The properties of composite materials in which spherical inclusions are embedded in a matrix of some kind, have been studied for many decades and many analytical models have been developed which measure these properties. There has been a steady progression in the complexity of models over the years, providing greater insight into the nature of these materials and improving the accuracy in the measurement of their properties. Some of the properties with which this thesis is concerned are, the elastic, thermal and electrical properties of such composites. The size of the spherical inclusion which acts as the reinforcing phase, has a major effect on the overall properties of composite materials. Once an inclusion is embedded into a matrix, a third region of different properties between the inclusion and matrix is known to develop which is called the interphase. It is well known in the composite community that the smaller the inclusion is, the larger the interphase region which develops around it. Therefore, with the introduction of nanoparticles as the preferred reinforcing phase for some composites, the interphase has a major effect on its properties. It is the aim of this thesis to consider the role of the interphase on the properties of composites by modeling it as an inhomogeneous region. There is much scientific evidence to support the fact that the interphase has an inhomogeneous nature and many papers throughout the thesis are cited which highlight this. By modeling the inhomogeneous properties by arbitrary mathematical functions, results are obtained for the various properties in terms of these general functions. Some specific profiles for the inhomogeneous region are considered for each property in order to demonstrate and test the models against some established results.

The present study addresses an optimization strategy for maximizing the structural ductility of Fiber Reinforced Concrete (FRC) with long textile fibers. Due to material brittleness of both concrete and fiber in addition to complex interfacial behavior between above constituents the structural response of FRC is highly nonlinear. Consideration of this material nonlinearity including interface is mandatory to deal with this kind of composite. In the present contribution three kinds of optimization strategies based on a damage formulation are described. The performance of the proposed method is demonstrated by a series of numerical examples; it is verified that the ductility can be substantially improved.

A composite part manufacturing mold was considered one of the most important factors that affected a successful composite part manufacturing process for this research. A highly durable surface was required for the mold to prevent surface damages and increase mold life. A high surface finish quality of the mold improved the surface quality of the composite part and lowered the demolding force. However, the surface of additively manufactured fiber reinforced composite molds usually had lower durability and surface finish quality compared to traditional metal molds. To solve these issues, the author applied an additional coating on top of the additively manufactured fiber reinforced composite mold surface. A thermal analysis of the additively manufactured fiber reinforced composite material and the coating material were performed to select an applicable coating technique and coating material. The thermoset polymer coating with ceramic particles that was applied with a liquid spray coating technique was selected as a coating material. Various surface property tests were performed to evaluate the coated surface compared to the non-coated surface. The additively manufactured fiber reinforced composite test specimen manufacturing process and the coating application process were demonstrated in this study. The surface durability of the test specimens was tested using a surface hardness test and an abrasion resistance test. The surface performance of the test specimens was measured using a surface roughness test and a demolding test. The sustainability of the coating material on the additively manufactured fiber reinforced composite was tested using coefficient of thermal expansion (CTE) test, coating adhesion test, and mold life experiment. In the mold life experiment, the non-coated and coated mold were used for multiple composite part manufacturing processes to investigate how the coating affected the life of the mold. The test results showed that the coated surface had a significantly improved surface abrasion resistance and demolding performance. However, the coating did not significantly improved surface hardness and roughness with the coating. The adhesion strength of the coating was not degraded even there was a coefficient of thermal expansion (CTE) mismatch between the additively manufactured fiber reinforced composite and the coating material. The coated additively manufactured fiber reinforced composite mold was able to be used for multiple autoclave composite part manufacturing cycles. The coating covered most of the small voids on the mold surface and provided a more homogeneous surface compared to the non-coated mold, but the voids which could not be covered with the coating caused a chipped coating issue. Once the chipped coating occurred, the size of chipped coating got larger each time the tool was used for a composite part manufacturing cycle. Although the additional coating provided some improvements for the surface properties, the coating applied in this research could not be an ultimate solution to meet all the surface property requirements for composite part manufacturing mold.

Carbonization of biomass is a type of pyrolysis that allows for the formation of byproducts that have applications in many other industries [1]. In the field of materials science concerned with environmental impact intersecting with desirable material properties and performance, the process of carbonization in particular with commonplace biomass such as food waste is of great interest. In this thesis, pistachio shell was used as the organic biomass of choice for carbonization, and reinforcement was provided by titanium powder. These two materials were milled together at two different compositions and milling times. Experimental conditions consisted of replicates of three bulk samples made from uniaxially pressed powder mixtures heat treated from 800 °C up to 1200 °C in increments of 100 °C. Heat treatment occurred in a tube furnace with a heating rate of 5 °C/min up to the heat treatment temperature, holding the temperature for 1 hour, then ramping back down to room temperature, all in an inert atmosphere. XRD was performed on heat treated samples before polishing, while optical microscopy and SEM were performed after mounting and polishing. TGA was performed on the milled powders, while hardness was performed on the heat treated bulk samples after mounting and polishing. Results obtained suggested that increasing heat treatment temperature and milling time decreased carbon matrix porosity. In addition, greater amounts of titanium seemed to result in increased porosity. However, at increased temperature, more surface cracking was observed, leading to the conclusion that an excessively high temperature is detrimental to mechanical properties. Finally, rutile TiO2 was formed as a result of the heat treatment process. In considering environmental impact, cost, and mechanical properties, a balance must be maintained between higher temperature processing, duration, milling time, and porosity present due to these factors. Future work includes further investigations into processing parameters and characterization such as XPS and abrasion testing. / Master of Science / Carbonization of organic materials such as wood or nut shells can be explained in short as a decomposition that occurs when those materials are heated up without allowing them access to oxygen as in a normal combustion like a fire. Because of that, carbonization can produce useful products and materials of interest to many. Adding titanium to pistachio shell powder, performing compaction and carbonization, then further heating up those samples, resulted in composite materials consisting of mostly carbon char and particles inside that improve the properties. After testing multiple experimental conditions and analyzing them using equipment such as X-Ray Diffraction (XRD), Thermogravimetric Analysis (TGA), optical microscopes, Scanning Electron Microscopy (SEM)/Energy Dispersive Spectroscopy (EDS), and a hardness tester, some trends in properties and structure were observed. Generally, increasing heat treatment temperature and milling time will reduce porosity in the matrix. On the other hand, decreasing amount of Ti powder added seems to reduce porosity. However, too high of a heat treatment temperature seems to have a detrimental effect on the part manufactured (i.e. surface cracking). In addition, considering processing costs and time costs could discourage one from using a very high temperature to heat treat these samples. Therefore, it is important to balance amount of energy used to heat treat, time spent, and resulting porosity of the final product for its applications. Future work should be done to further determine the effects of processing parameters by making more samples to test the properties of. Other characterization techniques like X-Ray Photoelectron Spectroscopy (XPS) and abrasion testing could be good to determine the exact makeup of the particles in the composite as well as see the sample's performance in its intended application (i.e. brake pads).

Man-made materials such as fiber-reinforced composites (FRCs) can be tailored for optimum performance in product design applications in terms of strength and weight. The current work is aimed at studying the behaviors of composite laminates based on E-glass CSM (Chopped Strand Mat) or WRM (Woven Roving Mat) plies with a polyester resin for impact protection applications. Detailed mechanical characterization of CSM and WRM laminates till failure is carried out for tensile, compressive and shear loads by varying manufacturing process, number of plies, and laminate thickness. The effect of fiber volume fraction on mechanical properties is shown. The efficacy of CSM and WRM laminates as energy- absorbing countermeasures is studied by performing quasi-static and axial impact tests on cylindrical tubes made of the stated FRCs. In addition to load-displacement and specific energy absorption attributes, failure modes are of interest in such studies. The potential of FRC laminates for protection against projectile impact is investigated by performing low velocity impact perforation tests with a falling tup fitted with an indentor, and medium to high velocity projectile impact tests in a gas gun-based device. The valuable results generated are used for the validation of nonlinear finite element-based CAE (Computer-Aided Engineering) procedures including application of a multi-modal failure criterion for explicit dynamic analysis. The present study not only throws light on complex mechanical behavior of an important class of lightweight materials under static and dynamic loads, but also simulation tools for the design of impact safety countermeasures such as bullet-proof laminates and energy–absorbing components for automotive body structures.

Os objetivos deste estudo foram: 1) avaliar a resistência à flexão em três pontos de um compósito para uso direto (Filtek Z350 XT, 3M ESPE) e um para uso indireto (Signum, Heraeus, Kulzer) reforçados por uma ou duas camadas de fibras de polietileno (Ribbond -THM, Ribbond®) ou de vidro (Interlig, Ângelus) tratados termicamente (170°C por 10 minutos), comparados com os grupos controle (não reforçados por fibras e/ou não tratados termicamente; 2) avaliar a sorção, a solubilidade e a estabilidade de cor dos compósitos reforçados, após armazenamento em água destilada à 37°C por 14 dias. A estabilidade de cor foi avaliada com auxílio de um espectrofotômetro de contato dental (Vita EasyShade, Vident, CA, USA). Para o ensaio de resistência à flexão, foram confeccionados espécimes retangulares com dimensões de 12 x 2 x 2mm (n=10), com os seguintes fatores de variação: a) compósito (para uso direto ou indireto); b) tipo e número de camadas de fibras (vidro ou polietileno/uma ou duas camadas); c) submetidos ou não a tratamento térmico. O tratamento térmico foi realizado 24 horas após fotoativação em estufa à temperatura de 170°C por 10 minutos. O ensaio foi realizado 24 horas após fotoativação ou tratamento térmico. Para avaliação de sorção/solubilidade e estabilidade de cor, foram confeccionados espécimes em forma de disco com dimensões de 15 x 2mm (n=5), em que foram analisados os seguinte fatores: a) compósito (para uso direto ou indireto); b) tipo de fibra (vidro ou polietileno); c) número de camadas de fibras (uma ou duas). Foi realizada análise dos parâmetros de cor antes e após imersão em água deionizada por 14 dias. Os resultados foram analisados por ANOVA e teste de contraste de Tukey, com nível de significância de 5% e revelaram que a fibra de vidro, quando utilizada em duas camadas, propiciou os maiores valores de resistência à flexão para os dois compósitos testados (165,4 MPa Z350XT e 208,7MPa Signum ). O tratamento térmico não apresentou significância estatística quanto à resistência à flexão do compósito direto. Para o compósito para uso indireto (Signum ) foi encontrada diferença estatisticamente significante para o fator tratamento térmico, que indicou valores de resistência à flexão inferiores para os grupos tratados termicamente. O compósito para uso direto apresentou valor de sorção superior (33,6/cm3) ao do compósito para uso indireto (19,1/cm3). Para solubilidade, foi encontrada interação para os fatores compósito e tipo de fibra, indicando maiores valores para o compósito para uso direto associado à fibra de vidro. A análise de alteração de cor demonstrou maior valor de E para a fibra de polietileno (E =1,5) quando comparado à fibra de vidro (E=1,0). Concluiu-se que: 1) a adição de fibras propicia aumento dos valores de resistência à flexão de compósitos para uso direto e indireto, o aumento da resistência foi observado quando do uso de duas camadas de fibras; 2) o tratamento térmico à 170°C por 10 minutos não indicou melhora nas propriedades mecânicas dos compósitos reforçados; 3) adicionar fibras aos compósitos não aumentou os valores de sorção/solubilidade quando imersos em água; 4) Imersão em água não produziu alterações de cor relevantes para os compósitos reforçados com fibras se comparados aos sem fibras. / The aims of this study were: 1) to evaluate the flexural strength of one composite for direct use (Filtek Z350 XT, 3M ESPE) and one for indirect use (Signum, Heraeus, Kulzer) as a function of the reinforcement by one or two layers of polyethylene (THM-Ribbond, Ribbond ®) or glass fibers (Interlig, Angelus) submitted to heat treatment (170°C for 10 minutes) compared with control groups (not reinforced by fibers and/or not heat-treated; 2) evaluate water sorption, solubility and color stability of the reinforced composites, after storage in distilled water at 37°C for 14 days. Color stability was evaluated using a spectrophotometer (Vita Easyshade, Vident, CA, USA). For three point flexural bending test, rectangular specimens were prepared with dimensions of 12 x 2 x 2 mm (n=10), according to the following variation factors: a) composite (for direct or indirect use); b) type of fibers and number of layers (glass or polyethylene/one or two layers; c) subjected or not to heat treatment. The heat treatment was performed 24 hours after curing, in a furnace, at 170 ° C for 10 minutes. Tests were performed 24 hours after curing or heat treatment. To evaluate the water sorption/solubility and color stability, disc-shaped specimens were prepared with dimensions of 15 x 2 mm (n=5) according to the following variation factors: a) composite (for direct or indirect uses); b) fiber type (glass or polyethylene); c) number of fiber layers (one or two). Color parameters were analyze before and after immersion in deionized water for 14 days. The results were analyzed by ANOVA and Tukeys test with significance level of 5%, and indicated that the glass fiber when used in two layers, showed the highest flexural strength for the two tested composites (165.4 MPa - Z350XT and 208.7 MPa - Signum ). The heat treatment did not significantly affect the flexural strength of the direct composite. For the composite for indirect use (Signum ), a statistical significance for the factor heat treatment was found, indicating lower values of flexural strength for heat-treated groups. The composite for direct use showed higher water sorption value (33.6 /cm3) when compared to the composite for indirect use (19.1 /cm3). For solubility, a significant interaction was found for composite and fiber type, indicating higher values for direct composite and glass fiber. Color stability analysis showed higher color difference value for polyethylene fiber (E =1.5) when compared to glass fiber (E=1.0). It was concluded that: a) adding fibers increased the flexural strength values of the composites for direct or indirect use, the increase in strength was more pronounced when using two fiber layers; 2) heat treatment at 170 ° C for 10 minutes showed no improvement of the mechanical properties of fiber reinforced composites; 3) adding fibers to the composite did not increase the sorption/solubility after water immersion, 4) Immersion in water did not change the color of the fiber reinforced composites when compared with those without fibers.

O objetivo desse trabalho foi preparar compósitos de matriz de PCL reforçados com microfibrilas de PLA preparadas in situ a partir do controle da morfologia de blendas PLA/PCL. Embora a formação da morfologia fibrilar não tenha sido observada nas condições de extrusão empregadas, estudos do comportamento reológico de blendas de composição 50% PLA / 45% PCL / 5% de compatibilizante (% em massa) mostraram que microfibrilas de PLA podem ser obtidas entre 102 e 104 s-1. Assim, a técnica de reometria capilar foi utilizada para controlar a morfologia de blendas PLA/PCL. Compósitos de matriz de PCL reforçados com 5, 10, 20 e 30% (% em massa) de microfibrilas de PLA foram preparados em extrusora rosca simples, utilizando perfil de temperatura acima da temperatura de fusão do PCL, mas abaixo da temperatura de fusão do PLA, visando preservar a morfologia do PLA. O comportamento morfológico, térmico e mecânico dos compósitos foram avaliados por microscopia eletrônica de varredura (MEV), microscopia óptica com luz polarizada (POM), calorimetria exploratória diferencial (DSC), análise térmica dinâmico-mecânica (DMA) e ensaios mecânicos de tração e de impacto Izod. As curvas DSC mostraram um aumento no grau de cristalinidade da matriz de PCL com o aumento do teor de microfibrilas, o que provavelmente justifica os altos valores de módulo de Young determinados nos compósitos. A aplicação da Regra das Misturas comprovou que os compósitos fabricados exibiram boa orientação das microfibrilas na direção do esforço mecânico aplicado, com valores de módulos próximos ao limite superior da curva. No entanto, a adesão não uniforme entre a matriz e o reforço observada por MEV, resultou na queda da resistência à tração e resistência ao impacto dos compósitos, quando comparados ao PCL puro. A composição com 10% de microfibrilas apresentou um bom balanço de módulo de Young e resistência ao impacto, com potencial de viabilidade em uma série de aplicações biomédicas. / The aim of this work is to prepare PCL composites reinforced with PLA microfibrils prepared in situ from the morphology of PLA/PCL blends control. Although the formation of fibrillar morphology has not been observed under the extrusion conditions employed, studies of the rheological behavior of 50% PLA/ 45% PCL / 5% compatibilizer blends have shown that PLA microfibrils can be obtained between 102 and 104 s-1. Thus, the capillary rheometry technique was used to control the morphology of PLA /PCL blends. PCL composites reinforced with 5, 10, 20 and 30% (% by mass) PLA microfibrils were prepared in a single screw extruder using a temperature profile above the PCL melting temperature, but below the melt temperature of PLA, to preserve the PLA morphology. The morphology, thermal and mechanical behavior of the composites were evaluated by scanning electron microscopy (SEM), optical polarized light microscopy (POM), differential scanning calorimetry (DSC), dynamic mechanical-mechanical analysis (DMA) and mechanical tensile tests and Izod impact. DSC curves showed an increase in the degree of crystallinity of the PCL matrix with increasing the PLA microfibrils content, which probably justify the high Young\'s modulus values determined in the composites. The application of the Mix Rule proved that the composites showed good orientation of the PLA microfibrils in the direction of applied mechanical stress, presenting modules values near the upper limit of the curve. However, the non-uniform adhesion between the matrix and the reinforcement observed by MEV, caused the decrease of the tensile and impact strength when compared to pure PCL. The composition with 10% of PLA microfibrils exhibited a good balance of Young\'s modulus and impact strength, with potential viability in a number of biomedical applications.

Este trabalho apresenta duas técnicas de ensaios não-destrutivos por ultra-som realizados em um tanque com água para determinar as constantes elásticas de materiais compostos de fibra de vidro/epóxi. A primeira técnica é a transmissão direta utilizando um par de transdutores. A segunda é a técnica de pulso-eco, utilizando um único transdutor. A água do tanque atua como um acoplante para transferir a energia mecânica do transdutor para a amostra. Como o transdutor não fica em contato direto com a amostra, pode-se garantir um acoplamento constante. O sistema de medição dota de um dispositivo que permite medir a velocidade da onda elástica sob diferentes ângulos de incidência, através da rotação manual da amostra. Devido ao fenômeno de conversão de modos com incidência oblíqua na interface amostra-água, ensaios por ultra-som em tanques com água fornecem as informações necessárias para o cálculo das constantes elásticas em amostras de materiais anisotrópicos, numa dada direção, a partir das medições das velocidades longitudinal e de cisalhamento. Numa dada direção de propagação em um meio anisotrópico, existem três ondas elásticas distintas: uma longitudinal e duas de cisalhamento. Se as constantes elásticas do material são conhecidas, é possível obter as três velocidades em uma dada direção bastando resolver a equação de Christoffel. Invertendo a equação de Christoffel, obtém-se as constantes elásticas a partir das velocidades medidas em uma dada direção. Os experimentos são realizados com amostras de fibra de vidro/epóxi unidirecionais e bidirecionais, utilizando transdutores com freqüências de 0,5 MHz, 1 MHz e 2,25 MHz. Os resultados experimentais obtidos utilizando ambas as técnicas são comparados com um modelo denominado “Regra das Misturas" e com resultados da literatura. / In this work, two ultrasonic non destructive techniques were implemented in a water tank and used to determine the elastic constants of glass-epoxy composites samples. The first is the through-transmission technique implemented with a pair of ultrasonic transducers. The second is the back-reflection technique that uses a single transducer in pulse-eco mode. The water acts as a couplant and transfers the mechanical energy from the transducer to the sample. As the transducer is not in direct contact with the sample, we can guarantee a good coupling with the immersion technique. With the system device, it is possible to measure the velocities of the elastic waves in different angles by manually rotating the sample. Due to wave mode conversion phenomenon at the sample-water interface with oblique incidence, ultrasonic immersion testing provides information to calculate the elastic constants of the specimen by measuring longitudinal and shear wave speeds. There are three different modes of waves, one longitudinal and two shear waves, for any given direction of propagation in an anisotropic medium. If the elastic constants of a medium are known, it is possible to obtain the three wave speeds in particular propagations directions by solving the Christoffel equation. Inverting the Christoffel equation, it is possible to obtain the elastic constants from the measured wave speed in several specific directions of the anisotropic material. Measurements were carried out on unidirectional and bidirectional glass-epoxy composite samples, using transducers with central frequency of 0.5 MHz, 1 MHz, and 2.25 MHz. The experimental results obtained with both techniques are compared with a model denominated “Rule of Mixture" estimation and with the literature.

Carbon nanotubes (CNTs), discovered by Ijima in 1991, are one of the allotropes of carbon, and can be described as cylinders of graphene sheet capped by hemifullerenes. CNTs have excellent electrical, mechanical, thermal and optical properties and very small size. Due to their unique properties and small size, CNTs have a great potential for use in electronics, medical applications, field emission devices (displays,scanning and electronprobes/microscopes) and reinforced composites. CNTs can be grown by different methods from a number of carbon sources such as graphite, CO,C2H4, CH4 and camphor. Under certain conditions, a metallic catalyst is used to initiate the growth. The three main methods used to grow CNTs are: Arc-discharge, laser ablation (LA) and chemical vapour deposition (CVD). In the present work CNTs were grown from a mixture of camphor (C10H16O) and ferrocene (C10H10Fe) using Chemical Vapour Deposition (CVD) and argon was used as a carrier gas. The iron particles from ferrocene acted as catalysts for growth. The substrates used for the growth of CNTs were crystalline Si and SiO2 (Quartz) placed in a quartz tube in a horizontal furnace. Several parameters have been found to affect the CNT growth process. The effects of three parameters: growth temperature, carrier gas (Ar) flow rate and catalyst concentration were investigated in the present work in order to optimize the growth conditions with a simple and economical CVD setup. The samples were characterized using electron microscopy (EM), thermogravimetirc analysis (TGA), Raman and FTIR spectroscopy techniques. It was found that the quality and yield of the CNTs were best at 800°C growth temperature, 80sccm flow rate and 4% catalyst concentration.

The aim of this study was to improve the mechanical and electrical properties of conductive polymer composites. For this purpose, different studies were performed in this dissertation. In order to investigate the effects of the carbon nanotube (CNT) surface treatment on the morphology, electrical and mechanical properties of the composites, poly(ethylene terephthalate) (PET) based conductive polymer composites were prepared by using as-received, purified and modified carbon nanotubes in a twin screw extruder. During the purification of carbon nanotubes, surface properties of carbon nanotubes were altered by purifying them with nitric acid (HNO3), sulfuric acid (H2SO4), ammonium hydroxide (NH4OH) and hydrogen peroxide (H2O2) mixtures. Electron Spectroscopy for Chemical Analysis (ESCA) results indicated the removal of metallic catalyst residues from the structure of carbon nanotubes and increase in the oxygen content of carbon nanotube surface as a result of purification procedure. Surface structure of the purified carbon nanotubes was also modified by treatment with sodium dodecyl sulfate (SDS), poly(ethylene glycol) (PEG) and diglycidyl ether of Bisphenol A (DGEBA). Fourier Transformed Infrared Spectroscopy (FTIR) spectra of the carbon nanotube samples indicated the existence of functional groups on the surfaces of carbon nanotubes after modification. All composites prepared with purified and modified carbon nanotubes had higher electrical resistivities, tensile and impact strength values than those of the composite based on as-received carbon nanotubes, due to the functional groups formed on the surfaces of carbon nanotubes during surface treatment. In order to investigate the effects of alternative composite preparation methods on the electrical and mechanical properties of the composites, in-situ microfiber reinforced conductive polymer composites consisting of high density polyethylene (HDPE), poly(ethylene terephthalate) and carbon nanotubes were prepared in a twin screw extruder followed by hot stretching of PET/CNT phase in HDPE matrix. Composites were produced by using as-received, purified and PEG treated carbon nanotubes. SEM micrographs of the hot stretched composites pointed out the existence of in-situ PET/CNT microfibers dispersed in HDPE matrix up to 1 wt. % carbon nanotube loadings. Electrical conductivity values of the microfibrillar composites were higher than that of the composites prepared without microfiber reinforcement due to the presence of continuous PET/CNT microfibers with high electrical conductivity in the structure. To investigate the potential application of conductive polymer composites, the effects of surfactant usage and carbon nanotube surface modification / on the damage sensing capability of the epoxy/carbon nanotube/glass fiber composite panels during mechanical loadings were studied. Surface modification of the carbon nanotubes was performed by using hexamethylene diamine (HMDA). 4-octylphenol polyethoxylate (nonionic) (Triton X-100) and cetyl pyridinium chloride (cationic) (CPC) were used as surfactants during composite preparation. Electrical resistivity measurements which were performed during the impact, tensile and fatigue tests of the composite panels showed the changes in damage sensing capabilities of the composites. Surface treatment of carbon nanotubes and the use of surfactants decreased the carbon nanotube particle size and improved the dispersion in the composites which increased the damage sensitivity of the panels.