Environmental concerns arising from the use of non-degradable plastics have resulted in search for suitable substitutes. The thesis deals with new nanostructured composites based on reinforcement of nanocellulose whiskers in "green" polymers such as xylan. Since the reinforcement filler and the matrix are both biobased and are thereby environmental friendly. Xylan incorporated with cellulose whiskers films provided with improved water and oxygen barrier properties. It appears that the high degree of crystallinity of cellulose whiskers, dense composite structure formed by the whiskers and rigidly hydrogen-bonded cellulose whiskers can cause cellulose whiskers to form integrated matrix which contribute to substantial benefit in the overall reduction of transmission rate. The spectral data obtained for the NCW/xylan nanocomposite films showed that the amount of xylan adsorbed to cellulose increases with the addition of NCW in the matrix. In addition, NMR T2 relaxation experiments studies were conducted to investigate the change in the nature of carbohydrate-water interactions as a result of NCW incorporation. These results facilitated an improved understanding of the mechanisms involved in the superior barrier and mechanical properties of xylan-whisker nanocomposite films. XRD studies show that when a xylan-whisker nanocomposite films is formed the mixing occurs on the atomic scale and NCW loading increases the matrix crystallinity.

This research is directed toward understanding the effect of nanoparticle attributes and polymer morphology on the properties of the nanocomposites with analogous nanoparticle chemistry. In order to develop this understanding, polymer nanocomposites containing calcium phosphate nanoparticles of different specific surface areas and shapes were fabricated and characterized through thermal and thermomechanical techniques. Nanoparticles were synthesized using reverse microemulsion technique. For nanocomposites with different surface area particles, the mobility of amorphous polymer chains was restricted significantly by the presence of particles with an interphase network morphology at higher loadings. Composites fabricated with different crystallinity matrices showed that the dispersion characteristics and reinforcement behavior of nanoparticles were governed by the amount of amorphous polymer fraction available. The study conducted on the effect of nanoparticle shape with near-spherical and nanofiber nanoparticles illustrated that the crystallization kinetics and the final microstructure of the composites was a function of shape of the nanoparticles. The results of this research indicate that nanoparticle geometry and matrix morphology are important parameters to be considered in designing and characterizing the structure-property relationship in polymer nanocomposites.

In view of the unfavorable panorama of actual energy supply practices, alternative sustainable energy sources and conversion approaches have acquired noteworthy significance in recent years. Among these, proton exchange membrane fuel cells (PEMFCs) are being considered as a pivotal building block in the transition towards a sustainable energy economy. The proton exchange membrane (PEM) is a vital component, as well as a performance-limiting factor, of the PEMFC. Consequently, the development of high performance PEM materials is of upmost importance for the advance of the PEMFC field. In this work, alternative PEM materials based on semi-interpenetrated networks from blends of poly(vinyledene fluoride) (PVDF) and sulfonated crosslinked acrylic polyelectrolytes (PE), as well as tri-phase PVDF/PE/zirconium-based composites, are studied. To alleviate the burden resulting from the vast number of possible combinations of the different precursors utilized in the preparation of the membranes, custom high throughput screening systems have been developed for their characterization. By coupling the data spaces obtained via these systems with the appropriate statistical and data analysis tools it was found that, despite not being directly involved in the proton transport process, the inert PVDF phase plays a major role on proton conductivity. Particularly, a univocal inverse correlation between the PVDF crystalline characteristics (i.e., crystallinity and crystallite size) and melt viscosity, and membrane proton conductivity was discovered. Membranes based on highly crystalline and viscous PVDF homopolymers exhibited reduced proton conductivity due to precluded segmental motion of the PE chains during crosslinking. In addition, a maximum effective amount of PE (55-60wt%) beneficial for proton conductivity was revealed. In the case of composite membranes, despite the fact that nanoparticle dispersion was thermodynamically limited, a general improvement in proton conductivity was evidenced at low to medium nanoparticle loadings (0.5 to 1wt%) in comparison to non-hybrid PVDF/PE references. This beneficial effect was particularly noticeable in membranes based on PVDF homopolymers (7% to 14.3% increment), where the nanoparticles induced a "healing" effect by providing proton-conducting paths between non-crosslinked PE channels separated by dense PVDF areas resulting from large PVDF crystallites. In general, the results presented herein are promising for the development of new cost-effective alternative PEMs.

Electrically conductive polymer composites are suitable for use in the manufacture of antistatic products and components for electronic interconnects, fuel cells and electromagnetic shielding. The most widely used processing techniques for producing electrically conductive polymer composites place an inherent constraint on the geometry and architecture of the part that can be fabricated. Hence, this thesis investigates selective laser sintering (SLS), a rapid prototyping technique, to fabricate and characterize electrically conductive nanocomposites of Nylon-12 filled with 4% by weight of carbon black. The objective of the dissertation was to study the effects of the SLS process on the microstructure and properties of the nanocomposite. The effect of laser power and the scan speed on the flexural modulus and part density of the nanocomposite was studied. The set of parameters that yielded the maximum flexural modulus and part density were used to fabricate specimens to study the tensile, impact, rheological and viscoelastic properties. The electrical conductivity of the nanocomposite was also investigated. The thermo-mechanical properties and electrical conductivity of the nanocomposites produced by SLS were compared with those produced by extrusion-injection molding. The structure and morphology of the SLS-processed and extrusion-injection molded nanocomposites were characterized using gas pycnometry, gel permeation chromatography, differential scanning calorimetry, electron microscopy, polarized light microscopy and x-ray diffraction. Physical models were developed to explain the effects of the processing technique on the structure and properties of the nanocomposites. Finally, a one-dimensional heat transfer model of the SLS process that accounted for sintering-induced densification and thermal degradation of the polymer was implemented in order to study the variation in part density with respect to the energy density of the laser beam. This dissertation demonstrated that SLS can be successfully used to fabricate electrically conductive polymer nanocomposites with a relatively low percolation threshold. This capability combined with the ability of SLS to fabricate complicated three-dimensional objects without part-specific tooling could open up several new opportunities.

In the past two decades polymer/clay nanocomposites (PCNs) have emerged as promising materials that exhibit remarkably improved properties when compared to conventional composites and pristine polymers. Such improvements strongly depend on the dispersion of clay nanoparticles in the polymer matrix. In spite of great efforts expended in characterizing clay dispersion, effective, simple and quantitative techniques are still needed. This work addresses this challenge by presenting new aspects of 1H solid-state NMR for quantifying clay dispersion in PCNs filled with clay containing paramagnetic ions. Employing these 1H solid-state NMR methods, some structure-processing-deformation relationships of PCNs were derived, and basic insights into nuclear relaxation and spin diffusion in PCNs were gained as well. Detailed models and analyses were described for 1H spin-lattice relaxation in the presence of paramagnetic clays in PCNs. Relaxation recovery was analytically correlated to clay dispersion in two ways: one is the initial relaxation recovery which is related to clay surface area, and the other is the spin-lattice relaxation time which is related to interparticle spacing. These two NMR observables were employed to quantitatively observe the evolution of clay morphology in poly(propylene)/clay (PP/MMT) nanocomposites upon equibiaxial stretching, as well as upon in situ uniaxial deformation. The initial relaxation recovery was independently utilized to determine the polymer-clay interfacial surface area and the degree of clay exfoliation. We demonstrated the capabilities of our models in quantitatively characterizing several materials, including poly(vinyl alcohol), nylon 6, poly(å-caprolactone) (PCL), poly(lactic acid) (PLA) and PP nanocomposites. These results were used to examine the dependence of clay morphology upon processing (strain ratio, strain rate, temperature), deformation (extension), component characteristics (polymer molecular weight, clay surface modification) and clay content. Effects of paramagnetic Fe3+ concentration and external magnetic field strength on 1H spin-lattice relaxation in PCNs were also investigated and discussed. In particular, low field separates the initial relaxation recovery into two stages: one related to clay content and the other related to the polymer-clay interfacial surface area. The low field was observed to enhance the paramagnetic contribution to the spin-lattice relaxation rate, increasing its sensitivity to clay morphology. In addition, measurements of long-distance spin diffusion coefficients for a variety of polymers and paramagnetic characteristics of organically modified clay were explored. Overall, the utility of NMR relaxometry in characterizing PCNs has been significantly expanded and successfully demonstrated in this dissertation.

Neste trabalho foram investigadas a morfologia, a estrutura cristalina e as propriedades térmicas e reológicas de uma blenda de polipropileno isotático (i-PP) e copolímero de etileno, propileno e dieno (EPDM), preparada em laboratório, por processo de mistura reativa, com a adição de argila Cloisite 15A e submetida à deformação uniaxial por tração e compressão à temperatura ambiente. As técnicas utilizadas para caracterização foram a Difração de Raios-X (DRX), o Espalhamento de Raios-X de Baixo Ângulo (SAXS), a Microscopia Eletrônica de Varredura (MEV), a Microscopia Eletrônica de Transmissão (MET), a Calorimetria Diferencial de Varredura (DSC), a Análise Termogravimétrica (TGA) e a Espectroscopia no Infravermelho por Transformada de Fourier (FTIR). A MEV permitiu observar que ocorreu interação entre a blenda e a argila, o que foi corroborado pelas imagens de MET, a qual permitiu verificar a existência de argila intercalada entre as lamelas da blenda, bem como a existência de alguns pontos de aglomeração da argila na blenda. A análise de DRX também confirmou a intercalação da argila pelo polímero. Da mesma forma, o SAXS nos mostrou que existe um aumento no espaçamento lamelar, com a introdução da argila. Por fim, foi observado também que a deformação uniaxial por compressão do material provocou a quebra de domínios cristalinos na blenda, enquanto na deformação uniaxial por tração o grau de cristalinidade inicial foi mantido. / Submitted by Ana Guimarães Pereira (agpereir@ucs.br) on 2015-10-07T17:04:58Z No. of bitstreams: 1 Dissertacao Arthur Thompson.pdf: 2821768 bytes, checksum: 1e4375e8bb47bdeb964a7ef45a77ae48 (MD5) / Made available in DSpace on 2015-10-07T17:04:58Z (GMT). No. of bitstreams: 1 Dissertacao Arthur Thompson.pdf: 2821768 bytes, checksum: 1e4375e8bb47bdeb964a7ef45a77ae48 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior. / In this work were investigated the morphological, themal and rheological properties of a isotactic polypropylene/ethylene-propylene-diene terpolymer rubber/nanoclay Cloisite 15A composite, prepared by mixed melt and submitted to uni-axial plane-strain compression and stretching deformations, both at room temperature. The techniques used for characterization were Wide Angle X-ray Diffraction (WAXD), Small Angle X-ray Scattering (SAXS), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis and Fourier Transform Infrared Spectroscopy (FTIR). The SEM images showed that interaction occured between the clay and the blend, which was corroborated by the TEM images, where it was show the intercalation between blend and clay, as well as the existence of some points of clay’s aglomeration in the blend. The WAXD analysis also confirmed the intercalation of the clay in the blend. Furthermore, the SAXS showed an increase in the lamellar long period with the addition of clay. With the mapping of chemical elements we could see the dispersion of clay’s organometalics into the blend. Finally, it was verified that the uni-axial plain strain compression deformation of the composites contribute to the break of crystalline domains in the blend, while in the uniaxial stretching deformation the degree of initial cristallinity was sustained.

Thesis (MTech (Biomedical Technology))--Cape Peninsula University of Technology, 2013. / Newly developed and commercial dental resins which are commonly used nowadays have to be tested for their antimicrobial susceptibility. The purpose of this in vitro study was to investigate the antimicrobial activity of a titanium oxide (Ti02) nano-composite which was prepared with different antibacterial substances and used as restoratives in dentistry to combat certain selected bacteria that are considered the principle causes of some tooth diseases, for example, tooth decay and to prevent unsuccessful dental restoration. The Ti02 nano-composite was prepared and divided into four groups: The first group was an untreated Ti02 nano-composite. The second group was silane-treated Ti02 nano-composite. The third group was treated Ti02 nano-composite which was combined with chlorhexidine gluconate (CHxG). The fourth group was treated Ti02 nano-composite which was combined with benzalkonium chloride (BzCI).

Neste trabalho foram investigadas a morfologia, a estrutura cristalina e as propriedades térmicas e reológicas de uma blenda de polipropileno isotático (i-PP) e copolímero de etileno, propileno e dieno (EPDM), preparada em laboratório, por processo de mistura reativa, com a adição de argila Cloisite 15A e submetida à deformação uniaxial por tração e compressão à temperatura ambiente. As técnicas utilizadas para caracterização foram a Difração de Raios-X (DRX), o Espalhamento de Raios-X de Baixo Ângulo (SAXS), a Microscopia Eletrônica de Varredura (MEV), a Microscopia Eletrônica de Transmissão (MET), a Calorimetria Diferencial de Varredura (DSC), a Análise Termogravimétrica (TGA) e a Espectroscopia no Infravermelho por Transformada de Fourier (FTIR). A MEV permitiu observar que ocorreu interação entre a blenda e a argila, o que foi corroborado pelas imagens de MET, a qual permitiu verificar a existência de argila intercalada entre as lamelas da blenda, bem como a existência de alguns pontos de aglomeração da argila na blenda. A análise de DRX também confirmou a intercalação da argila pelo polímero. Da mesma forma, o SAXS nos mostrou que existe um aumento no espaçamento lamelar, com a introdução da argila. Por fim, foi observado também que a deformação uniaxial por compressão do material provocou a quebra de domínios cristalinos na blenda, enquanto na deformação uniaxial por tração o grau de cristalinidade inicial foi mantido. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior. / In this work were investigated the morphological, themal and rheological properties of a isotactic polypropylene/ethylene-propylene-diene terpolymer rubber/nanoclay Cloisite 15A composite, prepared by mixed melt and submitted to uni-axial plane-strain compression and stretching deformations, both at room temperature. The techniques used for characterization were Wide Angle X-ray Diffraction (WAXD), Small Angle X-ray Scattering (SAXS), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis and Fourier Transform Infrared Spectroscopy (FTIR). The SEM images showed that interaction occured between the clay and the blend, which was corroborated by the TEM images, where it was show the intercalation between blend and clay, as well as the existence of some points of clay’s aglomeration in the blend. The WAXD analysis also confirmed the intercalation of the clay in the blend. Furthermore, the SAXS showed an increase in the lamellar long period with the addition of clay. With the mapping of chemical elements we could see the dispersion of clay’s organometalics into the blend. Finally, it was verified that the uni-axial plain strain compression deformation of the composites contribute to the break of crystalline domains in the blend, while in the uniaxial stretching deformation the degree of initial cristallinity was sustained.

Orientadores: Júlio Roberto Bartoli, Elizabeth Grillo Fernandes / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-22T08:51:19Z (GMT). No. of bitstreams: 1 Cecci_RicardoRodrigoRamos_M.pdf: 4182332 bytes, checksum: 4424cc557c439a1602d15a95921a2b25 (MD5) Previous issue date: 2013 / Resumo: Nanotubos de carbono (NTCs) apresentam características interessantes para aplicações em eletrodos transparentes. Quando dispersos em escala nanométrica são transparentes ao espectro da luz visível e são capazes de conduzir eletricidade após atingirem percolação em matrizes poliméricas isolantes. Neste trabalho, é descrito o uso de nanotubos de carbono de camadas múltiplas (NTCMs) na produção de filmes poliméricos flexíveis transparentes e condutores como alternativa ao uso do óxido de índio dopado com estanho (ITO) em células solares orgânicas. Os nanotubos foram dispersos e purificados em solução aquosa de dodecil sulfato de sódio (SDS) pelos processos de sonicação e centrifugação, e a dispersão monitorada por espectroscopia UV-Vis e potencial ?. Os nanocompósitos foram produzidos via polimerização in situ do monômero metacrilato de metila (MMA) na presença de 0 a 1% p/p NTCs e os filmes depositados através da técnica de revestimento por rotação a alta velocidade (spin coating). A reação de polimerização foi acompanhada pela calorimetria exploratória diferencial (DSC). Verificou-se que na presença de NTCs, a taxa de conversão do monômero é acelerada. A cinética de degradação térmica foi avaliada pelo método de Broido utilizando a análise termogravimétrica (TGA). Foi observado que os NTCs aumentam a estabilidade térmica do PMMA, retardando a degradação por despolimerização. Estudos por espectroscopia FT-IR mostraram uma banda de absorção em 1601 cm-1, (C=C), a qual não é característica do PMMA, indicando que os NTCs participam da polimerização do PMMA. Para concentrações de até 1% p/p de NTCs, os filmes PMMA/NTC apresentaram excelentes propriedades ópticas. Ou seja, baixo coeficiente de absorção, na ordem de 103 cm-1, altos valores de gap óptico (Eopt), entre 3,2 e 4,14 eV, e alta transparência por todo espectro visível, entre 88 e 93%. Nas mesmas concentrações, foi observada uma diminuição substancial na resistividade elétrica dos filmes em 8 ordens de grandeza (de 1016 para 108 ?/quadrado), comparados ao filme de PMMA puro. Entretanto, a faixa de resistividade alcançada ainda é típica de materiais isolantes. Estudos de otimização poderiam originar filmes PMMA/NTC como uma alternativa promissora para ITO em OPVs / Abstract: Carbon nanotubes (CNTs) have interesting features for applications in transparent electrodes. When dispersed at the nanoscale, they become transparent within the visible range and are able to conduct electricity after reaching the percolation threshold in an insulating polymer matrix. In this work, the use of multi-walled carbon nanotubes (MWCNTs) is described for the production of flexible transparent conducting polymer films as an alternative to the use of indium-tin oxide (ITO) in organic solar cells. The nanotubes were dispersed and purified in an aqueous solution of sodium dodecyl sulfate (SDS) by the process of sonication and centrifugation, and the dispersion monitored by UV-Vis spectroscopy and ? potential. The nanocomposites were produced via in situ polymerization of the monomer methyl methacrylate (MMA) in the presence of 0 to 1 %wt. of CNTs. The films were deposited by the spin-coating technique. The polymerization reaction was monitored by differential scanning calorimetry (DSC). It was found that in the presence of CNTs, the conversion rate of the monomer is accelerated. The kinetics of thermal degradation was measured according to the Broido's method by using thermogravimetric analysis (TGA). It was observed that CNTs increase the thermal stability of PMMA, slowing degradation by depolymerization. FT-IR data showed an absorption band at 1601 cm-1 (C = C), which is not characteristic of PMMA, indicating that the CNTs takes place in the polymerization of PMMA. For concentrations up to 1wt% of CNTs, the PMMA/CNT films had excellent optical properties, i.e., a low absorption coefficient in the order of 103 cm-1, wide optical gap (Eopt) between 3.2 and 4.14 eV, and high transparency within the whole visible range, between 88 and 93%. In the same concentrations, the electrical resistivity of the films dropped by 8 orders of magnitude (from 1016 to 108 ?/sqr), compared to the pure PMMA film. Even though this electrical resistivity value is typical of insulating materials, further optimization studies could provide PMMA/CNT films as a promising alternative to ITO in OPV / Mestrado / Ciencia e Tecnologia de Materiais / Mestre em Engenharia Química

As the miniaturization of functional devices in integrated circuit (IC) continues to scale down to sub-nanometer size, the process complexity increases and makes materials characterization difficult. One of our research effort demonstrates the development and application of novel Multiple Internal Reflection Infrared Spectroscopy (MIR-IR) as a sensitive (sub-5 nm) metrology tool to provide precise chemical bonding information that can effectively guide through the development of more efficient process control. In this work, we investigated the chemical bonding structure of thin fluorocarbon polymer films deposited on low-k dielectric nanostructures, using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Complemented by functional group specific chemical derivatization reactions, fluorocarbon film was established to contain fluorinated alkenes and carbonyl moieties embedded in a highly cross-linked, branched fluorocarbon structure and a model bonding structure was proposed for the first time. In addition, plasma induced damage to high aspect ratio trench low-k structures especially on the trench sidewalls was evaluated both qualitatively and quantitatively. Damage from different plasma processing was correlated with Si-OH formation and breakage of Si-CH3 bonds with increase in C=O functionality. In another endeavor, TiN hard mask defect formation after fluorocarbon plasma etch was characterized and investigated. Finding suggest the presence of water soluble amines that could possibly trigger the formation of TiN surface defect. An effective post etch treatment (PET) methods were applied for etch residue defect removal/suppression.