Due to entropy and Van der Waals¡¦ interaction, carbon nanotubes tend to aggregate degrading their excellent opto-electronic properties and limiting their applications. Chemical derivatizations were applied to the multi-wall carbon nanotube (MWCNT) by esterificating with different lengths of aliphatic pendants (COOC4H9, COOC10H21, and COOC18H37) to decrease the MWCNT aspect ratio to facilitate its dispersion, and to observe its percolation behavior. FTIR analysis revealed the more relevant absorption peaks of C-H at 2917 cm-1, 2846 cm-1 and C=O at 1733 cm-1 from the derivatization. H1-NMR showed that the aliphatic pendant functionalized MWCNT from the signals of OCH2 at £_ = 3.64 ppm, CH2 at £_ = 1.25 ppm, and CH3 at £_ = 0.88 ppm. Raman scattering indicated that esterification caused the ID/IG absorption peak area ratio to decrease. In applications, the electric conductivity was measured on thin-films of MWCNT:Poly-(3-hexylthiophene) (P3HT) as a function of nanotube content. Accompanied with nanotube doping concentration increased, the electric conductivity parallel to film surface (£m||) could range from an undoped value 1.4¡Ñ10-6 S/cm up to 1.2¡Ñ10-2 S/cm. The conductivity percolation threshold concentration decreased as the MWCNT aspect ratio increased due to the average distance between the nanotubes becoming sufficiently small for charges to hopping through P3HT. By incorporating [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM), bulk heterojunction photovoltaic (PV) cells of ITO/PEDOT:PSS/MWCNT:[PC61BM:P3HT]/LiF/Al were fabricated. By varying the ratio of MWCNT to the PC61BM:P3HT (0.8:1) mixtures, the PV cells showed the maximum power conversion efficiency (£bp) close to 4 % with MWCNT-COOC4H9 at a doping concentration of 0.01 wt. %.

Polymer light emitting diodes (PLED) were using a heterocyclic aromatic rigid-rod polymer poly-p-phenylene-benzobisoxazole (PBO) as an opto-electronically active layer; and poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonic acid) (PEDOT:PSS) as a hole transporting layer. Aluminum (Al) and indium tin oxide (ITO) were served as device cathode and anode, respectively. [6,6]-phenyl C61-butyric acid methyl ester (PC61BM) or derivatized multi-wall carbon nano-tube (MWCNT-C18), with great electron transporting ability, was doped into PBO to enhance the performance of PLED devices as well as the thin-film electrical conductivity. The optical length was changed by using different spin coating speeds and durations. From the research, the £fmax of electroluminescence (EL) was blue-shifted as PEDOT:PSS spin coating speed increased for a thinner layer. Once using a higher spin coating speed repeatedly to coat PEDOT:PSS, the £fmax of electroluminescence was red-shifted. If the PEDOT:PSS film thicknesses were similar, the EL spectra were almost the same, independent of device processing scheme. The injection current and EL intensity were enhanced by doping PC61BM or MWCNT- C18. The electric conductivity parallel to film surface (£m¡ü) was increased as the doping concentration increased. Because of the extremely different aspect ratio, the MWCNT-C18 had a lower percolation threshold concentration. Therefore, at a low MWCNT-C18 doping concentration, the injection current and the EL intensity were enhanced compared with those of PC61BM.

Opto-electronics of non-fully conjugated molecules was demonstrated successfully in this research as light emitting diodes (LEDs). A series of benzoxazole poly[2,2-(m-2-hydroxyl phenylene)-4-4¡¦-hexafluoroisopro- pane-bibenzoxazoles] (6F-PBO-OH, Am) and benzimidazole poly[2,2¡¦- (2-hydroxy-o-phenylene)-5,5¡¦-bibenzimiazole] (OH-Pbi, B(1-m)) were copolymerized for coil-like non-fully conjugated poly-(Am-co-B(1-m)) for luminescence investigation. UV-Vis absorption of the non-fully conjugated copolymers showed superposition of individual absorption response from the two chemical components of the copolymer. However, the photoluminescence (PL) and the electroluminescence (EL) emissions had a red shift with increasing OH-Pbi content. It seemed to suggest that OH-Pbi was more charge delocalized than 6F-PBO-OH. In mono-layer LEDs, the diode threshold voltages were about at 2 ~ 3 V and the EL showed a green emission. Tunable emission was not observed in varying the m value of the copolymers. Composites of copolymer, poly(Am-co-B(1-m)) and multi-wall carbon nanotube (MWNT) were in-situ synthesized for mono-layer LED fabrication. Few MWNT aggregation was observed via the field-emission scanning electron microscopy. It was a success in dispersing MWNT in the copolymers. There was a red shift with MWNT addition in the PL and the EL emissions. The diode threshold voltages were about at 2 ~ 5 V and the EL emission still showed a green emission. According to this study, MWNT was inconsequential on the PL and the EL emissions of the copolymers up to 2 wt. %.

Luminescent emission of non-fully conjugated homopolymers was successfully demonstrated as light emitting diodes (LEDs) in this research. Coil-like heterocyclic aromatic poly[2,2-(2,5-dialkyloxyphenylene)-4-4¡¦-hexafluoroisopropanebibenzoxazo- les] (6F-PBO-CnOTpA, with n = 10, 15, and 20) was synthesized, and polymer composites of 6F-PBO-CnOTpA was in-situ synthesized with acidified multi-wall carbon nanotube (MWNT- COOH). The non-fully conjugated coil-like heterocyclic aromatic homopolymer was synthesized by reacting 2,2,bis-(3-amino-4-hydroxy[henyl]-hexafluoropropane with 2,5-dialkyloxyterephthalic acid (CnOTpA) for 6F-PBO-CnOTpA, with n = 10, 15, and 20. In addition, MWNT was acidified for connecting the carboxylic group (-COOH) to reduce its aspect ratio and entropy induced aggregation. MWNT-COOH was analyzed using elemental analysis (EA) and viscometry to validate the effects of acidification period. The EA result seemed to suggest that the oxygen content increased, and the carbon and the hydrogen contents decreased with acidification period. The inherent viscosity (£binh) decreased according to acidification period suggesting that the aspect ratio was indeed decreased. A hole transport layer of PEDOT¡GPSS was applied for multi-layer LEDs,. The LEDs all showed a threshold voltage about 4 V also for the composites of 6F-PBO-CnOTpA in-situ polymerized with MWNT-COOH. The 6F-PBO-CnOTpA LEDs with and without MWNT-COOH showed an electroluminescence emission range of 400 to 750 nm.

No description available.

Poly(ethylene-co-methacrylic acid) (EMAA) ionomer polymers carry great potential for use in a wide variety of unique applications due to their property of “self-healing” following projectile impact. Following puncture, certain films based on these materials are observed to “heal”, with the penetration opening recovering to an air-tight condition. Specifically, four polymers of this class were examined, including DuPont™ Surlyn® 8920, Surlyn® 8940, Nucrel® 925, and Nucrel® 960. Though these differ in their amount of ionic content, all expressed a certain degree of self-healing. Thin films were prepared by a compression molding process and punctured at temperatures ranging from room up to that of the melt using a pellet gun. Samples were then assessed for self-healing. A quantitative post-puncture burst-test method examined the strength or quality of the healed site in the four examples. A comparison of this data provided an understanding of the importance of ionic content and the mechanism of puncture healing. Additional damage modes were also examined to determine other cases where healing occurs and the requirements necessary to elicit the healing response. In addition, interesting composite materials consisting of carbon nanotube filled ionomers were fabricated by a melt-mixing process which produced potentially self-healing composites with superior mechanical properties. By comparing peel testing, projectile testing, the quantitative healed strength, and other characteristics, it was determined that healing is not a function of the ionic content of the materials involved. Further, healing was determined to occur due to a synergy of thermomechanical properties facilitated by the addition of the methacrylic acid groups to the polymer backbone. / Master of Science

Vascularization of thick engineered tissue and organ constructs like the heart, liver, pancreas or kidney remains a major challenge in tissue engineering. Vascularization is needed to supply oxygen and nutrients and remove waste in living tissues and organs through a network that should possess high perfusion ability and significant mechanical strength and elasticity. In this thesis, we introduce a fabrication process to print vascular conduits directly, where conduits were reinforced with carbon nanotubes (CNTs) to enhance their mechanical properties and bioprintability. The generation of vascular conduit with a natural polymer hydrogel such as alginate needs to have improved mechanical properties in order to biomimic the natural vascular system. Carbon nanotube (CNT) is one of the best candidates for this goal because it is known as the strongest material and possesses a simple structure. In this thesis, multi-wall carbon nanotube (MWCNT) is dispersed homogenously in the hydrogel and fabricated through an extrusion-based system.In vitro evaluation of printed conduits encapsulated in human coronary artery smooth muscle cells was performed to characterize the effects of CNT reinforcement on the mechanical, perfusion and biological performance of the conduits. Perfusion and permeability, cell viability, extracellular matrix formation and tissue histology were assessed and discussed, and it was concluded that CNT-reinforced vascular conduits provided a foundation for mechanically appealing constructs where CNTs could be replaced with natural protein nanofibers for further integration of these conduits in large-scale tissue fabrication. It was concluded that MWCNT has a significant effect on mechanical properties, vascular conduit swelling ratio and biological characterization in short-term and long-term cellular viability.

Σκοπός της παρούσας Πτυχιακής Εργασίας είναι ανάπτυξη μιας διαδικασίας παρασκευής νανοσύνθετων εποξικής ρητίνης/ πολλαπλών νανοσωληνίσκων άνθρακα (MWCNT) σε ένα εύρος περιεκτικοτήτων από 0.1 έως και 1 % κατά βάρος (κ.β) MWCNT. Τα εμποτισμένων δοκίμια έναντι αυτών της καθαρής ρητίνης παρουσίασαν ενισχυμένες μηχανικές ιδιότητες όπως αντοχή σε εφελκυσμό και αυξημένο μέτρο ελαστικότητας. Η αύξηση αυτή μπορεί να αποδοθεί στο υψηλό λόγο μήκους /διαμέτρου καθώς και στην μεγάλη ελεύθερη επιφάνεια των νανοσωληνίσκων (CNTs). Επίσης από τα πειράματα δυναμικής ανάλυσης παρατηρήθηκε αύξηση της θερμοκρασίας υαλώδους μετάβασης με την αύξηση της περιεκτικότητας των CNTs. Στα πλαίσια της ίδιας εργασίας μελετήθηκαν οι ηλεκτρικές ιδιότητες καθώς και οι αισθητήριες ιδιότητες των MWCNT και εξερευνήθηκε η χρήση τους ως νανοαισθητήρες για την παρακολούθηση βλάβης στην εμποτισμένη εποξική ρητίνη. Για τον σκοπό αυτό πραγματοποιήθηκαν πειράματα φόρτισης-αποφόρτισης μονοαξονικού εφελκυσμού με ταυτόχρονη παρακολούθηση της ηλεκτρικής αντίστασης του δοκιμίου. Από την παραπάνω διαδικασία παρατηρήθηκε πως όσο μεγαλύτερη είναι η περιεκτικότητα CNTs στην ρητίνη, τόσο μεγαλύτερη είναι η ευαισθησία της ηλεκτρικής αντίστασης στις αλλαγές του εφαρμοζόμενου φορτίου. Σημειώνεται επίσης πως η εμποτισμένη σε CNTs εποξική ρητίνη παρουσιάζει ηλεκτρική αγωγιμότητα παρουσιάζοντας σε περιεκτικότητα 1% κ.β συμπεριφορά αγωγού, γεγονός που οφείλεται στην αγώγιμη φύση των CNTs. Από τις μετρήσεις ηλεκτρικής αγωγιμότητας παρατηρήθηκε πως το «κατώφλι» αγωγιμότητας επιτυγχάνεται σε περιεκτικότητα 0.3% κ.β MWCNT ενώ, επιβεβαιώνεται η ισχύς της θεωρίας «διήθησης» : σ~ (V-Vc)t δίνοντας τιμή «κρίσιμου» εκθέτη t ίση με 2.05. / The goal of the present study is the development of a manufacturing process of epoxy resin compounds with several multi-wall carbon nanotube (MWCNT) contents per weight. Enhanced mechanical properties of the doped specimens epoxy against the neat epoxy testpieces e.g. tensile strength and modulus of elasticity was achieved and attributed to the high surface area and high aspect ratio of the nanotubes. Moreover the dynamic properties of the nano-doped epoxy polymers were investigated and the relation of glass transition temperature with increasing CNT content was found to be inverse. Another goal of the present work was to use the electrical/sensing properties of MWCNTs as a nano-sensor for the damage detection within the doped matrix material. Therefore loading-unloading tensile tests were performed, along with on-line conductivity monitoring for the nano-doped epoxy polymers. It was noted that all the nano-doped samples were more sensitive to load changes and thus resistance changes. The higher the CNT content per weight was, the higher the sensitivity in load changes. The conductive nature of CNTs has produced conductive epoxy polymers, which exhibit “percolation threshold” at the content of 0.3% wt. MWCNT and enhanced sensing properties. The measurements of electrical conductivity confirm the validity of “percolation” theory: σ~ (V-Vc)t with the critical exponent t equal to 2.05.

<p>The spectroscopic, SEM and Raman measurements on carbon nanotubes under the exact conditions of which OES analysis were made showed that at<br /> a pressure of 400 Torr and a flow rate of 200 sccm, the quality and quantity of single-walled carbon nanotubes was the highest.</p>

<p>The spectroscopic, SEM and Raman measurements on carbon nanotubes under the exact conditions of which OES analysis were made showed that at<br /> a pressure of 400 Torr and a flow rate of 200 sccm, the quality and quantity of single-walled carbon nanotubes was the highest.</p>