Commonly used thermoplastic biodegradable polymers are generally brittle and lack appreciable elasticity at physiological temperature and thereby fail to mimic the elastic nature of many human soft tissues such as blood vessels. Thus, there is a need for biomaterials which exhibit elasticity. Biodegradable elastomers are promising candidates whose elasticity more closely parallels that of soft tissues. In this research, we developed hybrid biodegradable elastomers comprised of organic and inorganic polymer components in a block copolymer system: poly(e-caprolactone) (PCL) and poly(dimethylsiloxane) (PDMS), respectively. A block structure maintains the distinct properties of the PCL and PDMS components. These elastomers may be useful for the tissue engineering of soft tissues as well as for shape memory polymer (SMP) devices. Tri-block macromers of the form PCLn-block-PDMSm-block-PCLn were developed to permit systematic variations to key features including: PDMS block length, PCL block length, PDMS:PCL ratio, and crosslink density. The macromer was capped with acrylating groups (AcO) to permit their photochemical cure to form elastomers. Thus, a series of biodegradable elastomers were prepared by photocrosslinking a series of macromers in which the PCL blocks varied (n = 5, 10, 20, 30, and 40) and the PDMS block was maintained (m = 37). All elastomers displayed hydrophobic surface properties and high thermal stability. These elastomers demonstrated systematic tuning of mechanical properties as a function of PCL block length or crosslink density. Notable was strains at break as high as 814% making them suitable for elastomeric bioapplications. Elastomers with a critical PCL block length (n = 30 or 40) exhibited shape memory properties. Shape memory polymers based on an organic-inorganic, photocurable silicon-containing polymer system is a first of its kind. This SMP demonstrated strain fixity of 100% and strain recovery near 100% after the third thermomechanical cycle. Transition from temporary to permanent shape was quite rapid (2 sec) and at temperatures near body temperature (60 degrees C). Lastly, porous analogues of the biodegradable elastomers were created using a novel porogen - salt leaching technique. Resulting porous elastomers were designed for tissue engineering scaffolds or shape memory foams.

This thesis discusses two patterning techniques: Step and Flash Imprint Lithography, a nanoimprint technique, and patterning thin films utilizing electrohydrodynamic instabilities. Step and Flash Imprint Lithography, SFIL, is promising alternative approach to photolithography. SFIL replicates the relief pattern of a template in a photocurable liquid that has been dispensed on a substrate. The pattern is then crosslinked when the photocurable liquid is exposed to UV light through the template. In order to study the volume change in the created features upon exposure, a stochastic mesoscale model was formulated. This model allows the study of the possibility of defects forming, from under cured etch barrier, or particle contamination of the template. The results showed large defects should not occur regularly until the minimum feature size is below 3 nanometers. The mesoscale model proved to computationally intensive to simulate features of engineering interest. A base multiscale model was formulated to simulate the effects of the densification of the photocurable liquid as well as the effects of the polymerization on the feature integrity. The multiscale model combines a continuum model (compressible Mooney-Rivlin) coupled to the mesoscale code using the Arlequin method. The multiscale model lays the framework that may be adapted to the study of other SFIL processes like template release. Patterning thin films utilizing electrohydrodynamic instabilities allows for the creation of periodic arrays of pillar like features. These pillars form due to the electric field destabilizing the thin film. Prior work has focused on utilizing polymeric films heated above their glass transition temperatures. In order to decrease the process time in the pillar formation process, work was done to study photocurable systems. The systems which proved favorable to the pillar creation process were the thiol-ene system as well as the maleimide systems. Further work was done on controlling the packing and ordering of the formed pillar arrays by using patterned templates. The result of these studies is that control was only able to be achieved to the third generation of pillars formed due to the inability to fully control the gap over the entire active area. / text

Large Area Maskless Photopolymerization (LAMP) is a direct digital manufacturing technology being developed at Georgia Tech to produce ceramic molds for investment casting of turbine airfoils. In LAMP, UV light incident on a spatial light modulator is projected in the form of a structured black and white bitmap image onto a platform supporting slurry comprising a ceramic particle loaded photocurable resin. Curing of the resin is completed rapidly with exposures lasting 20~160ms. Three-dimensional parts are built layer-by-layer by sequentially applying and selectively curing resin layers of 25-100 micron thickness. In LAMP, diacrylate-based ceramic particle-loaded resins with photoinitiators sensitive in the range of spectral characteristics of the UV source form the basis for an ultra-fast photopolymerization reaction. At the start of the reaction, the monomer molecules are separated by van der Waals distance (~10⁴Å). As the reaction proceeds, these monomer molecules form a closely packed network thereby reducing their separation to covalent bond lengths (~ 1 Å). This results in bulk contraction in the cured resin, which accumulates as the part is fabricated layer-by-layer. The degree of shrinkage is a direct measure of the number of covalent bonds formed. Thus, shrinkage in LAMP is characterized by estimating the number of covalent bonds formed during the photopolymerization reaction. Polymerization shrinkage and accompanying stresses developed during photopolymerization of ceramic particle-loaded resins in LAMP can cause deviations from the desired geometry. The extent of deviations depends on the photoinitiator concentration, the filler loading, the degree of monomer conversion, and the operating parameters such as energy dose. An understanding of shrinkage and stresses built up in a part can assist in developing source geometry compensation algorithms and exposure strategies to alleviate these effects. In this thesis, an attempt has been made to understand the curing kinetics of the reaction and its relation to the polymerization shrinkage. Realtime Fourier Transform Infrared Spectroscopy (RTFTIR) is used to determine the conversion of monomers into polymer networks by analyzing the changes in the chemical bonds of the participating species of molecules. The conversion data can further be used to estimate the curing kinetics of the reaction and the relative volumetric shrinkage strain due to polymerization.

Made available in DSpace on 2016-12-08T17:19:34Z (GMT). No. of bitstreams: 1 RESUMO.pdf: 12083 bytes, checksum: a5f4ea45fd2de1b6b09e1ac6c1fa5377 (MD5) Previous issue date: 2010-02-26 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this study we used an epoxy-acrylate fotocurável reinforced with multi walls carbon nanotubes (MWCN) in proportions of 0.25% wt/wt and NCPM 0.75% wt/wt MWCN. For the cure of nanocomposites as thin films for periods of 12 and 24 hours, manufactured from a chamber of ultraviolet radiation (UV-A). Aiming to analyze aspects related to properties mechanical, thermal and tribological adding NCPM in an epoxy-acrylate fotocurável were evaluated: elastic modulus, hardness, storage modulus, loss modulus, damping, coefficient of friction, wear rate and temperature of transition glass. In addition to these properties described previously, there was also the behavior of these nanocomposites related to thermal aspects (cure degree and thermal stability) and morphology of regions of fracture and wear parts. Tests performed were: nanoindentation, microhardness, dynamicmechanical analysis (DMA), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), test pin-on-disk and profilometry. The present results have shown gains of 67% in modulus, hardness at 77%, 154% in the storage module, 38% of the loss modulus, 24% reduction in friction and 24% reduction in the rate of wear with the addition of NC's in the nanocomposite studied. / Neste trabalho foi utilizado uma resina epóxi-acrilato fotocurável reforçada com nanotubos de carbono de paredes múltiplas (NCPM), nas proporções de 0,25% m/m NCPM e 0,75% m/m NCPM. Para a cura dos nanocompósitos na forma de filmes finos , por períodos de 12 e 24 horas, fabricou-se uma câmara de radiação ultra-violeta (UV-A). Buscando-se analisar aspectos ligados a propriedades mecânicas, térmicas e tribológicas da adição de NCPM em uma resina epóxi-acrilato fotocurável foram avaliados: módulo de elasticidade, dureza, módulo de armazenamento, módulo de perda, amortecimento, coeficiente de atrito, taxa de desgaste e temperatura de transição vítrea. Além dessas propriedades descritas anteriormente, verificou-se também o comportamento desses nanocompósitos relacionados a aspectos térmicos (grau de cura e estabilidade térmica) e aspectos morfológicos de regiões de fratura e regiões de desgaste. Os ensaios realizados foram: nanoindentação, microdureza, análise dinâmico-mecânica (DMA), calorimetria exploratória diferencial (DSC), análise termogravimétrica (TGA), microscopia eletrônica de varredura (MEV), ensaio pino-disco e perfilometria. Os resultados obtidos nesse trabalho comprovaram ganhos de 67% no módulo de elasticidade, 77% na dureza, 154% no módulo de armazenamento, 38% no módulo de perda, 24% de redução do coeficiente de atrito e redução de 24% na taxa de desgaste com a adição de NC s no nanocompósito em estudo.