Certain hydrogel forming de novo proteins that utilize different crosslinking methods are studied experimentally on a rheometer. The stress reaxation modulus of CRC, a telechelic, triblock protein, is shown to be that of a stretched exponential function with a value of β ≅ 0.5. The insertion of an integrin binding domain and changes in pH within the range 6.5–8.5 are shown not to significantly affect the resulting rheological behavior. A selective chemical crosslinker is used on CRC hydrogel systems and is shown to change the rheological behavior of the system to that of a combination of a chemically and physically crosslinked system. Chemically crosslinked hydrogels composed of W6, a wheat gluten-based protein, demonstrate a storage modulus weakly dependent on the angular frequency that is much greater than the loss modulus, with a modulus concentration dependence of c^9/4.

Certain hydrogel forming de novo proteins that utilize different crosslinking methods are studied experimentally on a rheometer. The stress reaxation modulus of CRC, a telechelic, triblock protein, is shown to be that of a stretched exponential function with a value of β ≅ 0.5. The insertion of an integrin binding domain and changes in pH within the range 6.5–8.5 are shown not to significantly affect the resulting rheological behavior. A selective chemical crosslinker is used on CRC hydrogel systems and is shown to change the rheological behavior of the system to that of a combination of a chemically and physically crosslinked system. Chemically crosslinked hydrogels composed of W6, a wheat gluten-based protein, demonstrate a storage modulus weakly dependent on the angular frequency that is much greater than the loss modulus, with a modulus concentration dependence of c^9/4.

Grouting is performed in order to decrease the permeability and increase the stiffness of the material, especially soil and rock. For tunnelling and underground constructions, permeation grouting is done where cement based materials are pumped inside drilled boreholes under a constant pressure, higher than the ground water pressure. The aim of permeation grouting is to reduce the water flow into tunnels and caverns and to limit the lowering of the surrounding groundwater table. Cement based materials are commonly used as grout due to their availability and lower costs. To obtain a proper water sealing and reduce the lowering of the ground water table, a desired spread of grout must be achieved and the rheology of the cement grout is the governing factor for estimating the required spread. Rheological properties of cement grout such as viscosity and yield stress are commonly measured off-line using laboratory instruments, and some simple tools are available to make field measurements. Although the rheological properties of the grout that is used play a fundamental role in design and execution, no method has yet been developed to measure these properties in-line in field work. In addition to the real time measurement, there is no standard method for determining the yield stress for grouting applications. Despite the common usage of Bingham model fitting to determine the yield stress, the range of shear rate is often not specified or is neglected.   In this work, an in-line rheometry method combining the Ultrasound Velocity Profiling (UVP) technique with Pressure Difference (PD) measurements, known as “UVP+PD”, was successfully tested for continuous in-line measurements of concentrated micro cement based grouts. A major obstacle of using the ultrasound based methodology was the transducers, which would be capable of emitting sufficient acoustic energy and can be used in field conditions. The transducer technology was developed in a parallel project and the Flow-Viz industrial rheometer was found to be capable of detail measurement of the velocity profiles of cement grout. The shape of the velocity profiles was visualized, and the change in the shape of the profiles with concentration and time was observed. The viscosity and yield stress of the grout were determined using rheological models, e.g. Bingham and Herschel-Bulkley. In addition, rheological properties were determined using the non-model approach (gradient method) and the tube viscometry concept and were compared with results obtained using the rheological models. The UVP+PD method was found to be capable of determining the rheological behavior of cement grout regardless of the rheological model. The yield stress of cement grout was investigated using off-line rheometry techniques and UVP+PD in-line measurements. Tests were performed applying different shear histories and it was found that two ranges of yield stress indeed exist. Therefore, the design value of yield stress should be chosen with respect to the prevailing shear rate at the grout front for the required spread of grout. In addition, an appropriate shear rate range should be used when a Bingham fitting is done to determine the yield stress. In order to estimate the shear rate, plug thickness and velocity for one dimensional and two dimensional geometry, a non- dimensional nomogram was developed. The advantage of using the nomogram is that it does not depend on the applied pressure and the rheological properties of the grout and can therefore, be used as a simple design tool. Analytical approaches were used for the estimation and good agreements were found with numerical calculations and experimental results. In conclusion, in this work, it was found that it is possible to continuously measure the velocity profiles and determine the change of the rheological properties of cement grout using the ultrasound based UVP+PD method under field conditions. The yield stress was also investigated and it was found that two range of yield stress exist depending on the prevailing shear rate of the grout, which should be used for designing the grouting time at different conditions. In order to decide the design value of yield stress for grouting applications, a non-dimensional nomogram was developed that can be used to estimate the plug thickness, shear rate and velocity of the grout. / <p>Funding for the project was provided by the Swedish Rock Engineering Research Foundation (BeFo), The Swedish Research Council (FORMAS) and The Development Fund of the Swedish Construction Industry (SBUF), who are gratefully acknowledged. QC 20151112</p>

Certain hydrogel forming de novo proteins that utilize different crosslinking methods are studied experimentally on a rheometer. The stress reaxation modulus of CRC, a telechelic, triblock protein, is shown to be that of a stretched exponential function with a value of β ≅ 0.5. The insertion of an integrin binding domain and changes in pH within the range 6.5–8.5 are shown not to significantly affect the resulting rheological behavior. A selective chemical crosslinker is used on CRC hydrogel systems and is shown to change the rheological behavior of the system to that of a combination of a chemically and physically crosslinked system. Chemically crosslinked hydrogels composed of W6, a wheat gluten-based protein, demonstrate a storage modulus weakly dependent on the angular frequency that is much greater than the loss modulus, with a modulus concentration dependence of c^9/4.

Ce travail porte sur l'incorporation de nanorenforts biosourcés, c'est-à-dire des nanofibrilles de cellulose (NFC), dans les matériaux composites à matrice polymère et les mousses. Ces nouveaux matériaux biosourcés peuvent par exemple être utilisés pour la conception de structures sandwich. L'étude à caractère expérimental, théorique et numérique s'articule autour de trois axes visant à optimiser tant les procédés d'élaboration que les propriétés en service de ces matériaux.Dans un premier temps, la rhéologie des suspensions concentrées de NFC, fluides à seuil thixotropes, a été étudiée aux échelles macro- et mésoscopiques en utilisant un dispositif original de rhéométrie couplé à des mesures de champs cinématiques par vélocimétrie ultra-sonore. Nous montrons ainsi que l'écoulement des suspensions de NFC est fortement hétéro-gène et présente des glissements aux parois, de multiples bandes de cisaillement couplés avec des écoulements de type « bouchon ». Sur la base de cette étude, un modèle rhéolo-gique multi-échelles est proposé. Ce modèle tient compte d'une part de l'architecture aniso-trope des réseaux connectés de NFC dans ces suspensions, et d'autre part des interactions mécaniques et physico-chimiques aux échelles nanométriques. Il permet de montrer que les interactions colloïdales et hydrodynamiques, ainsi que la tortuosité et l'orientation des NFC jouent un rôle majeur sur la contrainte seuil et sur le comportement rhéofluidifiant de ces suspensions.Dans un deuxième temps, des nanocomposites à matrice polymère ont été élaborés sous forme de films en faisant varier sur une très grande plage la fraction volumique de NFC. En utilisant d'une part des techniques de microscopie (AFM, MEB) et de diffraction aux rayons X, et d'autre part des essais mécaniques (traction, DMA) nous montrons (i) que les NFC ont une orientation plane et s'organisent en réseaux connectés par des liaisons hydro-gènes, (ii) que ces réseaux jouent un rôle majeur sur le comportement mécanique des nano-composites et (iii) que le comportement élastique des nanocomposites est bien en deçà des prévisions données par les modèles micromécaniques de la littérature. De là, nous proposons un modèle multi-échelles alternatif où les principaux nano-mécanismes de déformation sont ceux se produisant dans les parties amorphes des NFC et au niveau des très nombreuses interfaces entre NFC.Enfin, nous avons étudié l'influence des conditions d'élaboration, de la nature et de la con-centration des NFC sur les microstructures (microtomographie synchrotron à rayons X), les propriétés mécaniques (essais de compression) et les micro-mécanismes de déformation (essai in situ en microtomographie) de mousses préparées par cryodessiccation de suspensions aqueuses de NFC. / This study focuses on the use of cellulose nanofibrils (NFCs) as bio-based nano-reinforcement in polymer composites and foams. These renewable materials can be used in place of traditional materials such as for instance to produce sandwich panels. This experi-mental, theoretical and numerical work aims at optimizing the processing of these NFC-based materials as well as their use properties.In the first part of this work, the rheology of concentrated NFC suspensions, that behave as thixotropic yield stress fluids, is investigated at macro- and mesoscales using an original rheo-ultrasonic velocimetry (rheo-USV) setup allowing the local flow kinematic to be obtai-ned. We show that the flow of NFC suspensions is highly heterogeneous and exhibits com-plex situations with the coexistence of wall slippage, multiple shear bands and plug-like flow bands. Using this experimental database, we develop an original multiscale rheological model for the prediction of the rheology of NFC suspensions. The model takes into account the anisotropic fibrous nature of NFC networks as well as colloidal and mechanical interaction forces occurring at the nanoscale. The model predictions prove that colloidal and hydrody-namic interaction forces together with the orientation and the wavy nature of NFCs play a major role on the yield stress and shear thinning behaviour of the suspensions.In the second part of this work, NFC-reinforced polymer nanocomposite films are processed for a wide range of NFC contents. Using advanced microscopy techniques (AFM, SEM), X-ray diffraction and mechanical tests (tensile and DMA tests), we show (i) that NFCs form highly connected nanofibrous structures with in-plane random orientation, (ii) that these connected NFC networks play a leading role on the mechanical behaviour of the nanocompo-sites and (iii) that the elastic properties of nanocomposite films are much lower than those predicted from the micromechanical models of the literature. In light of these observations, we propose an alternative multiscale model in which the main involved deformation nano-mechanisms are those occurring both in the amorphous segments of the nanofibers and in the numerous nanofiber-nanofiber contact zones.Finally, in a third part we focus on the influence of the processing conditions, the suspension type and the NFC concentration on the microstructure (using X-ray synchrotron microto-mography), the mechanical properties (using compression tests) and the deformation micro-mechanisms (using in situ compression test with X-ray microtomography) of various foams prepared from NFC suspensions by freeze-drying.

Nous étudions le comportement de gels, transitoires auto-assemblés et réticulés permanents, soumis à des contraintes mécaniques extrêmes. D'une part, nous étudions la déformation biaxiale de nappes libres produites par impact d'une goutte liquide (Newtonienne ou viscoélastique) ou d’une perle de gel polymère sur des surfaces solides dans des conditions de dissipation minimale, obtenues soit avec une petite cible solide, soit avec une surface répulsive. Lors de l'impact, la goutte ou perle est transformée en une nappe mince qui s’étend et se rétracte sous l’action de forces de rappel élastiques. Pour les fluides viscoélastiques avec un temps de relaxation plus petit que la durée de vie typique de la nappe, la dynamique de la nappe viscoélastique est similaire à d’un liquide visqueux Newtonien de même viscosité. L’expansion maximale de la nappe diminue avec la viscosité et est modélisée quantitativement en utilisant un bilan énergétique entre l'inertie, la tension superficielle et la dissipation du cisaillement visqueux sur la cible solide, qui peut être prise en compte en mesurant une vitesse effective de la nappe à temps court, en sortie de cible. Nous montrons en outre que la dissipation visqueuse peut être sensiblement éliminée en utilisant une surface solide sur la base d'un effet de Leidenfrost inverse. Les expériences effectuées à l'aide de perles élastiques de modules élastiques variables, de gouttes liquides de tensions superficielles variables et de gouttes viscoélastiques révèlent un comportement universel pour l’expansion maximale de la nappe avec la vitesse d'impact, avec une dynamique analogue à celle d'un système ressort-masse conventionnel. Nous montrons en outre que, pour les gouttes qui impactent une petite cible solide, une description similaire peut être utilisée une fois que la dissipation visqueuse est prise en compte en remplaçant la vitesse d'impact par la vitesse effective. Un autre comportement fascinant des fluides viscoélastiques est l’expansion hétérogène de la nappe associée à l’apparition de fissures, révélant la nature élastique du fluide viscoélastique. D’autre part, nous étudions la déformation uniaxiale et la facture de filaments de doubles réseaux transitoires en couplant rhéométrie extensionnelle et imagerie rapide des filaments étirés. Nous établissons un diagramme d'état qui délimite le régime de du filament, lorsqu'il est étiré à un taux supérieur à l'inverse du temps de relaxation du plus lent des deux réseaux. Nous démontrons quantitativement que les processus de dissipation ne sont pas pertinents dans nos conditions expérimentales et que, suivant la densité des nœuds dans les réseaux, la rupture se produit dans le régime élastique linéaire, ou non linéaire précédé d'une augmentation considérable de la viscosité extensionnelle. L'analyse des profils d'ouverture des fissures indique, pour des réseaux faiblement connectés, des écarts par rapport à une forme parabolique en pointe de fissure, caractéristique d’une fracture fragile en régime linéaire. Nous montrons une corrélation directe entre l'amplitude de la déviation de la forme parabolique et le caractère non linéaire de la déformation élastique. / We investigate the behavior of transient self-assembled and permanently crosslinked gels subjected to extreme mechanical stresses. On the one hand, we study the dynamics of freely expanding sheets produced by impacting a (Newtonian or viscoelastic) liquid drop or a bead of polymeric gel on solid surfaces in minimal dissipation conditions, achieved using either a small solid target or a repellent surface. Upon impact, the drop or bead is transformed into a thin sheet that expands and retracts due to elasticity. For viscoelastic fluids with a relaxation time smaller than the typical lifetime of the sheet, the dynamics of the viscoelastic sheet is similar to that of Newtonian liquids with equal viscosity. The maximal expansion of the sheet decreases with the viscosity and is quantitatively modeled using an energy balance between inertia, surface tension and viscous shear dissipation on the solid target that can be accounted by measuring an effective velocity of the expanding sheet at short time scale. We further show that the shear dissipation can be substantially eliminated by performing impact experiments on a solid surface based on an inverse Leidenfrost effect. Experiments performed using elastic beads of various elastic moduli, viscoelastic or liquid drops of various surface tensions reveal a universal scaling behavior of the maximum expansion with the impact velocity, with a dynamics that mimics that of a conventional spring-mass system. We furthermore show that, for drops impacting a solid target, a similar scaling holds once the viscous dissipation is accounted by replacing the impact velocity with the effective velocity. Another fascinating behavior of viscoelastic fluids is a heterogeneous expansion of the sheet with the occurrence of cracks, revealing the elastic nature of the viscoelastic fluid. On the other hand, we study the uniaxial deformation and the fracture of reversible double transient networks by coupling extensional rheology to fast imaging. We provide a state diagram that delineates the regime of fracture without necking of the filament, when it is stretched at a rate larger than the inverse of the slowest relaxation time of the networks. We quantitatively demonstrate that dissipation processes are not relevant in our experimental conditions and that, depending on the density of nodes in the networks, fracture occurs in the linear elastic regime, or in a non-linear elastic regime preceded by a considerable strain hardening. In addition, analysis of the crack opening profiles indicates, for weakly connected networks, deviations from a parabolic shape close to the crack tip, which is expected for the linear elasticity of a brittle fracture. We demonstrate a direct correlation between the amplitude of the deviation from the parabolic shape and the amount of non-linear elasticity.

Certain hydrogel forming de novo proteins that utilize different crosslinking methods are studied experimentally on a rheometer. The stress reaxation modulus of CRC, a telechelic, triblock protein, is shown to be that of a stretched exponential function with a value of β ≅ 0.5. The insertion of an integrin binding domain and changes in pH within the range 6.5–8.5 are shown not to significantly affect the resulting rheological behavior. A selective chemical crosslinker is used on CRC hydrogel systems and is shown to change the rheological behavior of the system to that of a combination of a chemically and physically crosslinked system. Chemically crosslinked hydrogels composed of W6, a wheat gluten-based protein, demonstrate a storage modulus weakly dependent on the angular frequency that is much greater than the loss modulus, with a modulus concentration dependence of c^9/4.

No / The shear viscosity of polymethylmethacrylate (PMMA) melt is particularly investigated by using a twin-bore capillary rheometer at four temperatures of 210, 225, 240, and 255 degrees C with different capillary dies. Experimental results show that the geometrical dependence of shear viscosity is significantly dependent on melt pressure as well as melt temperature. The measured shear viscosity increases with the decrease of die diameter at lower temperatures (210 and 225 degrees C) but decreases with the decrease of die diameter at higher temperatures (240 and 255 degrees C). Based on the deviation of shear viscosity curves and Mooney method, negative slip velocity is obtained at low temperatures and positive slip velocity is obtained at high temperatures, respectively. Geometrical dependence and pressure sensitivity of shear viscosity as well as temperature effect are emphasized for this viscosity deviation. Moreover, shear viscosity curve at 210 degrees C deviates from the power law model above a critical pressure and then becomes less thinning. Mechanisms of the negative slip velocity at low temperatures are explored through Doolittle viscosity model and Barus equation, in which the pressure drop is used to obtain the pressure coefficient by curve fitting. Dependence of pressure coefficient on melt temperature suggests that the pressure sensitivity of shear viscosity is significantly affected by temperature. Geometrical dependence of shear viscosity can be somewhat weakened by increasing melt temperature. (c) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3384-3394, 2013

[pt] A poliacrilamida parcialmente hidrolisada (HPAM) é amplamente empregada no processo de recuperação avançada de petróleo (EOR). No entanto, sua eficácia é prejudicada pela degradação das moléculas do polímero durante o fluxo através das linhas de injeção, válvulas e reservatório. Essa degradação leva a uma diminuição do peso molecular médio e, consequentemente, reduza viscosidade e as propriedades viscoelásticas da solução, afetando sua eficácia no deslocamento do petróleo. Para abordar essas questões, nossa pesquisa caracterizou o grau de degradação mecânica das soluções de HPAM usando reologia de cisalhamento e extensional. Induzimos a degradação fazendo as soluções fluírem por uma válvula com constrição e diferentes vazões através deum modelo microfluídico de um médio poroso. Os resultados revelam que aadição de nanopartículas de sílica (SiO2) tem um efeito insignificante sobreas viscosidades de cisalhamento e extensional de soluções frescas e minimiza a degradação mecânica das soluções de HPAM. As propriedades reológicas das soluções de HPAM com nanopartículas de SiO2 não são significativamente afetadas pela degradação mecânica, o que sugere que a incorporação de nanopartículas poderia aumentar a eficiência da injeção de polímeros em processosde EOR por meio da estabilização das soluções de HPAM. Além disso, nosso estudo explorou escoamento de deslocamento de óleo usando soluções de polímero HPAM frescas e degradadas em dispositivos microfluídicos usados como modelos de meios porosos. Os resultados sugerem que o HPAM fresco é mais eficiente na produção de óleo do que o HPAM degradado. Além disso, a adição de nanopartículas de sílica em soluções degradadas de NPs-HPAM resultou em um aumento de 9-13 por cento na recuperação de petróleo, destacando o enorme potencial das nanopartículas no aprimoramento dos processos de EOR. / [en] Partially hydrolyzed polyacrylamide (HPAM) is widely employed in enhanced oil recovery (EOR) process. However, its effectiveness is hindered by degradation of polymer molecules during flow through injection lines, valves and reservoir. This degradation leads to a decrease in average molecular weight and subsequently reduces the solution’s viscosity and viscoelastic properties, impacting its effectiveness on displacing oil. Our research characterized the degree of mechanical degradation of HPAM solutions using shear and extensional rheology. We induced degradation by flowing the solutions through a valve with varying constriction and flow rates and through a microfluidic porous medium model. Our findings reveal that the addition of silica (SiO2) nanoparticles has a negligible effect on the shear and extensional viscosities of fresh solutions and minimizes the mechanical degradation of HPAM solutions. The rheological properties of HPAM solutions with SiO2 nanoparticles are not significantly affected by mechanical degradation, suggesting that incorporating nanoparticles could enhance the efficiency of polymer injection in EOR processes by stabilizing HPAM solutions. In addition, our study explored oil displacement flow using both fresh and degraded HPAM polymer solutions in microfluidic devices used as models of porous media. The findings suggest that fresh HPAM is more efficient in displacing oil than degraded HPAM. Furthermore, the addition of silica nanoparticles into degraded NPs-HPAM solutions resulted in a 9-13 percent increase in oil recovery, highlighting the enormous potential of nanoparticles in enhancing EOR processes.

Compression of coated pellets is a practical alternative to capsule filling. The current practice is to add cushioning agents to minimize the stress on the coated pellets. Cushioning agents however add bulkiness and reduce the overall drug loading capacity. In this study, we investigated the performance of compressed coated pellets with no cushioning agent to evaluate the feasibility of predicting the coat behaviour using thermo-mechanical and rheological analysis techniques. Different coating formulations were made of ethyl cellulose (EC) as a coating polymer and two different kinds of additives were incorporated into the polymeric coating solution. Triethyl Citrate (TEC) and Polyethylene glycol 400(PEG400) were used as plasticizers at different levels to the coating formulations (10%, 20%, 30%). Thermal, mechanical and rheological measurements of the coating film formulations were achieved to investigate the effect of plasticizers. Thermal gravimetric analysis results (TGA) showed higher residual moisture content in films plasticised with PEG 400 compared to their TEC counterparts. Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA) and Parallel Plate Shear Rheometer (PPSR) were used to study the influence of the level and type of plasticisers incorporated in coating film formulation on the performance of the coating film. In this study, both DSC and DMA were used to investigate the Tg for each film coating formulation in order to evaluate the effect of the additives. In general DMA results for the Tg value of the films were always higher by 10-20% than those measured by the DSC. Furthermore, clamp size and the frequency of the oscillation have an influence on the evaluation of Tg. Complex viscosity for different coating film formulations revealed that the shear hinning gradient changes with temperature and plasticiser type and concentration. The value of complex viscosity from DMA and PPSR exhibits power law behaviour. The rheological moduli were indirectly affected by the level of plasticiser. There was a discrepancy between the complex viscosity results obtained from both DMA and PPSR at similar temperature but they follow the same trend. The non plasticized polymer showed a 10 time higher complex viscosity values when measured by DMA over that measured by PPSR. The difference was smaller in plasticized films but it was not consistent. Therefore a consistent coefficient to correlate the DMA and PPSR couldn’t be accurately determined Coated pellets were compressed and key process parameters were evaluated. The obtained results revealed that the coating thickness has a significant effect on the release profile of the final products. It was found that by increasing the coating film thickness, the percentage released decreased. Also the compression force has lower influence on the drug release profile, while the dwell time has very low effect on the percentage release from the final products. Optimum release profile was obtained at a coating level of 5.5% w/w and a compression force of 4700N In conclusion, the elasticity of the plasticised EC films in this study meant that the internal stress is not dissipated during compression and the dwell time range that was used in this experiment. Increasing the thickness therefore was necessary to enhance the strength of the film and avoid cracking. The mechanical and rheological profiling was helpful therefore to understand the behaviour of the coated pellets and predict the film properties at various steps of the process of coating and compression (i.e., various shear rate regimes). Experimental design approach to studying the key process and formulation parameters helped identify the optimum values for the process.