Because the gel-spinning process has the potential to yield fibers of high strength and high modulus, this technique was employed to process continuous filaments of PVA/CNT, having CNTs at ¡Ü1 weight percent of polymer. A gel aging technique was employed with the goal of increasing the draw ratio for composite fibers and for promoting the development of crystalline PVA. Since residual solvent can lower the mechanical properties of drawn fibers, solvent phases of water and dimethyl sulfoxide (DMSO) within the drawn fibers were also characterized. As embedded SWNTs were uniaxially aligned along the drawn fiber axis, they were found to induce preferential alignment in the PVA side groups as well as for the residual solvent. This was attributed to charge transfer between SWNT and the respective functional groups. This orientation behavior has been characterized using Raman spectroscopy and infra-red dichroism. The behaviors of gel crystallization and solvent freezing within PVA/CNT dispersions were studied using thermal analysis and rheology. Carbon nanotubes were found to nucleate PVA crystallization in the gel state. PVA/CNT gel aging behavior was characterized by structural, thermal, and mechanical, and dynamic mechanical means. Gel aging was shown to increase the draw ratio of PVA/CNT fibers, and the development of the higher temperature melting peak was attributed to the draw induced ordering of PVA along CNTs. The scanning electron micrographs of fractured PVA/CNT fibers showed fibrils having an average diameter of about 22 nm. The storage modulus of aged gel was a function of solvent diffusion, which changed with aging time. CNTs were shown to have stabilized the gel network, as characterized by the dynamic mechanical properties, and to provide nucleation sites for the ordering of PVA chains, as characterized by WAXD.

An investigation of surface structures formed on polycrystalline and single crystal TiO2 (titania) samples having under gone various heat treatments in a controlled hydrogen bearing atmosphere was conducted. The study included the recreation and examination of the process discovered by Sehoon Yoo at Ohio State University to form nanofibers on the surface of polycrystalline TiO2 disks. Fibers were formed by heating samples to 700??in a 5%H2 95%N2 gas stream. The nanofibers formed during this processes are approximately 5-20 nanometers in diameter and can be 100??f nanometers long. The fibers do not actually grow on the surface, but are what remain of the surface as the material around them is removed by the gas stream V i.e., nanocarving. The mechanism of fiber formation and the effect of varying experimental parameters remained unknown and were explored within this study. This included changing gas composition, flow rate, and changes in sample preparation. The effect of isovalent doping and impurities within the starting powder were examined. Sintering temperature and time was investigated to determine the effect of grain size and surface morphologies prior to nanocarving. The effect of elevated temperature and 5%H2 95%N gas on the surface of TiO2 single-crystal wafers was also investigated. Test methods include Thermogravimetric Analysis (TGA), Mass Spectrometry (MS), Scanning Electron Microscopy (SEM), and X-ray diffraction (XRD) analysis.

The overall goal of the present research is to provide a computationally based methodology to realize the projected extraordinary properties of Carbon Nanotube (CNT)- reinforced composites and polymeric nanofibers for engineering applications. The discovery of carbon nanotubes (CNT) and its derivatives has led to considerable study both experimentally and computationally as carbon based materials are ideally suited for molecular level building blocks for nanoscale systems. Research in nanomechanics is currently focused on the utilization of CNTs as reinforcements in polymer matrices as CNTs have a very high modulus and are extremely light weight. The nanometer dimension of a CNT and its interaction with a polymer chain requires a study involving the coupling of the length scales. This length scale coupling requires analysis in the molecular and higher order levels. The atomistic interactions of the nanotube are studied using molecular dynamic simulations. The elastic properties of neat nanotube as well as doped nanotube are estimated first. The stability of the nanotube under various conditions is also dealt with in this dissertation. The changes in the elastic stiffness of a nanotube when it is embedded in a composite system are also considered. This type of a study is very unique as it gives information on the effect of surrounding materials on the core nanotube. Various configurations of nanotubes and nanocomposites are analyzed in this dissertation. Polymeric nanofibers are an important component in tissue engineering; however, these nanofibers are found to have a complex internal structure. A computational strategy is developed for the first time in this work, where a combined multiscale approach for the estimation of the elastic properties of nanofibers was carried out. This was achieved by using information from the molecular simulations, micromechanical analysis, and subsequently the continuum chain model, which was developed for rope systems. The continuum chain model is modified using properties of the constituent materials in the mesoscale. The results are found to show excellent correlation with experimental measurements. Finally, the entire atomistic to mesoscale analysis was coupled into the macroscale by mathematical homogenization techniques. Two-scale mathematical homogenization, called asymptotic expansion homogenization (AEH), was used for the estimation of the overall effective properties of the systems being analyzed. This work is unique for the formulation of spectral/hp based higher-order finite element methods with AEH. Various nanocomposite and nanofibrous structures are analyzed using this formulation. In summary, in this dissertation the mechanical characteristics of nanotube based composite systems and polymeric nanofibrous systems are analyzed by a seamless integration of processes at different scales.

Today, ceramic, polymer, and composite nanofibers are among the most charming materials for nanotechnology. Because of their small characteristic dimension, high surface area, and microstructural features, they provide unique mechanical, optical, electronic, magnetic, and chemical properties for an extensive variety of materials applications. Electrospinning provides an effective way of the nanofiber production in a nanometer scale. This technique utilizes a high voltage DC to create a strong electric field and a certain charge density in a viscous solution contained in a pipette. As a result, fibers with diameters ranging from the micrometer to nanometer are formed from this charged solution. This study deals with, the fabrication of alumina borosilicate ceramic nanofibers using electrospinning technique. Alumina borosilicates contain important components having intriguing characteristics for many applications and have been widely studied with different compositions. In this study, alumina borosilicate/PVA solution was prepared using the conventional sol-gel method. Polyvinyl alcohol (PVA) was added into this solution to increase the viscosity for electrospinning. After the alumina borosilicate/PVA solution was electrospun into fibers, high temperature sintering was carried to obtain ceramic alumina borosilicate fibers. The products were characterized by scanning electron microscopy (SEM), X-ray diffractometry (XRD), Fourier transform-infrared spectroscopy (FT-IR), and thermogravimetric/differential thermal analysis (TG-DTA) techniques.

In this study a microbial polyester, poly(3-hydroxybutyrate-co-3- hydroxyvalerate) (PHBV), and its blends were wet or electrospun into fibrous scaffolds for tissue engineering. Wet spun fiber diameters were in the low micrometer range (10-50 &amp / #956 / m). The polymer concentration and the stirring rate affected the properties the most. The optimum concentration was determined as 15% (w/v). Electrospun fiber diameters, however, were thinner. Solution viscosity, potential, distance between the syringe tip and the collector, and polymer type affected the morphology and the thickness of beads formed on the fibers. Concentration was highly influential / as it increased from 5% to 15% (w/v) fiber diameter increased from 284 &plusmn / 133 nm to 2200 &plusmn / 716 nm. Increase in potential (from 20 to 50 kV) did not lead to the expected decrease in fiber diameter. The blends of PHBV8 with lactide-based v polymers (PLLA, P(L,DL-LA) and PLGA (50:50)) led to fibers with less beads and more uniform thickness. In vitro studies using human osteosarcoma cells (SaOs-2) revealed that wet spun fibers were unsuitable because the cells did not spread on them while all the electrospun scaffolds promoted cell growth and penetration. The surface porosities for PHBV10, PHBV15, PHBV-PLLA, PHBV-PLGA (50:50) and PHBV-P(L,DL)LA were 38.0&plusmn / 3.8, 40.1&plusmn / 8.5, 53.8&plusmn / 4.2, 50.0&plusmn / 4.2 and 30.8&plusmn / 2.7%, respectively. Surface modification with oxygen plasma treatment slightly improved the cell proliferation rates. Consequently, all scaffolds prepared by electrospinning revealed a significant potential for use in bone tissue engineering applications / PHBV-PLLA blend appeared to yield the best results.

Cellulose nanowhiskers reinforced poly(vinyl alcohol)(PVA) nanofiber web is successfully fabricated using electrospinning technique and the mechanical properties of the single electrospun fiber are measured using nanoindentation method. The morphology and mechanical properties of highly aligned electrospun fiber webs are investigated. It is found that the modulus and tensile strength of aligned webs are higher than those of isotropic electrospun fiber webs. Experimental results are compared with a longitudinal Halpin-Tsai model. Ice-templated(IT) cellulose microfibril porous foams are successfully fabricated via unidirectional freezing methods. The morphology and growth mechanism of IT surfaces are investigated successfully using cellulose microfibrils and hydrophillic substrates. By controlling the temperature gradient between cellulose microfibril suspensions and secondary freezing mediums, various surface structures including honey-comb like structures, ellipse-shape channel strcutures, fully developed multichannel structures are obtained. For the honey-comb like patterned surface, high contact angles are observed. On the other hand, for the layered patterned surface, anisotropic wetting properties are observed.

Bone defects caused by trauma, tumor resection or disease present a significant clinical problem. Failures in 'high risk' fractures and large bone defects have been reported to be as high as 30-50%. The drawbacks associated with current bone grafting procedures have stimulated the search for improved techniques for bone repair. Tissue engineering/regenerative medicine approaches promote tissue repair by providing a combination of physical and biological cues through structural scaffolds and bioactive agents. Though they have demonstrated significant promise for bone regeneration, very little has been translated to clinical practice. The goal of this thesis was to investigate the potential of electrospun nanofiber mesh scaffolds for bone regeneration. Nanofiber meshes were utilized in a three-pronged approach. First, we validated their ability to robustly support osteogenic cell functions, including proliferation and matrix mineralization. We also demonstrated their efficacy as a cell delivery vehicle. Second, we investigated the effects of modulating nanofiber bioactivity and orientation on stem cell programming. Our results indicate that functionalization of nanofiber meshes with a collagen-mimetic peptide enhanced the migration, proliferation and osteogenic differentiation of cells. Fiber alignment improved cell migration along the direction of fiber orientation. Finally, a nanofiber mesh based hybrid system for growth factor delivery was developed for bone repair and tested in a challenging animal model. The delivery of bone morphogenetic protein (BMP) via this system resulted in the functional restoration of limb function, and in fact proved more efficacious than the current clinical standard for BMP delivery. The studies performed in this thesis have suggested novel techniques for improving the repair of clinically challenging bone defects. They indicate that the delivery of BMP via the hybrid system may reduce the dose and side effects of BMP, thereby broadening the use of BMP based bone augmentation procedures. Therefore, this nanofiber mesh based system has the potential to become the standard of care for clinically challenging bone defects, including large bone defects, open tibial fractures, and nonunions.

Thesis (M.S.)--University of Alabama at Birmingham, 2009. / Title from PDF title page (viewed Jan. 29, 2010). Includes bibliographical references (p. 66-70).

Thesis (M.S.)--University of Central Florida, 2009. / Adviser: Kuo-Chi Lin. Includes bibliographical references (p. 84-92).

Polyamide 6 (PA6) was melt-blended with an intumescent flame retardant (FR) and nanoparticles (multi-wall carbon nanotubes [MWNTs] and nanoclays) to produce multi-component FR-PA6 nanocomposites. Thermal, flammability properties, char residue morphology, and mechanical properties of FR-PA6 nanocomposites were characterized. The flame retardant properties were enhanced according to UL 94 and microscale combustion calorimeter (MCC) measurements, whereas the thermal stability was decreased. Mechanical properties of the bulk material, especially elongation at break, were severely reduced, with the exception of tensile modulus which increased significantly. FR-PA6 nanofibers were processed via electrospinning. Electrospinnability, morphology of the nanofibers, combustion, and thermal properties were also analyzed. As for the bulk-form nanocomposite, improved combustion properties of these nanofibers were successfully achieved though thermal stability was compromised. With proper FR additive, the synergism between MWNTs and nanoclays was observed in PA6 resin. / text