The microelectronics industry strives for continued reduction in feature sizes to allow increased computing speed and power. This calls for continuous development of new materials. During the shift to 157 nm photolithography, it was discovered that fluorinated materials were necessary to provide sufficient transparency. Material design and synthesis to incorporate fluorine bearing norbornane based materials through an alternate means of polymerization to those used in traditional lithographic materials will be presented. Step and Flash Imprint Lithography represents a low cost alternative to optical lithography for production of nanoscale features. Sub-20 nm features have been produced using commercial tools however the contact between the imprint template and resist formulation leaves the template prone to fouling. A new imprint resist designed to facilitate wafer reworking and template cleaning is presented. The small amount of power available from deep ultraviolet light sources necessitates the use of systems that behave in a catalytic manner that is referred to as gain. The use of small molecules for gain necessitates a reliance on diffusion through the resist film and results in image bias. A polymeric material that undergoes depropagation catalyzed by a single photochemical event and causes a solubility change due to this event represents a system that possesses gain while removing diffusion bias. Progress towards such a system is presented. / text

No / Advances in micromoulding technology are leading to complex,net-shape products having sub-milligramme masses with micro-scale surface features in a range of polymer and nano-composite materials.For such small components subjected to the extreme stress,strain-rate and temperature gradients encountered in the micromoulding process,detailed process monitoring is desirable to highlight variations in moulding conditions and assist in creating a viable manufacturing process with acceptable quality products.This paper covers the implementation of a suite of sensors on a commercial micromoulding machine and detailed computer monitoring during processing of a polyacetal component over a range of processing conditions.The results determined that cavity pressure curve integral data provides the most sensitive factor for characterisation of a moulding process of a 0.34 mm~3(0.49 mg)product.The repeatability of the process is directly compared with that of a 15.6mm~3(22.2 mg)product and shown to beinferior.DSC measurements of the whole products indicated little variation in average crystallinity of the products manufactured over a mould temperature range of 30 to 130deg C.

Orientador: Prof. Dr. Derval dos Santos Rosa / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2016. / Polímeros vêm sendo cada vez mais utilizados em diversas aplicações e sua produção mundial cresce a cada ano. O polipropileno, material pertencente à família das poliolefinas, é um dos termoplásticos de maior produção entre os polímeros desta classe. O descarte inadequado de resíduos provenientes de materiais poliméricos, sendo o polipropileno o material com maior quantidade destes, gera grande preocupação por conta do impacto ambiental provocado pelos mesmos. Mediante tal problema, este trabalho tem como objetivo buscar uma solução ambientalmente adequada, investigando a possibilidade de degradação abiótica do polipropileno através da introdução de agentes pró-oxidantes orgânicos em sua cadeia, sendo estes o poliacetal e agente orgânico Eco-one®, por meio de dois envelhecimentos acelerados, térmico em estufa e fotooxidativo . A caracterização das amostras foi realizada por meio dos ensaios de índice de fluidez (IF), propriedades mecânicas (PM), espectroscopia na região do infravermelho com transformada de Fourier (FTIR), análise termogravimétrica (TGA), calorimetria diferencial de varredura (DSC), microscopia eletrônica de varredura (MEV) e cromatografia de permeação em gel (GPC). De acordo com os resultados de ensaio mecânico de tração, FTIR, TGA, DSC, MEV e GPC analisados, é possível afirmar que os envelhecimentos fotooxidativo e em estufa foram eficazes na degradação do polipropileno e de suas composições com Eco-one® e POM. Além disso, pode-se afirmar que os agentes pró-oxidantes incorporados à matriz de PP se mostraram eficientes no processo de degradação foto e termo-oxidativa, promovendo com os envelhecimentos, uma possível cisão das cadeias do PP. No entanto, a presença dos agentes pró-oxidantes na matriz de PP não promoveu sua degradação antes dos envelhecimentos. O envelhecimento acelerado em Weather-Omether® favoreceu igualmente a degradação tanto do PP puro quanto das composições com Eco-one® e POM. Já o envelhecimento acelerado em estufa favoreceu mais acentuadamente a degradação das composições com POM. / Polymers are being increasingly used in various applications, and their world production grows every year. Polypropylene, a material belonging to the family of polyolefins, is one of the most produced thermoplastic among the polymers of this class. The improper disposal of waste from polymeric materials, being polypropylene the material with the highest amount of waste produced, generates great concern because of the environmental impact caused by it. Upon such problem, this work aims to seek an environmentally sound solution, investigating the possibility of abiotic degradation of polypropylene by introducing organic pro-oxidants in its chain, these being Polyacetal and the organic agent Eco-one®, by two accelerated aging methods, thermal in air oven and photo-oxidative. The characterization of the samples was performed by melt flow index testing (IF), mechanical properties (PM), infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and gel permeation chromatography (GPC). According to the analyzed results of tensile tests, FTIR, TGA, DSC, SEM and GPC, it is clear that the aging photo-oxidative and oven air procedures are effective in degrading polypropylene and its compositions with Eco-one® and POM. In addition, it can be stated that the pro-oxidant agents incorporated into the PP matrix were efficient in the process of photo and thermo-oxidative degradation, promoting along with the aging procedures, the breaking of PP chains. However, the presence of pro-oxidant agents in the PP matrix does not promote its degradation before aging. The accelerated aging in Weather-Ometer® also favored the degradation of both the pure PP and the samples containing Eco-one® and POM. On the other hand accelerated aging in an oven favored more markedly the degradation of the compositions with POM.

The prevention and treatment of cancer and infectious diseases requires vaccines that can mediate cytotoxic T lymphocyte-based immunity. A promising strategy is protein subunit vaccines composed of purified protein antigens and immunostimulatory adjuvants, such as Toll-like receptor (TLR) agonists. In this research, we developed two new biodegradable polymeric delivery vehicles for protein antigens and TLR agonists, as model vaccine delivery systems. This work was guided by the central hypothesis that an effective vaccine delivery system would have stimulus-responsive degradation and release, biodegradability into excretable non-acidic degradation products, and the ability to incorporate various TLR-inducing adjuvants. The first vaccine delivery system is a cross-linked polyion complex micelle which efficiently encapsulates proteins, DNA, and RNA. The micelle-based delivery system consists of a block copolymer of poly(ethylene glycol) (PEG) and poly(L-lysine), cross-linked by dithiopyridyl side groups to provide transport stability and intracellular release. The second delivery system consists of solid biodegradable microparticles encapsulating proteins, nucleic acids, and hydrophobic compounds. The microparticles are composed of pH-sensitive polyketals, which are a new family of hydrophobic, linear polymers containing backbone ketal linkages. Polyketals are synthesized via a new polymerization method based on the acetal exchange reaction and degrade into non-acidic, excretable degradation products. In addition, the technique of hydrophobic ion pairing was utilized to enhance the encapsulation of ovalbumin, DNA, and RNA in polyketal microparticles via a single emulsion method. Using in vitro and in vivo immunological models, we demonstrated that the micelle- and polyketal-based vaccine delivery systems enhanced the cross-priming of cytotoxic T lymphocytes. The model vaccines were composed of ovalbumin antigen and various TLR-inducing adjuvants including CpG-DNA, monophosphoryl lipid A, and dsRNA. The results demonstrate that the cross-linked micelles and polyketal microparticles have considerable potential as delivery systems for protein-based vaccines.

A partir des mêmes briques élémentaires portant des fonctions aldéhydes et mettant en jeu des catalyseurs différents, trois types de nouveaux polymères ont été synthétisés par la polymérisation par étape dans ce travail. Dans la première partie, bis-cétone et bis-aldéhyde monomères ont directement polymérisé dans des conditions stoechiométriques par ce processus offrant polyaldols. Divers catalyseurs et des effets de la nature du solvant ont ensuite été étudiés. Dans la deuxième partie, nous avons travaillé sur la polymérisation organo-catalysée de monomères bis-aldéhydes par des précurseurs de carbènes N-hétérocycliques chiraux et achiraux pour synthétiser les polymères chiraux. Enfin, la directe polymérisation des monomères de type AB2 avec une fonction aldéhyde fournit une facile synthétique approche à polyacétals hyperbrramifiés portant nombreux périphéries aldehyiques. Ces polyacétals hyperramifiés sans défauts structuraux ont ensuit été introduirsé par des chaines de PEO par réaction de « PEGylation ». L’utilisation de la postpolymymérisation permet d’offre un large varité de la propriété du polymère, à l’aide ces périphéries aldéhydiques. Enplus, les polyacétals hyperramifiés sont dégradables, et facilement hydrolysés en milieu acide. / Using the same building blocks carrying aldehyde function with different catalysts, three types of new polymers were synthesized by step-growth polymerization in this work. In the fist part, bis-ketone and bis-aldehyde monomers have been directly polymerized under stoichiometric conditions by this process affording polyaldols. The effects of different catalysts and solvent nature have also been studied. In the second part, we have studied the organo-catalyzed polymerization of bis-aldehyde monomers by precursors of chiral and achiral N-heterocyclic carbene for synthesis of chiral polymer. Finally, polymerization of AB2-type monomers with one function of aldehyde provides a facile synthetic approach to hyperbranched polyacetals carrying numerous peripheral aldehydes. These defect free hyperbranched polyacetals have been introduced PEO chains by "PEGylation" reaction. A wide variety of other functional moieties could be introduced by postpolymerization with peripheral aldehydes. Besides, the hyperbranched polyacetals are degradable in essence, being readily hydrolyzed under acidic condition.