From medicine to aerospace, innovation in multiple fields will not occur without addressing current questions that still exist in polymer behavior and manipulation. This dissertation represents the research carried out over the course of three separate experiments using rheometry as the key technique to explore the behavior of polymer composites. In all three studies, polymer composites were investigated for changes to their known physical properties caused through the addition of a filler or functionalization. Chapter Two examines the possibility of enhancing poly(4-methyl-1-pentene) through the use of soluble carbon nanotubes. In this series of experiments, carbon nanotubes were covalently functionalized using reductive alkylation with a dodecyl group to render them easily soluble in the same organic solvents as low molecular weight poly(4-methyl-1-pentene). The polymer and the functionalized nanotubes were dissolved together in carbon tetrachloride then the solvent is removed leaving the functionalized nanotubes uniformly dispersed in the polymer matrix. The composites were then compression molded and the changes to the physical properties were explored. The functionalized nanotube filler generally acted to plasticize the samples producing transparent but colored polymers. The samples had a lower modulus and glass transition which was the opposite found by Clayton et al. using sonicated pristine carbon nanotubes. Polyurethanes have a growing significance in the biomedical field, and we explore the possibility fine tuning the properties of a polyurethane for such uses in Chapter Three. Here, self healing Polycarbonate polyurethanes (PCU) were synthesized with two different soft segments, Nippollan 964 and T-5652, and characterized with dielectric analysis (DEA), differential scanning calorimetry (DSC) and rheometry. The extra methyl group acted to produce a crystalline-like ordered hard segment that caused the 964 PCU to become Arrhenius in the glass transition region where the 5652 PCU had followed WLF behavior. Results showed the pendent methyl group acted to impart a crystalline-like character to the 964 PCU making it a candidate for applications that would be suited to a stiffer polymer. In Chapter Four we explore the possibility of increasing the wearability and comfort of contact lenses through increased hydration. The hydrogels 2-hydroxyethylmethacrylate (HEMA) and glycidyl methacrylate (GMA) solutions were created in three concentrations; neat, 50/50 and 60/40. Into these samples [Cu2({μ2-CO2}R)4(axial)2] (Cu(II) 4-hydroxybenzoic acid (MHBC) were dissolved 0.05% by weight. The samples were then polymerized via UV polymerization and compression molded. The experiments performed included penetration resistance , water absorption, micro hardness and glass transition. Addition of the MHBC acted to increase the water uptake of the samples but also reduced their ability to withstand mechanical penetration. With further study into crosslinking of the polymers, the MHBC could show promise in increasing hydration for commercial use.

Orientador: Flávio Luis Schmidt / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-18T08:06:35Z (GMT). No. of bitstreams: 1 Ros-Polski_Valquiria_D.pdf: 3723605 bytes, checksum: 58fdc4b5c478e54632a1364b0e29e441 (MD5) Previous issue date: 2011 / Resumo: A importância de se utilizar tratamento térmico de alimentos a altas temperaturas e curto tempo é que este garante a segurança microbiológica do produto e leva a uma maior preservação das características de qualidade, devido a parâmetros cinéticos que permitem que os fatores de qualidade tenham uma velocidade de destruição menor do que a de microrganismos. Dados reológicos em geral são obtidos a partir de ensaios realizados em equipamentos não pressurizados até temperaturas em torno de 90°C, devido à ebulição da água A altas temperaturas podem ocorrer alterações no produto causando mudança de viscosidade não prevista ao se extrapolar equações obtidas até 90°C. O aumento ou diminuição de viscosidade pode modificar o regime de escoamento do fluido, podendo chegar a causar um sub ou sobre-processamento, dependendo do caso. Por estas razões, é importante conhecer, às temperaturas de processo, as propriedades reológicas do produto, microrganismos alvo de tratamento térmico, pH, cinéticas de degradação de parâmetros de qualidade para que se possa otimizar o dimensionamento de tratamentos térmicos para produtos específicos. O objetivo deste projeto foi a realização de medidas reológicas de soluções-modelo e fluido alimentício a altas temperaturas e obtenção de dados cinéticos de alteração de qualidade como escurecimento, construindo-se, para este fim, um equipamento, que possa ser utilizado como um reômetro capilar pressurizado e como um reator. Um reômetro capilar foi dimensionado e construído com aquecimento por meio de tecnologia de microondas. Foi possível a utilização do equipamento para realização de medidas de propriedades reológicas acima de 100°C de soluções de sacarose a 64 e 63,5°Brix e de purê de banana a 22°Brix. Observou-se um desvio da curva de Arrhenius para o comportamento reológico do purê de banana acima de 100°C, mas não para a solução de sacarose. Foi desenvolvida e aperfeiçoada a metodologia para obtenção da região ótima de tratamento térmico e aplicada para purê de banana com minimização de escurecimento (valor de L menor ou igual a 56,2) e garantia de segurança microbiológica baseado em dados cinéticos para Clostridium botulinum. Esta região compreende temperaturas de tratamento térmico acima de 123°C e tempos abaixo de 2 minutos / Abstract: The importance of using food thermal processing at high temperatures and short time (HTST) is that it guarantees the microbiological security of the product and leads to a higher preservation of quality characteristics, due to kinetic parameters that allow quality factors to have a lower destruction rate than that of microorganisms. There is a lack of data on rheological fluid behavior at high temperatures due to the difficulties brought by the experimental assembly and originated from the thermal degradation that the product can undergo during the long time required for reaching the equilibrium temperature. Product alterations can occur at high temperatures causing unexpected changes of viscosity, invalidating extrapolations obtained from equations that are true just for around 90°C (rheological measurements in non-pressurized equipment due to boiling of water). The increase or reduction of viscosity can modify the flow behavior of the fluid, thus causing an under or over-processing, depending on the case. For these reasons, it is important to know the rheological properties of the product, thermal treatment target microorganisms, pH, degradation kinetics of quality parameters at process temperatures, such as to make possible the design of optimized thermal treatments for specific products. The objective of this project was to study the rheological properties and degradation kinetics at high temperatures of products (food and model solutions) and to obtain quality degradation kinetic data such as browning, in order to optimize thermal treatments. In order to perform the experiments, the objective is to build a device (pressurized capillary rheometer and heat exchanger) capable of rapidly increasing the product temperature, thus minimizing changes due to heat. The capillary rheometer could be built, using microwave as the heating device. It was tested with sucrose solution and banana puree. It was observed a deviation from the Arrhenius curve for the rheological behavior of banana puree above 100°C, but not for sucrose solution. It was possible to model and study the dielectric properties at 915 MHz for different formulations of banana puree at thermal treatment temperatures. The methodology for obtaining the optimal region of thermal treatment was developed and improved. It was tested for banana puree in order to minimize browning (L value lower or equal to 56.2) and to guarantee safety based on Clostridium botulinum kinetics data. This region has 123°C as lower thermal processing temperature and 2 minutes as higher thermal treatment time / Doutorado / Tecnologia de Alimentos / Doutor em Tecnologia de Alimentos

Master of Science / Food Science Institute / Jayendra K. Amamcharla / Milk protein concentrate (MPC) powders are high-protein dairy ingredients obtained from membrane filtration processes and subsequent spray drying. MPC powders have extensive applications due to their nutritional, functional, and sensory properties. However, their flow properties, rehydration behavior, and morphological characteristics are affected by various factors such as processing, storage, particle size, and composition of the powder. Literature has shown that knowledge about the powder flowability characteristics is critical in their handling, processing, and subsequent storage. For this study, FT4 powder rheometer (FT4, Freeman Technologies, UK) was used to characterize the flowability of MPC powders during storage. This study investigated the flowability and morphological characteristics of commercial MPC powders with three different protein contents (70, 80, and 90%, w/w) after storage at 25ºC and 40ºC for 12 weeks. Powder flow properties (basic flowability energy (BFE), flow rate index (FRI), permeability, etc.) and shear properties (cohesion, flow function, etc.) were evaluated. After 12 weeks of storage at 40ºC, the BFE and FRI values significantly increased (P < 0.05) as the protein content increased from 70 to 90% (w/w). Dynamic flow tests indicated that MPC powders with high protein contents displayed higher permeability. Shear tests confirmed that samples stored at 40ºC were relatively less flowable than samples stored at 25ºC. Also, the lower protein content samples showed better shear flow behavior. The results indicated that MPC powders stored at 40ºC had more cohesiveness and poor flow characteristics than MPC powders stored at 25ºC. The circle equivalent diameter, circularity, and elongation of MPC powders increased as protein content and storage temperature increased, while the convexity decreased as protein content and storage temperature increased. Overall, the MPC powders evidently showed different flow properties and morphological characteristics due to their difference in composition and storage temperature. Literature has shown various methods for determining the solubility of dairy powders, but it requires expensive instruments and skilled technicians. The front-face fluorescence spectroscopy (FFFS) coupled with chemometrics could be used as an efficient alternative, which is commonly used as fingerprints of the various food products. To evaluate FFFS as a useful tool for the non-destructive measurement of solubility in the MPC powders, commercially procured MPC powders were stored at two temperatures (25 and 40ºC) for 1, 2, 4, 8, and 12 weeks to produce powders with different rehydration properties, which subsequently influenced their fluorescence spectra. The spectra of tryptophan and Maillard products were recorded and analyzed with principal components analysis. The solubility index and the relative dissolution index (RDI) obtained from focused beam reflectance measurement was used to predict solubility and dissolution changes using fluorescence spectra of tryptophan and Maillard products. The solubility index and RDI showed that the MPC powders had decreased solubility as the storage time and temperature increased. The results suggest that FFFS has the potential to provide rapid, nondestructive, and accurate measurements of rehydration behavior in MPC powders. Overall, the results indicated that solubility and dissolution behavior of MPC powders were related to protein content and storage conditions that could be measured using FFFS.

Ce travail a pour objectifs d’évaluer le potentiel d'une technique spécifique de caractérisation des propriétés d'écoulement des poudres : le rhéomètre à poudre FT4. L'objectif est de pouvoir mettre en place une analyse complète sur les avantages, les inconvénients et les limites d'utilisation des tests, l'impact de la cohésion des poudres et la répétabilité des mesures. Tout d'abord, des efforts sont faits pour explorer les différences entre la consolidation test de FT4 et le tap-tap. Les résultats indiquent que la consolidation test de FT4 a une bonne répétabilité, mais il peut sous-estimer la compressibilité des poudres. Cette méthode peut être optimisée en améliorant sa procédure d'initialisation pour donner des résultats cohérents en tant que le tap-tap. Deuxièmement, le cisaillement test de FT4 est comparé avec Schulze Ring Shear Tester et Evolution Powder Tester. Cette comparaison indique que le cisaillement test de FT4 peut sous-estimer la cohésion des poudres. Par conséquent, les dimensions des accessoires doivent être optimisées. Enfin, une nouvelle technique de caractérisation a été mise au point. Dans cette méthode, les poudres présentent des mouvements périodiques et la période correspondant peut être liée aux propriétés d'écoulement des poudres. Cette méthode a une très bonne capacité à identifier et à catégorier les propriétés d'écoulement de la poudre dans les conditions de faible contrainte. / This research has been dedicated to evaluate the reliability of the FT4 and to improve the current tests for a better and convenient powder characterization. Firstly, efforts are made to explore the differences between the compaction test provided by the FT4 and the traditional tapped density measurement. Results indicate that the FT4 compaction test has good repetability but it may underestimate powder compressibility. This method can be optimized by improving its initialization procedure to give consistent results as the tapped density measurement. Secondly, the shear tests provided by the FT4 are evaluated by comparing with the methodologies provided by Schulze Ring Shear Tester and Evolution Powder Tester. This comparison indicates that the FT4 shear cell test may underestimate powder strength, especially when a cohesive powder sample is measured, which may cause blockage when using the FT4 method to design a silo. To overcome this shortage, the dimensions of the shear accessories should be optimized. Most importantly, a new characterization technique has been developed. ln this method, powder materials present periodic motions and the cycle time of the periodic flow can be linked to the powder flow properties. This method has very good capability to identify and classify powder flow properties under low stress conditions.

No description available.

The objective of this study was to investigate the effects of melamine and ether contents on the curing and performance properties of UF resins as binders for wood composites. Various UF and UMF resins were synthesized with three different synthesis procedures. These resins were examined by 13C NMR, rheometer, and other methods and evaluated as particleboard binders. Three-layer particleboards were prepared with the resins catalyzed with various catalysts and levels, applied in face and core layers. The board test results were compared. Only about half of added melamine had reacted with formaldehyde. UMF resins were found to be catalyzed with stronger catalysts at suitable levels depending on melamine levels and on which layer of particleboard the UMF resins are to be applied. Even catalyzed with a stronger catalyst, the curing rates of UMF resins were still slower, and storage stabilities were shorter than UF resins, but the pot lives were longer, and internal bond strength and water resistance were higher. Moreover, resins synthesized with procedures 2 and 3 showed obviously longer storage times, longer pot lives, and longer gel times, and the particleboards bonded with these resins showed significant improvements in internal bond strength and water absorption values but the formaldehyde contents increased. The increased formaldehyde content test values indicated that linear methylene-ether groups in UF resins decompose in the hot-pressing of boards to emit formaldehyde, most of which is not captured back into the UF resin matrix. Uron-type methylene-ether groups decompose in the hot-pressing of boards to participate in the curing process and enhance the bonding of boards, but it could also emit extra formaldehyde which may not be effectively captured by UF resins but more effectively by UMF resins if the amount of melamine is high enough because of the increased reactive capacities of melamine. The results of this research offered a new hypothesis that the linear methyleneether bonds in UF resins might be a major contributor of the high free formaldehyde contents of particleboards. Decreasing the linear methylene-ether groups contents might effectively bring down the formaldehyde content of boards.

The quality of continuous fiber reinforced polymer matrix composite parts and structures depends strongly on the friction during the composite forming process. The two major types of friction that cause deformations during this process are ply-ply friction and tool-ply friction. One of the challenges in the composite forming process is the occurrence of wrinkling and shape distortion of the fabric caused by the surface differences between the forming tool and surface of the laminate. Frictional measurements of composites can vary widely depending on processing parameters, measurement technique, and instruments used. In this study, a commercial rheometer was used to evaluate tool-ply friction of unidirectional carbon fiber epoxy prepreg at various contact pressures, temperatures and sliding velocities. Viscoelastic properties such as the complex viscosity (η*), storage modulus (G'), loss modulus (G"), and loss factor (tan δ) were used to determine the critical transition events (such as gelation) during cure. An understanding of changes in viscoelastic properties as a function of time, temperature, and cure provides insight for establishing a suitable processing range for compression forming of prepreg systems. Surface imaging results were coupled with rheological results to qualitatively examine the effects of processing parameters on prepreg distortions. Changes in gap height over the measurement interval qualitatively describe the changes in contact area and contact mechanisms between the tool-ply surfaces. The results indicate that friction behavior of the prepreg system is a contribution of adhesive and frictional forces, where increase in viscosity, reduction in gap height, and cure of the sample correlate to higher friction values. / Master of Science / The quality of composite parts and structures depends strongly on the friction present during the composite forming process. One of the major challenges in the forming process is the occurrence of wrinkling and shape distortions of the fabric caused by the surface differences between the forming tool and material. The presence of these defects can compromise the final material property and lead to failure when in use. Frictional measurements of composites can vary widely depending on processing parameters, measurement technique, and instruments used. The extent of interaction between the tool and surface of the material depends on the tooling height, and by extension, contact area, which cannot easily be monitored with traditional test designs. A commercial rheometer was used in this study to evaluate tool-ply friction of unidirectional carbon fiber epoxy prepreg at various contact pressures, temperatures, and sliding velocities. Gap height and torque were monitored to provide information on the frictional dependence of processing parameters. In addition, surface-imaging results were coupled with rheological results to examine the relationship between friction and fiber distortions. The understanding of changes in material property with respect to the tooling process is the key to optimizing the composite forming process.

Transient viscosity growth measurements at the startup of shear flow were performed on long glass fiber-filled polypropylene. Samples were prepared with fibers pre-oriented either in 1-direction, 3-direction or random in 1-3 plane, where the 1-direction is the direction of shear motion, the 2-direction is perpendicular to the shear plane and the 3-direction is the neutral direction. A sliding plate rheometer incorporating a shear stress transducer was constructed in the lab. It was shown that this device works well for the tested materials including a Newtonian oil, a low density polyethylene (LDPE) and short glass fiber-filled polypropylene. The transient viscosity growth behavior for long glass fiber suspensions was subsequently investigated. The results suggested that both, fiber length and fiber concentration have pronounced effect on the steady state suspension viscosity. It was also observed that the transient behavior of the pre-oriented samples was highly dependent on the initial orientation state of the fibers. / Master of Science

Yes / The viscoelastic nature of polymeric formulations utilised in drug products imparts unique thermomechanical attributes during manufacturing and over the shelf life of the product. Nevertheless, it adds to the challenge of understanding the precise mechanistic behaviour of the product at the microscopic and macroscopic level during each step of the process. Current thermomechanical and rheological characterisation techniques are limited to assessing polymer performance to a single phase and are especially hindered when the polymers are undergoing thermomechanical transitions. Since pharmaceutical processing can occur at these transition conditions, this study successfully proposes a thermomechanical characterisation approach combining both mechanical and rheological data to construct a comprehensive profiling of polymeric materials spanning both glassy and rubbery phases. This approach has been used in this study to assess the mechanical and rheological behaviour of heterogenous polymer blends of hydroxypropyl cellulose (HPC) and hydroxypropyl methylcellulose (HPMC) over a shearing rate range of 0.1–100 s−1 and a temperature range of 30–200 °C. The results indicate that HPC and HPMC do not appear to interact when mixing and that their mixture exhibits the mechanistic properties of the two individual polymers in accordance with their ratio in the mixture. The ability to characterise the behaviour of the polymers and their mixtures before, throughout, and after the glassy to rubbery phase transition by application of the combined techniques provides a unique insight towards a quality-by-design approach to this and other polymer-based solid dosage forms, designed with the potential to accelerate their formulation process through obviating the need for multiple formulation trials.

La production des boues résiduaires au niveau de l’Union Européenne ne cesse d’augmenter et devient un défi sociétal majeur. Pour réduire les volumes et faciliter la réutilisation de la matière organique, le séchage thermique est l’une des opérations les plus couramment mises en œuvre dans les stations d’épuration de grande capacité. Cependant le procédé reste énergivore : maîtriser la facture énergétique implique de contrôler les paramètres opératoires, parmi lesquels le temps de séjour, et donc la vitesse d’écoulement dans le sécheur. Contrôler le temps de séjour implique donc de connaître l’évolution des propriétés rhéologiques des boues au cours du séchage. Or, la littérature scientifique s’est avérée très peu documentée sur la caractérisation rhéologique des boues fortement concentrées, principalement en raison de difficultés techniques rencontrées pour effectuer les mesures telles que les fractures et l’évaporation lorsque les boues sont chauffées. Pour tenir compte de ces phénomènes perturbateurs, nous avons développé deux procédures expérimentales compatibles avec tous les rhéomètres rotatifs conventionnels. La première procédure dont le principe est basé sur la détermination de la surface réellement cisaillée, permet de corriger l’impact des fractures sur une gamme de déformations allant de 0 à 200 %. La deuxième procédure a pour objectif de limiter efficacement l’évaporation de l’eau jusqu’à 80 °C pendant au moins 2 h d’expérience. De plus, au-dessus de la limite de plasticité SiP =43 %, la boue étudiée devient un matériau granulaire-divisé. L’utilisation d’un rhéomètre à poudres, basée sur le principe de Jenike et classiquement utilisé dans les milieux granulaires, a ainsi été validée pour les plus fortes concentrations, notamment par la comparaison avec un rhéomètre classique. Ensuite, l’impact de la concentration sur la nature du comportement rhéologique a été évalué. Nous montrons qu’il existe 4 différents régimes dans la gamme de siccité allant de 2 à 48 %. Pour des siccités inférieures à 6 %, la boue est définie comme une suspension très diluée et son comportement rhéologique est dominé par les forces visqueuses (interactions physico-chimique et/ou hydrodynamique). Lorsque la siccité est dans la gamme 14-43 %, la boue ressemble à un matériau pâteux/plastique dont le comportement est régi par des forces frictionnelles qui se manifestent par l’apparition de la dilatance. Dans la gamme intermédiaire de siccité, 6-14 %, le comportement rhéologique de la boue est gouverné par une compétition entre les forces visqueuses et les forces de frictionnelles. Au delà de 43 %, la boue déshydratée de consistance granulaire se comporte comme une poudre cohésive. Nous démontrons que la relation entre les paramètres de type solide (comme la contrainte seuil) et la siccité peut être modélisée par un modèle composé d’une loi de puissance et d’une loi d’Eilers. La première composante domine dans le régime visqueux, la deuxième dans le régime frictionnel et aucune des deux composantes n’est dominante dans le régime intermédiaire. L'ensemble de ces résultats nous permet de construire un diagramme rhéophysique qui relie le comportement rhéologique de la boue à sa consistance. / In EU, sludge production is increasing every year and is becoming a real challenge for the waste water treatment plants (WWTP). To reduce volumes and facilitate the reuse of organic matter, thermal drying is one of the most commonly used operations in large WWTP. Optimisation of the paddle dryer energy consumption can be obtained by an accurate control of the operating parameters, among which the residence time which is directly connected to the flow velocity in the dryer. Controlling the residence time implies the knowledge of the rheological parameters of sludge for total solid contents (TS) higher than 20 wt.% and their temperature dependency during drying. However, rheological measurements are difficult to perform at high TS as uncontrolled effects such as fractures and evaporation appear. Consequently, the obtained rheological measurements are not fully representative of a controlled state of the sludge.In this work, we show how to correct fractures impact with a well-controlled procedure allowing the exact determination of the surface really sheared in the range of strain 0-200 %, and so, of intrinsic rheological parameters. Moreover, we show how to control the evaporation of water at high temperatures, up to 80 °C, during at least 2 h of rheological measurements. These procedures are suitable for sludge having a pasty/plastic consistency and are compatible with any commercial rotational rheometer. Furthermore, above the plasticity limit TSP=43 wt.%, the studied sludge looks like a divided material that we characterize using a powder rheometer. The use of a powder rheometer, based on the Jenike principle and conventionally used in granular media, has been validated for the highest concentrations, in particular by means of a comparison with a conventional rheometer. Then, based on these procedures, the impact of concentration on the nature of sludge rheological behaviour has been investigated. We show the existence of 4 different regimes in the 2 48 wt.% TS range. Under 6 wt.% TS, the sludge is defined as a diluted suspension and the rheological behaviour is governed by viscous forces (physico-chemical and/or hydrodynamic interactions). When the TS content is higher than 14 but lower than 43 wt.%, the sludge looks like a pasty/plastic material and the behaviour is governed by frictional forces which manifested by the appearance of dilatancy. In the intermediate range of TS, that is 6-14 wt.%, the rheological behaviour is governed by a competition between viscous and frictional forces. Above 43 wt.%, the divided granular-like sludge behaves like a cohesive powder. We demonstrate that the relation between solid-like parameters (such as the yield stress) and the TS content can be modelled using a model combining a power and an Eilers laws. The power law dominates in the viscous regime, the Eilers law in the frictional regime and neither is dominant in the transitional regime. All of these results allowed us to propose a rheophysical scheme that links the rheological behaviour of the sludge to its consistency.