The purpose of this study is to identify and quantify factors governing extrudate swell and melt fracture. In the first part, the factors which control the extrudate swell of carbon black (N330) filled styrene-butadiene rubber (SBR) compounds at various states-of-mix were investigated. State-of-mix is quantified by effective filler volume fraction (EFVF), based on an estimate of the amount of rubber immobilised in the carbon black agglomerates. Extrudate swell was found to be dominated by recoverable strain and relaxation time, which are controlled by EFVF. In contrast, shear rate and the rubber-carbon black tridimensional transient network were not found to influence extrudate swell significantly. In the second part, melt fracture of the rubber compounds was investigated in terms of surface texture wavelength. The longer the wavelength, the greater the severity of the surface disruption. It was found that wavelength was controlled strongly by state-of mix (or by EFVF). In addition, a mechanism for melt fracture of the compounds studied has been proposed, based on average energy at the extrudate surface (t.E). Lastly, the influences of additives; paraffinic processing oil, stearic acid or a mixture of predominantly calcium fatty acid soaps on extrudate swell and melt fracture were investigated. For the rubber compounds with paraffinic processing oil or stearic acid, EFVF was found to play an important role in extrudate swell. The mixture of fatty acid soaps was shown to reduce significantly extrudate swell due to the presence of wall slip. The influence of the fatty acid soaps on extrudate swell is more noticeable for extrudates obtained from long dies, in which flow is dominated by shear. The major factors shown to exert a significant influence on melt fracture for the compounds with paraffinic processing oil or stearic acid are EFVF and green strength of the extrudate. Wall slip, promoted by a mixture of fatty acid soaps, was also found to decrease the melt fracture severity, particularly for long dies in which shear stresses are dominant.

In situ gelled acids that are based on polymers have been used in the field for several years as an acid diversion agent. These acids should not cause permanent formation damage, and should clean-up rapidly and completely when the well is put back on production. However, recent lab studies indicated that a significant amount of gel was retained inside the core even when the recommended breaker concentration was used. This gel significantly reduced the core permeability. Therefore, the objective of this study is to examine the working mechanisms of the solid breaker and the factors that affect the breaking time. The flowback of the spent acid and the core damage induced by it will also be assessed in detail. Viscosity and rheological experimental studies were conducted using polymer-based in situ gelled acids that used Zr as a crosslinker agent. To form the gel, this acid was neutralized using Pink Desert limestone to pH 3.5-4.The rheological properties of the gel were measured under different breaking conditions for 2 hr using HPHT rotational and oscillatory rheometers. Temperature (150 to 250 degrees F), shear rate (0.1 to 1000 s^-1), and breaker concentrations (0 to 32 lb/Mgal) were the main parameters that were investigated in this study. Experimental results showed that there is no need to add more than 16-ppg breaker concentration at 150 degrees F, while 4-ppg breaker concentration is enough at temperatures higher than 200 degrees F. A full breaking of these acids was obtained when the values of elastic modulus (G') were equalized with the viscose modules (G"). An HPHT filter press was used to simulate the flowback of the spent acid. Viscosity measurements of filtered fluids were used to determine the degree of gel degradation. Carbonate cores that had a 2.5 in. diameter and 0.25 in.thickness were used. Temperature (75 to 250 degrees F) and breaker concentrations (0 to 16 lb/Mgal) were the main parameters that were investigated in this study. Experimental results showed that there was always a gel left inside the rock, and such caused permeability reduction. Time needed to flowback the solution decreased by 50% when the temperature was increased from 150 to 200 degrees F, while it decreased by only 30% when the breaker concentration was doubled. At 150 degrees F, 16-ppg breaker concentration was recommended for breaking the gel. At higher temperatures (>150 degrees F), 8-ppg breaker concentration was enough to help degrade the gel.

Master of Science / Department of Grain Science and Industry / Yong-Cheng Shi / Jon Faubion / The rheological properties of two waxy and two normal wheat flours were investigated and the observed differences between them were explained by biochemical analysis. Protein analysis showed that waxy flour had lower polymeric to monomeric ratio (0.70 and 0.58 for waxy flour compared to 0.75 and 0.76 for normal flour) and higher gliadin content in waxy wheat dough (43.9 and 47.3 for waxy wheat dough compared to 41.0 and 41.7 for normal wheat dough). Waxy flour had high amounts of insoluble (IPP) and unextractable (UPP) polymeric protein despite the poor dough forming properties of the waxy flours, contrary to previous correlations made between IPP, UPP and dough strength. Gluten index determination showed a clear difference between waxy and normal flour; there was no gluten aggregation when the waxy samples were tested. The determination of gluten index done on a variety of water washed flour samples indicated that the water-extractable fraction may contain compounds that affect gluten aggregation. HPLC analysis coupled with arabinose/xylose ratio and viscosity determination of the water extractable portion of the flour indicated that water extractable arabinoxylans (WEAX) in waxy wheat flour were different in composition and conformation. Further research is needed to determine if they could be responsible for the lack of gluten aggregation in waxy flour.

Statics, dynamics, rheology and scission-recombination kinetics of self-assembling linear micelles are investigated at equlibrium state and under shear flow by computer simulations using a newly proposed mesoscopic model. We model the micelles as linear sequences of Brownian beads whose space-time evolution is governed by Langevin dynamics. A Monte Carlo algorithm controls the opening of a bond or the chain-end fusion. A kinetic parameter omega modelling the effect of a potential barrier along a kinetic path, is introduced in our model. For equilibrium state we focus on the analysis of short and long time behaviors of the scission and recombination mechanisms. Our results show that at time scales larger than the life time of the average chain length, the kinetics is in agreement with the mean-field kinetics model of Cates. By studying macroscopic relaxation phenomena such as the average micelle length evolution after a T-jump, the monomer diffusion, and the zero shear relaxation function, we confirm that the effective kinetic constants found are indeed the relevant parameters when macroscopic relaxation is coupled to the kinetics of micelles. For the non-equilibrium situation, we study the coupled effects of the shear flow and the scission-recombination kinetics, on the structural and rheological properties of this micellar system. Our study is performed in semi-dilute and dynamically unentangled regime conditions. The explored parameter omega range is chosen in order for the life time of the average size chain to remain shorter than its intrinsic (Rouse) longest relaxation time. Central to our analysis is the concept of dynamical unit of size Lambda, the chain fragment for which the life time tau_Lambda and the Rouse time are equal. Shear thinning, chain gyration tensor anisotropy, chain orientation and bond stretching are found to depend upon the reduced shear rate Beta_Lambda=gamma dot*tau_Lambda while the average micelle size is found to decrease with increasing shear rate, independently of the height of the barrier of the scission-recombination process.

A new type of viscoelastic amphoteric surfactants (amidoamine oxide) has been examined as a diverting agent during acidizing treatment. Rheological properties of viscoelastic surfactants are a function of surfactant concentration, acid additives, pH, temperature and shear rate. A HPHT rheometer was used to test the effect of common acid additives and organic acids/chelating agents on the apparent viscosity of amidoamine oxide-based acids. The compatibility and thermal stability of surfactants with corrosion inhibitor were also investigated. Rotating disk apparatus was used to examine the kinetic studies of surfactant-based acids with limestone. The results show that the apparent viscosity of surfactant solutions prepared in deionized water, live acid, and spent acid was found to be a function of temperature. Apparent viscosity of live surfactant-based acids was also found to be a function of HCl concentration. Most of acid additives could adversely affect the rheological properties of spent acids. Compatibility tests should be done prior the field application. Cryo-TEM studies show the changes of rod-like micelle structures with the addition of additives. The reaction between surfactant-based acid and limestone was found to be mass transfer limited at 170 degrees F.

In this work, EPDM rubber was compounded with increasing amount of filler (FEF N 550 type carbon black), process oil (saturated mineral oil), vulcanizing agent [di (t-butylperoxy) diisopropyl benzene, i.e., BBPIB] and diene [5-ethylidenebicyclo(2.2.1)-hept-2-ene, i.e., ENB] in order to investigate mechanical and rheological properties. Effect of Increasing amount of filler was investigated by using FEF N 550 type carbon black in 35, 70, 87.5, 105 phr. Decrease in scorch times of vulcanization reactions, ts2 (25, 21, 19, and 18 s, respectively) and slight increase in rate constants for vulcanization reactions (0.0270, 0.0274, 0.0301 and 0.0302 s-1, respectively) were explained in terms of nature of semi-active filler. Effect of increasing amount of process oil was investigated by using saturated mineral oil (TUDALEN 3909) in 15, 30, 45 phr. Scorch time for vulcanization reaction and rate constants were measured as 95, 103, 97 s and 0.0277, 0.0274, 0.0291 s-1, respectively. Effect of increasing amount of vulcanizing agent was investigated by using BBPIB (PERKADOX 14/40 MB-gr) in 2.5, 5, 7.5, 10 phr. The compound with 5 phr vulcanizing agent gave optimum rheometer data, crosslink density,, ultimate tensile strength, hardness, deflection and damping. Vulcanization reaction rate constant reached 0.0335 s-1 with 7.5 phr vulcanizing agent. Effect of increasing ENB ratio was investigated by using 4 different EPDM with ENB ratios 5.0, 5.6, 7.5, 8.9%. With two different cure systems, compounds with 5.6 and 7.5% ENB ratio gave optimum results. Vulcanization cure time, reaction rate constant and compression set properties changed in irregular manner.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniversitet, 2009. / Härtill 3 uppsatser.

Orientadores: Rosiane Lopes da Cunha, Fernanda Yumi Ushikubo / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-24T20:14:36Z (GMT). No. of bitstreams: 1 Oliveira_DaviRochaBernardesde_M.pdf: 18877035 bytes, checksum: 1668d21b0c81ea31f26e9d7c85a25644 (MD5) Previous issue date: 2014 / Resumo: A emulsificação em dispositivos microfluídicos destaca-se pela sua capacidade em gerar gotas de maneira individual em um processo totalmente controlado. Através dele, é possível a obtenção de emulsões com coeficientes de variação de tamanho de gotas inferiores a 5%. Soluções de glicerol (fluidos Newtonianos) com concentrações variando entre 10 e 75% (m/m) foram utilizadas como fase dispersa para obtenção de emulsões água em óleo em microcanais planares com junções do tipo T e Y. Como fase contínua foi utilizado óleo de soja contendo 5% (m/m) de emulsificante PGPR. Como condições de processo, quatro diferentes razões entre as vazões das fases contínua e dispersa foram avaliadas. Paralelamente, quatro soluções de goma xantana (fluidos não-Newtonianos) com concentrações variando de 0,05 a 0,50% (m/m) foram avaliadas como fase dispersa num microcanal com junção em Y, e submetidas às mesmas condições das soluções de glicerol. Em todos os sistemas avaliados, a razão entre as fases foi o fator de maior influência no tamanho das gotas formadas. Em relação aos fluidos Newtonianos, a emulsificação no canal em T se mostrou menos sensível às propriedades físicas dos fluidos, enquanto na geometria em Y, notou-se, através do cálculo dos números adimensionais de Weber e Capilar, grande influência da tensão interfacial sobre o tamanho das gotas formadas, superando a ação das forças viscosas. Em relação aos fluidos não-Newtonianos, foi observada grande diferença no processo de formação das gotas e nas características da emulsão. Gotas com elevada polidispersão foram obtidas, em especial nas soluções mais concentradas e nas maiores razões entre as vazões das fases. Esse fato se deu devido à formação das gotas ter ocorrido longe da junção dos canais, através da formação de um jato de fase dispersa. Esse jato foi intensificado nas soluções de goma xantana de maior concentração e nas condições de maiores velocidades da fase contínua. Ensaios reológicos extensionais confirmaram que, de fato, a viscosidade elongacional da solução de goma xantana aumenta com a concentração e também com a taxa de deformação elongacional, o que explicaria a formação do jato. Na solução de menor concentração de goma xantana foi possível a obtenção de gotas altamente monodispersas, embora tenha ocorrido a formação do jato no rompimento das gotas, estando essa solução numa região de transição do regime de jateamento para o regime de gotejamento. Dessa forma, pode-se verificar que no regime de gotejamento, típico dos fluídos Newtonianos, a monodispersão é uma característica bem definida. No caso do uso de fluídos viscoelásticos na fase dispersa, a obtenção de gotas monodispersas é um desafio, devido ao efeito da elevada viscosidade elongacional. Assim, torna-se necessária a avaliação de condições de processo e geometria de canal mais adequadas a esta situação de forma a diminuir a polidispersidade desses sistemas / Abstract: Emulsification in microfluidic devices is distinguished by its ability to generate droplets in a controlled and individual way, in which it is possible to obtain emulsions with polydispersity lower than 5%. Glycerol solutions (Newtonian fluids) at concentrations ranging from 10 to 75% (w/w) were used as dispersed phase in order to obtain water in oil emulsions, using Y - and T - junction microchannels. As continuous phase, soybean oil containing 5% (w/w) of emulsifier PRPG was used. Four different ratios of the flow rates of continuous and dispersed phases were evaluated in both microfluidic devices. Similarly, four xanthan gum solutions (non-Newtonian fluids) with concentrations ranging from 0,05 to 0,50% were evaluated as dispersed phase in a Y ¿ junction microchannel. In all systems, the ratio of the flow rates of the phases was the most influential factor in the size of the droplets. Regarding Newtonian fluids, the T ¿ junction microchannel was less sensitive to the fluids physical properties, while in Y ¿ junction geometry it was noted that the interfacial tensions played the main role in droplet size, overcoming the viscous forces. Regarding the non-Newtonian fluids, a large difference in the droplet generation was observed. Droplets with high polydispersity were obtained, especially in the most concentrated xanthan gum solution, when high shear forces were applied. This fact may have occurred due to the formation of a jet of the dispersed phase, from which droplets were detached without any control. This jet was intensified in xanthan solutions of higher concentration and under high velocities of the dispersed phase. Indeed, extensional rheology confirmed that the elongational viscosity of xanthan gum solution increases with concentration and also with the rate of elongational deformation, which would explain the formation of the jet. In the solution at lower concentration of xanthan, it was possible to obtain highly monodisperse droplets, although the droplets detachment still occurred in the jetting regime. This solution is herefore in a transition region between jetting and dripping regime. Thus, it was verified that the dripping regime, typical of Newtonian fluids, the monodispersity is a well-defined characteristic. On the other hand, when using viscoelastic fluids as dispersed phase, obtaining monodispersed droplets is still a challenge, due to the effect of high elongational viscosity of this fluids. In this way, it becomes necessary evaluate new process conditions and microchannel geometries in order to reach emulsions with low polydispersity / Mestrado / Engenharia de Alimentos / Mestre em Engenharia de Alimentos

Les inhalateurs à poudre sèche (DPI) sont une alternative attractive aux inhalateurs pressurisés à valve doseuse (pMDI) du fait de leur absence de gaz propulseur. Pour pénétrer dans les poumons profonds, la taille optimale du principe actif est généralement inférieure à 5 μm. Leur mélange avec un transporteur de taille plus importante, principalement le lactose alpha monohydrate, est classiquement utilisé pour améliorer leur écoulement, faciliter le remplissage dans les inhalateurs et améliorer leur dispersion. Cependant, la formulation et la production des mélanges de poudres pour inhalation demandent une optimisation adéquate pour des-agglomérer les particules cohésives de principe actif et assurer l’homogénéité de ces mélanges contenant un faible pourcentage de principe actif (1,5 à 2,5 %). De plus, l’amélioration de la performance aérodynamique de ces mélanges est nécessaire. Le contrôle des propriétés physico-chimiques du principe actif et du transporteur est critique pour atteindre et maintenir la qualité de la formulation des poudres pour inhalation. Dans cette étude, le lactose alpha monohydrate est utilisé comme transporteur. Des lactoses de grade et de qualité différents sont comparés. Le propionate de fluticasone et le sulfate de terbutaline sont utilisés comme principes actifs modèles. Différentes techniques sont utilisées pour caractériser les principes actifs et les transporteurs: la distribution granulométrique mesurée par la méthode de diffraction laser, les propriétés thermiques par la méthode de calorimétrie (DSC), l’analyse d’image par microscopie électronique à balayage (MEB), l’énergie de surface par la méthode de chromatographie gazeuse inverse (iGC)…Le mélange principe actif et transporteur est réalisé grâce au mélangeur type Turbula, l’influence des conditions opératoires a été étudiée. La performance aérodynamique est évaluée par l’impacteur à cascade en verre (Pharmacopée Européenne). Nous avons développé des techniques de caractérisation des mélanges : l’évaluation de l’adhésion par le tamiseur à dépression d’air, la perméabilité des poudres mesurée par le perméabilimètre de Blaine ; la taille des agglomérats de principe actifs déterminée par la méthode de diffraction laser en milieu liquide. Enfin, les propriétés rhéologiques de poudre et en particulier sa fluidisation sont évaluées par un nouveau rhéomètre, le Freeman FT4. La taille des particules de transporteur exerce une influence importante sur la performance des mélanges pour inhalation. La réduction de taille du transporteur diminue les interactions entre le principe actif et le transporteur. Le détachement du principe de son transporteur est ainsi facilité ce qui augmente le pourcentage de principe actif susceptible de pénétrer dans les poumons c’est-à-dire la fraction respirable de principe actif. Différents grades et qualités de lactose de répartition granulométrique similaire mais obtenus par différentes méthodes de production ont été étudiés et comparés. Ces lactoses différaient essentiellement par le procédé de préparation (broyage ou tamisage) et la teneur en fines particules de lactose. Le lactose broyé présente un potentiel d’adsorption mesuré par iGC supérieur à celui du lactose tamisé et sa teneur en fines particules de lactose est plus importante. Les fines particules de lactose peuvent former des agglomérats avec les particules de principe actif ce qui permet une libération plus facile du principe actif lors de la fluidisation car les forces d’adhésion entre ces particules sont moins importantes. Les mélanges ayant une teneur en fines particules de lactose plus importante permettent d’obtenir une fraction respirable de principe actif supérieure lors de l’évaluation aérodynamique du mélange. Dans ce cas, le pic maximal déterminé par iGC est décalé vers les valeurs supérieures de potentiel d’adsorption ce qui est en accord avec l’hypothèse d’agglomération. [...] / Dry Powder Inhalers (DPIs) are attractive alternatives of pressurized Metered Dose Inhalers (pMDI) in pulmonary delivery, thanks to its being free of CFC and ease of use. The typical size of respirable drug particles is generally less than 5 micrometers. Formulations with fine drug particles and coarse carrier particles, usually lactose have been commonly used to facilitate dispersion and flow. Nevertheless, DPI formulation and production require an adequate optimization in order to de-agglomerate the cohesive drug particles and to produce a uniform mixture with a coarser carrier. Furthermore, improvement of the aerodynamic performance of drug mixtures has recently drawn the great attention of pharmaceutical company. Indeed, the close control of drug and carrier physicochemical properties is crucial to obtain and to maintain the quality of formulation during development and manufacturing. In this study, lactose alpha monohydrate was used as carrier. Different grades and qualities of lactose were compared. Fluticasone propionate and terbutaline sulphate served as model drug. Different techniques were used to characterize the properties of drug and carrier: particle size distribution (by laser diffraction), thermal properties by differential scanning calorimetry (DSC), image analysis by Scanning Electronic Microscopy (SEM), and surface energy by inverse gas chromatography (iGC)... Drug and carrier were mixed by low-shear tumble blending mixer, the influence of operating conditions was studied. The aerodynamic performance of drug mixtures was determined by Twin Stage Impinger (European Pharmacopoeia). Several novel techniques were developed during this study in order to characterize drug mixtures. Drug – carrier adhesion was quantified by Alpine Air jet Siever. Powder permeability was measured by permeametry with the Blaine apparatus. Agglomerate size of drug in mixture was also determined by method developed based on laser diffraction in liquid. The rheological properties of powder were determined by Freeman FT4, a new powder rheometer. Carrier particle size plays an important role on the inhalation performance of interactive mixture. Decrease in carrier particle size leads to a decrease of particulate interaction between drug and carrier. The reduced adhesion between drug and carrier particles increased drug detachment, and thus increased the respirable fraction of drug. Different batches of lactose with similar particle size but different production method (milling or sieving) were investigated. Among the parameters tested, the differences are the preparation processes and the content of fine lactose particles. Lactose obtained by milling process shows a higher adsorption potential measured by iGC and it contains more fine particles which could form agglomerates with the drug. Because of their increased detachment mass, drug particles may be more easily detached from the coarse lactose in the air flow. With higher FPF values, which correspond to higher fines content, the peak maxima determined by IGC are shifted to higher adsorption potentials which support the agglomeration hypothesis. [...]

This diploma thesis deals with the characterization of rheological properties and biodegradation of a poly(3-hydroxy-co-4-hydroxybutyrate), a copolymer produced by a strain of Cupriavidus malaysiensis. The theoretical part focuses on the rheology and degradation of polymers in general. It also contains the basic characteristics of polyhydroxyalkanoates and deals in more details with the description of the studied copolymer, its properties, synthesis, decomposition and possibilities of its applications. In the experimental part, the given copolymer was investigated in its native form and also in the form of copolymer mixtures filaments, which were enriched with additives (stabilizers and plasticizers). In terms of rheology, the samples showed pseudoplastic behaviour, which was slightly limited by the plasticization of the material. The highest thermal stability observed as a function of changes in complex viscosity over time was observed in a sample of a copolymer mixture containing stabilizers and plasticizer Citrofol BII. The plasticization also caused significant changes in thermal properties, especially crystallinity, which decreased compared to the native copolymer. In vitro degradation studies of samples in the form of films prepared by dissolving copolymer mixtures in chloroform were performed in phosphate buffer with lipase, in simulated body fluid and in synthetic gastric juice. The course of the process itself was characterized by the method of determining the molecular weight (SEC-MALLS) and the weight loss over time (gravimetrically). The results showed that the analysed samples are subject to degradation in all used environments. The most considerable molecular weight loss after 105 days (76 %) was observed in the sample containing stabilizers and plasticizer Citrofol BII in the environment of synthetic gastric juice. The most extensive gravimetric weight loss was attributed to the sample with stabilizers and without plasticizers, in the environment of phosphate buffer with lipase, specifically by 79%.