The goal of this research is to investigate the combined effects of glass fibre reinforcement and molecular orientation in polypropylene-short glass fibre composites. Specimens have been fabricated using the injection moulding process and drawn using a small die drawing rig. The effects of die drawing on the fibre composites are complex, with the drawing process orienting both the polymer molecules and the glass fibres. This may be accompanied by the creation of voids in the polymer matrix and their destruction in the compressive stress field thus restoring the interfacial contact area between fibre and matrix. Unfilled and short glass fibre filled polypropylene specimens, with fibre content 7% wt, 13%wt, 27%wt, and 55%wt, were injection moulded prior to the die drawing process. An experimental program of die drawing within an oven at elevated temperature was conducted for polypropylene filled to various levels and at different strain rates. The specimens drew to draw ratios in the range ¿=1.41 to ¿=5.6. Mechanical characterization of the test materials has been conducted by examining the tensile stress strain and fracture behaviour under uniaxial conditions. The influence of glass fibre content and drawing conditions (draw ratio) on the fracture toughness and crack propagation was investigated using the double edge notched fracture test. The notch lengths ranged from 1.5 to 2.5 mm for 10 mm wide specimens. The critical stress intensity factor increased as the fibre content increased up to a limiting filler level. The fracture toughness of both unfilled and fibre filled polypropylene were found to be highly dependent on draw ratio. The results were analysed to find out the optimal draw ratio and fibre content that yielded the maximum modulus, strength and fracture toughness. Data showed that, at a given draw ratio, modulus, strength and fracture toughness increased with increasing fibre content to a maximum and then decreased. The optimum material was obtained at a draw ratio of 2.5 and filler loading 13wt%.

No description available.

Cavity ring-down spectroscopy (CRDS) and cavity enhanced absorption spectroscopy (CEAS) are two well-established absorption spectroscopic techniques originally developed for gas-phase samples. Condensed-phase applications of these techniques still remain rare, complicated as they are by additional background losses induced by condensed-phase samples as well as the intracavity components in which the sample is constrained. This thesis is concerned with the development and application of optical-cavity-based techniques in the condensed phase. Polarization-dependent evanescent wave CRDS (EW-CRDS) has been used to study the molecular orientation at the solid/air and solid/liquid interfaces. An increase in average orientation angle with respect to the surface normal has been observed for both methylene blue and coumarin molecules as a function of coverage at the fused silica/air interface. An orientation-angle-dependent photobleaching of pyridin molecules at the fused silica/methanol interface have also been observed. EW-CRDS has also been used to monitor slow in situ photobleaching of thin dye films deposited on the prism surface. The photobleaching dynamics is interpreted as a combination of first- and second-order processes. A significant fraction of this thesis has been devoted to studying magnetic field effects (MFEs) on the kinetics of the radical pair (RP) reactions in solution, in an effort to understand the ability of animals to sense the geomagnetic field. Two novel optical-cavity-based techniques – broadband CEAS (BBCEAS) and CRDS have been developed for this purpose. BBCEAS uses a supercontinuum (SC) source as the cavity light source and a CCD camera as photodetector, enabling simultaneous acquisition of absorption spectrum across the whole visible region (400 – 800 nm). In CRDS, a tunable optical parametric oscillator has been used as the cavity light source. Combined with the switching of external magnetic field (SEMF) method, this technique allows the decay kinetics of the geminate RPs to be monitored, with nanosecond resolution. Both BBCEAS and CRDS provide sensitivity superior to single-pass transient absorption (TA), a technique traditionally used in the MFE studies. A series of photochemical systems have been studied by BBCEAS and CRDS, respectively, among which, the MFEs of drosophila melanogaster cryptochrome has been observed. Importantly, this is the first time an MFE has been observed in an animal cryptochrome, and provides key supporting evidence for the cryptochrome hypothesis of magnetoreception in animals. Besides the optical-cavity-based techniques, a novel fluorescence detection method of MFEs has also been demonstrated. This technique proved ultrahigh sensitivity when applicable.

Wir haben blau, grün und orange leuchtende organische Nanofäden oder Nanonadeln und Mikroringe aus para-Hexaphenyl (p-6P), alpha-Quaterthiophen (alpha-4T) und alpha-Sexithiophen (alpha-6T) mittels Organischer Molekularstrahlepitaxie (OMBE) auf Muskovit Glimmer hergestellt. Die Aggregate haben wir mit der Atomkraftmikroskopie, mit der Fluoreszenz-Mikroskopie und durch UV-vis Spektroskopie charakterisiert. Auf der Muskovit Oberfläche wachsen p-6P Fäden parallel zueinander auf und zeigen zwei verschiedene Orientierungsdomänen entlang [110] und [1-10]. Mit Hilfe einer systematischen statistischen Analyse diskutieren wir das Wachstum dieser p-6P Nadeln für verschiedene Wachstumsbedingungen. Zusätzlich zu den Fäden haben wir p-6P Cluster auf der Oberfläche beobachtet. Nadeln werden durch die Aggregation solcher Cluster gebildet. Ein Realraummodell der Morphologie der Nadeln sowie ein Modell für deren Wachstum werden vorgestellt. Indem wir Glimmer zunächst mit einer dünnen Goldschicht bedecken und die Wachstumsparameter variieren, erreichen wir eine weitgehende Kontrolle der Morphologie der Nadeln (Länge von 0,5 Mikrometer bis 1 mm, Höhe von 25 bis 300 nm und Breite von 100 bis 600 nm). Im Gegensatz zu p-6P orientieren Thiophene ihre Wachstumsrichtungen an allen hoch symmetrischen Richtungen von Glimmer. Es wird gezeigt, dass die Mechanismen für das Fadenwachstum von beiden Oligomere gleich sind, nämlich eine Kombination aus Epitaxie und einer Dipol-unterstützten Ausrichtung. Auch die Strukturen dieser Fäden sind ähnlich: die Moleküle liegen parallel angeordnet auf der Oberfläche, ihre Längsachsen orientieren sich schräg zur Längsachse der Fäden. Auf mit Wasser oder Methanol vorbehandeltem Glimmer wachsen diese beiden Oligomere als gebogene Fäden und Mikroringe auf. Diese Oberflächenvorbehandlungen sowie das Wachstum von p-6P auf Gold/Glimmer unterstützen auch den Wachstumsmechanismus auf der sauberen Glimmer-Oberfläche. / By using organic molecular beam epitaxy (OMBE) blue, green and orange light emitting organic nanofibers or nanoneedles and microrings from para-hexaphenyl (p-6P), alpha-quaterthiophene (alpha-4T) and alpha-sexithiophene (alpha-6T), respectively, on muscovite mica surfaces are generated. The aggregates are characterized by atomic force microscopy, fluorescence microscopy and UV-vis spectroscopy. On muscovite mica, p-6P fibers usually grow mutually parallel showing two domains of their orientations with an angle of 120 degree in between. The detail growth of nanofibers from p-6P by performing a systematic statistical analysis of fibers as a function of various growth conditions is discussed. Furthermore, the morphology exhibits p-6P clusters, which are found to be fibers´ building blocks. A real space model of the fiber and a model for their growth are also presented. By introducing a thin gold layer on mica prior to p-6P deposition together with varying growth parameters, the morphology of fibers is controlled in a wide range (length from 0.5 micrometer to 1 mm, height from 25 to 300 nm and width from 100 to 600 nm). In contrast to p-6P, thiophene fibers exhibit various orientations close to mica high symmetry directions. It is shown that the mechanism behind the fiber growth from all molecules on mica is the same, i.e. a combination of epitaxy and dipole assisted growth process. The fiber microscopic structures are similar, too: molecules take lying orientations and they hold themselves parallel pointing their long axes along an oblique direction off the long fiber axis. The growth of both types of oligomers on water or methanol treated mica surfaces leads to the formation of bent fibers and microrings. This surface pretreatment and the growth of p-6P on gold/mica support the fiber growth mechanism on plain mica.

In this thesis the structure and hydration of small organic and amphipilic compounds adsorbed at the air-liquid interface, have been studied using the nonlinear optical technique Vibrational Sum Frequency Spectroscopy (VSFS). The second order nature of the sum frequency process makes this technique particularly surface sensitive and very suitable for interfacial studies, as molecules at the surface can be distinguished even in the presence of a vast excess of the same molecules in the bulk. Particular emphasis was given to the surface water structure and how it is affected by the presence of small model compounds such as acetic acid and formic acid, and also non-ionic surfactants with sugar based and ethylene oxide based polar headgroups. Understanding the structure of water at these interfaces is of considerable fundamental importance, and here VSFS provided unique information. Upon addition of tiny amounts of these surface active compounds, the ordered surface structure of water was found to be significantly perturbed, as revealed by the changes observed in the characteristic spectroscopic signature of the dangling OH bond of water molecules, which vibrate free in air and are present in the top monolayer. Dramatic differences between the different compounds were also observed in the bonded OH region, providing a valuable insight into the hydration of polar groups at interfaces. Additionally, by employing different polarization combinations of the laser beams involved in the sum frequency process, information about the different water species present at the surface and their average orientation were extracted. In particular an unusual state of water was found with a preferred orientation in a non-donor configuration in close proximity to the hydrophobic region formed by the hydrocarbon tails of the surfactant molecules. The conformation and orientation of the different adsorbates were also characterized, targeting their specific vibrational frequencies. Noteworthy is the orientation of the fluorocarbon chain of ammonium perfluorononanoate (APFN), which in contrast to the hydrocarbon chains of the other surfactant molecules studied, remained constant over a wide range of surface densities. This behaviour was also observed for the anionic headgroup of sodium dodecyl sulphate (SDS). Other interesting findings were the formation of a cyclic dimer bilayer at the surface of concentrated aqueous solutions of acetic acid and the water structuring effect induced by poly(ethylene-oxide) headgroups, in spite of being themselves disordered at the air-liquid interface.

<p>In this thesis the structure and hydration of small organic and amphipilic compounds adsorbed at the air-liquid interface, have been studied using the nonlinear optical technique Vibrational Sum Frequency Spectroscopy (VSFS). The second order nature of the sum frequency process makes this technique particularly surface sensitive and very suitable for interfacial studies, as molecules at the surface can be distinguished even in the presence of a vast excess of the same molecules in the bulk. Particular emphasis was given to the surface water structure and how it is affected by the presence of small model compounds such as acetic acid and formic acid, and also non-ionic surfactants with sugar based and ethylene oxide based polar headgroups. Understanding the structure of water at these interfaces is of considerable fundamental importance, and here VSFS provided unique information. Upon addition of tiny amounts of these surface active compounds, the ordered surface structure of water was found to be significantly perturbed, as revealed by the changes observed in the characteristic spectroscopic signature of the dangling OH bond of water molecules, which vibrate free in air and are present in the top monolayer. Dramatic differences between the different compounds were also observed in the bonded OH region, providing a valuable insight into the hydration of polar groups at interfaces. Additionally, by employing different polarization combinations of the laser beams involved in the sum frequency process, information about the different water species present at the surface and their average orientation were extracted. In particular an unusual state of water was found with a preferred orientation in a non-donor configuration in close proximity to the hydrophobic region formed by the hydrocarbon tails of the surfactant molecules.</p><p>The conformation and orientation of the different adsorbates were also characterized, targeting their specific vibrational frequencies. Noteworthy is the orientation of the fluorocarbon chain of ammonium perfluorononanoate (APFN), which in contrast to the hydrocarbon chains of the other surfactant molecules studied, remained constant over a wide range of surface densities. This behaviour was also observed for the anionic headgroup of sodium dodecyl sulphate (SDS). Other interesting findings were the formation of a cyclic dimer bilayer at the surface of concentrated aqueous solutions of acetic acid and the water structuring effect induced by poly(ethylene-oxide) headgroups, in spite of being themselves disordered at the air-liquid interface.</p>

Process-induced Long-term Deformation Behavior of Injection Molded Semicrystalline Thermoplastics Injection molding is a very complex process because the polymer experiences a complex thermorheological history during molding that influences the molecular orientation, residual stresses, frozen-in free volume and crystallinity inside the part. These generally govern the final part properties. Therefore it is highly desirable to anticipate the effect of process parameters on the resulting microstructure and mechanical properties of the finished part in the long run. In the case of a semicrystalline thermoplastic part, the problem in understanding the deformation behavior arises from its two-phase structure and a tendency exists to concentrate primarily on the effect of the crystalline phase on the deformation behavior, while the contribution of the amorphous phase is less investigated. In this work, the influence of the processing parameters on the deformation behavior of injection molded semicrystalline thermoplastic parts, viz., syndiotactic Polystyrene (sPS) and Polybutylene terepthalate (PBT), has been monitored through creep. The resulting internal structures due to processing have been determined and the deformation behavior has been analyzed. It has been observed that only the rate of cooling shows a remarkable effect on the long-term viscoelastic behavior of an injection molded semicrystalline thermoplastic part as it influences not only the crystalline, but also the free volume fraction, whereas the different states of frozen-in orientations and pressure-induced densification have only a negligible effect. Besides, physical aging also plays an important role in the deformation behavior of the injection moldings which was manifested with the decrease in the tendency to creep. Therefore, it was suggested that the cooling rate during injection molding and the aging time can significantly affect the long-term deformation behavior of the injection molded semicrystalline thermoplastics. The results also showed that when no significant effect is observed in terms of short-term mechanical properties by changing the processing conditions, but while considering the long-term behavior they show a significant effect.

Η παρούσα διδακτορική διατριβή αποτελείται από δύο ξεχωριστές ενότητες οι οποίες έχουν σαν στόχο τη μελέτη τροποποιημένων πολυμερικών μεμβρανών για χρήση σε κυψελίδες καυσίμου αγωγής πρωτονίων και σε εφαρμογές διαχωρισμού αερίων. Στην πρώτη ενότητα έγινε εκτίμηση του μοριακού προσανατολισμού μονοαξονικά εφελκυσμένων πολυμερικών μεμβρανών Nafion-115 με τη βοήθεια πολωμένων φασμάτων UV-Raman. Πειράματα δυναμικής μηχανικής ανάλυσης επαλήθευσαν τις προσδοκίες για βελτίωση των μηχανικών ιδιοτήτων του πολυμερικού ηλεκτρολύτη κατά μήκος της διεύθυνσης εφελκυσμού. Η θερμική ανάλυση των δειγμάτων με τις τεχνικές της διαφορικής θερμιδομετρίας σάρωσης και της θερμοσταθμικής ανάλυσης δεν έδειξε κάποια ιδιαίτερη διαφοροποίηση μεταξύ εφελκυσμένων και μη δοκιμίων Nafion-115, πέραν της βελτίωσης της ικανότητας των τανυσμένων μεμβρανών να συγκρατούν το όποιο νερό υπάρχει στο ιονομερές. Μικρή ήταν η αύξηση της ιοντικής αγωγιμότητας που παρατηρήθηκε στα τανυσμένα δείγματα κατά μήκος της διεύθυνσης εφελκυσμού. Η προσπάθεια τροποποίησης του Nafion® με διαξονικό εφελκυσμό είχε σαν αποτέλεσμα τη λήψη λεπτών πολυμερικών ηλεκτρολυτικών μεμβρανών με αποτελεσματικότερες ιδιότητες στην τάση διέλευσης της μεθανόλης, σε σχέση με τις μη τροποποιημένες μεμβράνες. Επιπρόσθετα, με τον ελεγχόμενο διαξονικό και σταθερού πλάτους μονοαξονικό εφελκυσμό κατέστη δυνατό να επιτευχθεί η εξισορρόπηση των ποσοστών διαστολής κατά το μήκος και πλάτος της επιφάνειας του Nafion, μετά τον εμποτισμό του με νερό. Όσον αφορά στην τροποποίηση του Nafion με εναπόθεση στοιβάδας αγώγιμου πολυμερούς πολυανιλίνης (PAni) ή πολυπυρρόλης (PPy) με ενσωματωμένα αντισταθμιστικά ιόντα SO42- ή Nafion-, η φασματοσκοπική μελέτη, μέσω ATR-FTIR, σε συνδυασμό με τις μικροφωτογραφίες SEM που ελήφθησαν, οδήγησαν στα εξής συμπεράσματα: Για τις σύνθετες μεμβράνες Nafion/PAni που παρασκευάστηκαν με την τεχνική της διάχυσης, από τη μία ελήφθησαν δείγματα με ικανοποιητική συνάφεια μεταξύ του κυρίως όγκου της πολυμερικής μεμβράνης Nafion και της PAni, από την άλλη όμως, υπάρχει και κάποιο ποσοστό μονομερούς ανιλίνης (Ani) που εγκλωβίζεται στο εσωτερικό του Nafion, και μάλιστα σε σημαντικό βαθμό, που εξαρτάται από το χρόνο σύνθεσης. Αντίθετα, οι αντίστοιχες μελέτες στις μεμβράνες Nafion/PPy δε φανερώνουν την ύπαρξη διείσδυσης της PPy ή του μονομερούς στην κύρια μάζα του Nafion, ή τουλάχιστον όχι σε τέτοιο βαθμό που να μπορεί να ανιχνευθεί μέσω της τεχνικής που χρησιμοποιήθηκε. Ιδιαίτερο είναι το ενδιαφέρον που προκύπτει από τις φασματοσκοπικές μετρήσεις στην πλευρά του σύνθετου πολυμερούς όπου εναποτίθετο το πολυμερισμένο αγώγιμο υλικό, καθώς με το χρόνο σύνθεσης παρατηρούνται μετατοπίσεις κορυφών του Nafion προς χαμηλότερες συχνότητες, υποδεικνύοντας ενδεχόμενη αλληλεπίδραση με το αγώγιμο πολυμερές. Στη δεύτερη ενότητα μελετήθηκαν οι σύνθετες (ή “mixed matrix”) πολυμερικές μεμβράνες πολυσουλφόνης (PSF) με ενσωματωμένες φυλλώδεις αργυλοφωσφορικές νανονιφάδες τύπου AlPO. Αρχικά πραγματοποιήθηκε η σύνθεση των νανονιφάδων AlPO. Με στόχο τη βελτίωση της συμβατότητάς τους με την πολυμερική μήτρα έγινε παρεμβόλιση με κατάλληλη επιφανειοδραστική ουσία και χαρακτηρισμός με XRD που έδειξε τη διεύρυνση της απόστασης μεταξύ των διαδοχικών στρωμάτων του κρυστάλλου από 9Å σε 33Å περίπου. Στη συνέχεια παρασκευάσθηκαν οι σύνθετες μεμβράνες με διαφορετικές συγκεντρώσεις της ανόργανης φάσης, με τη μέθοδο του film casting. Με βάση τις εικόνες SEM οι νανονιφάδες φαίνεται να έχουν ικανοποιητική διασπορά στη μάζα της πολυσουλφόνης, ενώ τα φάσματα XRD δείχνουν πως η ενσωμάτωση των παρεμβολισμένων νανονιφάδων στην πολυμερική μήτρα δεν επέφερε κάποια σημαντική αλλαγή στη δομή τους. Οι νανονιφάδες, ακόμα και σε μικρές συγκεντρώσεις, βελτιώνουν σε σημαντικό βαθμό τη διαχωριστική ικανότητα των αμιγώς πολυμερικών μεμβρανών για τα ζεύγη αερίων H2/N2 και Η2/CH4 όχι όμως και για το ζεύγος Η2/CO2. Αντίθετα, η αύξηση του ποσοστού των νανονιφάδων AlPO οδηγεί σε μείωση της διαπερατότητας του H2. Oι σύνθετες μεμβράνες PSF/AlPO δείχνουν μια μικρή βελτίωση του μέτρου ελαστικότητας αποθηκευόμενης ενέργειας σε σχέση με τις πολυμερικές μεμβράνες PSF, εμφανίζουν επίσης ελαφρώς μειωμένη θερμοκρασία υαλώδους μετάβασης και, κατά τη θέρμανσή τους, ακολουθούν τρία στάδια απώλειας μάζας λόγω αποσύνθεσης της επιφανειοδραστικής ουσίας σε συνδυασμό με απώλεια φυσικά και χημικά ροφημένου νερού. / The present thesis consists of two separate parts which focus on the study of modified polymer membranes for use in fuel cells applications and gas separation processes. In the first part, the molecular orientation of uniaxially drawn Nafion-115 membranes was estimated utilizing polarized UV-Raman spectra. Dynamic mechanical analysis revealed the enhanced strength of the drawn samples along the draw axis. Thermal analysis, carried out via differential scanning calorimetry, and thermogravimetric analysis did not show any difference between drawn and undrawn specimens, except from a slight enhanced capability of the drawn membranes to water content retain. Proton conductivity is slightly enhanced along the stretching direction, as well. The attempts for biaxial stretching of Nafion® had as a result the production of very thin polymer electrolyte membranes with lower permeability to methanol than the commercial one. In addition, with biaxial and constant width uniaxial stretching, the swelling of Nafion along and across its surface can be controlled. The process of modifying Nafion by embedding conducting polymer layers of polypyrrole or polyaniline with SO42- or Nafion- incorporated into the film as counter-ions is studied via ATR-FTIR spectroscopy in combination with SEM microphotographs. Nafion/PAni composite membranes synthesized by the diffusion method showed very good adherence between Nafion and PAni layers but it seems that there is some Ani monomer still remaining inside the bulk structure of Nafion, depending on the time of synthesis. In contrast, the corresponding studies on Nafion/PPy membranes show that there is no penetration of PPy or Py inside Nafion, at least not to the extent that it could be traced using ATR-FTIR spectroscopy. The spectroscopic measurements from the conducting polymer side show red-shifts of absorption bands of Nafion revealing possible specific interactions with the conducting polymer. In the second part, composite (or mixed matrix) polymeric membranes with dispersed aluminophosphate nanoflakes were studied. At the beginning AlPO nanoflakes were synthesized. To enhance the compatibility with the polymer matrix conventional AlPO nanoflakes were intercalated using suitable surfactant. XRD characterization showed a further individual layers` separation since the distance between them is increased from 9Å to 33Å. Subsequently, mixed matrix membranes with different nanoflakes loading were synthesized, using film casting method. Based on SEM images nanoflakes seem to be well dispersed in the mass of polysulfone, while XRD graphs implied that the incorporation of intercalated nanoflakes into the polymer matrix did not affect their structural characteristics. Nanoflakes incorporation, even at very low concentrations, improves the H2/N2 and H2/CH4 selectivity and deteriorates the H2/CO2 selectivity compared with the pure polymer. On the other hand, the higher the percentage of the AlPO flakes, the more pronounced the decrease in hydrogen permeability. PSF/AlPO membranes exhibit improved storage modulus, appear to have slightly lower glass transition temperature compared with PSF membranes and during their heating, follow a three steps mass loss due to the surfactant decomposition and the loss of physically and chemically absorbed water.

Αντικείμενο της παρούσας διατριβής αποτέλεσε η μελέτη μιγμάτων αλειφατικών/αρωματικών πολυεστέρων. Αρχικά υπήρχε η πρόθεση να επικεντρωθούμε στη μελέτη της βιοαποικοδόμησης μίγματος ενός αλειφατικού και ενός αρωματικού πολυεστέρα. Για τη διερεύνηση όμως της αναμειξιμότητάς τους εστιάσαμε στην έμμεση μελέτη του μοριακού προσανατολισμού μονοαξονικά εφελκυσμένων μιγμάτων αλειφατικών/αρωματικών πολυεστέρων, με τη χρήση πολωμένων φασμάτων δόνησης. Πιο συγκεκριμένα, εξετάστηκε η σύγχρονη παρουσία σ’ ένα μόνο πολωμένο φάσμα Raman της μη-συμβατικής συμπεριφοράς της δόνησης τάσης της χαρακτηριστικής ομάδας του καρβονυλίου (C=O) των αρωματικών πολυεστέρων με την αντίστοιχη συμβατική συμπεριφορά της ίδιας ομάδας των αλειφατικών πολυεστέρων. Μετά από πολλές προσπάθειες διαφόρων παρεμφερών μιγμάτων στα οποία παρουσιάστηκαν διάφορα προβλήματα, κυρίως αναμειξιμότητας, καταλήξαμε στο μίγμα του βιοαποικοδομήσιμου αλειφατικού πολυεστέρα L-PLA με τον αρωματικό πολυεστέρα PBT. Παρασκευάστηκαν φιλμ των ομοπολυμερών L-PLA και PBT καθώς και του μίγματος L-PLA/PBT, με ανάμιξη των συστατικών σε τήγμα και στη συνέχεια μορφοποίησή τους σε υδραυλική θερμοπρέσα. Για τον προσδιορισμό των θερμικών ιδιοτήτων των υλικών χρησιμοποιήθηκε η τεχνική Διαφορικής Θερμιδομετρίας Σάρωσης (DSC). Δοκίμια των ομοπολυμερών και του μίγματος εφελκύστηκαν μονοαξονικά σε θερμοκρασίες μεγαλύτερες από τη μετάβαση υάλου τους και ο προσανατολισμός τους εκτιμήθηκε με τη χρήση πολωμένων φασμάτων Raman. Σε κάθε περίπτωση, επειδή παρά τις πολλές προσπάθειες δεν ήταν δυνατό κυρίως και πάλι λόγω προβλημάτων αναμειξιμότητας να συνεχιστεί μια τέτοια μελέτη και στο επίπεδο της βιοαποικοδόμησης ενός αλειφατικού και ενός αρωματικού πολυεστέρα, αποφασίσαμε να συνεχίσουμε με ένα αναμείξιμο σε κάθε αναλογία μίγμα, ενός βιοαποικοδομήσιμου και ενός μη-αποικοδομίσιμου πολυμερούς. Το μίγμα αυτό των πολυμερών ήταν το PCL/PVC με το οποίο και συνεχίστηκε και ολοκληρώθηκε η παρούσα διατριβή εξειδίκευσης. Το ενδιαφέρον επικεντρώθηκε στη μελέτη μιγμάτων PCL/PVC διαφόρων συστάσεων, δύο πολυμερών τα οποία είναι αναμίξιμα σε όλο το εύρος των αναλογιών τους. Το ομοπολυμερές του αλειφατικού πολυεστέρα PCL και τα μίγματα που προέκυψαν μελετήθηκαν ως προς τις θερμικές τους ιδιότητες και χαρακτηρίστηκαν φασματικά με Raman. Επιπλέον, επιχειρήθηκε η μελέτη της βιοαποικοδόμησης τόσο της PCL όσο και των μιγμάτων της με PVC, μετά από εμβάπτιση σε φυσιολογικό ορό για χρονικό διάστημα άνω των 3 μηνών. Για τον προσδιορισμό των θερμικών ιδιοτήτων των μιγμάτων PCL/PVC και του ομοπολυμερούς PCL χρησιμοποιήθηκε η τεχνική DSC, στη συνέχεια χαρακτηρίστηκαν με τη δονητική φασματοσκοπία Raman ενώ ακολούθησαν πειράματα Χρωματογραφίας Διαπιδύσεως μέσω Πηκτής (GPC) και Δυναμικής Σκέδασης Φωτός (DLS) ώστε να προσδιοριστεί η βιοαποικοδόμηση των υλικών. Η βιοποικοδόμηση των PCL/PVC και κατ’ επέκταση της PCL μελετήθηκε υπό διαφορετικές συνθήκες (θερμοκρασίας, χρόνου, συγκέντρωσης) και σε διαφορετικό βαθμό. / The aim of this dissertation was the study of aliphatic/aromatic copolyesters. At the beginning, the main purpose was to investigate the biodegradation behavior of an aliphatic/aromatic polyester blend. In order to examine the miscibility of the two polymers comprising the blend we have studied the molecular orientation of melt blends utilizing polarized vibrational spectroscopy. After plenty of essays on resembling blends and due to the problems that we have faced (mainly miscibility problems) we decided to study the polymer blend of the biodegradable aliphatic polyester Poly(L-lactic acid) (L-PLA) and the aromatic polyester Poly(butylene terephthalate) (PBT). In particular, the interest centered to the peculiar and unexpected behavior of the C=O stretching carbonyl Raman band of the aromatic polyesters (in case PBT) comparing to the corresponding conventional behavior of the aliphatic polyesters, (in case L-PLA). L-PLA/PBT blends were prepared through reaction extrusion (melt mixing). Films prepared by melt pressing have been uniaxially hot drawn. Polarized laser Raman spectroscopy has been used to estimate the molecular orientation of drawn films of L-PLA and PBT homopolymers and L-PLA/PBT polymer blends. The crystallization behavior of the samples was investigated by using a differential scanning calorimeter (DSC). Finally, the polymers L-PLA and PBT have found to be partially miscible so we took the decision of studying another totally miscible blend consisted of PCL and PVC, a mixture of an aliphatic biodegradable polyester and a non-biodegradable thermoplastic polymer. Blends of PCL and PVC are under development with various potential applications in view, including controlled delivery of agrichemicals, and it is important to investigate their biodegradation behavior. The thermal properties of the homopolymer PCL and PVC blends were investigated under nitrogen by using DSC. Samples of the homopolymer PCL and PCL/PVC blends were placed in glass bottles with serum for more than 3 months. Raman Spectroscopy, Gel Permeation Chromatography and Dynamic Light Scattering have been used to estimate the biodegradation of the samples.

Process-induced Long-term Deformation Behavior of Injection Molded Semicrystalline Thermoplastics Injection molding is a very complex process because the polymer experiences a complex thermorheological history during molding that influences the molecular orientation, residual stresses, frozen-in free volume and crystallinity inside the part. These generally govern the final part properties. Therefore it is highly desirable to anticipate the effect of process parameters on the resulting microstructure and mechanical properties of the finished part in the long run. In the case of a semicrystalline thermoplastic part, the problem in understanding the deformation behavior arises from its two-phase structure and a tendency exists to concentrate primarily on the effect of the crystalline phase on the deformation behavior, while the contribution of the amorphous phase is less investigated. In this work, the influence of the processing parameters on the deformation behavior of injection molded semicrystalline thermoplastic parts, viz., syndiotactic Polystyrene (sPS) and Polybutylene terepthalate (PBT), has been monitored through creep. The resulting internal structures due to processing have been determined and the deformation behavior has been analyzed. It has been observed that only the rate of cooling shows a remarkable effect on the long-term viscoelastic behavior of an injection molded semicrystalline thermoplastic part as it influences not only the crystalline, but also the free volume fraction, whereas the different states of frozen-in orientations and pressure-induced densification have only a negligible effect. Besides, physical aging also plays an important role in the deformation behavior of the injection moldings which was manifested with the decrease in the tendency to creep. Therefore, it was suggested that the cooling rate during injection molding and the aging time can significantly affect the long-term deformation behavior of the injection molded semicrystalline thermoplastics. The results also showed that when no significant effect is observed in terms of short-term mechanical properties by changing the processing conditions, but while considering the long-term behavior they show a significant effect.