Thesis (Ph.D.)--Duquesne University, 2007. / Title from document title page. Abstract included in electronic submission form. Includes bibliographical references (p. 32-55; 109-116; 185-191; 290-299; 330-332).

Thesis (Ph.D)--Chemical Engineering, Georgia Institute of Technology, 2009. / Committee Chair: J. Carson Meredith; Committee Member: Amyn Teja; Committee Member: F. Joseph Schork; Committee Member: Lawrence Bottomley; Committee Member: Mark Prausnitz. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Cette thèse de doctorat a été réalisée dans le cadre du projet Fiabilin, qui regroupe 15 partenaires industriels et académiques, et vise à structurer une filière industrielle de production de biocomposites polyamide-11/fibres de lin. Ces travaux ont pour objectif de déterminer des performances multi-échelles de ce composite 100% biosourcé, afin d’envisager son usage en substitution de composites pétrosourcés. Nous avons tout d’abord mis en évidence la sensibilité des fibres de lin aux cycles temps-température des procédés de mise en œuvre, tant du point de vue de leurs propriétés mécaniques que de leur structure biochimique. Ensuite, nous avons montré les capacités du système PA11-lin à produire des performances mécaniques en traction compétitives vis-à-vis d’autres composites pétrosourcés. La qualité de l’interface fibre/matrice du biocomposite a également été étudiée à différentes échelles, montrant une compatibilité supérieure à celles de systèmes lin-résines thermodurcissables. La fin de vie du composite PA11-lin a été envisagée à travers le recyclage par broyages et injections successives. Les propriétés mécaniques du biocomposite à fibres courtes ainsi obtenu sont semblables au composite PPgMA-lin, avec une déformation à rupture accrue et qui augmente significativement avec le nombre de recyclages. Une analyse des cycles de production de plusieurs composites révèle les plus faibles impacts environnementaux du PA11-lin lors d’un dimensionnement des pièces en rigidité équivalentes. / This thesis has been carried out as part of the project Fiabilin, which includes 15 different academic and industrial partners, with an aim to develop industrial production of polyamide-11/flax biocomposite. The purpose of this work is to determine multi-scale performances of 100% biosourced composite, in order to substitute composite materials containing glass fibers and/or matrix derived from petroleum. First, we highlighted the flax fiber sensibility toward processing cycles (time and temperature), from mechanical and biochemical structure aspects. Then, we revealed the capacity of PA11-flax association to produce competitive mechanical properties compared to others usual composites. Fiber-matrix interface of the biocomposite was studied at micro and macro scales, showing a higher compatibility than some flax-thermoset resin systems. The end-of-life of the biocomposite was considered by recycling with successive grinding and injections. Then stiffness and strength at break of short fiber biocomposites thus obtained are similar to PPgMA-flax composites, whereas a strong increase of the strain at break according to the number of injection cycles was observed. A life cycle analysis of some composites production steps shows lower environmental impacts of PA11-flax when sizing was made through equivalent material stiffness.

Orientador: Sandro Donnini Mancini / Banca: Marcia Aparecida da Silva Spinacé / Banca: Maria Zanin / O Programa de Pós-Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi da Unesp / Resumo: A reciclagem química de Poliamida 6,6 já é conhecida em patentes e aplicada por empresas de matéria-prima. Entretanto, a reciclagem química de poliamida 6,6 com cargas de fibras de vidro é pouco conhecida. O presente trabalho buscou estudar em escala laboratorial e Reciclagem Química, via Hidrólise, de resíduos dos processos de injeção de Poliamida 6,6 reforçada com 25% de fibras de vidro, descartados pela indústria automotiva após a reciclagem mecânica. Um procedimento de experimentos foi realizado para determinar qual a melhor proporção de água e do material compósito deveria ser reagido para obter o maior teor de fibras de vidro em um menor tempo. Os resultados mostraram que foi possível despolimerizar a Poliamida 6,6 partindo de um material já submetido a três ciclos de reciclagem mecânica com Massa Molar Viscosimétrica Média de 27.604 g.mol-1 obtendo Sal de Nylon com 322 g.mol-1 e 39,29% dos monômeros de base como Ácido adípico e hexametileno diamina em reações a 260ºC por 3 horas e 30 minutos apenas com água desmineralizada. Já a separação das fibras do material polimérico foi bem sucedida por filtragem a vácuo seguida de queima do resíduo orgânico, obtendo até 97,87 das fivras de vidro. Com base nestes resultados, concluiu-se que a reciclagem química deste material foi viável para a obtenção de Ácido Adípico, Hexametileno diamina e o reaproveitamento das fibras de vidro / Abstract: Chemical recycling of polyamide 6,6 is already known in patents and applied by companies of raw material. However, the chemical recycling of polyamide 6,6 with fillers of glass fibers is not well known. The present work studies in laboratory scale the Chemical Recycling, via hydrolysis, waste injection processes of Polyamide 6,6 reinforced with 25% glass fibers, discarded by the Automotive Industry. A procedure of experiments was conducted to determine the best rate water and composite should be reacter to obtain the highest level of glass fibers in less time. The experimental results show that it was possible to depolymerize the polyamide 6,6 starding form a material already subjected to threee cycles of mechanical recycling with molecular weight of 27.604 g.mol-1 and obtained salt of Nylon with 322 g.mol-1 and 39,29% of basis monomers as Adipic acid and hexamethilene diamina in reactions at 260ºC for 3 hours and 30 minutes only with demineralised water. Now the separation of the fibers of polymeric material succeeded by filtration under vacuum, followed by burning the organic residue, to obtain 97.87% of glass fibers. Based on these results, it was concluded that chemical recycling of this material was feasible to obtain adipic acid, hexamethylene diamine and reusing glass fibers / Mestre

Made available in DSpace on 2014-06-11T19:30:19Z (GMT). No. of bitstreams: 0 Previous issue date: 2013-01-18Bitstream added on 2014-06-13T20:00:21Z : No. of bitstreams: 1 machadoneto_ll_me_bauru.pdf: 3083706 bytes, checksum: 728b4d33580fd5aa924ed37190f283ca (MD5) / A reciclagem química de Poliamida 6,6 já é conhecida em patentes e aplicada por empresas de matéria-prima. Entretanto, a reciclagem química de poliamida 6,6 com cargas de fibras de vidro é pouco conhecida. O presente trabalho buscou estudar em escala laboratorial e Reciclagem Química, via Hidrólise, de resíduos dos processos de injeção de Poliamida 6,6 reforçada com 25% de fibras de vidro, descartados pela indústria automotiva após a reciclagem mecânica. Um procedimento de experimentos foi realizado para determinar qual a melhor proporção de água e do material compósito deveria ser reagido para obter o maior teor de fibras de vidro em um menor tempo. Os resultados mostraram que foi possível despolimerizar a Poliamida 6,6 partindo de um material já submetido a três ciclos de reciclagem mecânica com Massa Molar Viscosimétrica Média de 27.604 g.mol-1 obtendo Sal de Nylon com 322 g.mol-1 e 39,29% dos monômeros de base como Ácido adípico e hexametileno diamina em reações a 260ºC por 3 horas e 30 minutos apenas com água desmineralizada. Já a separação das fibras do material polimérico foi bem sucedida por filtragem a vácuo seguida de queima do resíduo orgânico, obtendo até 97,87 das fivras de vidro. Com base nestes resultados, concluiu-se que a reciclagem química deste material foi viável para a obtenção de Ácido Adípico, Hexametileno diamina e o reaproveitamento das fibras de vidro / Chemical recycling of polyamide 6,6 is already known in patents and applied by companies of raw material. However, the chemical recycling of polyamide 6,6 with fillers of glass fibers is not well known. The present work studies in laboratory scale the Chemical Recycling, via hydrolysis, waste injection processes of Polyamide 6,6 reinforced with 25% glass fibers, discarded by the Automotive Industry. A procedure of experiments was conducted to determine the best rate water and composite should be reacter to obtain the highest level of glass fibers in less time. The experimental results show that it was possible to depolymerize the polyamide 6,6 starding form a material already subjected to threee cycles of mechanical recycling with molecular weight of 27.604 g.mol-1 and obtained salt of Nylon with 322 g.mol-1 and 39,29% of basis monomers as Adipic acid and hexamethilene diamina in reactions at 260ºC for 3 hours and 30 minutes only with demineralised water. Now the separation of the fibers of polymeric material succeeded by filtration under vacuum, followed by burning the organic residue, to obtain 97.87% of glass fibers. Based on these results, it was concluded that chemical recycling of this material was feasible to obtain adipic acid, hexamethylene diamine and reusing glass fibers

Orientador: Maria Isabel Felisberti / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-09T13:26:12Z (GMT). No. of bitstreams: 1 Desidera_Cassiane_D.pdf: 2267266 bytes, checksum: 9f026acbcd18caa17f017b257c7f0b46 (MD5) Previous issue date: 2007 / Resumo: Blendas de poliamida e polietileno são exemplos de misturas imiscíveis e incompatíveis. Entretanto, a compatibilidade pode ser alcançada adicionando-se compatibilizantes ou promovendo a mistura reativa. Neste projeto teve-se como objetivo o preparo e a caracterização de blendas de poliamida-66 reciclada (rPA-66) e diferentes polietilenos, incluindo materiais virgens e reciclados: 1) vPEBD - polietileno de baixa densidade virgem, 2) vEMAA - poli(etileno-co-ácido metacrílico) virgem, 3) rPEBD - uma mistura reciclada contendo PEBD e EMMA, e 4) PEAI - uma mistura reciclada contendo PEBD, EMMA e alumínio particulado. As blendas foram preparadas em extrusora dupla rosca e os corpos de prova, obtidos por injeção, foram caracterizados por análise dinâmico-mecânica (DMA), microscopia eletrônica de varredura (SEM), calorimetria exploratória diferencial (DSC), análise termogravimétrica (TG), espectroscopia de infravermelho com transformada de Fourier (FTIR), ensaios de solubilidade seletiva, índice de fluidez (IF) e testes mecânicos de tração e de resistência ao impacto. Foi constatada a formação de um copolímero de enxertia (PE-g-rPA66) gerado in situ durante o processamento, o qual promoveu uma maior adesão interfacial para as blendas rPA-66/vEMAA, rPA-66/rPEBD e rPA-66/PEAI em relação à blenda rPA-66/vPEBD. A degradação prévia sofrida pelos polímeros reciclados (rPEBD e PEAI) durante sua vida útil e etapas de reciclagem, mostrou ser um fator importante para a obtenção do copolímero de enxertia. Em especial, o PEAI apresenta a maior susceptibilidade à degradação devido ao efeito catalítico das partículas de alumínio, fator este que levou a maior formação do copolímero PE-g-rPA-66 em relação aos outros polietilenos. De maneira geral, as blendas apresentaram resistência ao impacto e deformação na ruptura superiores às da poliamida e estabilidade térmica superior a do polietileno / Abstract: Polyamide and polyethylene blends are examples of immiscible and incompatible systems. However, the compatibility can be reached adding compatibilizer to the system or promoting the reactive blending. The aim of this work was to prepare and characterize blends of recycled polyamide-66 (rPA-66) with different grades of polyethylenes, including virgin and recycled materials obtained from recovered multilayer packaging: 1) vLDPE - virgin low density polyethylene, 2) vEMAA - virgin ethylene-methacrylic acid copolymer (EMAA), 3) rLDPE - a recycled mixture of two polymers: LDPE and EMAA and 4) PEAI - a mixture of three materials: LDPE, EMAA and aluminum particles. The blends were prepared in a twin screw extruder and characterized by dynamic-mechanical analysis (DMA), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier Transformed Infra Red Spectroscopy (FTIR), solubility tests, melt flow index (MFI) and impact and tensile tests. The grafted copolymer (PE-g-rPA66) was generated in situ during the processing. This copolymer provided higher interfacial adhesion of rPA-66/EMAA, rPA-66/rLDPE and rPA-66/PEAI blends in comparison with the PA-66/vLDPE blend. The previous degradation suffered by the recycled polymers (rLDPE and PEAI) in their usefull life and the recycling stages, as well their higher susceptibility to the thermal degradation in the processing step, seems to be an important factor for obtaining the grafted copolymer (PE-g-rPA66). The aluminum particles accelerated the LDPE degradation and also improved the grafting copolymerization in comparison with others polyethylenes. In general, the blends showed higher impact strength and elongation at break that polyamide and higher thermal stability that polyethylene / Doutorado / Físico-Química / Doutor em Ciências

Solvent suspensions of a high performance polymer, Polyamide-imide (PAI) are widely used in magnetic wire coatings. Here we investigate the effect that the introduction of montmorillonite (MMT) has on PAI. MMT was introduced into an uncured PAI suspension; the sample was then cured by step-wise heat treatment. Polarized optical microscopy was used to choose the best suitable MMT for PAI matrix and to study the distribution of MMT in PAI matrix. Concentration dependent dispersion effect was studied by x-ray diffraction (XRD) and was confirmed by Transmission electron microscopy (TEM). Differential scanning Calorimetry (DSC) and Thermogravimetric analysis (TGA) was used to study impact of MMT on glass transition temperature (Tg) and degradation properties of PAI respectively. Micro-hardness testing of PAI nanocomposites was also performed. A concentration dependent state of dispersion was obtained. The glass transition (Tg), degradation and mechanical properties were found to correlate to the state of dispersion.

Yes / The present work deals with the flow-induced multiple orientations and crystallization structure of polymer melts under a complex flow field. This complex flow field is characteristic of the consistent coupling of extensional “pulse” and closely followed shear flow in a narrow channel. Utilizing an ingenious combination of an advanced micro-injection device and long chain aliphatic polyamides (LCPA), the flow-induced crystallization morphology was well preserved for ex-situ synchrotron micro-focused wide angle X-ray scattering (μWAXS) as well as small angle X-ray scattering (SAXS). An inverted anisotropic crystallization structure was observed in two directions: perpendicular and parallel to the flow direction (FD). The novel anisotropic morphology implies the occurrence of wall slip and “global” fountain flow under the complex flow field. The mechanism of structure formation is elucidated in detail. The experimental results clearly indicate that the effect of extensional pulse on the polymer melt is restrained and further diminished due to either the transverse tumble of fountain flow or the rapid retraction of stretched high molecular weight tails. However, the residual shish-kebab structures in the core layer of the far-end of channel suggest that the effect of extensional pulse should be considered in the small-scaled geometries or under the high strain rate condition.

The polyamide poly(ε-caprolactam) or "nylon 6" is a very important fiber forming polymer which finds many applications in the carpet industry and elsewhere due to the very high strength of this fiber. However, a major drawback is its hydrophilicity. This feature influences both the surface and bulk mechanical behavior. Siloxane based macromolecules are hydrophobic, thermally stable and exhibit dimensional stability over a wide temperature range. Unlike the polyamide nylon 6, these hydrophobic materials display relatively low surface free energy. Thus, they can be used for the surface modification of nylon 6, provided a suitable adhesion or "anchoring" method is feasible. Polyamide-polydimethylsiloxane segmented or block copolymers were found to be suitable "interfacial" agents. They were synthesized by reacting aminopropyl-terminated polydimethylsiloxane (PDMS) oligomers with sebacyl chloride via an interfacial polymerization in which methylene chloride was used as the solvent or organic phase. A second diamine "chain extender" was also utilized, if desired. By varying the mole ratio of soft segment to the chain extender p-aminocyclohexylmethane (PACM-20), copolymers with various percentages of hard segments can be synthesized. Weight fractions of 2, 5, or 10% of the polyamide-poly-dimethylsiloxane block copolymers were physically melt mixed with nylon 6 in an extruder. The presence of polydimethylsiloxane on the surface of the blend was detected by determining the critical surface tensions of wetting using water as the contact angle test liquid. Such modified polyamides were successfully melt spun into fibers which displayed good mechanical properties and enhanced soil resistance. Fibers spun from these modified nylon 6 blends showed surface hydrophobicity. These modified polyamides or related materials may become technologically important in carpeting applications. Additional studies involving attempts at directly polymerizing ε-caprolactam via hydrolytic ring opening polymerization from functional polysiloxanes are also reported. In general, the structural integrity of these copolymers is less well defined. Certain procedures utilizing the aminopropyl polydimethylsiloxane initiated lactam oligomerization, followed by adipic acid chain extension produced interesting materials and should be further examined. / Master of Science / incomplete_metadata

Polymer synthesis and functionalization enabled the tailoring of polymer functionality for additive manufacturing (AM), elastomer, and biological applications. Inspiration from academic and patent literature prompted an emphasis on polymer functionality and its implications on diverse applications. Critical analysis of existing elastomers for AM aided the synthesis and characterization of novel photopolymer systems for lithography-based 3D printing. Emphasis on structure-processing-property relationships facilitated the attainment of success in proposed applications and prompted further fundamental understanding for systems that leveraged poly(dimethyl siloxane)s (PDMS), aliphatic polyesters, polyamides, and polyethers for emerging applications. The thiol-ene reaction possesses many desirable traits for vat photopolymerization (VP) AM, namely that it proceeds rapidly to high yield, does not undergo significant side reactions, remains tolerant of the presence of water or oxygen, and remains regiospecific. Leveraging these traits, a novel PDMS-based photopolymer system was synthesized and designed that underwent simultaneous chain extension and crosslinking, affording relatively low viscosity prior to photocuring but the modulus and tensile strain at break properties of higher molecular weight precursors upon photocuring. A monomeric competition study confirmed chemical preference for the chain-extension reaction in the absence of diffusion. Photocalorimetry, photorheology, and soxhlet extraction measured photocuring kinetics and demonstrated high gel fractions upon photocuring. A further improvement on the low-temperature elastomeric behavior occurred via introduction of a small amount of diphenylsiloxane or diethylsiloxane repeating units, which successfully suppressed crystallization and extended the rubbery plateau close to the glass transition temperature (Tg) for these elastomers. Finally, a melt polymerization of PDMS diamines in the presence of a disiloxane diamine chain extender and urea afforded isocyanate-free polyureas in the absence of solvent and catalyst. Dynamic mechanical analysis (DMA) measured multiple, distinct α-relaxations that suggested microphase separation. This work leverages the unique properties of PDMS and provides multiple chemistries that achieve elastomeric properties for a variety of applications. Similar work of new polymers for VP AM was performed that leveraged the low Tg poly(propylene glycol) (PPG) and poly(tri(ethylene glycol) adipate) (PTEGA) for use in tissue scaffolding, footwear, and improved glove grip performance applications. The double endcapping of a PPG diamine with a diisocyanate and then hydroxyethyl acrylate provided a urethane/urea-containing, photocurable oligomer. Supercritical fluid chromatography with evaporative light scattering detection elucidated oligomer molecular weight distributions with repeat unit resolution, while the combination of these PPG-containing oligomers with various reactive diluents prior to photocuring yielded highly tunable and efficiently crosslinked networks with wide-ranging thermomechanical properties. Functionalization of the PTEGA diol with isocyanatoethyl methacrylate yielded a photocurable polyester for tissue scaffolding applications without the production of acidic byproducts that might induce polymer backbone scission. Initial VP AM, cell viability experiments, and modulus measurements indicate promise for use of these PTEGA oligomers for the 3D production of vascularized tissue scaffolds. Similar review of powder bed fusion (PBF) patent literature revealed a polyamide 12 (PA12) composition that remained melt stable during PBF processing, unlike alternative commercial products. Further investigation revealed a fundamental difference in polymer backbone and endgroup chemical structure between these products, yielding profound differences for powder recyclability after printing. An anionic dispersion polymerization of laurolactam in the presence of a steric stabilizer and initiator yielded PA12 microparticles with high sphericity directly from the polymerization without significant post-processing requirements. Steric stabilizer concentration and stirring rate remained the most important variables for the control of PA12 powder particle size and melt viscosity. Finally, preliminary fusion of single-layered PA12 structures demonstrated promise and provided insight into powder particle size and melt viscosity requirements. / PHD / Additive manufacturing (AM) enables the creation of unique geometries not accessible with alternative manufacturing techniques such as injection molding, while also reducing the waste associated with subtractive manufacturing (e.g. machining). However, AM currently suffers from a lack of commercially-available polymers that provide elastomeric properties after processing. Poly(dimethyl siloxane)s (PDMS) possess distinctive properties due to their organosilicon polymer backbone that include chemical inertness, non-flammability, high gas permeability, and low surface energy. For these reasons, siloxanes enjoy wide-ranging applications from personal care products, contact lenses, elastomeric sealants, and medical devices. This dissertation focuses on the synthesis and functionalization of novel PDMS-, polyether-, polyester-, and polyamide-containing photopolymers or powders for improved performance in diverse applications that employ processing via vat photopolymerization (VP) or powder bed fusion (PBF) AM. Examples from this work include a novel photopolymer composition that undergoes simultaneous chain extension and crosslinking, affording low molecular weight and low viscosity precursors prior to VP-AM but the properties of higher molecular weight precursors, once photocured. Related work involved the characterization and VP-AM of siloxane terpolymers that suppress crystallization normally observed in PDMS, resulting in 3D printed objects that retain their elastomeric properties close to the glass transition temperature (Tg). Separate work leveraged the unique PDMS backbone for the melt polymerization of PDMS diamines in the presence of a chain extender and urea, yielding isocyanate-free PDMS polyureas in the absence of solvent or catalyst. This reaction creates ammonia as the only by-product and avoids the use of isocyanates, as well as their highly toxic precursors, phosgene. Finally, another research direction facilitates the understanding of observed differences in melt stability between commercially-available grades of polyamide 12 (PA12) powders for powder bed fusion. An anionic dispersion polymerization based in the patent literature facilitated further understanding of the polymerization process and produced melt-stable PA12 microparticles directly from the polymerization process, without requiring additional post-processing grinding or precipitation steps for powder production.