In this study, novel lamination techniques are introduced for the coating of fabrics in order to enhance their ballistic/needle penetration resistance properties. Pressure sensitive adhesive (PSA) was used to create flexible ballistic composite panels with ultra-high molecular weight polyethylene (UHMWPE) fabric. An increase in processing pressure from 0.1 to 8 MPa significantly improved the ballistic performance against 9 mm FMJ ammunition of UHMWPE composite. The number of layers required to stop the bullet were reduced from 45 to 22 layers after lamination without a significant increase in stiffness. The backface signature (BFS) was reduced from 19.2 mm for the 45 layer neat samples to 11.7 mm for the 25 layer laminated samples pressed at 8 MPa. The second lamination technique used patterned thermoplastic hot film to create flexible UHMWPE composite laminates. Hexagonal patterns were cut through a heat transfer vinyl carrier sheet using a vinyl cutter and was used as a mask between the UHMWPE fabric and hot film during heat treatment in order to have the fabric coated only on those regions. The patterns had a nominal diameter of 27.9 mm with a 1 mm gap between each region. A significant improvement in the ballistic performance of UHMWPE fabric is observed after coating each individual layer with patterned hot film and 25 layers of laminated fabric were sufficient to stop a .357 magnum FMJ ammunition compared to unlaminated neat fabric which required 45 layers to stop the bullet. Patterning of the hot film did not negatively affect the ballistic performance of the composite laminates whilst increasing their flexibility in relation to using plain hot film with no patterning involved. It resulted in a 21% increase in bending angle of the 25 layer samples v and 9.5% reduction in bending length of the single plies which both relate to greater flexibility because a higher bending angle and lower bending length correlates to more flexibility. The same technique of patterning of hot film is used in the lamination of woven cotton fabric to enhance needle penetration resistance properties whilst maintaining the flexibility. Patterns used in this study were either hexagonal or a combination of hexagons and triangles and the nominal diameter ranged from 2.6-13.5 mm. The lamination significantly improved the 25G hypodermic needle penetration resistance of the fabric. By increasing the number of laminated fabric plies from 1 to 2, the needle resistance force increased by up to 150%. However, in comparison to just one layer, the flexibility decreased by about 12% to 26% for two and three layers, respectively. It was observed that reducing the sizes of the patterns improved the flexibility of the samples by up to 30% without compromising the needle penetration resistance. / Thesis / Master of Applied Science (MASc)

No description available.

No description available.

Polymers containing poly(1,3-cyclohexadiene) were synthesized using a novel pre-formed initiator comprised of an alkyllithium and a tertiary diamine. The use of a pre-formed intiator at moderate temperatures (25° C) enabled the synthesis of high molecular weight poly(1,3-cyclohexadiene) homopolymers (<Mn> = 50000) with narrow molecular weight distributions (<Mw>/<Mn> = 1.20). In contrast, the use of a conventional anionic initiation approach resulted in polymerizations that lacked significant degrees of livingness, which limited the polymer molecular weights to approximately 10000. Use of the preformed initiator resulted in a reduction in the degree of both chain termination and chain transfer. In addition, the livingness of the polymerization was shown to be a function of the monomer concentration and the polymerization temperature. The regiochemistry of the polymers were shown to be dependent on the tertiary amine used in the polymerization, which provided a route for the synthesis of polymers with a microstructure rich in either high 1,2-addition (70%) or high 1,4-addition (90%). A range of analytical methods were employed to determine the stereo and regiochemistry of poly(1,3-cyclohexadiene). These methods included 1H NMR, 13C NMR, and endgroup functionalization of the propagating center with chlorotrimethylsilane. The impact of regiochemistry on the thermal properties was examined using differential scanning calorimetry. In addition, the thermooxidative properties of these poly(1,3-cyclohexadiene) polymers were characterized in a series of oxidative studies and the onset of oxidative degradation occurred at 110° C. Perfectly alternating copolymers of poly(1,3-cyclohexadiene-alt-styrene) were synthesized, and the reactivity ratios for these copolymers (r1,3CHD = 0.022, rstyrene = 0.024) were determined using a conventional Mayo-Lewis approach. The effect of aromatization and hydrogenation on the thermal properties of these copolymers was determined using thermal gravimetric analysis and differential scanning calorimetry. The synthesis of poly(1,3-cyclohexadiene) DVB coupled star-shaped polymers was performed using a convergent arm-first approach in combination with a divinylbenzene coupling agent (PDI = 1.25). Well-defined poly(1,3-cyclohexadiene-block-isoprene)-star shaped polymers were synthesized and utilized for the development of novel high temperature thermoplastic elastomers, with excellent elastomeric properties (percent elongation = 745 %, tensile strength = 7.2 MPa). Atomic force microscopy in combination with differential scanning calorimetry verified the presence of microphase separation between the blocks. / Ph. D.

Poly-γ-glutamic acid (γ-PGA) is a biopolymer made up of repeating units of L-glutamic acid, D-glutamic acid or both. γ-PGA is water soluble, non-toxic and biodegradable, and can be used safely in a variety of applications that are increasing rapidly. This study investigated the production of HMW γ-PGA by five Bacillus species (B. licheniformis 1525, B. licheniformis NCTC 6816, B. licheniformis ATCC 9945a, B. licheniformis ATCC 9945a and B. subtilis (natto) ATCC 15245) in GS, C and E media for the removal of heavy metals in wastewaters. The highest γ-PGA yields of 11.69 g/l and 11.59 g/l were produced by Bacillus subtilis (natto) ATCC 15245 in GS medium and medium C respectively. Upon characterization, γ- PGAs with different properties (crystallinity, acid/salt form and molecular weights ranging from 2.56 × 105 Da to 1.65 × 106 Da) were produced. The water soluble, non-toxic, HMW (Mw 1.65 × 106 Da) γ-PGA produced by B. subtilis (natto) ATCC 15245 in medium C was investigated as a sorbent for the removal of heavy metal ions including Cu2+, Zn2+, Ni2+, Cd2+ and Ag+. The results showed that the removal of metals by γ-PGA was more dependent on the concentration of γ-PGA than the solution pH. The highest metal ions removal of 93.50%, 88.13%, 90.21%, 90.56% and 86.34% by HMW γ-PGA were obtained for Cu2+, Zn2+, Ni2+, Cd2+ and Ag+ respectively. The presence of interfering metal ions could hinder the adsorption of individual metal ions by γ-PGA. The affinities of heavy metal ions for γ-PGA followed the order: Cu2+ > Zn2+ > Ni2+ > Cd2+. The effect of molecular weight of γ-PGA on metal removal was also investigated, and it was found that metal ion adsorption capacity of γ-PGA strongly depended on its molecular weight. The maximum amount (93.50%) of Cu2+ sorbed by HMW γ-PGA was higher compared to that (59.48%) sorbed by LMW γ-PGA. Isotherm models showed that the Redlich-Peterson best described the metal adsorption capacity of γ-PGA. It was also found that a multisite adsorption mechanism occurred via the complexation of metal ions with the free α-carboxyl and possibly the amide functional groups in γ-PGA.

Les techniques de séquençage ont connu un extraordinaire développement depuis plus de 40 ans et ont permis une véritable révolution dans le domaine de l’analyse biologique avec l’entrée dans l’ère de la génomique. Le développement de nouvelles méthodes de séquençage est néanmoins associé à des contraintes sur la préparation et le contrôle qualité des échantillons d’ADN. La 3ème génération de séquenceurs nécessite notamment l’utilisation de fragments d’ADN de très grande taille, supérieurs à 50000 paires de bases, qui sont complexes à préparer et à caractériser avec les techniques actuelles. Dans la perspective d’accélérer et d’améliorer ces procédures de préparation d’échantillons, nous avons développé un instrument basé sur la technologie µLAS permettant la concentration et la séparation de grands fragments d’ADN. Nous avons en particulier développé une méthode permettant la concentration, l’isolation et le séquençage de régions génomiques ciblées en les découpant avec l’enzyme de restriction Cas9. Nous avons également développé un prototype pour la purification d’ADN de haut poids moléculaire dans un mélange complexe. Cet instrument permet d’effectuer une vanne de sélection d’ADN accordable pilotée par champ électrique. Adaptée à l’enrichissement sélectif d’ADN selon sa taille de 200 bp à 50 000 bp, notre méthode permet d’effectuer une purification de 20 ng d’ADN génomique de taille supérieure à 20 kb avec la technologie de 10X Genomics. Nous avons ainsi montré le potentiel de la technologie µLAS dans l’analyse et la purification d’ADN de haut poids moléculaire. / In forty years only, DNA sequencing technologies triggered a revolution in biological analysis with the beginning of the genomic era. Nevertheless, this booming technological field is still hampered by unmet technological needs for DNA sample preparation and quality control. The most recent third generation sequencing technologies require very long DNA fragments of more than 50,000 base pairs, the manipulation and characterization of which remains a technological challenge. In the prospect of accelerating and improving state of the art protocols for sample preparation, we developed an instrument, based on the µLAS technology that allows the concentration and separation of high molecular weight DNA fragments with high sensitivity. With this technology, we developed a method for the isolation and sequencing of target genomic regions in complex genomes. We report the isolation, the sequencing and the assembly of a locus of 31.5 kb extracted from the genome of the plant Medicago Truncatula. We finally developed a prototype for high molecular weight DNA purification in complex samples, which is based on a size-accordable DNA valve for the size selection in the range 200 – 50,000 bp. In this manuscript we highlighted the relevance of µLAS technology for the analysis and purification of high molecular weight DNA.

This work examines the chemical and physical effects of a material treatment process on the biopolymers PEEK, POM-h, POM-c, PTFE and UHMWPE. The polymers are analyzed physically and chemically using atomic force microscopy, profilometry, scanning electron microscopy, optical microscopy, contact angle measurement, FT infra-red spectroscopy and energy dispersive X-ray spectrometry. PEEK is found to be the most suitable polymer and FT Infra-red spectroscopy an informative analytic tool.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-04-13T17:46:55Z No. of bitstreams: 1 MÁRCIA CRISTINA DE MORAES REIS RIBEIRO - DISSERTAÇÃO PPG-CEMat 2014..pdf: 1739612 bytes, checksum: 483de315f077aaf3a1be5bb9bddc6639 (MD5) / Made available in DSpace on 2018-04-13T17:46:55Z (GMT). No. of bitstreams: 1 MÁRCIA CRISTINA DE MORAES REIS RIBEIRO - DISSERTAÇÃO PPG-CEMat 2014..pdf: 1739612 bytes, checksum: 483de315f077aaf3a1be5bb9bddc6639 (MD5) Previous issue date: 2014-07-16 / O polietileno de ultra alto peso molecular (PEUAPM) é um polímero com excelentes propriedades físicas e mecânicas tendo como mais notáveis a sua inércia química, a lubricidade, resistência impacto e resistência a abrasão. Exibe um papel relevante no sucesso na Artroplastia Total de Joelho (ATJ) e Artroplastia Total de Quadril (ATQ). A Artroplastia se caracteriza pela substituição da articulação natural por uma articulação artificial. As articulações artificiais são formadas por um conjunto de componentes, sendo fabricados de matéria prima metálica ou cerâmica e um componente, normalmente feito em PEUAPM, que é interposto entre componentes metálicos. Alguns fatores contribuem para um maior desgaste do componente de polietileno. Os componentes fabricados em polietileno PEUAPM não possuem fotoestabilizadores. E em inspeções realizadas em fabricantes e distribuidores destes produtos foi observado que durante seu processamento fabril e comercialização eles não são adequadamente protegidos da iluminação direta. As características consideradas importantes para o desempenho in vitro destes dispositivos estão definidas em normas técnicas, mas muitas destas normas somente recomendam determinados requisitos considerados importantes do ponto de vista técnico. Atualmente a área de materiais de uso em saúde trabalha em regulamentos que visam instituir os requisitos mínimos para registro de implantes ortopédicos. Desta forma, este trabalho propôs avaliar as possíveis alterações de componentes fabricados em polietileno de ultra alto peso molecular utilizados em procedimentos cirúrgicos de artroplastia e joelho e quadril, exposto a radiação ultravioleta. O trabalho foi dividido em 4 grupos: grupo 1 (material não exposto a UV); grupo 2 (material exposto a UV por 1h); grupo 3 (material exposto a UV por 24h) e grupo 4 (material exposto a UV por 48h). Todas as amostras foram caracterizadas por Difração de Raio X (DRX), Espectroscopia de Absorção de Infravermelho por Transformada de Fourier (FTIR), Microscopia Ótica (MO), Microscopia Eletrônica de Varredura (MEV) com mapeamento por EDS e Microscopia de Força Atômica (AFM) com o intuito de avaliar as possíveis degradações do PEUAPM submetidos a radiação UV. Os resultados demonstraram que a exposição do polímero a radiação UV em todos os tempos testados neste trabalho promoveu alterações nas amostras, pois foi observado, principalmente, nos ensaios de DRX e EDS que ocorreu respectivamente, um discreto aumento da cristalinidade do material e diminuição no percentual de oxigênio. Desta forma, pode-se concluir que o aumento da cristalinidade pode, pela ação da radiação UV, afetar nas propriedades do material contribuindo para o aumento do desgaste e diminuição do tempo de vida útil do implante. / The polyethylene, ultra high molecular weight (UHMWPE) is a polymer with excellent physical and mechanical properties with the most notable its chemical inertness, lubricity, impact resistance and abrasion resistance. Displays a relevant role in the successful Total Knee Arthroplasty (TKA) and Total Hip Arthroplasty (THA). The arthroplasty is characterized by replacement of the natural joint with an artificial joint. Artificial joints are formed by a set of components, being manufactured from metal or ceramic raw material and a component normally done in UHMWPE, which is interposed between the metal components. Some factors contribute to increased wear of the polyethylene component. Components manufactured in polyethylene UHMWPE not have photostabilizers. And inspections on manufacturers and distributors of these products was observed that during its industrial processing and marketing they are not adequately protected from direct light. Characteristics considered important for the in vitro performance of these devices are set in technical standards, but many of these standards only recommend certain requirements considered important from a technical standpoint. Currently the area of materials for use in healthcare working on regulations that seek to establish the minimum requirements for registration of orthopedic implants. Thus, this study aimed to evaluate the possible changes of components manufactured in polyethylene, ultra high molecular weight used in surgical procedures and knee arthroplasty and hip, exposed to ultraviolet radiation. The work was divided into 4 groups: group 1 (material not exposed to UV); group 2 (material exposed to UV for 1 h); group 3 (material exposed to UV for 24 h) and group 4 (material exposed to UV for 48 h). All samples were characterized by X-Ray Diffraction (XRD), Absorption Spectroscopy Fourier Transform Infrared (FTIR), optical microscopy (OM), scanning electron microscopy (SEM) with EDS mapping and Atomic Force Microscopy (AFM) in order to evaluate the possible degradation of UHMWPE subjected to UV radiation. The results showed that exposure of the polymer to UV radiation at all times tested in this study modified the samples, it was observed mainly in the experimental XRD and EDS which occurred respectively a slight increase in crystallinity and decrease in the percentage oxygen. Thus, it can be concluded that the increase in crystallinity can by the action of UV radiation, affect the material properties contributing to increased wear and reduced useful life of the implant.

This work examines the chemical and physical effects of a material treatment process on the biopolymers PEEK, POM-h, POM-c, PTFE and UHMWPE. The polymers are analyzed physically and chemically using atomic force microscopy, profilometry, scanning electron microscopy, optical microscopy, contact angle measurement, FT infra-red spectroscopy and energy dispersive X-ray spectrometry. PEEK is found to be the most suitable polymer and FT Infra-red spectroscopy an informative analytic tool.

No description available.