Στην παρούσα πτυχιακή παρασκευάστηκαν νανοσύνθετα υλικά TiO290-HALL10 και TiO280-HALL20 ώστε να εφαρµοστούν στην φωτοκαταλυτική αποδόµηση αερίων ρύπων. Τα νανοσύνθετα παρασκευάστηκαν µε τη µέθοδο διασποράς-επικάθισης του TiO2 και στους επιµήκεις κρυστάλλους του Αλλουσίτη.Η κρυσταλλική µορφή του TiO2 που συντέθηκε ήταν ο ανατάσης. Εφαρµόστηκαν οι παρακάτω τεχνικές:περιθλασιµετρία ακτίνων X(XRD), υπέρυθρη φασµατοσκοπία µετασχηµατισµού κατά Fourier(ATR-FTIR), ηλεκτρονική µικροσκοπία σάρωσης(SEM),προσδιορισµός µεγέθους και κατανοµής πόρων καθώς και ειδικής επιφάνειας. Tα νανοσύνθετα υλικά λόγω των ιδιοτήτων τους φαίνεται να είναι αποτελεσµατικά στην εφαρµογή τους στους αέριους ρύπους και έτσι µπορούν να χρησιµοποιηθούν και στις οργανικές πτητικές ενώσεις. / In this study were prepared nanocomposites TiO290-HALL10 and TiO280-HALL20 order to be applied in several environmental applications. The samples were prepared by dispersing TiO2 nanoparticles on the microfabers of alloysite. The crystal form of TiO2 that was synthesized was anatase. The nanocomposites were characterized using the following techniques:X-ray diffraction(XRD), scanning electron microscopy(SEM), attenuated total reflection using Fourier transform infrared spectroscopy (ATR-FTIR) and N2 surface analysis by BET. The nanocomposites due to their characteristics showing to be effective in decomposing air pollutants and can be used in volatile organic compounds.

Το αντικείμενο της παρούσας διατριβής ήταν η σύνθεση και ο χαρακτηρισμός νανοσύνθετων πολυμερικών μεμβρανών για την εφαρμογή τους σε κυψελίδες καυσίμου. Τα κελιά καυσίμου είναι ηλεκτροχημικές διατάξεις που μετατρέπουν με συνεχή τρόπο τη χημική ενέργεια ενός καυσίμου και ενός οξειδωτικού σε ηλεκτρική με ταυτόχρονη παραγωγή νερού. Μια πολύ σημαντική κατηγορία κελίων, είναι τα κελιά καυσίμου μεμβράνης πολυμερούς (PEMFC, Polymer Exchange Membrane Fuel Cell) τα οποία χρησιμοποιούν ως ηλεκτρολύτη μια πολυμερική μεμβράνη. Ανάλογα με τη θερμοκρασία λειτουργίας τα PEMFCs χωρίζονται σε αυτά που λειτουργούν σε θερμοκρασίες μέχρι 80ºC και στα υψηλής θερμοκρασίας που λειτουργούν στους 120-200ºC. Λειτουργία σε θερμοκρασίες πάνω από 100ºC έχει διάφορα πλεονεκτήματα, όπως αύξηση της κινητικής των αντιδράσεων, δυνατότητα χρησιμοποίησης άλλων καυσίμων εκτός από υδρογόνο, η χρήση όχι υψηλής καθαρότητας υδρογόνου και/ή χαμηλότερης ποσότητας του ακριβού καταλύτη Pt στα ηλεκτρόδια. Ένας από τους ηλεκτρολύτες για εφαρμογές σε PEMFC υψηλών θερμοκρασιών είναι το συμπολυμερές αρωματικού πολυαιθέρα με ομάδες πυριδίνης Advent TPS. Το συμπολυμερές Advent TPS έχει εξαιρετική ικανότητα σχηματισμού φιλμ, υψηλό Tg (>280ºC), υψηλή θερμική σταθερότητα (Τd>400ºC), υψηλή οξειδωτική σταθερότητα, ενώ μετά από εμποτισμό με Η3ΡΟ4 85% η ιοντική αγωγιμότητα είναι επίσης της τάξης του 10-2 S/cm. Στη παρούσα εργασία παρασκευάστηκαν νανοσύνθετες μεμβράνες, με την εισαγωγή υδρόφιλων, ανοργάνων προσθέτων στην υδρόφοβη πολυμερική μήτρα του Advent TPS με απώτερο σκοπό τη παρασκευή ενός νανοσύνθετου πολυμερικού ηλεκτρολύτη ο οποίος έχει την ικανότητα να εμποτίζεται με νερό βελτιώνοντας έτσι την αγωγιμότητα του συστήματος TPS/H3PO4.Τα ανόργανα εγκλείσματα που χρησιμοποιήθηκαν ήταν ο τροποποιημένος μοντμοριλλονίτης (H+-MMT), το οξείδιο του τιτανίου (ΤiΟ2) και το TiO2-P2O5. Οι νανοσύνθετες μεμβράνες εμφάνισαν ικανότητα εμποτισμού στο Η2Ο, οξειδωτική σταθερότητα και η ιοντική τους αγωγιμότητα ύστερα από τον εμποτισμό τους με Η3ΡΟ4 πλησίασε τη τιμή του Advent TPS. Επιπλέον στη περίπτωση των μεμβρανών με τον Η+-ΜΜΤ το H3PO4 συγκρατείται ισχυρότερα στη μεμβράνη, λόγω της μορφολογίας του ΜΜΤ, μειώνοντας έτσι το πρόβλημα διάχυσης του H3PO4 από τον ηλεκτρολύτη κατά τη διαδικασία της ψύξης του κελιού. / The objective of this thesis was the synthesis and characterization of nanocomposite membranes for use in fuel cells. Fuel cells are devices that convert the chemical energy of a fuel and an oxidant to electrical with simultaneous production of water. Polymer Exchange Membrane Fuel Cell (PEMFC) represents an important class of fuel cells, which uses a polymer membrane as its electrolyte. Operating above 150ºC has many advantages such as increased reaction rate, flexibility to use not so pure hydrogen as fuel and/or lower loading of the expensive metal (Pt) on the electrode. Advent TPS is an electrolyte for high temperature PEMFC that exhibits excellent film-forming properties, mechanical integrity, high glass transition temperature (2800C) as well as high thermal stability up to 4000 C. In addition to the above properties, Advent TPS shows high oxidative stability and acid doping ability, enabling proton conductivity in the range of 10-2 S/cm. The main goal of this thesis was to synthesize a nanocomposite electrolyte by adding inorganic, hydrophilic fillers in Advent TPS polymer matrix in order to fabricate a membrane that reveals ability to absorb water. The hydration of electrolyte can increase the proton conductivity. Inorganic fillers such as modified montmorillonite (H+-MMT), TiO2, TiO2-P2O5 were used. The nanocomposite membranes showed doping water ability, oxidative stability and proton conductivity in the range of 10-2 S/cm. Furthermore, the nanocomposite membranes with H+-MMT can retain the acid into the membrane, reducing the leaching problem during the cooling process of the cell. Finally the hybrid membranes were characterized with conventional techniques and showed thermal and mechanical stability.

This dissertation work addresses two important aspects of nanotechnology - stable dispersion and self-assembly of colloidal nanostructures. Three distinctly different types of nano-scaled materials have been studied: 0-dimensional ZnO quantum dots (QDs), 1-dimensional carbon nanotubes (CNTs), and 2-dimensional alpha-zirconium phosphate (ZrP) nanoplatelets. Specifically, highly crystalline ZrP layered compounds with differences in diameters have been synthesized and fully exfoliated into monolayer platelets with uniform thickness, followed by their self-assembly into liquid crystalline structures, i.e., nematic and smectic. A novel colloidal approach to debundle and disperse CNTs has been developed by utilizing nanoplatelets to gather and concentrate sonication energy onto nanotube bundles. In such a fashion, CNTs are fully exfoliated into individual tubes through physical means to preserve their exceptional physical properties. Moreover, monodisperse ZnO QDs with high purity have been synthesized through a simple colloidal approach. Exfoliated ZrP nanoplatelets are used to tune the dispersion of ligand-free ZnO QDs from micron-sized aggregates to an individual QD level depending on the ratio between nanoplatelets and QDs. Dynamic analysis suggests that the dispersion mechanism mainly involves the change of QD dispersion free energy due to the presence of nanoplatelets, so that QDs can interact favorably with the surrounding media. In addition, the nanoplatelet-assisted dispersion approach has been utilized to disperse QDs and CNTs into polymeric matrices. Dispersion - property relationship in polymer nanocomposites has been systematically investigated with emphasis on optical properties for QDs and mechanical properties for CNTs.

Computational Fluid Dynamics (CFD) codes are being increasingly used in the field of fire safety engineering. They provide, amongst other things, velocity, species and heat flux distributions throughout the computational domain. The various sub-models associated with these have been developed sufficiently to reduce the errors below 10%-15%, and work continues on reducing these errors yet further. However, the uncertainties introduced by using material properties as an input for these models are considerably larger than those from the other sub-models, yet little work is being done to improve these. Most of the data for these material properties comes from traditional (standard) tests. It is known that these properties are not intrinsic, but are test-specific. Thus, it can be expected that the errors incurred when using these in computations can be significant. Research has been held back by a lack of understanding of the basic factors that determine material flammability. The term “flammability” is currently used to encompass a number of definitions and “properties” that are linked to standardised test methodologies. In almost all cases, the quantitative manifestations of “flammability” are a combination of material properties and environmental conditions associated with the particular test method from which they were derived but are not always representative of parameters linked intrinsically with the tested material. The result is that even the best-defined parameters associated with flammability cannot be successfully introduced into fire models to predict ignition or fire growth. The aim of this work is to develop a new approach to the interpretation of standard flammability tests in order to derive the (intrinsic) material properties; specifically, those properties controlling ignition. This approach combines solid phase and gas modelling together with standard tests using computational fluid dynamics (CFD), mass fraction of flammable gases and lean flammability limits (LFL). The back boundary condition is also better defined by introducing a heat sink with a high thermal conductivity and a temperature dependant convective heat transfer coefficient. The intrinsic material properties can then be used to rank materials based on their susceptibility to ignition and, furthermore, can be used as input data for fire models. Experiments in a standard test apparatus (FPA) were performed and the resulting data fitted to a complex pyrolysis model to estimate the (intrinsic) material properties. With these properties, it should be possible to model the heating process, pyrolysis, ignition and related material behaviour for any adequately defined heating scenario. This was achieved, within bounds, during validation of the approach in the Cone Calorimeter and under ramped heating conditions in the Fire Propagation Apparatus (FPA). This work demonstrates that standard flammability and material tests have been proven inadequate for the purpose of obtaining the “intrinsic” material properties required for pyrolysis models. A significant step has been made towards the development of a technique to obtain these material properties using test apparatuses, and to predict ignition of the tested materials under any heating scenario. This work has successfully demonstrated the ability to predict the driving force (in-depth temperature distribution) in the ignition process. The results obtained are very promising and serve to demonstrate the feasibility of the methodology. The essential outcomes are the “lessons learnt”, which themselves are of great importance to the understanding and further development of this technique. One of these lessons is that complex modelling in conjunction with current standard flammability test cannot currently provide all required parameters. The uncertainty of the results is significantly reduced when using independently determined parameters in the model. The intrinsic values of the material properties depend significantly on the accuracy of the model and precision of the data.

Chitin is an important reinforcing component in load-bearing structures in many organisms such as insects and crustaceans (i.e. shrimps, lobsters, crabs etc.). It is of increasing interest for use in packaging materials as well as in biomedical applications. Furthermore, biological materials may inspire the development of new man-made material concepts. Chitinmolecules are crystallized in extended chain conformations to form nanoscale fibrils of about 3 nm in diameter. In the present study, novel materialshave been developed based on a new type of chitin nanofibers prepared from the lobster exoskeleton. Improved understanding about effects of chitin from crustaceans and chitin material preparation on structure is provided through Atomic Force Microscopy(AFM) (paper I&amp;II), Scanning Transmission Electron Microscopy(STEM) (paper I&amp;II), X-Ray Diffraction (XRD), Intrinsic Viscosity, solid state 13C Nuclear Magnetic Resonance (NMR) (paper II), Field Emission Scanning Electron Microscopy(FE-SEM) (paper I, II, III, IV &amp; V), Ultraviolet-Visible Spectrophotometryand Dynamic Light Scattering (DLS) (paper III). The presence of protein was confirmed through colorimetric method(paper I &amp; II). An interesting result from the thesis is the new features of chitin nanofiber including small diameter, high molar mass or nanofiber length,and high purity. The structure and composition of the nanofibers confirms this (paper I &amp; II). Furthermore, the structure and properties of the corresponding materials confirm the uniqueness of the present nanofibers: chitin membrane (I &amp; II), polymer matrix composites (III),and hydrogels (paper IV). Improved mechanical properties compared with typical data from the literature were confirmed for chitin nanofiber membranes in paper II, chitin-chitosan polymer matrix composites in paper III, and chitin hydrogel in paper IV. Mechanical tests included dynamic mechanical analysis and uniaxial tensile tests. Mechanical properties of chitin hydrogels were evaluated based onrheological and compression properties (paper IV). The values were the highest reported for this kind of chitin material. Furthermore, the relationships between materials structure and properties were analyzed. For membranes and polymer matrix nanocomposites, the degree of dispersion is an important parameter. For the hydrogels, the preparation procedure is very simple and has interesting practical potential. Chitin-binding characteristics of cuticular proteins areinteresting fornovel bio-inspired material development. In the present work(paper V), chitin nanofibers with newfeaturesincluding high surface area and low protein content were combined with resilin-like protein possessing the chitin-binding characteristics. Hydrated chitin-resilin nanocomposites with similar composition as in rubber-like insect cuticles were prepared. The main objective was to improve understanding on the role of chitin-binding domain on mechanical properties. Resilin is a rubber-like protein present in insects. The exon I (comprising 18 N-terminal elastic repeat units) together with or without the exon II (a typical cuticular chitin-binding domain) from the resilin gene CG15920 found in Drosophila melanogasterwere cloned and the encoded proteins were expressed as soluble products in Escherichia coli.Resilin-like protein with chitin-binding domain (designated as ResChBD) adsorbedin significant amount to chitin nanofiber surface andprotein-bound cuticle-like soft nanocomposites were formed. Although chitin bindingwas taking place only in proteinswith chitin-binding domain, the global mechanical behavior of the hydrated chitin-resilin nanocomposites was not so sensitive to this chitin-resilin interaction. In summary, chitin is an interesting material component with high potential as mechanical reinforcement in a variety of nanomaterials. The present study reports the genesisof novel chitin nanofibers and outlines the basic relationships between structure and properties for materials based on chitin. Future work should be directed towards both bio-inspired studies of the nanocomposite chitin structures in organisms, as well as the industrial applications of chitin waste from the food industry. Chitin nanofibers can strengthen the properties of materials, andprovide optical transparency as well as biological activities such as antimicrobial properties. / <p>QC 20141110</p>

Piezoresistivity in conductive polymer nanocomposites occurs because of the disturbance of particle networks in the polymer matrix. The piezoresistance effect becomes more prominent if the matrix material is compliant making these materials attractive for applications that require flexible force and displacement sensors such as e-textiles and biomechanical measurement devices. However, the exact mechanisms of piezoresistivity including the relationship between the matrix polymer, conductive particle, internal structure and the composite’s piezoresistance need to be better understood before it can be applied for such applications. The objective of this thesis is to report on the development of conductive polymer nanocomposites for use as flexible sensors and electrodes. Electrically conductive and piezoresistive nanocomposites were fabricated by a scalable melt compounding process. Particular attention was given to elucidating the role of matrix and filler materials, plastic deformation and porosity on the electrical conduction and piezoresistance. These effects were parametrically investigated through characterizing the morphology, electrical properties, rheological properties, and piezoresistivity of the polymer nanocomposites. The electrical and rheological behavior of the nanocomposites was modeled by the percolation-power law. Furthermore, a model was developed to describe the piezoresistance behavior during plastic deformation in relation to the stress and filler concentration.

A Portuguese clay (BRN) from the North East city of Bragança was collected and characterized in terms of health treatment and applied towards the preparation of nanocomposites with Polylactide (PLA). The silt-clay fraction of BRN is mainly composed of smectite with less illite, kaolinite and other minerals. The physicochemical properties are applicable for the topical applications and are mainly influenced by smectite. With the hazardous elements present, further bioavailability tests should be conducted. PLA nanocomposites with BRN and Wyoming montmorillonite SWy-2 (MMT) were respectively prepared through the solution casting method with ultrasonic stirring and using cetyltrimethylammonium bromide (CTAB) as the surfactant. The X-ray diffraction patterns show the exfoliated structures in most samples. Thermal gravimetric analysis reveals the increased thermal stability of the nanocomposites. The complexes were also characterized by nitrogen adsorption, infrared analysis and nuclear magnetic resonance for comparing the differences between BRN and MMT.

This thesis focuses on the generation of fine cell polymer foams using a heterogeneous nucleating agent (nanoclay), appropriate polymer blending strategies and accurate control of foam processing parameters. Foaming behaviour of HMSPP/ clay nanocomposites and HMS-PP/EVA/clay nanocomposite blends is studied using a batch and a continuous foam injection moulding system. Morphological studies using TEM and SEM led to a few interesting deductions. It is very difficult to attain complete exfoliation in case of HMS-PP/clay nanocomposites even at low clay loadings due to a non polar nature and low graft efficiencies of HMS-PP matrix. The addition of clay to an immiscible blend of HMS-PP/EVA results in compatibilization between the dispersed and the continuous phase. Nanocellular foams (290 nm) were subsequently generated in the batch process at a foaming temperature of 147oC and 25 seconds foaming time. The addition of immiscible EVA-28 to the HMS-PP matrix in presence of clay particles further results in reduction of foam cell sizes to 100 nm. The effect of gas concentration, foaming temperature, injection pressure, and foaming time on foam cell size was studied. It was found that the foam cell size was highly sensitive to the injection pressure at the mould gate (hence pressure drop rate) and foaming temperature. The cell size linearly decreased with increase in gas concentration and foaming time. The sensitivity of foam cell sizes to changes in processing parameters decreases with increase in clay concentration. The effect of addition of clay particle on gas solubility was modelled using the Guggenheims contact fraction approach and subsequently a new model to predict gas solubility was developed using statistical thermodynamic tools. Additionally the effect of shear and extensional rheology on foam cell morphology was modelled. It was found that the viscoelasticity of the polymer matrix greatly affects cell sizes as compared to extensional viscosity.

Thesis (Ph. D.)--University of Texas at El Paso, 2009. / Title from title screen. Vita. CD-ROM. Includes bibliographical references. Also available online.

Thesis (M. S.)--Materials Science and Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Gerhardt, Rosario; Engineering: Dr. Arun M. Gokhale; Engineering: Dr. Preet Singh; Engineering: Dr. Mohan Srinivasarao; Engineering: Dr. Meisha Shofner.