Yes / Understanding structure-property relationships is critical for the development of new drug delivery systems. This study investigates the properties of Pluronic smart hydrogel formulations for future use as injectable controlled drug carriers. The smart hydrogels promise to enhance patient compliance, decrease side effects and reduce dose and frequency. Pharmaceutically, these systems are attractive due to their unique sol-gel phase transition in the body, biocompatibility, safety and injectability as solutions before transforming into gel matrices at body temperature. We quantify the structural changes of F127 systems under controlled temperature after flow, as experienced during real bodily injection. Empirical formulae combining the coupled thermal and shear dependency are produced to aid future application of these systems. Induced structural transitions measured in-situ by small angle x-ray and neutron scattering reveal mixed oriented structures that can be exploited to tailor the drug release profile.

L'impact de traitements hydrodrothermiques complémentaires au procédé classique de fabrication des pâtes alimentaires a été étudié afin de définir les relations "procédé / structure / propriétés". Des pâtes 100% blé dur, éventuellement enrichies en protéines, monoglycérides et amylose, ont été produites, puis traitées à la vapeur selon différents couples temps-température, puis cuites de façon conventionnelle ou stérilisées. Les caractéristiques structurales des pâtes ainsi obtenues ont été étudiées à différentes échelles après chaque étape du procédé pour déterminer l'influence des opérations unitaires et de leurs paramètres. Les traitements vapeur induisent principalement une perte de la structure cristalline d'amidon natif, la formation de complexes amylose-lipides avec l'augmentation de la température et de la teneur en eau des pâtes. De plus, la réticulation du réseau protéique est accrue avec la température et la durée du traitement. Ces modifications structurales ont été synthétisées dans un digramme d'état. Toutefois, lorsque les pâtes sont chauffées en excès d'eau, le réseau protéique peut être rompu, les complexes disparaître et l'amylopectine rétrograder. La mesure des propriétés de texture de ces produits a permis d'établir les contributions respectives du mécanisme de plastification par l'eau et des différentes entités structurales présentes dans la pâte. Ces dernières renforcent mécaniquement les pâtes et l'addition des ingrédients permet ainsi d'améliorer les propriétés des produits. Un diagramme de fabrication a été proposé à partir de l'ensemble des résultats obtenus et son application à une formulation appropriée devrait permettre de répondre à l'objectif technique de ces travaux. / The impact of hydrothermal treatments in addition to those of traditional process of pasta manufacturing has been studied to define the relationship "process / structure / properties". Pasta exclusively based on durum wheat semolina and other enriched in protein, amylose and lipids, were produced and then steamed for different time-temperature values, then boiled or sterilized. The structural characteristics of pasta were studied at different scales after each step of the process to determine the influence of unit operations and their parameters. The steam treatments mostly induce a loss of the crystal structure of native starch and the formation of complexes amylose-lipids with increasing temperature and moisture content of pasta. Moreover, the protein network was enhanced by cross-linking as much as temperature and duration of treatment increased. Theses structural changes are synthesized in a states diagram. When the pasta is heated in an excess of water, the protein network can be disrupted, complexes may disappear and amylopectine retrograde. The measurement of the rheological properties of these products have helped to assign the contribution of the mechanism of plasticization by water and of the presence of these structures. These latter mechanically reinforce the pasta and the additions of various ingredients may then improve their properties. based on these overall results, a diagram of the process has been proposed and its application with an appropriate formulation could allow to meet the technical objective of this work.

Les mortiers colles (prêts à l’emploi) sont caractérisés par une formulation très complexe mettant en contribution plusieurs constituants. En plus des constituants de base (ciment, chaux, différents sables…), des adjuvants d’origine minérale et/ou organique sont souvent ajoutés. Ces derniers permettent de répondre à un certain nombre d'exigences liées essentiellement à la mise en place de ces matériaux. En effet, lors de l’application d’un mortier colle le produit doit adhérer au support, mais pas à l’outil. En se basant sur les normes actuelles, les propriétés adhésives des mortiers colles sont mesurées au jeune âge mais jamais à l’état frais. Or l’encollage s’effectue généralement dans un temps dit ouvert relativement court (quelques heures) qui dépend du type du mortier colle utilisé. Il est donc nécessaire de s’intéresser à l’évolution des propriétés adhésives à l’état frais ainsi qu’à celle des propriétés rhéologiques. Pour caractériser le comportement rhéologique d’un mortier colle, en régime quasi statique, il faut utiliser une loi de comportement à trois paramètres comprenant un seuil d’écoulement, une viscosité et un indice de fluidité. L’aspect collant du mortier peut être caractérisé en identifiant trois forces caractéristiques : force d’adhérence (par rapport au support), force d’adhésion et enfin la cohésion du matériau. L’objectif de cette de thèse est de déterminer le rôle que jouent différents adjuvants d’origine organique (Ethers de Cellulose, Résines) et/ou minérale (argiles) sur les propriétés de mise en place des mortiers colles, notamment leurs propriétés adhésives et leur comportement rhéologique. / Nowadays, with the development of the construction industry, mortars are produced in factory by specifically designed dry-mix plants, in which mineral binders and aggregates are mixed together in the appropriate way. These dry-mix mortars (ready to use) are characterized by a very complex formulation involving various constituents. In addition to the basic components (cement, lime, sand), different additives and admixtures are often added in the mortar formulations to improve their characteristic and to achieve different technical properties. Indeed, when applying an adhesive mortar, the product must adhere to the application support instead of to the working tool. Depend on their application purposes, the usage of these additives and admixtures must be fully investigated in order to observe the most effective contributions. Based on current standards, the adhesive properties of cement-based mortars are often measured at the early age. However the adhesive properties of mortar is usually said to be open in a relatively short duration (several hours) depending on the type of the mortar used. It is therefore necessary to examine the evolution of adhesive properties in the fresh state as well as the rheological properties with the variation of polymer concentrations. An adhesive mortar in fresh state can be considered as a granular suspension in a complex fluid. The study of the rheological behavior of such materials involves the rheology of complex fluids, including granular suspensions, colloidal dispersions, etc. Many scientific questions still exist in this domain, for example: the problem of shear localization and interpretation of the corresponding rheological measurements. The investigation of these problems in the variation of different types of additives and admixtures help answer these questions. To characterize the rheological behavior of an adhesive mortar, in quasi-static regime, we use a three-parameter behavior law that includes a yield stress, a viscosity coefficient and a fluidity index. The adhesiveness of the mortar can be characterized by identifying the evolution of the adhesive force, the cohesive stress and the adherence force. The objective of this thesis is to determine the roles of various additives of organic origin (cellulose ethers, re-dispersible resins powders) and/or mineral (clays, silica fume, etc.) on the fresh state properties of these mortars, including their adhesive properties and rheological behaviors.

Made available in DSpace on 2014-12-17T15:41:41Z (GMT). No. of bitstreams: 1 OldemarRC.pdf: 2134736 bytes, checksum: bf80e72f9b5d1ebc0b3148367e30383f (MD5) Previous issue date: 2007-10-30 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The aim of this work was the preparation of polyols from reactions between castor oil and dietanolamine to increase the hydroxyl content and the network degree in the products to application in electronic devices. The polyols and the mixtures obtained were characterized by nuclear magnetic ressonance. Castor oil (CO) is a natural triglyceride - based polyol possessing hydroxyl groups, which allow several reactions that produce many different products. Among them are the polyurethanes (PU), which have been considered an ideal product for the covering of electricelectronic circuits, due to their excellent electrical, shock-absorbing, solvents resistance and hydrolytic stability properties. About 90% of the fatty acids present in the castor oil are ricinoleic acid (12-hydroxyoleic acid), while the remaining 10% correspond to non-hydroxylated fatty acids, mainly linoleic and oleic acids. The chemical analysis of castor oil indicates a hydroxyl number of 2.7. In this work, a polyol was obtained by the reaction of the CO with diethanolamine (DEA), in order to elevate the hydroxyl value from 160 to 230 or to 280 mgKOH/g, and characterized by nuclear magnetic resonance (NMR) 1H and 13C (Mercury 200). The polyadition of the resulting polyol with isophorone diisocianate (IPDI) was carried out at 60?C, and the reaction kinetics was followed by rheological measurements in a Haake RS150 rheometer. The electrical properties were determined in a HP LCR Meter 4262A, at 1.0 Hz and 10.0 KHz. The chemical analysis showed that the polyols obtained presented hydroxyl number from 230 to 280 mgKOH/g. The polyadition reaction with IPDI produced polyurethane resins with the following properties: hardness in the range from 45 shore A to 65 shore D (ASTM D2240); a dielectric constant of 3.0, at 25?C (ASTM D150). Those results indicate that the obtained resins present compatible properties to the similar products of fossil origin, which are used nowadays for covering electric-electronic circuits. Therefore, the PUs from castor oil can be considered as alternative materials of renewable source, free from the highly harmful petroleum - derived solvents / O presente trabalho teve como objetivo a obten??o de poli?is a partir das rea??es do ?leo de mamona (OM) com dietanolamina (DEA), visando elevar o ?ndice de hidroxila e consequentemente o grau de reticula??o dos produtos finais, cuja aplica??o se destinou ao encapsulamento de circuitos eletroeletr?nicos. A caracteriza??o desses poli?is e respectivas misturas foram feitas utilizando-se a t?cnica da resson?ncia magn?tica nuclear (NMR). O OM (triglicer?deo do ?cido ricinoleico) ? um poliol vegetal natural por apresentar grupo funcional hidroxila que permite v?rias rea??es e produ??o de diferentes produtos. Entre eles est?o as poliuretanas (PU) que t?m sido consideradas como produtos ideais para encapsulamento de componentes de circuitos eletro-eletr?nicos, devido as suas excelentes propriedades com rela??o ? resist?ncia mec?nica e qu?mica. As poliuretanas derivadas do ?leo de mamona podem ser consideradas materiais alternativos de fonte renov?vel e, para as produzidas neste trabalho, n?o foram empregados nenhum tipo de solvente. Cerca de 90% dos ?cidos graxos que comp?em o ?leo de mamona s?o ?cido ricinoleico (?cido 12-hidroxioleico), enquanto os outros 10% s?o ?cidos graxos n?o hidroxilados (?cidos linoleico e oleico). As an?lises qu?micas do ?leo de mamona indicam uma funcionalidade m?dia de 2,7, em rela??o aos grupos hidroxila. A poliadi??o entre o poliol resultante e o isocianato de isoforona (IPDI) teve sua cin?tica aco mpanhada com o aux?lio do re?metro Haake RS 150 ? temperatura de 60 ?C. As propriedades el?tricas foram determinadas em uma ponte HP LCR Meter 4262 A a 1,0 Hz e 10,0 KHz. As an?lises qu?micas mostraram que os poli?is obtidos apresentaram ?ndice de hidroxila entre 230 e 280 mgKOH/g. A rea??o de poliadi??o com IPDI produziu resinas de poliuretana com as seguintes propriedades: dureza entre 45 e 65 shore D (ASTM D2240); constante diel?trica de 3,0 a 25 ?C (ASTM D150). Os resultados, de um modo geral, indicaram que as resinas, cujo extensor de cadeia foi a DEA, apresentaram propriedades compat?veis e em muitos casos superiores, quando comparadas ?s dos produtos atualmente dispon?veis no mercado, sintetizados ? base de trietanolamina (TEA)

Submitted by Silvana Teresinha Dornelles Studzinski (sstudzinski) on 2016-11-17T15:28:54Z No. of bitstreams: 1 Márcio Lembi Teles_.pdf: 1859021 bytes, checksum: 5dc2746be44c5f2b865c68ec0b4c0db0 (MD5) / Made available in DSpace on 2016-11-17T15:28:54Z (GMT). No. of bitstreams: 1 Márcio Lembi Teles_.pdf: 1859021 bytes, checksum: 5dc2746be44c5f2b865c68ec0b4c0db0 (MD5) Previous issue date: 2016-09-16 / Nenhuma / Este trabalho apresenta uma análise fatorial, através de fluidodinâmica computacional, do escoamento e transferência de calor para fluidos viscoplásticos a partir de um cilindro confinado entre paredes paralelas. Considera-se que as propriedades reológicas sensíveis à temperatura, o que acopla os problemas térmico e fluidodinâmico de forma bilateral. Foi desenvolvida uma formulação baseada no método estabilizado de elementos finitos Galerkin Mínimos Quadrados (GLS – Galerkin Leart-Squares) para a aproximação de escoamentos não newtonianos com transferência de calor e propriedades reológicas termodependentes. Esta formulação foi implementada em um código computacional próprio. Para a modelagem das tensões viscosa, foi utilizado um modelo de líquido newtoniano generalizado, com função viscosidade dada pelo modelo de Herschel-Bulkley regularizado conforme Papanastasiou e propriedades termodependentes – a tensão inicial de escoamento e o índice de consistência. Os resultados numéricos foram investigados utilizando os adimensionais: número de Reynolds (Re), número de Herschel-Bulkley (Hb), número de Prandtl (Pr), índice de potência (n) e coeficientes de dependência térmica (a* e b*). Foi realizado um planejamento experimental fatorial completo 2K, com objetivo de avaliar a influência destes parâmetros na taxa de transferência de calor, através do número de Nusselt (Nu), e na perda de carga localizada devido à obstrução do canal pelo cilindro. / This paper presents a factor analysis using computational fluid dynamics, flow and heat transfer for viscoplastic fluids from a cylinder confined between parallel walls. It is considered that the rheological properties sensitive to temperature, which couples the thermal and fluid dynamic problems bilaterally. It was developed a formulation based on stabilized finite element method Galerkin Least Squares (GLS - Galerkin Leart-Squares) for approaching non-Newtonian flow with heat transfer and rheological properties dependent terms. This formulation has been implemented in a proper computer code. For the modeling of viscous stresses, a generalized Newtonian fluid model was used, with viscosity function given by the Herschel-Bulkley regularized model as Papanastasiou and properties dependent terms – the initial yield stress and consistency index. The numerical results were investigated using the dimensionless: Reynolds number (Re), Herschel-Bulkley number (Hb), Prandtl number (Pr), potency index (n) and temperature dependence coefficients (a* and b*). It conducted a full factorial experimental design 2K, with objective to evaluate the influence of these parameters on the heat transfer rate, through the Nusselt number (Nu), and localized head loss due to the cylinder by duct obstruction.

Chemical modification is an important way to improve the properties of existing polymers, and one of the important examples is the hydrogenation of nitrile butadiene rubber (NBR) in organic solvent by homogeneous catalysis in order to extend its application. This process has been industrialized for many years to provide high performance elastomers (HNBR) for the automotive industry, especially those used to produce components in engine compartments. In the current commercial process, a batch reactor is employed for the hydrogenation step, which is labor intensive and not suitable for large volume of production. Thus, novel hydrogenation devices such as a continuous process are being developed in our research group to overcome these drawbacks. In order to make the process more practical for industrial application, high concentration polymer solutions should be targeted for the continuous hydrogenation. However, many problems are encountered due to the viscosity of the high concentration polymer solution, which increases tremendously as the reaction goes on, resulting in severe mass transfer and heat transfer problems. So, hydrogenation kinetics in high concentration NBR solution, as well as the rheological properties of this viscous solution are very essential and fundamental for the design of novel hydrogenation processes and reactor scale up. In the present work, hydrogenation of NBR in high concentration solution was carried out in a batch reactor. A commercial rhodium catalyst, Wilkinson’s catalyst, was used with triphenylphosphine as the co-catalyst and chlorobenzene as the solvent. The reactor was modified and a PID controller was tuned to fit this strong exothermic reaction. It was observed that when NBR solution is in a high concentration the kinetic behavior was greatly affected by mass transfer processes, especially the gas-liquid mass transfer. Reactor internals were designed and various agitators were investigated to improve the mechanical mixing. Experimental results show that the turbine-anchor combined agitator could provide superior mixing for this viscous reaction system. The kinetic behavior of NBR hydrogenation under low catalyst concentration was also studied. It was observed that the hydrogenation degree of the polymer could not reach 95% if less than 0.1%wt catalyst (based on polymer mass) was used, deviating from the behavior under a normal catalyst concentration. The viscosity of the NBR-MCB solutions was measured in a rotational rheometer that has a cylinder sensor under both room conditions and reaction conditions. Parameters that might affect the viscosity of the solutions were studied, especially the hydrogenation degree of polymer. Rheological properties of NBR-MEK solutions, as well as NBR melts were also studied for relevant information. It is concluded that the hydrogenation kinetics deviates from that reported by Parent et al. [6] when polymer is in high concentration and/or catalyst is in low concentration; and that the reaction solution (HNBR/NBR-MCB solution) deviates from Newtonian behavior when polymer concentration and hydrogenation degree are high.

In several applications of casting, dendritic microstructure is not desirable as it results in poor mechanical properties. Enhancing the fluid flow in the mushy zone by stirring is one of the means to suppress this dendritic growth. The strong fluid flow detaches the dendrites from the solid-liquid interface and carries them into the mold to form slurry. The detached dendrites coarsen in the slurry and form into rosette or globular particles based on processing conditions. This slurry offers less resistance to flow even at a high solid fraction and easily flow into the die-cavity. The above principle is the basis of a new manufacturing technology called “semi-sold forming” (SSF), in which metal alloys are cast in the semi-solid state. This technique has several advantages over other existing commercial casting processes, such as reduction of macrosegregation, reduction of porosity and low forming efforts. A major challenge existing in semisolid manufacturing is the production of metallic slurry in a consistent manner. The main difficulty arises because of the presence of a wide range of process parameters affecting the quality of the final product. An established method of producing slurry is by stirring the alloy using an electromagnetic stirrer. From an elaborate review of literature, it is apparent that solidification in presence of electromagnetic stirring involves a wide range of shear and cooling rates variation. However, the CFD models found in the literature are generally not based on accurate rheological properties, which are known to be functions of the relevant process parameters. Hence, there is a clear need for a comprehensive numerical model for such a solidification process, involving accurate rheological data for the semisolid slurry subjected to a range of processing conditions. The objective of the present work is to develop a numerical model for studying the transport phenomena during solidification with linear electromagnetic stirring. The study is presented in the context of a billet making process in a cylindrical mould using linear electromagnetic stirring. The mould consists of two parts: the upper part of the mould is surrounded by a linear electromagnetic stirrer forming the zone of active stirring, and the lower part of the mould is used to cool the liquid metal. The material chosen for the study is Al-7.32%Si (A356) alloy, commonly used for die casting applications. A complete numerical model will therefore have two major components: one dealing with rheological behavior of the semisolid slurry, and the other involving macroscopic modeling of the process using computational fluid dynamics (CFD) techniques. For the latter part of the model, determination of rheological behavior of the slurry is a pre-requisite. The rheological characteristics of the stirred slurry, as a function of shear rate and cooling rate, is determined experimentally using a concentric cylinder viscometer. Two different series of experiments are performed. In the first series, the liquid metal is cooled at a constant cooling rate and sheared with different shear rates to get the effect of shear rate on viscosity. In the second series of experiments, the liquid metal is cooled at different cooling rates and sheared at a constant shear rate to obtain the effect of cooling rate on viscosity. During all these experiments, the shear rate is calculated from the measured angular velocity of spindle using inductive position sensor; viscosity of the slurry is calculated based on the torque applied to the slurry and angular velocity of the spindle; and the solid fraction is calculated from measured temperature of the slurry based on Schiel equation. From these data, a constitutive relation for variable viscosity is established, which is subsequently used in a numerical model for simulating the transport phenomena associated with the solidification process. The numerical model uses a set of single-phase governing equations of mass, momentum, energy and species conservation. The set of governing equations is solved using a pressure based finite volume technique, along with an enthalpy based phase change algorithm. The numerical simulation of this process also involves modeling of Lorentz force field. The numerical study involves prediction of temperature, velocity, species and solid fraction distribution. First, studies are performed for a base case with a moderate stirring intensity of 250A primary current and 50 Hz frequency. It is found that the electromagnetic forces have maximum values near the mould periphery, which results in an ascending movement of the slurry near the mould periphery. Because of continuity, this slurry comes down along the axis of the mould. Stirring produces a strong fluid flow which results good mixing in the melt. Correspondingly, a homogenized temperature distribution is found in the domain. Because of strong stirring, the solid fraction in the slurry is found to be distributed almost uniformly. It is also found that fragmentation of dendrites increases solid fraction in the slurry with processing time. During processing, the continuous rejection of solute makes the liquid progressively solute enriched. It is predicted from the present study that the remaining liquid surrounding the primary solid phase finally solidifies with a near-eutectic composition, which is desirable from the point of view of semisolid casting. Correspondingly, a set of experiments are performed to validate the numerically predicted results. The numerical predictions of temperature variations are in good agreement with experiments, and the predicted flow field evolution correlate well with the microstructures obtained through experiments at various locations, as observed in the numerical results. Subsequently the study is extended to predict the effect of process parameters such as stirring intensity and cooling rate on the distributions of solid fraction and solute in the domain. It is found, from the simulation, that the solidification process is significantly affected by stirring intensity. At increasing primary excitation current, the magnitude of Lorentz force increases and results in increase of slurry velocity. Correspondingly, the fragmentation of dendrites from the solid/liquid is more during solidification at higher stirring intensity, which increases the fraction of solid in the slurry to a high value. It is also found that the solute and fraction of solid in the liquid mixes well under stirring action. Thus, a near uniform distribution of solute and solid fraction is found in the domain. It is found that stirring at high currents produces high solid fraction in the liquid. Also, at very low cooling rate, the solid fraction in the liquid increases. The present study focuses on the model development and experimental validation for solidification with linear electromagnetic stirring for producing a rheocast billet. Further studies highlighting the effects of various process parameters on the thermal history and microstructure formation are also presented.

In der Milchindustrie spielt die Auswahl der Starterkulturen eine wichtige Rolle bei der Herstellung fermentierter Produkte mit gewünschter Textur und entsprechenden sensorischen Eigenschaften. Milchsäurebakterien mit der Fähigkeit extrazelluläre Polysaccharide (EPS) zu synthetisieren sind von besonderem Interesse, da auf Grund der in situ gebildeten Hydrokolloide der Einsatz von Zusatzstoffen vermieden werden kann. Die Wirkung von EPS auf die Produkt-eigenschaften ist in der Literatur bereits mehrfach beschrieben, wird jedoch auf Grund der Vielzahl an unterschiedlichen Stämmen und Fermentationsparametern bzw. einer fehlenden Systematisierung immer noch sehr kontrovers diskutiert. Des Weiteren stellt die wissenschaftliche Aufklärung der komplexen Struktur-Funktionsbeziehungen und der Wechselwirkungen mit anderen Produktkomponenten eine große Herausforderung dar. Um die Zusammenhänge besser verstehen zu können, wurde in dieser Arbeit ein neuer Ansatz gewählt: isolierte und aufgereinigte EPS wurden der Milch vor der Säuerung zugesetzt und die daraus hergestellten Milchgele mit jenen mit in situ produzierten EPS verglichen. In Milchgelen aus Einzelstammkulturen von Streptococcus thermophilus oder Lactobacillus delbrueckii ssp. bulgaricus wurden EPS‑Gehalte von 40 - 150 mg/kg ermittelt. Die Gele unterschieden sich hinsichtlich ihrer Viskosität und ihres fadenziehenden Charakters, was erste Hinweise auf die Art der gebildeten EPS liefert. Die Synthese größerer Mengen an EPS zur Charakterisierung und Untersuchung ihrer Funktionalität erfolgte entkoppelt von der Produkt­herstellung mit ausgewählten Stämmen in Batch-Fermentationen mit konstantem pH in komplexen oder semidefinierten Medien. S. thermophilus ST‑143 produzierte ~ 300 mg/L fadenziehende EPS, die durch entsprechende Aufreinigungsschritte als drei EPS‑Fraktionen gewonnen werden konnten: freie EPS (EPSf), kapsuläre EPS (EPSk) und ein Gemisch aus beiden (EPSf+k). EPSf haben eine höhere Molekülmasse (M = 2,6 x 10^6 Da) und eine höhere intrinsische Viskosität (1,14 mL/mg) im Vergleich zu EPSk (M = 7,4 x 10^3 Da, 1,4 x 10^5 Da; intrinsische Viskosität = 0,06 mL/mg) und führten bereits in geringen Mengen zu rheologischen Veränderungen. Allerdings scheinen die EPSk Wechselwirkungen zwischen EPSf Molekülen zu unterstützen. In chemisch gesäuerten Milchgelen konnte durch den definierten Zusatz aufgereinigter Fraktionen von EPSf und EPSf+k vor der Säuerung (c = 0 - 0,35 mg/g) erstmals eine konzentrationsabhängige Wirkung aufgezeigt werden. Mit EPSf stieg der maximale Speichermodul der Milchgele als Maß für die Gelsteifigkeit linear an (457 - 722 Pa). EPSk zeigten hingegen keinen Einfluss. Als Modellpolysaccharid wurde vergleichend das gut beschriebene, ebenfalls ungeladene und nicht gelbildende Homopoly­saccharid Dextran herangezogen (c = 0 - 300 mg/g). EPSf und Dextran veränderten die Gelbildung, erhöhten die Steifigkeit stichfester Gele und die Viskosität gerührter Gele in ähnlichem Maße, es waren jedoch deutlich unterschiedliche Konzentrationen notwendig. Die in den Milchgelen beschriebenen Einflüsse können unter anderem auf Depletionseffekte zwischen gleichgeladenen Polymeren (hier Proteine und Polysaccharide) zurückgeführt werden. / The selection of suitable starter cultures for the production of fermented milk with a desired texture and corresponding sensory attributes is of great importance for the dairy industry. Lactic acid bacteria with the ability to synthesise extracellular polysaccharides (EPS) are of particular interest, because these in situ produced hydrocolloids may allow to omit the use of additives. Many effects of EPS on product properties are already described in the scientific literature, but are still discussed controversially because of the multitude of different strains and fermentation parameters and, hence, a lack of systematisation. Furthermore, research on the mechanisms behind the structure-function relationship and interactions with other product components is a challenging area. To obtain a deeper understanding of this complex system, a new approach was chosen for the present study: EPS were isolated, purified and added to the milk prior to acidification, and the respective milk gels were compared with those with in situ produced EPS. In milk gels acidified by single strains of Streptococcus thermophilus or Lactobacillus delbrueckii ssp. bulgaricus, EPS contents of 40 - 150 g/kg were determined. The gels differed in viscosity and their ropy character, which is a first indicator for the type of the EPS. To allow for their chemical and technofunctional characterisation, the synthesis of higher amounts of EPS was performed by batch-fermentation at constant pH and decoupled from the product manufacturing with selected strains in complex or semidefined media. S. thermophilus ST‑143 synthesised ~ 300 mg/L ropy EPS, which were isolated as three different EPS fractions by applying particular purification steps: free EPS (EPSf), capsular derived EPS (EPSk) and a mixture of both EPS (EPSf+k). EPSf had a higher molecular mass (M = 2.6 x 10^6 Da) and a higher intrinsic viscosity (1.14 mL/mg) compared to EPSk (M = 7.4 x 10^3 Da, 1.4 x 10^5 Da; intrinsic viscosity = 0.06 mL/mg) and affected the rheological properties of aqueous solutions already at low concentration. However, EPSk appear to support interactions between the EPSf molecules. In chemically acidified milk gels a concentration dependent impact of EPSf and EPSf+k, which were added to the milk prior to acidification (c = 0 - 0,35 mg/g), was described for the first time. The maximum of the storage modulus as a measure for stiffness of the milk gels linearly increased with EPSf content (457 - 722 Pa). With EPSk no effects were observed. For the purpose of comparison dextran, a well described also uncharged and non gelling homopolysaccharide, was used as a model polysaccharide (0 - 300 mg/g). EPSf and dextran affected the gelation, increased gel stiffness of set gels and viscosity of stirred gels to a similar way, but the concentrations needed for that found to be completely different. The effects described for milk gels can be ascribed among others to depletion interactions between similar charged polymers (here proteins and polysaccharides).

Chemical modification is an important way to improve the properties of existing polymers, and one of the important examples is the hydrogenation of nitrile butadiene rubber (NBR) in organic solvent by homogeneous catalysis in order to extend its application. This process has been industrialized for many years to provide high performance elastomers (HNBR) for the automotive industry, especially those used to produce components in engine compartments. In the current commercial process, a batch reactor is employed for the hydrogenation step, which is labor intensive and not suitable for large volume of production. Thus, novel hydrogenation devices such as a continuous process are being developed in our research group to overcome these drawbacks. In order to make the process more practical for industrial application, high concentration polymer solutions should be targeted for the continuous hydrogenation. However, many problems are encountered due to the viscosity of the high concentration polymer solution, which increases tremendously as the reaction goes on, resulting in severe mass transfer and heat transfer problems. So, hydrogenation kinetics in high concentration NBR solution, as well as the rheological properties of this viscous solution are very essential and fundamental for the design of novel hydrogenation processes and reactor scale up. In the present work, hydrogenation of NBR in high concentration solution was carried out in a batch reactor. A commercial rhodium catalyst, Wilkinson’s catalyst, was used with triphenylphosphine as the co-catalyst and chlorobenzene as the solvent. The reactor was modified and a PID controller was tuned to fit this strong exothermic reaction. It was observed that when NBR solution is in a high concentration the kinetic behavior was greatly affected by mass transfer processes, especially the gas-liquid mass transfer. Reactor internals were designed and various agitators were investigated to improve the mechanical mixing. Experimental results show that the turbine-anchor combined agitator could provide superior mixing for this viscous reaction system. The kinetic behavior of NBR hydrogenation under low catalyst concentration was also studied. It was observed that the hydrogenation degree of the polymer could not reach 95% if less than 0.1%wt catalyst (based on polymer mass) was used, deviating from the behavior under a normal catalyst concentration. The viscosity of the NBR-MCB solutions was measured in a rotational rheometer that has a cylinder sensor under both room conditions and reaction conditions. Parameters that might affect the viscosity of the solutions were studied, especially the hydrogenation degree of polymer. Rheological properties of NBR-MEK solutions, as well as NBR melts were also studied for relevant information. It is concluded that the hydrogenation kinetics deviates from that reported by Parent et al. [6] when polymer is in high concentration and/or catalyst is in low concentration; and that the reaction solution (HNBR/NBR-MCB solution) deviates from Newtonian behavior when polymer concentration and hydrogenation degree are high.

Neste trabalho de Dissertação de Tese, composições do copolímero de butadieno-acrilonitrila (NBR) foram vulcanizadas utilizando como agentes de vulcanização, a resina fenólica e o enxofre, com diferentes proporções de resina fenólica e uma única proporção de enxofre. O sistema ativador foi composto por policloropreno e óxido de zinco para as composições com resina fenólica, enquanto que por ácido esteárico e óxido de zinco para a composição com enxofre. Os materiais foram vulcanizados em uma temperatura de 190C. Foi avaliada a influência da variação dos componentes das composições sobre as propriedades reométricas, físico-mecânicas e reológicas dos materiais. Para auxiliar na interpretação dos resultados obtidos para as propriedades reométricas e físico-mecânicas, foi utilizado um planejamento estatístico de análise de variância para verificar a possibilidade da influência das variáveis e suas possíveis combinações nas propriedades avaliadas. Para as composições vulcanizadas com resina fenólica, os resultados mostraram que a composição de borracha nitrílica se tornou mais rígida com a presença da resina. Também foi observada a ocorrência de pós-cura nas composições vulcanizadas com resina fenólica. Os ensaios reológicos revelaram uma homogeneidade nas amostras submetidas aos testes de varredura de deformação, com desvio de linearidade a partir de 10% de deformação. / In this Thesis Dissertation, acrylonitrile-butadiene rubber (NBR) compositions were vulcanized using phenolic resin and sulfur as vulcanization agents with different proportions of phenolic resin and only one proportion of sulfur. The activator system was composed of polycloroprene and zinc oxide to phenolic resin compositions, while stearic acid and zinc oxide to sulfur composition. The materials were vulcanized in a temperature of 190C. The influence of the components content on rheometric, physico-mechanical and rheological properties of the materials was evaluated. In order to assist in the interpretation of the to physico-mechanical and rheometric properties results, a statistical planning of variant analysis was used to observe a possible influence of the variables and also their possible associations into the evaluated properties. The results showed that the nitrile rubber become more stiffness with the presence of phenolic resin. It was also observed the occurrence of post-vulcanization on the compositions vulcanized with phenolic resin. The rheological results showed homogeneity of the samples submitted to a strain sweep test, with a linear plateau until 10% of strain.