure the PEA/PANI-PA mixture. UV-vis absorption studies suggested a maximum allowed PANI-PA content of around 4 wt.% in order not to affect the UV curing behavior in the UV-C region. Real-time FTIR spectroscopy studies, using a laboratory UV source, revealed longer initial retardation of the photocuring and lower rates of crosslinking reactions for dispersions containing PANI-PA of higher than 3 wt.%. The presence of PANI-PA also made the formulations more sensitive to changes in UV light intensity and oxygen inhibition during UV curing. Nevertheless, curing of the dispersions with high PANI-PA content, of up to 10 wt.%, was demonstrated to be possible at either low UV light intensities provided the oxygen replenishment into the system was prevented, or by increasing the UV light intensity to very high levels. In the last phase of my project, the PEA and PEA/PANI-PA coatings, cured under high intensity UV lamps, were characterized. SEM analysis showed small PANI-PA particles to be closely packed within the matrix, and the electrical conductivity of the composite films was measured to be in the range of semiconductors. This suggested the presence of a connected network of PANI-PA, as confirmed by investigations of mechanical and electrical variations at the nanoscale by PeakForce TUNA AFM. The data revealed the presence of a PEA-rich layer at the composite-air interface, and a much higher population of the conductive network within the polymer matrix. High current signal was correlated with a high elastic modulus, consistent with the level measured for PANI-PA, and current-voltage studies on the conductive network showed non-Ohmic characteristics. Finally, the long-term protective property of the coatings was characterized by OCP and impedance measurements. Short-term barrier-type corrosion protection provided by the insulating PEA coating was turned into a long-term and active protection by addition of as little as 1 wt.% PANI-PA. A large and stable ennoblement was induced by the coatings containing PANI-PA of up to 3 wt.%. Higher content of PANI-PA led to poorer protection, probably due to the hydrophilicity of PANI-PA facilitating water transport in the coating and the presence of potentially weaker spots in the film. An iron oxide layer was found to fully cover the metal surface beneath the coatings containing PANI-PA after final failure observed by electrochemical testing. / <p>QC 20141103</p>

Textiles of today are materials with applications in almost all our activities. We wear clothes all the time and we are surrounded with textiles in almost all our environments. The integration of multifunctional values in such a common material has become a special area of interest in recent years. Smart Textile represents the next generation of textiles anticipated for use in several fashion, furnishing and technical textile applications. The term smart is used to refer to materials that sense and respond in a pre-defined manner to environmental stimuli. The degree of smartness varies and it is possible to enhance the intelligence further by combining these materials with a controlling unit, for example a microprocessor. As an interdisciplinary area Smart Textile includes design spaces from several areas; the textile design space, the information technology design space and the design space of material science. This thesis addresses how Smart Textiles affect the textile design space; how the introduction of smart materials and information technology affects the creation of future textile products. The aim is to explore the convergence between textiles, smart materials and information technology and to contribute to providing a basis for future research in this area. The research method is based on a series of interlinked experiments designed through the research questions and the research objects. The experiments are separated into two different sections: interactive textile structures and health monitoring. The result is a series of basic methods for how interactive textile structures are created and a general system for health monitoring. Furthermore the result consists of a new design space, advanced textile design. In advanced textile design the focus is set on the relation between the different natures of a textile object: its physical structure and its structure in the context of design and use.

Nanostructured composites are attracting intense interest for electronic and optoelectronic device applications, specifically as active elements in thin film photovoltaic (PV) device architectures. These systems implement fundamentally different concepts of enhancing energy conversion efficiencies compared to those seen in current commercial devices. This is possible through considerable flexibility in the manipulation of device-relevant properties through control of the interplay between the nanostructure and the optoelectronic response. In the present work, inorganic nanocomposites of semiconductor Ge embedded in transparent conductive indium tin oxide (ITO) as well as Ge in zinc oxide (ZnO) were produced by a single step RF-magnetron sputter deposition process.It is shown that, by controlling the design of the nanocomposites as well as heat treatment conditions, decreases in the physical dimensions of Ge nanophase size provided an effective tuning of the optical absorption and charge transport properties. This effect of changes in the optical properties of nanophase semiconductors with respect to size is known as the quantum confinement effect. Variation in the embedding matrix material between ITO and ZnO with corresponding characterization of optoelectronic properties exhibit notable differences in the presence and evolution of an interfacial oxide within these composites. Further studies of interfacial structures were performed using depth-profiling XPS and Raman spectroscopy, while study of the corresponding electronic effects were performed using room temperature and temperature-dependent Hall Effect. Optical absorption was noted to shift to higher onset energies upon heat treatment with a decrease in the observed Ge domain size, indicating quantum confinement effects within these systems. This contrasts to previous investigations that have involved the introduction of nanoscale Ge into insulating, amorphous oxides. Comparison of these different matrix chemistries highlights the overarching role of interfacial structures on quantum-size characteristics. The opportunity to tune the spectral response of these PV materials, via control of semiconductor phase assembly in the nanocomposite, directly impacts the potential for the use of these materials as sensitizing elements for enhanced solar cell conversion efficiency.

Climatic conditions inside the dairy barn do not concern dairy farmers until those conditions begin to affect productivity and, consequently, profits. As heat and humidity increase beyond the cow's comfort levels, milk production declines, as does fertility and the welfare of the cow in general. To reinforce the cooling mechanisms currently used, this work proposes an alternative system for reducing the risk of heat stress. This innovative conductive cooling system does not depend on current weather conditions, and it does not require significant modifications when it is installed or during its operation. Also, the system circulates water that can be reused. Given that a review of the literature found very few related studies, it is suggested that each freestall be equipped with a viable prototype in the form of a waterbed able to exchange heat. Such a prototype has been simulated using Computational Fluid Dynamics (CFD) and later verified by a set of experiments designed to confirm its cooling capacity. Furthermore, this investigation sets the foundation for modeling temperature in a water supply system linked to the waterbeds. EPANET, a software program developed by the Environmental Protection Agency, simulates the hydraulic model. Its Water Quality Solver has been modified according to an analogy in the governing equation that compares mass to heat transfer and serves to simulate water temperature as the water is transported from its source to the point of delivery and then as it returns to the same source.

We report the synthesis of ultra-high aspect ratio copper nanowires (CuNW) and fabrication of CuNW-based transparent conductive electrodes (TCE) with high optical transmittance (> 80%) and excellent sheet resistance (R-s < 30 Omega/sq). These CuNW TCEs are subsequently hybridized with aluminum-doped zinc oxide (AZO) thin-film coatings, or platinum thinfilm coatings, or nickel thin-film coatings. Our hybrid transparent electrodes can replace indium tin oxide (ITO) films in dye-sensitized solar cells (DSSCs) as either anodes or cathodes. We highlight the challenges of integrating bare CuNWs into DSSCs, and demonstrate that hybridization renders the solar cell integrations feasible. The CuNW/AZO-based DSSCs have reasonably good open-circuit voltage (V-oc = 720 mV) and short-circuit current-density (J(sc) = 0.96 mA/cm(2)), which are comparable to what is obtained with an ITO-based DSSC fabricated with a similar process. Our CuNW-Ni based DSSCs exhibit a good open-circuit voltage (V-oc = 782 mV) and a decent short-circuit current (J(sc) = 3.96 mA/cm2), with roughly 1.5% optical-to-electrical conversion efficiency.

This thesis presents the design and development of a hand-held electronic reader, designed to decode conductive patterns printed on a paper substrate. Data read from the patterns, by the reader, is used to trigger events in the digital domain. The reader and associated conductive patterns are devices for linking paper documents with the digital world. The patterns are formed by masking conductive-coated paper with a non-conductive, printed lacquer. The reader is a low cost and ergonomic device, capable of transmitting the embedded data from the conductive paper to the computer. The first reader designed and developed was tethered to a computer by data cable, using the USB communication protocol. The second design was developed further, with transmission of data achieved by replacing the cable with short-range Bluetooth wireless technology. Both devices were designed and developed using embedded systems and low cost electronic components. Additional work was undertaken to optimise the device's mechanical structure, ergonomics and integration of hardware. Alongside the development of the reader, test and development work was carried out to optimise the printed media, in materials and design. User trials demonstrated that the complete printed and reading system was functional, with varied rates of success among participants. Further work is required to improve the conductivity of the coated paper, and the accuracy of the decoding algorithm.

As técnicas de Espectroscopia de Alta Resolução em Sólidos e Relaxação por RMN são largamente utilizadas no estudo da estrutura e dinâmica de polímeros. Neste trabalho estudamos, utilizando estas técnicas, duas classes distintas de polímeros: os condutores iônicos e os condutores eletrônicos. O polímero condutor iônico estudado foi o Diesterato de Polietileno Glicol (PEGD) complexado com sais de metais alcalinos, LiClO4 ou NaClO4. A metodologia básica que empregamos para o estudo destes materiais foi a análise da forma de linha e do tempo de relaxação longitudinal para os núcleos associados tanto aos portadores de carga, 7Li e 23Na, quanto à cadeia polimérica, 1H e 13C. Todas estas medidas foram realizadas em função da temperatura e da concentração de sal de metal alcalino presente na amostra. Estudos adicionais, por condutividade elétrica, análise térmica e viscosidade foram realizados para complementar o conhecimento obtido por RMN sobre a mobilidade e estrutura das cadeias poliméricas e dos portadores de carga. Os polímeros com ligações de elétrons-\'pi\' conjugados apresentam propriedades eletrônicas especiais, particularmente a condutividade elétrica, e formam uma classe de polímeros condutores eletrônicos que podem ser facilmente oxidados ou reduzidos através de um agente dopante. Estudamos dois polímeros deste tipo: As polianilinas dopadas com 1H ou 7Li. A metodologia básica que empregamos para o estudo destes polímeros foi a análise das formas de linhas espectrais de um dos núcleos que compõem a cadeia polimérica, 13C, e de um dos agentes dopantes, 7Li, em função do método de preparação e da condutividade elétrica, de forma a poder elucidar características estruturais e dinâmicas deste grupo de polímeros. A partir do estudo destas duas classes de polímeros, conseguimos coletar uma quantidade muito grande de resultados experimentais por RMN, a partir de diferentes núcleos atômicos, que contribuíram para elucidar várias de suas características estruturais e dinâmicas / High resolution solid-state NMR spectroscopic techniques are widely used in the study of polymer structure and dynamics. In the present work we are studying, with the employment of these techniques, two distinct kinds of polymers: the ionic conductors and the electronic conductors. The ionic conductor polymer considered was the Poliethyleneglycol Distereate - 400)/MclO4, (M=Li,Na), DPEG/MclO4. The basic methodology employed for the study of these materials were the line shape analysis of the resonance lines and the longitudinal relaxation time, for the nuclei associated with the charge carriers, 7Li and 23Na, and with the polymeric chain, 1H and 13C. The measurements were related to temperature and to the alkali metal salt concentration in the sample. Additional studies, of electrical conductivity, thermal analysis and viscosity were also conducted for the complementation of the information obtained by NMR about the mobility and structure of polymeric chains and the charge carriers. The polymers with conjugated n-electron bounds present special electronic properties, particularly related to the electrical conductivity, and are easily oxidized or reduced by the action of a doping agent. We studied two of these kind of polymers: the 1H and 7Li doped Polyaniline. The basic methodology employed for the study of these polymers was the line shape analysis of the resonance lines related to one of the component nuclei of the polymeric chain, 13C , and the lines related to one of doping agents, 7Li, as a function of the preparation method and the electrical conductivity, as a way of elucidate structural and dynamic characteristics of this class of polymers. From the study of these two classes of polymers we could collect a huge quantity of NMR data from different atomic nuclei, and it led to the elucidation of important structural and dynamic characteristics of the polymers

O presente trabalho tem como objetivo o estudo e o desenvolvimento de dispositivos eletrônicos, para o monitoramento de gás de amônia, confeccionados com filmes ultrafinos de polianilina e ftalocianinas metálicas. Foram fabricados três diferentes tipos de sistemas: polianilina/PVS, polianilina/ftalocianina de níquel e polianilina/ftalocianina de cobre, sendo a espessura dos filmes o parâmetro de análise. Foram preparadas amostras com 10, 20 e 40 bicamadas. Os filmes foram caracterizados por profilometria e espectroscopia de absorção na faixa da radiação do UV - visível. Observou-se um aumento linear da espessura dos filmes com o aumento do número de bicamadas depositadas. Os dispositivos foram preparados a partir da deposição dos filmes ultrafinos de polianilina e ftalocianinas sobre substratos de vidro com eletrodos interdigitados de ouro evaporados termicamente. Os dispositivos foram caracterizados eletricamente por medidas de variação da resistência elétrica, em regime de corrente contínua e alternada, para diferentes concentrações de amônia. Também foi analisado o efeito da temperatura e da umidade relativa do ar na sensibilidade dos dispositivos. Todas as estruturas apresentaram uma dependência direta do valor da resistência elétrica com a concentração de amônia. Os dispositivos baseados em filmes de polianilina e ftalocianina de níquel apresentaram a menor variação do valor de resistência elétrica com a umidade relativa do ar. Esta característica é bastante desejável já que os ambientes nos quais se pretende utilizar este tipo de dispositivo para de monitoramento do gás de amônia, pode sofrer grandes variações no valor da umidade relativa do ar, como é o caso de granjas em geral. / The aim of this work is the study and development of electronic devices for ammonia gas monitoring based on polyaniline and metal phthalocyanines ultrathin films. It was produced three different systems: polyaniline/PVS, polyaniline/nickel phthalocyanine of and polyaniline/copper phthalocyanine and the analysis parameter of the films is the thickness. Samples were prepared with 10, 20 and 40 bilayers. The films were characterized by profilometry and spectroscopy of absorption of radiation in the range of UV-visible. There was a linear increase the thickness of the films with the increase in the number of deposited bilayers. The devices were prepared from the deposition of polyaniline and ftalocianines ultrathin films on glass substrates with interdigited electrodes of gold evaporated thermally. The devices were prepared from the polyaniline and phthalocyanine deposition of ultrathin films over glass substrates with gold interdigited electrodes. The devices were characterized electrically by measures of variation of electrical resistance, under the direct current and alternating, for different concentrations of ammonia. It was also examined the effect of temperature and relative humidity of the air in the sensitivity of the devices. All structures had a direct dependence of the value of the electrical resistance with the ammonia concentration. Devices based on films of polyaniline and nickel phthalocyanine of had the slightest variation in the amount of electrical resistance with the relative humidity. This feature is desirable because the environments in which it intends to use this type of device for tracking of ammonia gas, may undergo major changes in the value of the relative humidity of the air, such as poultry houses in general.

Objetivo: Verificar o desempenho de crianças diagnosticadas com deficiência auditiva, de grau leve, condutiva e sensorioneural, no Teste da Habilidade de Atenção Auditiva Sustentada (THAAS) visando constatar se este teste sofre influência da presença de uma deficiência auditiva. Modelo: Estudo do Teste da Habilidade de Atenção Auditiva Sustentada-THAAS em três grupos: grupo 1 (G1) grupo controle, formado por crianças com audição normal; grupo 2 (G2) crianças com deficiência auditiva sensorioneural bilateral de grau leve e grupo 3 (G3) composto por crianças com perda auditiva condutiva bilateral de grau leve. Local: Divisão de Saúde Auditiva ? Hospital de Reabilitação de Aanomalias Craniofaciais ?Universidade de São Paulo (HRAC/USP). Participantes: 90 crianças com idade entre 7 e 11 anos de idade, sendo 30 de cada grupo. Intervenções: Audiometria Tonal Limiar, Imitanciometria e THAAS Resultados: não houve indícios estatisticamente significativos entre sexo e idade, em todos os grupos estudados. Os grupos sensorioneural e condutivo apresentaram desempenho inferior ao grupo controle, em todas as respostas do THAAS. Conclusões: o teste THAAS sofreu influência das perdas auditivas de grau leve, condutivas e sensorioneurais na população estudada, sendo o pior comprometimento para perdas sensorioneurais. / Objective: To verify the performance of children diagnosed with a hearing loss of mild degree, conductive and sensorineural, at Sustained Auditory Attention Ability Test (SAAAT), aiming to observe if this test suffers the influence of the presence of a hearing loss. Model: A study of the Sustained Auditory Attention Ability Test ? SAAAT in three groups: group 1 (G1) control group comprising children with normal hearing, group 2 (G2) children with a bilateral sensorineural hearing loss of a mild degree and group 3 (G3), comprising children with a bilateral conductive hearing loss of a mild degree. Place: Division for Hearing Health ? Craniofacial Anomaly Rehabilitation Hospita, University of São Paulo (HRAC/USP). Participants: 7 to 11 year old children, 30 for each group. Interventions: Pure Tone Audiometry, Immitance Acoustic and SAAAT. Results: There were not any statistically significant indications between sex and age in all studied groups. Sensorineural and conductive groups showed a lower performance related to control group in all answers for SAAAT. Conclusions: SAAAT test suffered the influence of conductive and sensorineural hearing losses of light degree in studied population, the worse compromise occurring for sensorineural losses.

Blendas poliméricas de PAni dopada com ácido dodecilbenzeno sulfônico (PANI-DBSA) e copolímero etileno-propileno-monômero dieno desvulcanizado por microondas (dEPDM) foram obtidas por processo mecânico em diferentes concentrações. Caracterizações físico-químicas, morfológicas e elétrica foram realizadas para analisar as blendas. Um estudo sobre a desvulcanização da borracha EPDM foi descrito. Os ensaios de DSC mostraram temperaturas de transição vítrea diferentes nas blendas indicando que os componentes poliméricos não são totalmente miscíveis, o que permite a formação de uma rede condutora (PANI-DBSA) na matriz isolante (dEPDM). As análises de FTIR indicaram uma interação basicamente física entre o polímero PANI-DBSA e o copolímero dEPDM. As análises de raios-X confirmaram a presença de uma fase cristalina no interior das blendas atribuída à PANI-DBSA. Os ensaios de TGA mostraram que a PAni-DBSA diminuiu, significativamente, a estabilidade térmica do dEPDM. As análises de DMTA apresentaram a diminuição do amortecimento do sistema ocasionado pela presença da PAni, que é mais rígida, no segmento flexível do EPDM; ou seja, a mobilidade da cadeia fica mais limitada. Finalmente, o estudo de condutividade elétrica das blendas foi realizado e como esperado, esta aumenta com a concentração de PANIDBSA nas blendas, e um baixo limite de percolação pode ser observado devido à condutividade ocorrer para baixas concentrações de material condutor (<20%). A condutividade máxima alcançada foi de, aproximadamente, 102 S/cm para a composição de 50% de PANI-DBSA em massa. / Polyaniline doped with dodecylbenzenesulfonic acid (PAni-DBSA) and ethylene-propylene-diene-monomer (EPDM) rubber devulcanizated by microwave (dEPDM) blends have been prepared by mechanical process. Flexible, free-standing and stretchable films have been obtained, which have been characterized by electrical conductivity measurements, FTIR, XRD, DSC, TGA, DMTA and SEM. Study about EPDM rubber devulcanization has been described. DSC analysis have showed different glass-transition temperatures in the blends and it has been observed that the compositions present enough compatibility to form a conductive network (PAni-DBSA) in the elastomeric matrix (dEPDM). By FTIR analysis, it has been noted that there was not modification about the spectrum of blends; therefore the interactions between the components were, basically, physics. X-ray analysis have confirmed the presence of a crystalline phase into the blends that is attributed by PAni-DBSA. TGA analysis have showed that the PAni-DBSA decreased significantly the rubber thermal stability. DMTA analysis have indicated that the system damping decreased according to the presence of PAni because of its stiffness. Finally, blends electric conductivity study has been carried out and as expected, the conductivity have increased with PAni-DBSA concentration in the blends and a low percolation threshold has been observed with the onset of conductivity occurring at lower concentrations of the conductive materials (<20%).