The ecological effects and mechanistic efficiency of chemical oil spill countermeasures must be evaluated prior to their ethical application during real spill response scenarios. Equally important is the ability to monitor the effectiveness of any spill response in real time, permitting informed response management. In-situ sensors are key components of such event based monitoring and continuous monitoring programs. This project investigates crude oil toxicity as a particulate suspension, suitability of in-situ instrumentation to measure crude oil suspensions, and the applicability of using acoustic backscatter to measure suspended solids and sub-surface oil droplet suspension concentrations. The ecological effects to inter- and sub-tidal sediment dwelling organisms exposed to crude oil, both treated with a chemical dispersant and un-treated, was evaluated. Elevated toxicity, expressed as percent mortality and reduced luminescence, and oil concentrations were observed in inter-tidal sediments receiving oil only treatments compared to oil-plus-dispersant treatments. Sub-tidal sediments showed heterogeneous distribution of crude oil with elevated amphipod mortality compared to no oil controls suggesting an oil-sediment aggregation mechanism. A separate laboratory scale study found that the soluble crude oil fractions were responsible for the observed mortality in pelagic species while the more dominant oil droplet fractions were relatively non-toxic. Subsequent studies focused on the in-situ detection of crude oil and particle suspensions in aqueous environments. The first showed that both in-situ fluorescence spectroscopy and Laser In-Situ Scattering Transmissometry (LISST) can effectively measure crude oil concentrations in aqueous environments. The applicability of the LISST implies that crude oil in an aqueous medium can be measured as a particle suspension. Acoustic backscatter (ABS) was investigated for its applicability as a surrogate measurement technology for aqueous particle suspensions. This study showed a log linear correlation between ABS and volume concentration (VC) over a variable particle size distribution. This correlation is due to the dependency of both ABS and VC to the particle size distribution. Log-linear ABS responses to oil-droplet suspension volume concentrations were also demonstrated. However, the inability to reproduce response factors suggests that more work is required to produce viable calibrations that may be used for sub-surface oil plume detection.

This project consists of two parts. One area of focus in the first part is understanding the interactions between a non-ionic, block copolymer type dispersant and hydrophobically-modified, ethoxylated urethane (HEUR) associative thickeners in water. The dispersant was mixed at various concentrations (0-2% by weight) with HEUR thickeners at 1% by weight concentration in the aqueous medium. This study is an integral part of our attempts to determine mechanisms of viscosity drop when colorant dispersions are added to latex tint base formulations thickened with associative thickeners. One of the HEUR thickeners is a product that has been available for over three decades (HEUR RM-825), whereas the other, HEUR RM-995 is a product recently introduced to minimize the tint base viscosity drop. The old HEUR showed a definitive viscosity maximum as a function of the dispersant concentration. However, the new generation product did not indicate a viscosity maximum within the dispersant concentration range studied; instead it showed a small, but linear increase in viscosity as dispersant level was increased. The next area of focus was on understanding the phase behavior, rheology, and interactions between polymer latex particles and a hydrophobically-modified, ethoxylated urethane (HEUR) associative thickener in water. The influence of the addition of surfactant in some of the systems was also studied. Several types of dispersions were made using two types of polymer latex, two associative thickeners, and two surfactants. Mixtures containing a small particle size acrylic latex and HEUR RM-825 exhibited the most interesting and complex phase behavior and rheology. In experiments wherein the latex particle volume fraction was kept constant, the addition of HEUR caused stable, followed by phase separated (syneresis) and stable mixtures as HEUR concentration was increased. The observed phase behavior is consistent with previous work reported by other investigators. However, detailed rheological data on systems such as these have not been reported, and this report presents the rheological data and correlate rheology with the phase behavior. The stable latex-HEUR mixtures at low HEUR levels show shear-thinning viscosity with well-defined low-shear Newtonian plateaus. As HEUR level is increased wherein syneresis is observed, erratic rheological profiles with shear-thickening are observed. When HEUR level is increased to a region where no syneresis is observed, low shear Newtonian plateaus re-appeared albeit at higher viscosities. The effects of added non-ionic and anionic surfactants on the dispersion are also studied. The main focus of the second part of this project is hybrid organic-inorganic photovoltaics. They have been the focus of recent studies due to their promising use in low-cost, flexible electronics, which can be processed from solution by printing and coating techniques. Understanding the rheology of these nanocomposites is essential in controlling shear flows during printing and application processes. Through rheology, we can determine different properties of poly(3-hexylthiophene) and dodecanethiol (DDT) modified zinc oxide (ZnO-DDT). Semiconductor nanowires such as ZnO have rigid or rod-like macromolecule geometry. Therefore, they have a tendency to have a lytropic liquid crystal (LLC) phase. LLC orders occur spontaneously in solutions with rod-shaped or anistropic objects from isotropic phase to nematic phase above a critical volume fraction which was studied using ZnO-DDT. The shear-induced alignment of the liquid crystal molecules was analyzed, serving as a guide for LLC printing. Furthermore by using this nanocomposite we are able to induced gelation using the ZnO-DDT nanowires in what is considered as a “good solvent,” dichlorobenzene. The kinetics of this gelation process was determined to be of first-order reaction kinetics. Furthermore, a mechanism of this gelation process is also presented.

Existing specifications for asphalt cement employ insufficient aging and conditioning times prior to testing and low strains during the actual test which are insufficient to predict asphalt performance, especially if the materials are modified with additives such as those used for warm mix technology. However, slightly modified protocols, like increasing the conditioning time in the bending beam rheometer (BBR) test and increasing the aging duration in the pressure aging vessel (PAV), predict asphalt performance better than the current Superpave™ specification. These improved protocols are published as new test standards through the collaborative effort between the Ontario Ministry of Transportation and Queen’s University. In this study, the effects of warm mix and other additives on rheological, aging and failure properties are investigated. The properties are measured by regular tests and by modified protocols. The latter include the extended BBR test (LS-308) and the double-edge-notched tension (DENT) test (LS-299). Changes in ductile strain tolerance within base asphalts due to the various additives as measured with the DENT test were found to be very significant. The DENT results like essential work of fracture, we, plastic work of fracture term, βwp, and critical crack tip opening displacement, CTOD, are usually helped to correlate with the cracking distress survey results of the pavement in service. The addition of amide and polyethylene waxes risks increasing the cracking susceptibility in the pavement. They show a negative effect on strain tolerance in the ductile state, which is likely to show up as premature and/or excessive cracking in service which is similar to their physical hardening behavior from low temperature grading and extended BBR testing. / Thesis (Master, Chemistry) -- Queen's University, 2013-02-26 11:10:41.08

Made available in DSpace on 2015-03-26T13:53:14Z (GMT). No. of bitstreams: 1 texto completo.pdf: 1644038 bytes, checksum: 68d3f82cdf154a7375fea21660c0f3e0 (MD5) Previous issue date: 2010-07-27 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / In laboratories in different regions of the country and in some cases, even in the same region, the procedures of particle size analysis are not standardized. There are differences in the chemical and physical dispersion techniques and in texture fraction quantification. There is no agreement on the most indicated chemical dispersant for particle-size analysis. Solutions of sodium hydroxide, sodium hexametaphosphate and sodium carbonate are the most commonly used. It is believed that the high pH of the NaOH solution favors the dispersion of variable-charge clay soils. Based on this statement the efficiency of NaOH, of [(NaPO3)n + Na2CO3] and of [(NaPO3)n + NaOH] solutions as chemical dispersants was tested in the particle-size analysis of two horizons of 26 reference soils of the state of Pernambuco. The treatments were arranged in a 26 x 2 x 3 factorial design (26 representative soils of Pernambuco, two horizons and three chemical dispersants {NaOH (D1), [(NaPO3)n + NaOH] (D2) and [(NaPO3)n + Na2CO3] (D3)}. A complete randomized block design was used with four replications. The dispersants were compared by the L&O test, which consists of a decision rule based on the F statistics and analysis of the average error and the correlation coefficient. The efficiency of dispersants was interpreted based on the clay proportion; the higher the clay proportion, the more effective the solution. A comparison of D2 = f (D1) and D3 = f (D1) showed no agreement between the dispersants. The intercept in the linear regression equation for the clay fraction was significant at 1% and negative, with highest clay values when using D1, while D2 and D3 were statistically equal. It was concluded that, given the higher clay proportion in the particle size analysis, NaOH was the most suitable dispersant to determine the texture of two horizons with 26 soil profiles in Pernambuco, representative of 82% of the total area of the state. / Laboratórios de diferentes regiões do País e, em alguns casos, da mesma região, não utilizam procedimentos uniformes para a execução da análise granulométrica. Há diferenças quanto à dispersão química, à dispersão física e a quantificação das frações texturais. Para o dispersante químico, não há unanimidade na indicação do mais apropriado para realização da análise granulométrica. Soluções de hidróxido de sódio e de hexametafosfato de sódio e carbonato de sódio são as mais utilizadas. Acredita-se que o elevado pH da solução de NaOH favorece a dispersão de solos com argilas de carga variável. Baseado nesta afirmativa objetivou-se testar a eficiência de soluções de NaOH, de [(NaPO3)n + Na2CO3] e de [(NaPO3)n + NaOH] como dispersantes químicos na análise granulométrica de dois horizontes de 26 solos de referência do Estado de Pernambuco. Os tratamentos corresponderam a um arranjo fatorial 26 x 2 x 3 (26 solos representativos do Estado de Pernambuco, 2 horizontes e 3 dispersantes químicos {NaOH (D1), [(NaPO3)n + NaOH] (D2) e [(NaPO3)n + Na2CO3] (D3)}. Utilizou-se delineamento experimental em blocos casualizadoscom quatro repetições. As análises granulométricas foram realizadas segundo a rotina do Laboratório de Física do Solo do Departamento de Solos da UFV. Na comparação dos dispersantes foi utilizado o teste L&O que consiste em uma regra decisória construída com base na estatística F, na avaliação do erro médio e na análise do coeficiente de correlação linear. O critério para considerar um dispersante mais efetivo foi a maior proporção de argila resultante da utilização dessa solução. Na comparação de D2 = f(D1) e D3 = f(D1) observou-se que não houve identidade entre os dispersantes. O intercepto encontrado na equação de regressão linear para a fração argila, significativo a 1 % e negativo, indica a obtenção de teores mais elevados de argila com D1. Houve igualdade na comparação de D2 com D3. Conclui-se assim que, considerando a maior proporção de argila na análise granulométrica, o NaOH foi o dispersante mais adequado na determinação da textura de dois horizontes de 26 perfis de solos do Estado de Pernambuco, representativos de 82 % da área total do Estado.

Nanoparticles promise many interesting applications because of their exceptional chemical and physical properties. Therefore nanoparticles offer a pathway for the fabrication of new functional, smart materials. Since the primary particle strongly tends to strong agglomeration, and since the surface of nanoparticles is often not compatible with polymers, it is not possible to disperse single particles homogeneously in a polymer melt. Formations of agglomerates are responsible for strong differences in concentration of the nanoparticles in the material matrix and therefore impede a homogeneous property profile. Furthermore properties of compounds are not only determined by single components, but considerably by the interface between these single components. Hence, a strong chemical and physical adhesion between the constituents is required. Thus, surface modification of nanoparticles is a crucial issue. This work focuses on the control of the particle/polymer interface in composite materials which has a thickness of some nanometers. This interface regulates the compatibility of the surface of the nanoparticles and their environment. This interface is also the place where the transmission of energy between nanoparticle and polymer occurs. The interlayer of this boundary surface should be occupied with functional “primer”-macromolecules that provide at least two types of functional groups: one species of functional group should assure the bonding of the primer to the surface of the nanoparticle, and the second type enables the compatibilizing to the matrix, and when indicated also the covalent adhesion to the ambient polymer system. The macromolecular scaffold of the primer permits the selective adjustment of important interface properties as elasticity, durability and the surface energy of the particle – matrix interface. Within this thesis hyperbranched polyethylene (PEI) imine was used as starting platform for “Quat-Primer Polymers” bearing a multitude of functional moieties in form of primary, secondary and tertiary amino groups. Chapter 2 gives a literature – review on hyperbranched polymers – with focus on PEI, stabilization of colloids by polymers, as well as polymer – “nanocomposites”. In Chapter 3 the reaction of PEI with glycidyltrimethylammonium chloride will be described to obtain hyperbranched polymers that consist of (i) the hyperbranched PEI scaffold, (ii) primary, secondary and tertiary amino groups that can be used for further modification reactions with amino-reactive compounds, and (iii) ammonium moieties that can adsorb to negatively charged surfaces. It will be shown that these Quat-Primer polymers have the ability to stabilize several nanoparticles in water to form aqueous dispersions and that they are capable to partially deagglomerate nanoparticles leading to smaller diameters of the particles in the dispersion. Additionally the reaction of hyperbranched polyethylene imine with glycidol will be described displaying a possibility to change the reactivity of the functional groups and exhibiting that also the generated hydroxyl groups generated by the ring-opening reaction of epoxides with PEI react with epoxide rings to form ether linkages. In Chapter 4 the synthesis of several amino-reactive ATRP initiators will be described and two methods to graft PMMA arms to “Quat-Primer polymers” presented in the previous chapter including the “grafting from” and the “grafting to” technique. These synthesized Quat-Primer polymers bearing ammonium moieties, as well as PMMA arms can be used to fabricate PMMA nanocomposites with homogeneously distributed nanoparticles. The developed method allow for grafting monomers that can be used in ATRP polymerization, including acrylates, acrylonitriles and styrenes, to hyperbranched polyethylene imine. Chapter 5 will display pathways to graft caprolactam derivatives to hyperbranched polyethylene imine to generate Quat-Primer polymers bearing ammonium moieties, as well as caprolactam rings. These quat-primer polymers can be used for the fabrication of PA-6 nanocomposites by dispersing nanoparticles in presence of these Quat-Primer polymers and subsequent polymerization.

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Made available in DSpace on 2016-03-15T19:36:35Z (GMT). No. of bitstreams: 1 Thais dos Santos Souza.pdf: 11169057 bytes, checksum: 6c199918f7217137c24070f2ea4f8e6e (MD5) Previous issue date: 2012-02-13 / Universidade Presbiteriana Mackenzie / The suitable superplasticizers admixtures usage has become fundamental in the cementitious systems production (like concretes and mortars), because they interact with cement particles surfaces, causing their dispersion and deflocculation without the excessive water addition. The hardened material with a smaller water quantity acquires better positive, like higher compressive strength, lower permeability and extended durability. The major dispersants admixtures are negative charged polymers (polyelectrolytes) that are capable to adsorb on the cement particles and cause their electrostatic dispersion. Given the current environmental and economic interest in reuse of discarded materials, the purpose of this study was to assess the viability of use and application of modified post-consumer expanded polystyrene (EPS) as an admixture to cementitious systems becoming it a higher added value material. The modification of the EPS was performed by sulfonation and the interfering variables in the reaction were evaluated. The performance of the stabilized polyelectrolyte already formed (sodium polystyrene sulfonate NaPSS) as dispersant was verified in cement paste and mortar. The study showed that modification of post-consumer EPS by sulfonation reaction was carried out efficiently regarding to the production of a polyelectrolyte with a maximum degree of modification, within the conditions studied, and which variables most influence the reaction. Moreover, the product with a maximum degree of modification (most likely to interact with the cement) was not effective as a dispersant for cementitious systems, causing a decrease in the mechanical strength and plasticity evaluated. / O uso de aditivos plastificantes adequados tornou-se fundamental na produção de sistemas cimentícios (como por exemplo, concretos e argamassas), pois interagem com a superfície das partículas de cimento, provocando a dispersão e defloculação das mesmas, sem adição excessiva de água. O material endurecido adquire assim melhores propriedades, como maior resistência, menor permeabilidade e maior durabilidade. Grande parte dos aditivos dispersantes são polímeros dotados de cargas negativas (polieletrólitos), capazes de adsorver nas partículas de cimento e provocar sua dispersão eletrostática. Diante do atual interesse ambiental e econômico de reutilização dos materiais descartados, o propósito deste trabalho foi verificar a viabilidade do uso e aplicação do EPS pós-consumo modificado como aditivo plastificante de sistemas cimentícios, tornando-o um material de maior valor agregado. A modificação do EPS foi realizada via sulfonação, e as variáveis interferentes na reação foram avaliadas. O polieletrólito formado já estabilizado (poliestireno sulfonado de sódio PSSNa), teve seu desempenho como dispersante verificado em pasta de cimento e argamassa. O estudo mostrou que a modificação do EPS pós-consumo a partir da reação de sulfonação realizada foi eficiente com relação à produção de um polieletrólito com máximo grau de modificação, dentro das condições estudadas, e quais as variáveis que mais influenciam na reação. Por outro lado, o produto com máximo grau de modificação (mais passível de interação com o cimento) não se mostrou eficiente como dispersante de sistemas cimentícios, causando a diminuição da plasticidade e das resistências mecânicas avaliadas.

Cette thèse en partenariat industriel s’intéresse aux peintures polyuréthane et époxy utilisées à des fins protectrices pour des applications ferroviaires. L’objectif de ce projet est de développer de nouveaux additifs spécifiques à ces peintures afin d’améliorer les propriétés mécaniques et adhésives des films sur acier, tout en gardant une bonne dispersion des charges minérales présentes dans la formulation. Des additifs polymères ont été développés. Ces polymères miscibles avec la résine ont été synthétisés par polymérisation cationique (technique du monomère activé) ou anionique coordinée, et présentent différents degrés de polymérisation. Ces polymères sont fonctionnalisés d’une part par un groupement réactif vis-à-vis des charges minérales afin d’assurer leur dispersion, et d’autre part par un groupement réactif vis-à-vis de la résine (polyuréthane ou époxy) afin d’optimiser les propriétés mécaniques des films finaux par ancrage des charges au réseau. Des études par analyses thermogravimétrique et granulométrie laser ont permis de sélectionner les additifs les plus pertinents et de mettre en évidence leur efficacité sur la désagglomération des charges, notamment par rapport aux dispersants commerciaux actuellement utilisés. Des essais mécaniques sur des films de peintures libres ont montré l’impact positif des additifs sur les propriétés mécaniques et adhésives des films sur acier, tant pour les peintures polyuréthane que pour les peintures époxy. Ces nouveaux additifs jouent donc le rôle d’agent dispersant et de promoteur d’adhésion. / Polyurethane and epoxy paints are used in rail applications for protective purposes. The aim of this Ph.D thesis was to develop new additives to improve mechanical and adhesive properties of polyurethane and epoxy paints on steel, keeping good dispersion of pigments and fillers present in paint formulation. Additives were designed as dispersing agents. A polymer which is miscible with the resin paint is synthesized by ring-opening polymerization with different polymerization degrees. Post-modifications were realized to introduce reactive functions ensuring the dispersion of fillers and pigments, and to optimize mechanical properties of paint films (anchoring fillers and pigment to the resin). Thermogravimetry analysis and dynamic light scattering were used to select the best additives and to underline their efficiency on the deagglomeration of pigments and fillers, especially compared to commercial dispersing agents currently used. Mechanical tests highlight that new additives enhanced mechanical and adhesives properties of paint films on steel, both for polyurethane and epoxy paints. Additives, designed as coupling agents, are used at as dispersing agents and adhesion promoters.