A new method for determining viscoelastic properties on the interfacial interface called interfacial rheology was intoduced and investigated. Measured data were compared with data from tanziometer for model system of surfactant. Three concentration renge of surfactant, namely SDS (anionic), TTAB (cationic) and Tween (nonionic), were measured. From the measured data the influence of structure, critical micellar concentration and charge on the viscoelastic properties of the interfacial interface was determined. Furthermore, this new method was used for biological systems and specifically for biofilms of two bacterial strains. First, the viscoelastic properties of biofilms on the agar were determined, and the viscoelastic properties dependence on temperature

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第17828号 / 工博第3771号 / 新制||工||1576(附属図書館) / 30643 / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 渡辺 宏, 教授 金谷 利治, 教授 山本 量一 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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The impact of particle size, size distribution, and particle shape on the rheology of precipitated calcium carbonate (PCC) based coatings was studied. Evaluating the interactions between different particle sizes and shapes leads to a better understanding of the packing fraction of PCC. HIgh packing fraction is desirable because of the positive impact on the fluidity of suspensions. Suspension with higher levels of fluidity can potentially load larger amounts of solids while keeping low viscosities. High solids suspensions are key factors to improve the efficiency of coating processes. To address this issue, PCC of different sizes and shapes where mixed in different ratiosto find mixtures with higher packing fractions that could result in coatings with lower viscosities. When coatings containing 90% of large particles and 10% by weight of small particles of different shape, viscosity decreases by 50% for one combination. The effect is caused by the higher packing fraction achieved. Future research is also described here.

Les objectifs de cette thèse concernent la caractérisation des polymères à l’état fondu via la rhéologie non linéaire dans les modes de cisaillement ou en élongationnel et les procédés faisant intervenir de fortes élongations tel que l’électrospinning en voie solvant et en voie fondue. Pour atteindre le premier objectif, nous nous sommes concentrés sur la caractérisation des polymères fondus enchevêtrés dans les régimes viscoélastiques linéaires et non linéaires. L'influence de la masse moléculaire, Mw et de sa distribution MWD, la présence de longues chaînes branchées (LCB) ou encore l'addition de nanoparticules dans la matrice de polymère à l'état fondu ont été étudiées en utilisant des techniques rhéologiques en cisaillement et en élongationnel. Dans le cas des écoulements de cisaillement oscillatoires à grandes amplitudes (LAOS), nous avons proposé de nouveaux paramètres mécaniques qui ont permis de définir les relations structure-propriétés des différents systèmes étudiés. / The goals of this thesis are the characterization of polymer melts using mainly non-linear shear and extensional rheological techniques. The fabrication of scaffolds with excellent physical and mechanical properties using solution electrospinning technology for tissue engineering applications and the development of melt electrospinning equipment to facilitate the fabrication of solvent free scaffolds. To achieve the first goal, we focused on the characterization of entangled polymer melts in the linear and nonlinear viscoelastic regimes. The influence of molecular weight, Mw, molecular weight distribution (MWD), long-chain branching (LCB) and addition of particles to the polymer matrix on polymer melt properties were investigated using shear and extensional rheological techniques. The resulting structure-property relationships were established using newly introduced mechanical parameters under large amplitude oscillatory shear (LAOS) flow.

Thesis (PhD (Process Engineering))--Stellenbosch University, 2008. / The feasibility of predicting paint properties directly from the raw material formulation as well as the rheological data is investigated in this study. Although extensive work has been carried out on the prediction of paint properties in terms of the raw material data, very little research has been carried out on the prediction of paint properties in terms of the rheological data. Little is known about the relationship between fundamental rheological properties and real-world performance. The paint under investigation consists of fourteen raw materials. These raw materials interact in a very complex manner to produce certain desired paint properties. Evaluation of these interactions in terms of constitutive equations is almost impossible and the relationships between paint properties, raw materials and rheology can only be modelled in a statistical way. Linear relationships are investigated with linear parameter estimation techniques such as multiple linear regression. However, it has been found that many of these relationships are non-linear and that linear modelling techniques are no longer applicable for certain situations, e.g. at very high concentrations of specific raw materials. Non-linear techniques such as neural networks are used in these situations. The relationship between the raw materials, paint properties and rheology are evaluated using the following three models: · MODEL 1: The relationship between rheology and raw materials · MODEL 2: The relationship between paint properties and raw materials · MODEL 3: The relationship between paint properties and rheology MODEL 1 makes use of techniques such as principal component analysis and preliminary modelling to respectively reduce redundancy and to capture as much data as possible. MODELS 2 and 3 make use of linear screening techniques in order to identify relevant raw materials and paint properties. The validity of every model is checked to ensure that predictions and interpretations are unbiased and efficient. MODEL 1 revealed that emulsion, extender particles, pigment, water, organic pigment and solvent are the six most important raw materials affecting the rheology of the specific paint. The rheology curves that are predicted most accurately by means of multiple linear regression are the “Amplitude Sweep” (AS), “3-Interval-Thixotropy-Test” (3-ITT) and the “Flow Curve” (FC). Non-linear rheological behaviour is encountered at high pigment volume concentrations (PVC) and volume solids (VS), due to the strong dependency of the rheology of the paint on these properties. It has been shown that neural networks perform better than multiple linear regression in predicting the rheological behaviour of these paint samples for which the raw materials vary by more than 20% from the standard formulation. On average, neural networks improve predictability of the rheological parameters of these samples by 54%. The largest improvement in predictability is made on the rheological variable “Extra Low Frequency” value (CXLF), where multiple linear regression resulted in relative errors of 59%, while neural networks resulted in errors of only 5%. Other predictions of rheology curves where neural networks have shown a major improvement on predictability are the “Time Sweep” (TS) – 68% increase in accuracy and “Low Shear” curve (LS) – 63% increase in accuracy. The smallest increase that the neural network had on the predictability of a rheology curve, was a 33% increase in accuracy of the “Amplitude Sweep” (AS) predictions. Multiple linear regression models of MODEL 2 predict the critical paint properties of Opacity, Gloss, Krebs Viscosity and Dry Film Thickness with relative errors smaller than 10%. It has been shown that 90% of all new predictions fall within the allowable error margin set by the paint manufacturer. Paint properties that can be predicted with an expected error of between 10% and 20% are Dry and Wet Burnish, Open Time and Water Permeability. Paint properties that are predicted the most inaccurately by MLR, that results in errors larger than 20% are Dirt Pick-Up and Sagging. Non-linear techniques such as neural networks are used to predict the paint properties of these paint samples for which the raw materials vary by more than 20% from the standard formulation. The neural networks show a major improvement on the predictability of the paint properties for those paint samples that vary more than 20% from the standard formulation. On average, neural networks improve predictability of the paint properties by 47%. The largest improvement in predictability is made on the Wet Burnish20 prediction, where multiple linear regression resulted in relative errors of 66%, while neural networks resulted in errors of only 0.6%. Other paint property predictions where neural networks have shown a major improvement on predictability of 80% or more in accuracy are Gloss – 80% increase in accuracy and Dry Film Thickness – 81% increase in accuracy. The smallest increase that the neural network had on the predictability of a paint property, was a 33% increase in accuracy of the Sag predictions. MODEL 2 makes it possible for the paint manufacturer to test tolerances around certain paint properties during manufacturing. Rheology is still a very under-utilised tool for explaining certain paint properties. MODEL 3 quantified the correlation between fundamental rheological properties and real world performance of a paint. It has been shown that rheological measurements can be used accurately to predict certain critical paint properties such as Opacity, Krebs Viscosity, Dry Film Thickness and Gloss within the allowable error margin given by the paint manufacturer. Multiple linear regression models predict the paint properties of Opacity, Krebs Viscosity and Dry Film Thickness with relative errors smaller than 10%, with rheology as input to the model. A neural network of MODEL 3 was developed to predict the paint properties of those paint samples that vary more than 20% from the standard formulation, by using rheology data as input to the model. The neural networks perform better than multiple linear regression in predicting the paint properties of these paint samples. On average, neural networks that use rheology data as input, predict the paint properties 49% more accurate than equivalent multiple linear regression models. The greatest improvement in model predictability is for Water Permeability - 73% increase in accuracy and Gloss - 70% increase in accuracy....

Thesis (MScEng)--Stellenbosch University, 2003. / ENGLISH ABSTRACT: Desired behaviour of paint during processing, storage, application and after application is of great importance in the coatings industry. Rheology (the study of flow and deformation behaviour) is used as a method to investigate the behaviour of the flow and deformation properties of the paint during these stages. Some of the more important phenomena that can occur during these stages, which were examined rheologically, are: 1. The rheological behaviour of certain complex raw materials during processing - vesiculated beads suspensions 11. The paint behaviour during storage - in-can stability, e.g. phase separation and sedimentation of particles; Ill. The paint during application - ease of application, spatter, etc.; IV. The paint behaviour after application - sag, layer thickness, levelling (ability to hide brush marks), etc. A rheometer was used to obtain rheological curves from a paint sample (± 1 ml). Correct interpretation of these curves, which display rheological properties of the sample such as the viscosity, shear stress, structural strength and many more, produced information about the properties mentioned in i, ii, iii and iv above. It was found that the rheological data correlated well with empirical tests carried out in the laboratory for spatter, sag, levelling behaviour and in-can stability of the paint. A wide variety of paints were studied ranging from tough/durable outdoor paints to smooth/velvety indoor paints. The rheological behaviour explained the specific end-use properties of the paints. Paints from two different companies were compared on a rheological basis. In some cases large differences in rheological behaviour were observed. Rheology modifiers were tested on a new paint. It was found that specific rheology modifiers could be incorporated into the formulation to give the specific rheological behaviour required. Rheological modelling was performed and it was found that the flow behaviour of paint cou1d be modelled accurately with existing viscosity models (Ostwald/de Waal, Bingham, Casson, Herschel-Bulkley, Cross and Philips-Deutsch). Other rheological properties of paint were also modelled successfully with a simple linear regression model. Rheology was also used as a method to examine the flow and deformation properties of vesiculated beads, a component of paint with very complex rheology. The most important factors that influence the rheological behaviour of the vesiculated beads were determined. It was found that the type of manufacturing process for the beads affected the rheological behaviour. The effect of the raw materials used to manufacture the vesiculated beads were rheologically determined. / AFRIKAANSE OPSOMMING: Dit is baie belangrik dat verf die gewenste gedrag moet toon tydens berging, vervaardiging, tydens aanwending en direk na aanwending. Reologie (die studie van vloei- en vervorming) word gebruik as a metode om die vloei- en vervormingseienskappe van verf gedurende bogenoemde stadia te ondersoek. Sommige van die belangriker verskynsels wat gedurende hierdie stadia kan plaasvind, is d.m.v reologiese toetse ondersoek. Die verskynsels is as volg: i. Die reologiese gedrag van komplekse grondstowwe soos gevesikuleerde partikel suspensies. ll. Verfgedrag tydens berging - stabiliteit van verf in die blik, bv. faseskeiding en sedimentasie van partikels lll. Verfgedrag tydens aanwending - gemak van aanwending, spatsels IV. Verfgedrag direk na aanwending - afsakking, dikte van verflaag, vloei-eienskappe 'n Reometer is gebruik om die reologiese kurwes te bepaal deur gebruik te maak van ± 1 ml monster. Korrekte interpretasie van hierdie kurwes, wat onder meer eienskappe soos viskositeit, spanning en struktuursterkte insluit, lei tot inligting wat die verskynsels in i, ii, iii en iv kan verklaar. Daar is gevind dat inligting wat verkry is i.v.m die verskynsel van spatsels, afsakking, vloei en die stabiliteit van verf in die blik, goed korreleer met empiriese toetse wat in die laboratorium uitgevoer is. 'n Groot verskeidenheid van verwe, wat wissel van duursame/sterk buitemuurse verf, tot fluweelsagte binnenshuise verf, isondersoek. Die reologiese toetse het daarin geslaag om die eienskappe van die eindproduk suksesvol te verduidelik. Verf van twee verskillende maatskappye is ook met mekaar vergelyk op 'n reologiese grondslag. Daar is by sommige van die verwe aansienlike verskille in die reologiese gedrag gevind. 'n Nuwe verf is gebruik om die uitwerking van reologie modifiseerders te ondersoek. Daar is gevind dat daar spesifieke reologie modifiseerders bestaan wat unieke reologiese gedrag verseker. Reologiese modellering is gedoen op verf en daar is gevind dat die vloeigedrag van die verf akkuraat gemodelleer kan word deur van die bestaande viskositeitsmodelle gebruik te maak (Ostwald/de Waal, Bingham, Casson, Herschel- Bulkley, Cross en Philips-Deutsch). Ander reologiese eienskappe is gemodelleer deur gebruik te maak van eenvoudige regressie modelle. Daar is ook van reologiese tegnieke gebruik gemaak om die vloei en vervormingseienskappe van gesuspendeerde gevesikuleerde partikels, wat as 'n grondstof vir verf gebruik word, te ondersoek. Die belangrikste faktore wat die reologiese gedrag beïnvloed het, was onder meer die verskillende prosesse waarmee die gevesikuleerde partikels vervaardig is. Die effek van sekere van die grondstowwe wat gebruik word om die gevesikuleerde partikels te vervaardig, is ook reologies ondersoek.

<p>The fiber suspensions in the production line from wood topaper are subjected to many types of chemical and mechanicalprocesses, in which the flow of the suspension is of vitalimportance. The flow of the suspension determines the degree ofuniformity of the fibers through the processing, which inreturn affects the properties of the fiber suspension. In orderto optimise the process, thorough knowledge of the suspensionflow is necessary, both on the level of suspension, fibernetworks and individual fibers. Knowledge of the fibersuspension behaviour combined with commercial CFD simulationprovides an efficient design method for any unit operation inthe papermaking process.</p><p>This work concentrates on macroscopic modeling of thebehaviour of fiber suspensions from 0.5-5% dry content, purefiber suspensions without fillers or additives. Any mechanismscausing the characteristic behaviour of the pulp suspensionhave not been included, they are only included through theirinfluence on the suspension parameters. Excluded mechanismsare, for instance, the fiber-fiber coupling mechanisms that arethe reason for the formation of fiber networks and parts offiber network, flocs.</p><p>By combining a rheology model for the bulk suspension, awall function that accounts for the slip layer and finallyintroducing turbulence, a model has been created that is ableto simulate the flow of most fiber suspensions. The flow of thesuspension is not constrained to any particular flowconditions; the models discussed in this work aim at describingthe behaviour of the suspension for all flow rates and flowtypes. The models are developed under simple flow conditions,where all variables can be controlled, but the models areintended for usage within the industry-based flows in real pulpand papermaking applications.</p><p><b>Keywords:</b>rheology, fiber, suspension, CFD, model, wall,slip, turbulence</p>

<p>This thesis uses results of systematic numerical models to argue that externally inactive salt structures, which are potential targets for radioactive waste disposal, might be internally active due to the presence of dense layers or blocks within a salt layer.</p><p>The three papers that support this thesis use the Gorleben salt diapir (NW Germany), which was targeted as a future final repository for high-grade radioactive waste, as a general guideline.</p><p>The first two papers present systematic studies of the parameters that control the development of a salt diapir and how it entrains a dense anhydrite layer. Results from these numerical models show that the entrainment of a dense anhydrite layer within a salt diapir depends on four parameters: sedimentation rate, viscosity of salt, perturbation width and the stratigraphic location of the dense layer. The combined effect of these four parameters, which has a direct impact on the rate of salt supply (volume/area of the salt that is supplied to the diapir with time), shape a diapir and the mode of entrainment. Salt diapirs down-built with sedimentary units of high viscosity can potentially grow with an embedded anhydrite layer and deplete their source layer (salt supply ceases). However, when salt supply decreases dramatically or ceases entirely, the entrained anhydrite layer/segments start to sink within the diapir. In inactive diapirs, sinking of the entrained anhydrite layer is inevitable and strongly depends on the rheology of the salt, which is in direct contact with the anhydrite layer. During the post-depositional stage, if the effective viscosity of salt falls below the threshold value of around 10¹⁸-10¹⁹ Pa s, the mobility of anhydrite blocks might influence any repository within the diapir. However, the internal deformation of the salt diapir by the descending blocks decreases with increase in effective viscosity of salt.</p><p>The results presented in this thesis suggest that it is highly likely that salt structures where dense and viscous layer/blocks are present undergo an internal deformation processes when these dense blocks start sinking within the diapir. Depending on size and orientation of these blocks, deformation pattern is significantly different within the diapir. Furthermore, model results applied to the Gorleben diapir show that the rate of descent of the entrained anhydrite blocks differs on different sides of the diapir. This suggests that if the anhydrite blocks descent within the Gorleben diapir, they initiate an asymmetric internal flow within it.</p>