The main objective in this work was to learn how the instrument, the Interfacial Shear Rheometer (ISR400), worked and to investigate how the rheological properties, storage modulus (elasticity), G' and loss modulus (viscous), G'', changes when the surface pressure at the air-liquid interphase changes. The second objective were to examine the different kind of magnetic needles used in the experiments and to conclude which type of needle is best for its specific field of analysis. It was concluded that the relative heavy needle with mass 70.6 mg and length 50 mm was best for systems where the viscous and elastic components are significantly large, where the inertia of the needle is not dominant. It also worked of using the heavier needle for a system of phospholipids. For the hydroxystearic acid (HSA) experiment that were tested on NaCl sub-phase there was a clear improvement after switching from the heavy needle (mass 41.5 mg; length 51 mm) to the relative lighter needle (mass 6.94 mg; length 34.7 mm). The values for the dynamic modulus therefore had a better agreement with reference literature. A spread layer of class II hydrophobins (HFBII) could be compressed to a surface pressure of 46 mNm-1. The G' and G'' values from the frequency sweep were discarded because the monolayer turned into a very viscous-like liquid, and the oscillating needle, after compression, was kind of stuck in the sub-phase and moved very staggering during a frequency sweep. The needle comparison experiment with silica particles 10 wt% Bindzil CC30 (BCC30), at pH 3.5 was done to see if there was any difference in the sensitivity for the needles at the interface which consisted of a pure 10 mM NaCl solution or a 10 mM NaCl solution with BCC30 added to it. The differences were negligible in terms of surface tension but there was a clear difference between the heavy needle and the light needle, when oscillating at higher frequencies (>≈6 rad/s). With this study, the understanding of ISR400 has increased largely. Several issues have been addressed and the results provide a good basis for further studies within the many areas the instrument can be used for. Despite the project's time limit, and the fact that the instrument was new and untested where the project was carried out, focus areas were prioritized so good results could be achieved within reasonable goals. / Huvudmålet med detta arbete var att lära sig hur instrumentet ytskiktsreometern (ISR400) fungerade och undersöka hur de reologiska egenskaperna, elasticitetsmodulen G' och viskositetsmodulen G'', kommer att förändras när det sker en förändring för yttrycket vid gränsskiktet mellan luft och vätska. Det sekundära målet var att undersöka vilken typ av magnetiska nålar som är bäst att använda för respektive gränsskiktssystem. Av att använda den tyngre nålen med massan 70.6 mg och längden 50 mm kunde man dra slutsatsen att den är bäst att använda för system där de viskösa och elastiska komponenterna är signifikant stora, där nålens tröghet inte är dominant. Den fungerade även att mäta med i ett fosfolipidsystem. I experimentet med 12-hydroxy-stearinsyra (HSA) som utfördes på en subfas av NaCl, syntes en klar förbättring efter att byta från en tyngre nål (massa 41.5 mg; längd 51 mm) till en lättare (massa 6.94 mg; längd 34.7 mm). Värdena för dynamiska modulen stämde därför bättre överens med referenslitteraturen. Det utspridda lagret av klass II hydrophobins (HFBII) kunde komprimeras upp till yttrycket 46 mNm-1. Värdena för G' och G'' förkastades därför att monolagret förvandlades till en väldigt viskösliknande vätska, och den oscillerande nålen, efter kompressionen, satt fast i denna tröga vätska och rörde sig väldigt hackigt och oregelbundet under tiden ett frekvenssvep utfördes. Då en jämförelse av olika typer av nålar genomfördes med kiseldioxidpartiklar (10 % (viktsprocent) Bindzil CC30 med pH 3.5), för att se om det är någon skillnad i känslighet för nålarna vid gränssnittet, som bestod av en ren 10 mM NaCl-lösning eller en 10 mM NaCl-lösning med tillsatt BCC30. Skillnaderna var försumbara gällande ytspänningen, men det var en klar skillnad mellan den tunga nålen och den lätta nålen vid oscillering vid höga frekvenser (>≈6 rad/s). I och med detta arbete så har förståelsen för hur ISR400 fungerar förbättrats mycket sedan starten. Flera frågeställningar har behandlats och resultaten ger en bra grund för fortsatta studier inom de många områden som utrustningen kan användas till. Trots projektets tidsbegränsning, och det faktum att instrumentet var nytt och oprövat på platsen där detta arbete utfördes, så prioriterades fokusområden så att goda resultat kunde uppnås inom rimliga mål.

As argamassas colantes são produtos constituídos por areia natural ou artificial, ligantes e aditivos químicos que cumprem uma função de adesivo para assentamento de revestimentos em pisos e paredes. Sob o ponto de vista reológico, a argamassa colante é um material multifásico formado por uma pasta que envolve agregados minerais. Atualmente, o único teste preconizado em norma a fresco é o ensaio de deslizamento, que apesar de ter baixo custo e relativa facilidade de execução em laboratório. As grandes desvantagens desse método são: imprecisão e a baixa repetibilidade, além de ser insuficiente para efetuar uma avaliação mais completa desses produtos no estado fresco. Assim, técnicas de caracterização reológica (Squeeze Flow, Pull Out Flow e reometria rotacional) foram especificadas e aplicadas, como alternativa tecnológica para avaliação de argamassas colantes. Porém, o potencial da configuração tradicional do ensaio de Squeeze Flow e a reometria rotacional foram pouco explorados neste tipo de argamassa. Neste estudo foi necessário empreender ajustes de configuração. O objetivo desta dissertação foi o de aplicar métodos de caracterização reológica em argamassas colantes de mercado (ACI e ACIII) de certo fabricante e ACI formulada em laboratório composta por areias com morfologias diferentes que permitissem identificar suas características relevantes no estado fresco, avaliar a influência dos parâmetros experimentais do método de Squeeze Flow (principalmente em relação à configuração e parâmetros), avaliar a adesividade das argamassas no estado fresco e aplicar o método de reometria rotacional para avaliação das energias de mistura e reológica. Os experimentos para avaliação das configurações e parâmetros do ensaio de Squeeze Flow e Pull Out Flow mostraram que tais métodos foram sensíveis para diferenciar as argamassas e refletiram o que, na prática, é percebido: ACIII (Argamassa Colante do Tipo III) tem maior consistência que ACI (Argamassa 7 Colante do Tipo I), além de mostrar que são sensíveis às diferentes taxas de deslocamento, teores de água e morfologia de agregados. Já a reometria rotacional mostrou-se sensível para identificar e diferenciar a cinética de mistura das argamassas colantes ACI e ACIII. Os resultados indicaram que o tempo de mistura de 150 segundos foi eficiente e suficiente para homogeneizar e estabilizar as argamassas testadas, e que a argamassa do tipo ACI apresenta maior dificuldade de mistura e resulta em uma suspensão com maior viscosidade e tensão de escoamento do que a argamassa ACIII. Por fim, a aplicação dos métodos de caracterização reológica em argamassas ACI compostas por areias com morfologias diferentes, indicou que o método de Squeeze Flow mostrou ser sensível para diferentes teores de água, em argamassas compostas por areia artificial. As curvas de carga de compressão da argamassa ACI com areia artificial mostraram serem superiores às formuladas argamassas com areia natural, indicando que, com a mesma proporção de insumos e teor de água (volume), as argamassas não possuem perfis reológicos similares. / Adhesive mortars are products constituted of natural or artificial sand, binder (cement) and chemical additives which serve as an adhesive for laying floor and wall tiles. From the rheological point of view, the adhesive mortar is a multiphase material consisting of a paste that coats mineral aggregates. Currently, the only test done is the slip test, which has low cost and has a relatively easy execution. The disadvantage of this method is not to have a good repeatability and is not sufficient to evaluate products in fresh state. Thus, techniques of rheologic characterization (flow squeeze, pull out flow and rotational rheometry) were applied as technologic alternatives for evaluation of adhesive mortars. However, the potential of the traditional configuration of the Squeeze Flow test and rotational rheometry were not explored in this type of product due to the requirement of configuration settings. The purpose of this dissertation is to apply advanced methods for rheological characterization of adhesive mortars in order to identify important characteristics of fresh-state application; evaluation of the influence of the squeeze-flow experimental method (mainly due to configuration and parameters); applied rheometry techniques to evaluate the mixing energy; and to evaluate the adhesiveness of fresh mortars. The evaluation of the configuration and parameters of the Squeeze Flow and Pull Out Flow showed that the methods were sensible enough to differentiate mortars in the same way that is perceived in practice: ACIII has greater consistency than ACI, also shows that are sensitive to different rates of displacement, water content and morphology of aggregates. The mixing and rotational rheometry showed that the method is sensitive to identify and differentiate the kinetics of mixing for ACI and ACIII mortars. The results indicate that the mixing time of 150 seconds was effective to homogenize and disperse the mortars. The mixing and flow torque values are higher for ACI than for ACIII, indicating that ACI is more difficult to be mixed and has a higher viscosity and yield stress than ACIII.

The impact storage has on function of platelet concentrates is not completely known, although some factors have been discovered and measures have been taken to counteract them, such as adding platelet additive solution. There are several methods for analysing platelet function. In this study, the aim was to analyse change of platelet function in platelet concentrates over time and to see what effect fibrogen has on the coagulation. A technique using free oscillation rheometry (FOR), ReoRox®, was used to analyse function in platelet concentrates, both over time and after addition of fibrinogen. The platelets were analyzed at a concentration of 800 x109 Ptl/L and activated with thrombin receptor antigen peptide (TRAP). For fibrinogen efect analysis, four different concentrations were used, 10 g/L, 2,25 g/L, 1,0 g/L and 0,1 g/L. The results showed no statistically significant change in the function over time. However an increase in elasticity and decrease in the decline of elasticity could be seen. While analysing the platelets with fibrinogen it showed that up to 2,25 g/L the aggregation increased, while it decreased significantly at 10 g/L. In conclusion, the platelet concentrates retained a good clotting function from day one to day seven of storage, while the clot became stronger and fibrinolysis decreased. Fibrinogen proved important for coagulation, however a too high concentration inhibits coagulation.

La relation scalaire entre contrainte et déformation obtenue par le cisaillement simple dans les rhéomètres classiques n'est pas assez riche pour décrire les écoulements complexes. Pour obtenir plus d'information, nous superposons deux écoulements orthogonaux en utilisant la géométrie plan-plan. Le fluide, sous forme cylindrique, peut alors être cisaillé par la rotation mais aussi écrasé par le rapprochement (ou étiré par l'éloignement) des disques. Nous détaillons les calculs théoriques permettant de déterminer les liens entre contraintes et taux de cisaillement et les efforts et vitesses macroscopiques associés. Ensuite, nous décrivons précisément le dispositif expérimental mis en place pour imposer toutes sortes d'écoulements combinant des cisaillements stationnaires ou oscillants, en rotation ou en écrasement. Puis nous présentons les résultats de la comparaison entre l'écoulement de rotation et l'écoulement d'écrasement. Nous présentons enfin les expériences de superposition des deux écoulements. Nous créons des écoulements complexes et divers afin, entre autres, de mesurer et comprendre la loi d'écoulement 3D et le critère d'écoulement 3D des fluides à seuil / The scalar relation between stress and strain obtained by simple shear within classical rheometers is not rich enough to describe complex flows. To obtain more information, we shall superimpose two orthogonal flows and for that, we shall use the parallel-plate geometry. The volume of fluid has a cylindrical shape and can be sheared by the rotation of a plate or squeezed by the move closer (or stretched by the move away) of the plates. We detail theoretical considerations that allow us to determine the link between stresses and shear rates and associated macroscopic efforts and velocities. Then we precisely describe the experimental setup developed to impose all kind of flows : steady or oscillating flows, rotation or squeeze. After that, we present the results of comparison between rotational and squeeze flow. Finally, we present the experiments with both superimposed flows. We create complex flows to measure and understand, among others, 3D behavior and 3D flow criteria of yield stress fluids

The study deals with interactions of polyelectrolytes polystyrene sulfonate and hyaluronic acid with nitrogenic amphiphilic substances, represented by lysine and albumine. To study the interactions pH-metry, conductance, viscositic and turbidity measurement, DLS and reometry were used. All mixtures of different concentrations were measured and the data were compered with data obtained from measurement of samples with amphiphilic sumstances without polyelectrolytes. Observed interactions occured in the aminoacid concentrations between 0 to 20 mmoldm-3, then the PSS interaction groups were fully bonded by lysine and no more interactions were recognized. The same behaviour were observed in albumine solutions with concentration under 2 gdm-3.

High surface area of used nanoparticles and their comparable size with polymer chains, are the most important characteristics of fillers in the preparation of non-Newtonian suspensions. Such structures at different concentrations have major influence on the rheological behavior of polymer solution in solvent. With increasing volume fraction of nanofiller, there is pseudoplastic or dilatant behavior present in the dissolved elastomers. Diploma thesis studies the influence of the concentration of different elastomers (SBR and SEBS copolymers) and nanofiller (hydrophobic nanosilica) in suspension, of rheological properties.

No description available.

A novel on-line capillary rheometer (OLR) was used to examine the shear and extensional characteristics of polyolefin melts during twin screw extrusion (TSE). Comparisons with off-line rheometry were made using a twin-bore capillary rheometer and a modular in-line slit die rheometer (ILR) provided in-line rheometry comparisons. Both capillary rheometers were controlled via PCs running dedicated software, and the extrusion line and ELR were fully instrumented allowing real-time process monitoring to be carried out by IBM compatible PCs via data acquisition hardware and software. The prototype OLR was developed by the re-design of several key features including an instrumented transfer section and capillary die block which facilitated the use of various die geometries. Shear and extensional on-line rheometry of three polyethylenes (linear and branched), and four molecular weight grades of polypropylene were examined, and a direct comparison with off-line capillary rheometry showed a good correlation. The effect of a high loading of filler on two of the polyethylenes was investigated. In-line shear stress and entry pressure measurements showed a reasonable correlation with on-line rheometry. A study of entry flows in the OLR using capillary dies approaching orifice showed non-linearities occurred at very low capillary length to diameter(L:D) ratios, and this was repeatable using off-line rheometry. Predicted zero length entry pressures (Po) were used to estimate apparent extensional viscosity using a number of standard models. Melt instability and capillary wall slip were also investigated using on-line rheometry. Melt pressure and temperature in the twin screw extruder and OLR were monitored at various process conditions to examine the ability of the OLR to condition melt during testing, and the effect of OLR testing on extrusion conditions. Pressure variation in the extruder, OLR and off-line rheometer were compared in order to quantify process noise. The effect of OLR testing on melt rheology and polymer molecular weight were examined using off-line rheometry and gel permeation chromatography(GPC). / Rosand Precision Ltd. and Raychem Ltd.

Cette étude s'inscrit dans le cadre du projet Européen VEGEPHY (VEGEtale-PHYtosanitaire) dont le but est de développer un produit support destiné à être pulvérisé pour protéger les plantes des viroses. Le produit étudié est une émulsion de type eau-dans-huile (E/H) à base d’une solution aqueuse de polysaccharide et d’esterméthylique de colza comme phase continue. Le polysaccharide est utilisé sous forme d'adjuvant afin de modifier les propriétés rhéologiques de la préparation phytosanitaire (bouillie) et ainsi de limiter la dérive des gouttelettes lors de la pulvérisation. Le but est également d’améliorer le contact des gouttes sur le végétal traité. L'objectif de ce travail est de formuler une émulsion (E/H) avec une concentration maximale de polysaccharide, qui soit stable sur le long terme (environ 2 ans) et d'étudier, lors de la mise en œuvre du produit, les mécanismes de relargage dans un laps de temps efficace devant rester inférieur à 600 s. Les émulsions (E/H) concentrées ont été réalisées à l'aide d'un système rotor stator à température ambiante. La phase aqueuse contenant le polysaccharide et du glycérol a été dispersée dans une phase huileuse agitée dans laquelle un surfactant (lécithine ou PolyRicinoléate de PolyGlycérol, PGPR) a préalablement été dissous. Des tests de stabilité ont été menés immédiatement après les phases de préparation ou par un vieillissement accéléré. Différents paramètres qui ont une influence sur cette stabilité ont été étudiés par DSC, observations microscopiques, diffraction laser et mesure des propriétés rhéologiques. Les analyses DSC ont été utilisées poursuivre l'évolution de la taille des gouttes en fonction du temps. En effet, le comportement thermique des émulsions pendant les phases de congélation et de fusion permet de calculer la fraction d’eau congelée dans les gouttelettes et sa mise en relation avec l’évolution de la stabilité des émulsions. Le relargage du polysaccharide (CarboxyMethylCellulose, CMC) est obtenu en deux étapes : déstabilisation de l'émulsion primaire E/H par un produit chimique puis dilution dans l'eau pour obtenir une émulsion (H/E) avec la concentration désirée de polysaccharide dans la phase aqueuse. La déstabilisation a été étudiée en observant l'évolution des gouttelettes par DSC. Le procédé de dilution a été étudié par une mesure de la conductivité de la solution aqueuse couplée à un modèle cinétique de relargage du CMC.La formulation et la stabilité de l'émulsion (E/H) ont montré que la DSC, complétée par d'autres techniques, est une méthode appropriée pour déterminer les caractéristiques des émulsions. L'étude du comportement lors de la congélation montre que la proportion de glace formée dans les gouttelettes durant les tests DSC est en bonne adéquation avec les mesures DSC et les calculs thermodynamiques. L'utilisation du PGPR comme tensioactif et l'ajout du glycérol dans la formulation permettent d'augmenter la stabilité de l'émulsion à long terme. La formulation optimum obtenue contient 3.5 % (m/m) de CMC, 10 % (m/m) de glycérol dans 75 % (v/v) de phase dispersée et 14 % (m/m) de PRPG dans la phase continue. Un modèle empirique peut être utilisé pour décrire la cinétique de relargage. Pour déstabiliser l'émulsion (E/H), la quantité optimum de tensioactif anionique Cynthiorex PMH1125 est de 10 % (m/m) dans première émulsion avec NRe ≥ 4200 et T ≥ 20°C. Dans les conditions réelles d’utilisation de la préparation au champ, le temps minimum de relargage est d'environ 200 secondes. / This study is a part of the European project VEGEPHY (VEGEtale-PHYtosanitaire) to develop a product for the crop protection purposes. The product is a concentrated W/O emulsion trapping of a polysaccharide in the aqueous phase and rapeseed methyl ester oil as a continuous phase. Polysaccharide is used as a thickening adjuvant to modify the rheology properties of the water-based spray solution in order to reduce the drift of thespray. The objective of this study is to formulate concentrated W/O emulsions incorporation with the maximum amount of polysaccharide which show long stability (for over 2 years) and to study the release mechanism of polysaccharide in suitable conditions with a goal of an efficiency time less than 600 seconds.Concentrated W/O emulsions were realized by using a rotor stator system at room temperature. Aqueous phase containing polysaccharide and glycerol was dispersed into the stirred oil continuous phase where in a surfactant (lecithin and/or polyglycerol polyricinoleate, PGPR) has been previously dissolved. Stability tests were performed immediately after preparation and after ageing tests. Various parameters having an influence on thestability have been interpreted from DSC thermogram parallel with microscopic observation, laser diffraction granulometry and rheology measurement. DSC technique was used to study the emulsions by following the evolution of the droplet size versus time. Thermal behaviour of emulsions may be evaluated when they under gofreezing and melting in which the proportion of ice formed in the droplets may be calculated and their link with the evolution of the emulsion versus time. The release of the polysaccharide (CarboxyMethyl Cellulose, CMC)from the emulsion system is obtained by a two steps process : destabilization of the primary W/O emulsion by achemical product and dilution in water that gives an O/W emulsion containing the required concentration of polysaccharide. Destabilization was observed by following the evolution of dispersed droplets using DSC. Dilution process was assessed by measuring electrical conductivity of the water solution and a mathematical model to represent the kinetic release of CMC in water was proposed.The formulation and the stability of concentrated W/O emulsion has shown that DSC completed with granulometry and rheometry is an appropriate technique to study the emulsion characteristics. The study offreezing behaviour of emulsions show that the proportion of ice formed in the dispersed droplets during DSC test indicates good agreement between DSC measurements and thermodynamics calculation. The use of PGPRas surfactant and the introduction of glycerol in the formulation are beneficial to improve the long‐term stabilityof the emulsion. The optimum formulation of concentrated W/O emulsion was obtained containing : 3.5% w/wof CMC, 10% w/w of glycerol in 75% v/v of dispersed phase and 14% w/w of PGPR in the continuous phase. From the release study, an empirical model may be used to describe the released kinetic. The optimum amount of nonionic surfactant Cynthiorex PMH 1125 to break primary W/O emulsion was found at 10% w/w in the primary emulsion with NRe ≥ 4200 and T ≥ 20°C. Under practical field conditions, the minimum release time isthen around 200 seconds.

L'enjeu des travaux contenus dans cette thèse est la caractérisation rhéologique de suspensions concentrées d'objets viscoplastiques suspendus dans une matrice viscoplastique. Trois contraintes physiques se présentent : l'hétérogénéité des objets, la taille des objets au regard de la taille du système étudié, et la proximité entre la consistance de la phase suspendante et celle des objets. Dans notre contexte alimentaire, il faut ajouter des contraintes d'ordre biologique : les faibles durées de vie des produits, les prélèvements in vivo et la conservation des conditions de températures et d'humidité. L'ensemble de ces contraintes aboutit à une rhéométrie spécifique, aux frontières de la mécanique des milieux continues, avec pour objectif de mesurer des propriétés rhéologiques pertinentes. Pour cela, deux instrumentations originales ont été construites pour effectuer la caractérisation rhéologique le plus vite et au plus près de la génération des échantillons.Appliquée aux bols alimentaires issus de fromage, leur rhéologie vient gouverner les écoulements en bouche et induire la création de surface d'échange en bouche, au travers de la mastication. Au travers de ces interfaces, les arômes et les sapides sont libérés et transportés vers les récepteurs sensoriels. Les résultats montrent le lien entre le seuil de contrainte à l'écoulement du bol et la libération d'arômes de différents hydrophobicités, fonction de la fermeté et du taux de matières grasses du fromage. Plus particulièrement, la phase suspendante fluide, semble jouer un rôle majeur dans la création et la persistance des surfaces d'échanges. Appliquée aux jus gastriques issus de pain, l'enjeu est de savoir si des modifications des contenus en glucides pouvaient impacter la rhéologie des jus gastriques, modifier les cinétiques de vidange en sortie d'estomac, et diminuer l'excursion glycémique. Les résultats montrent l'effet d'un ajout d'amylose sur l'augmentation de la viscosité aux temps de digestion longs, lorsque la rhéologie n'est plus gouvernée par l'encombrement des particules de pain gonflées d'eau. Cependant, l'amylose ne semble pas avoir d'impact sur les cinétiques de vidange, ce qui vient conforter que le débit en sortie d'estomac est régulé par la charge énergétique contenue dans le repas. / The challenge of this work is to carry out the rheological characterization of concentrated suspensions of viscoplastic objects suspended in a viscoelastic matrix. Three structural constraints are faced: the heterogeneity of the particles, the size of particle in relation to the size of the whole system studied, and the proximity between the consistency of the suspending phase and that the consistency of the particles. In the food context, some biological constraints are added: small lifetimes of bolus, in vivo sampling and test conditions of temperature and humidity. All these constraints lead to a compromise in rheometry, at the edge of continuum mechanics, aiming to measure useful rheological properties. To carry out the rheological characterizations quickly and efficiently, two original devices has been designed trough this work. Applied to food bolus from cheese, rheology comes to govern flows in the mouth and induce the creation of exchange area in the mouth, during the chewing process. Through these interfaces, the savors and flavors are released and transported to the sensory receptors. The results show the relationship between the yield stress of the bolus and flavors release of different hydrophobic aromas, depending on the firmness and fat content of the cheeses. Specifically, fluid suspending matrix appears to play a major role in the creation and persistence of exchange area.Applied to gastric juice from bread, the issue is whether changes in carbohydrate content could impact the rheology of gastric juice, modify the kinetics of stomach flow rate, and decrease the glycemic excursion. The results show the effect of amylose addition on increasing the viscosity for long digestion time, when the rheology is no longer governed by the jamming effect of the particles made of water-swollen bread. However, amylose does not seem to have any impact on the kinetics of emptying, which reinforces that the stomach flow rate is regulated by the caloric charge contained in the meal.