Silica Nanoparticles in Xanthan Gum Solutions: Oil Recovery Efficiency in Core Flooding Tests.

Polymer flooding is one of the enhanced oil recovery (EOR) methods that increase the macroscopic efficiency of the flooding process and enhanced crude oil recovery. In this study, the effect of silica nanoparticles (NP-SiO2) in xanthan gum (XG) solutions was investigated through the analysis of efficiency in core flooding tests. First, the viscosity profiles of two polymer solutions, XG biopolymer and synthetic hydrolyzed polyacrylamide (HPAM) polymer, were characterized individually through rheological measurements, with and without salt (NaCl). Both polymer solutions were found suitable for oil recovery at limited temperatures and salinities. Then, nanofluids composed of XG and dispersed NP-SiO2 were studied through rheological tests. The addition of nanoparticles was shown to produce a slight effect on the viscosity of the fluids, which was more remarkable over time. Interfacial tension tests were measured in water-mineral oil systems, without finding an effect on the interfacial properties with the addition of polymer or nanoparticles in the aqueous phase. Finally, three core flooding experiments were conducted using sandstone core plugs and mineral oil. The polymers solutions (XG and HPAM) with 3% NaCl recovered 6.6% and 7.5% of the residual oil from the core, respectively. In contrast, the nanofluid formulation recovered about 13% of the residual oil, which was almost double that of the original XG solution. The nanofluid was therefore more effective at boosting oil recovery in the sandstone core.

Particles' Organization in Direct Oil-in-Water and Reverse Water-in-Oil Pickering Emulsions.

This paper addresses the impact of the particle initial wetting and the viscosity of the oil phase on the structure and rheological properties of direct (Oil/Water) and reverse (Water/Oil) Pickering emulsions. The emulsion structure was investigated via confocal microscopy and static light scattering. The flow and viscoelastic properties were probed by a stress-controlled rheometer. Partially hydrophobic silica particles have been employed at 1 and 4 wt.% to stabilize dodecane or paraffin-based emulsions at 20 vol.% of the dispersed phase. W/O emulsions were obtained when the particles were dispersed in the oily phase while O/W emulsions were prepared when the silica was introduced in the aqueous phase. We demonstrated that, although the particles adsorbed at the droplets interfaces for all the emulsions, their organization, the emulsion structure and their rheological properties depend in which phase they were previously dispersed in. We discuss these features as a function of the particle concentration and the oil viscosity.

Effect of Silica Nanoparticles in Xanthan Gum Solutions: Evolution of Viscosity over Time.

The effect of silica nanoparticles (NP-SiO2) in xanthan gum (XG) solutions was investigated through the analysis of viscosity profiles. First, hydrocolloid XG solutions and hydrophilic NP-SiO2 suspensions were characterized individually through rheological measurements, with and without salt (NaCl). Then, nanofluids composed of XG and NP-SiO2 dispersed in water and brine were studied through two different aging tests. The addition of nanoparticles was shown to produce a slight effect on the viscosity of the fresh fluids (initial time), while a more remarkable effect was observed over time. In particular, it appears that the presence of NP-SiO2 stabilizes the polymer solution by maintaining its viscosity level in time, due to a delay in the movement of the molecule. Finally, characterization techniques such as confocal microscopy, capillary rheometry, and Zeta potential were implemented to analyze the XG/NP-SiO2 interaction. Intrinsic viscosity and relative viscosity were calculated to understand the molecular interactions. The presence of NP-SiO2 increases the hydrodynamic radius of the polymer, indicating attractive forces between these two components. Furthermore, dispersion of the nanoparticles in the polymeric solutions leads to aggregates of an average size smaller than 300 nm with a good colloidal stability due to the electrostatic attraction between XG and NP-SIO2. This study proves the existence of interactions between XG and NP-SiO2 in solution.

Interfacial viscoelastic moduli in a weak gel.

HYPOTHESIS: The measurement of interfacial viscoelastic moduli provides information on the ability of surface-active agents to texture the interface. However, the contribution of the bulk rheology cannot be ignored in particular when the continuous phase exhibits a gel-like behavior, even with low modulus. EXPERIMENTS: Between 2 and 6 g/L, κ-carrageenan aqueous solutions have no significant activities at interfaces. At low concentrations or high temperatures, they behave like Newtonian liquids. Upon heating or cooling, a reversible liquid/gel transition appears with a hysteresis where the rheological behavior can be easily modulated by adjusting κ-carrageenan concentration. The frequency dependence of bulk and interfacial viscoelastic moduli are determined using a conventional shear rheometer and a drop tensiometer with a polyisobutene oil, respectively. FINDINGS: The effect of concentration and temperature is analyzed and the frequency dependence of interfacial moduli is correlated with those of the bulk. In presence of a gelled κ-carrageenan solutions, an elastic behavior of the interface appears and strengthens as the elastic modulus of the suspended phase is high. It turns out that the oscillating pendant drop method could be a sensitive indicator of the presence of very weak gels, even hardly detected by a shear classical rheometry.

Evaluation of the repartition of the particles in Pickering emulsions in relation with their rheological properties.

HYPOTHESIS: The distribution of particles in Pickering emulsions can be estimated through a percolation-type approach coupled to the evolution of their rheological features with the dispersed phase volume fraction ϕ. EXPERIMENTS: The rheological behavior of water-in-dodecane Pickering emulsions stabilized with hydrophobic silica nanoparticles is addressed. The emulsions viscosity and elastic modulus are investigated at ϕ varying from 0.1 to 0.75. Various rheological models are adjusted to the experimental data. FINDINGS: The comparison of the elastic modulus evolution of the Pickering emulsions with those of emulsions stabilized with surfactants confirms a major contribution of the particles to the rheological behavior of Pickering emulsions and supports the existence of a three-dimensional network between the droplets. The applied percolation approach allows to quantitively estimate a nanoparticles viscoelastic link between the droplets and opposes the classic vision of interfacial monolayers stabilizing the Pickering emulsions. This network of interconnected particles and droplets contributes significantly to the viscosity as well as the elastic modulus of these emulsions. To our knowledge, the applied percolation-based model is the only one capable of providing a structural explanation while describing the abrupt viscosity and elastic modulus growth of Pickering emulsions across the range of ϕ.

Improving and fine-tuning the properties of peptide-based hydrogels via incorporation of peptide nucleic acids.

Peptide self-assemblies have attracted intense research interest over the last few decades thanks to their implications in key biological processes (e.g., amyloid formation) and their use in biotechnological and (bio)material fields. In particular, peptide-based hydrogels have been highly considered as high potential supramolecular materials in the biomedical domain and open new horizons in terms of applications. To further understand their self-assembly mechanisms and to optimize their properties, several strategies have been proposed with the modification of the constituting amino acid chains via, per se, the introduction of d-amino acids, halogenated amino acids, pseudopeptide bonds, or other chemical moieties. In this context, we report herein on the incorporation of DNA-nucleobases into their peptide nucleic acid (PNA) forms to develop a new series of hybrid nucleopeptides. Thus, depending on the nature of the nucleobase (i.e., thymine, cytosine, adenine or guanine), the physicochemical and mechanical properties of the resulting hydrogels can be significantly improved and fine-tuned with, for instance, drastic enhancements of both the gel stiffness (up to 70-fold) and the gel resistance to external stress (up to 40-fold), and the generation of both thermo-reversible and uncommon red-edge excitation shift (REES) properties. To decipher the actual role of each PNA moiety in the self-assembly processes, the induced modifications from the molecular to the macroscopic scales are studied thanks to the multiscale approach based on a large panel of analytical techniques (i.e., rheology, NMR relaxometry, TEM, thioflavin T assays, FTIR, CD, fluorescence, NMR chemical shift index). Thus, such a strategy provides new opportunities to adapt and fit hydrogel properties to the intended ones and pushes back the limits of supramolecular materials.

Identification of environmental factors controlling wine quality: A case study in Saint-Emilion Grand Cru appellation, France.

Soil is a key component of the terroir concept for wine production. Indeed, the soil provides water and nutrients to the vine plants depending on its properties and environmental conditions. A part of the complexity in the production of high-quality wines is the adaptation of the winegrowing practices to soil conditions variability in space and time. Then, a deep understanding of the environmental conditions that modulate soil-plant system functioning and control the production of quality wine is crucial for future global change adaptation. This study aimed to identify environmental factors controlling red wine quality by merging both winemaker and scientist knowledge. This work was performed on a vineyard in Saint-Emilion Grand Cru appellation, France. First, we conducted field investigations for micro-terroir scale soil mapping in 2017, based on pedological prospections (pits and auger borings) and both water table levels and main meteorological parameters monitoring (from November 2017 to November 2018). Additionally, we collected for each vineyard plot the corresponding wine quality rank established each year since 2012 and based on wine tasting sessions supervised by the winemakers. Subsequently we investigated both nutrients and water availability for the vine. This was achieved through correlative analysis using soil description, roots observation and water table level, stratified according to both soil functional units and wine quality ranks maps. Results show that the water table dynamic and the soil texture have a major impact on the root pattern of vines. Our study suggests that explanatory factors for wine quality are interactions between soil-water and roots during vine crop season. Here, best soils for fine wines could be observed for both non-severe water deficit and no-limited nutrient conditions.

Dilational rheology of oil/water interfaces covered by amphiphilic polysaccharides derived from dextran.

This work studied the adsorption at dodecane/water interface of amphiphilic polysaccharides derived from dextran (a nonionic bacterial polysaccharide) by random attachment of phenoxy groups along the chains (between 10 and 20 attached phenoxy groups per 100 glucose repeat units). The long-time kinetics of interfacial tension decrease was satisfactorily described assuming diffusion-limited adsorption of hydrophobic units (over 4h). Dilational rheology of dodecane/water interface was studied for the first time with that kind of amphiphilic polysaccharides and evidenced a significant elastic component. For all dextran derivatives, experimental results were conveniently described using Lucassen-van den Tempel model which assumed diffusion-limited of surface active species. The characteristic frequency increased with the number of attached phenoxy groups and its order of magnitude (10-3-10-2rad.s-1) was consistent with estimations based on the previous model. Experimental results were compared to those obtained with commercial stabilizers like Pluronics (L64, P105, F68 and F127) and Tween 80.

Impact of shear stress and impeller design on the production of biogas in anaerobic digesters.

Today, intensification of anaerobic digestion is still a scientific and technical challenge. The present study proposed combined experimental and computational fluid dynamics simulations to characterize the impact of shear stress and impeller design on the biogas production after sequential additions of substrate. Liquid phase (cattle manure digestate) rheological law was experimentally determined and input in numerical simulations. The results showed that the original use of a double helical ribbon in digester allowed a significantly faster dispersion of fresh substrate than the use of a classical Rushton turbine, leading to a 50% higher methane production rate. However, with both impellers, too high agitation rates entailed a clear slow-down of production rate and a decrease in CH4 content. To avoid this loss of productivity, it was shown that the maximal value of shear stress, determined by numerical simulations, was a consistent parameter to set the upper agitation conditions in digesters.

Multiscale study of bacterial growth: Experiments and model to understand the impact of gas exchange on global growth.

Using a millifluidics and macroscale setup, we study quantitatively the impact of gas exchange on bacterial growth. In millifluidic environments, the permeability of the incubator materials allows an unlimited oxygen supply by diffusion. Moreover, the efficiency of diffusion at small scales makes the supply instantaneous in comparison with the cell division time. In hermetic closed vials, the amount of available oxygen is low. The growth curve has the same trend but is quantitatively different from the millifluidic situation. The analysis of all the data allows us to write a quantitative modeling enabling us to capture the entire growth process.

Moisture-induced caking of beverage powders.

BACKGROUND: Beverage powders can exhibit caking during storage due to high temperature and moisture conditions, leading to consumer dissatisfaction. Caking problems can be aggravated by the presence of sensitive ingredients. The caking behaviour of cocoa beverage powders, with varying amounts of a carbohydrate sensitive ingredient, as affected by climate conditions was studied in this work. Sorption isotherms of beverage powders were determined at water activities (a(w) ) ranging from 0.1 to 0.6 in a moisture sorption analyser by gravimetry and fitted to the Brunauer-Emmett-Teller (BET) or the Guggenheim-Anderson-de Boer (GAB) equation. Glass transition temperatures (T(g) ) at several a(w) were analysed by differential scanning calorimetry and fitted to the Gordon-Taylor equation. Deduced T(g) = f(a(w) ) functions helped to identify stability or caking zones. Specific experimental methods, based on the analysis of mechanical properties of powder cakes formed under compression, were used to quantify the degree of caking. Pantry tests complemented this study to put in evidence the visual perception of powder caking with increasing a(w) . RESULTS: The glass transition approach was useful to predict the risks of caking but was limited to products where T(g) can be measured. On the other hand, quantification of the caking degree by analysis of mechanical properties allowed estimation of the extent of degradation for each product. CONCLUSION: This work demonstrated that increasing amounts of a carbohydrate sensitive ingredient in cocoa beverages negatively affected their storage stability.

Highly concentrated emulsions: 1. Average drop size determination by analysis of incoherent polarized steady light transport.

The analysis of incoherent polarized steady light transport is reported as a convenient technique for the drop size determination in highly concentrated oil-in-water emulsions. The studied system consists in heptane-in-water emulsions stabilized with a copolymeric surfactant (Synperonic PE®/L64). Hundred grams of parent emulsions, at two volume fractions of dispersed phase (φ=0.958 and 0.937) were prepared using a semi-batch process. Then, they were diluted with the aqueous phase to obtain volume fractions ranging from 0.886 to 0.958. The use of a copolymeric surfactant allows the dilution of the highly concentrated emulsions without any change in the particle size distribution as confirmed by laser diffraction measurements. We found that the polarization technique allows the determination of the film thickness between water drops rather than their sizes. Consequently, we propose a geometrical relationship to determine an average drop size from the film thickness. The sensitivity of this alternative technique to detect changes in average drop size was studied by changing some process and formulation parameters. Drop size determination in highly concentrated emulsions via this method is useful since the measurement protocol neither involves dilution nor induces structural changes in the emulsion.

Influence of Tg, viscosity and chemical structure of monomers on shrinkage stress in light-cured dimethacrylate-based dental resins.

OBJECTIVES: The aim of this study was to investigate the influence of the molecular mobility and the chemical structure of dimethacrylates most commonly used in dental composites on shrinkage stress from experimental matrices. METHODS: Three established neat monomers BisGMA (B), UEDMA (U) and TEGDMA (T), two experimental comonomers BisGMA-based (B-T(70/30) and B-T(50/50)) and two comonomers UEDMA-based (U-T(88/11) and U-T(66/33)) in weight%, were elaborated. Camphorquinone (CQ) and N,N-cyanoethylmethylaniline (CEMA), as photoinitiator and reducing agent, were added. Then the matrices were mixed by centrifugal force at room temperature. The viscosity (eta), the glass transition temperature of the monomers and comonomers systems (T(g(monomer)) and the maximum shrinkage stress (MSS) of each material (five replications) were statistically analysed by one-way ANOVA/Tuckey's test and Pearson's correlation procedure (p = 0.05). RESULTS: All formulations exhibited a newtonian rheological behavior. The viscosity of the comonomers systems can be divided in two groups: the pair B-T(70/30)/U-T(88/11) with the viscosity 3.5+/-3.10(-3)Pa.s and the pair B-T(50/50)/U-T(66/33) with the viscosity 0.28+/-3.10(-3)Pa.s. This pairs constituted samples allowing to compare the shrinkage stress of the BisGMA and UEDMA-based matrices with each other. The T(g(monomer)) of each group showed equivalent statistically values: -37.1 +/- 0.02 degrees C (U-T(88/11)) with -39.3 +/- 0.02 degrees C (B-T(70/30)) for the 3.5 Pa.s pair, and -53.1 +/- 0.03 degrees C (U-T(66/33)) with -58.5 +/- 0.01 degrees C (B-T(50/50)) for the 0.28 Pa.s one. There was a correlation between eta and T(g(monomer)) (r < 0.45 and p < 0.01). In decreasing order, the shrinkage stress was 14.11 +/- 0.3 MPa (T), 10.64 +/- 0.6 MPa (U-T(66/33)), 8.16 +/- 0.25 MPa (B-T(50/50)) without a significant difference compared to 8.04 +/- 0.5 MPa (U-T(88/11)), 6.83 +/- 0.52 MPa (U), 4.44 +/- 0.25 MPa (B-T(70/30)) and 0.33 +/- 0.3 MPa (B). There was a negative correlation between eta (r < -0.42 and p < 0.01), T(g(monomer)) (r < -0.41 and p < 0.01) and MSS. Whatever the viscosity, the UEDMA-based matrices developed higher shrinkage stresses than the BisGMA homologues. SIGNIFICANCE: The shrinkage stress development increase with the molecular mobility of the reacting medium. For the same molecular mobility, the large differences in stress values of the matrices studied are correlated to the structure and particularly the functionality of the monomers used.

New physically and chemically crosslinked hyaluronate (HA)-based hydrogels for cartilage repair.

When dissolved in aqueous solutions, sodium hyaluronate substituted with low amounts of alkyl chains [amphiphilic hyaluronate (HA)] can give rise to hydrogels thanks to intermolecular reversible hydrophobic interactions, leading to a three-dimensional (3D) network. Such hydrogels possess shear-thinning properties and can thus be injected in cartilage defect to promote chondrocyte proliferation and cartilage repair. However, these hydrogels are only physically crosslinked and can progressively loose their 3D structure when they are in contact with aqueous fluids. To overcome this drawback, HA derivatives substituted with dodecyl chains were chemically crosslinked by a difunctional reagent, tetraethylene glycol ditosylate (TEG-diOTs). To preserve the shear-thinning properties of amphiphilic HA, small amounts of TEG-diOTs were used so as to obtain a low chemical crosslinking ratio. After optimization of the synthesis parameters, aqueous solutions of the HA derivatives, crosslinked both physically and chemically, were obtained, with rheological properties improved compared to the amphiphilic polymers. As the hydrogels are aimed to cartilage repair, they were sterilized by wet heating; the effect of this treatment on the polymer characteristics was analyzed by different techniques. A similar study was carried out on HA derivatives stored under conditions mimicking physiological ones.

Modeling of the linear viscoelastic properties of oil-in-water emulsions.

The aim of this work is to use a recently developed statistical model of dispersions with nonhydrodynamic interactions to describe the linear viscoelastic properties of emulsions of Newtonian liquids. None of the existing models can describe the rheological behavior of such systems, particularly the elastic properties, in the linear regime. We first present the results of numerical simulations of our model applied to emulsions. We show that taking nonhydrodynamic interactions into account allows to predict that emulsions of two purely viscous liquids have a complex viscoelastic behavior. We then compare the model to experimental results on oil/water emulsions, stabilized with ionic and nonionic surfactants. We find out that our statistical mechanical approach gives a much better description of the viscoelastic behavior of these samples than purely hydrodynamic models do. However, the elasticity observed is underestimated by our model. We indicate further theoretical developments which could improve the description of the viscoelastic properties of emulsions.

Increased diffusion of soluble adhesion molecules in meningitis, severe sepsis and systemic inflammatory response without neurological infection is associated with intrathecal shedding in cases of meningitis.

OBJECTIVE: Sepsis and systemic inflammatory response syndrome (SIRS) result in the release in plasma of inflammatory cytokines and soluble forms of adhesion molecules in relation to endothelial activation. This study was designed to compare cerebrospinal fluid (CSF) concentrations of adhesion molecules in meningitis and SIRS without neurological infection and to evaluate in meningitis whether they originate from passive diffusion through damaged blood-CSF barrier or from local production. DESIGN: Prospective observational study. SETTING: University hospital medical intensive care unit. PATIENTS: Nineteen patients with meningitis and 41 patients with sepsis or SIRS without cerebrospinal infection consecutively admitted to the critical care unit over an 18-month period. INTERVENTIONS: Soluble forms of adhesion molecules (ICAM-1, VCAM-1, E-selectin) and cytokines (interleukin (IL)-1beta and TNF-alpha) were measured in paired CSF and blood samples. RESULTS: Serum concentrations of soluble adhesion molecules and cytokines were increased in the two groups, without significant differences. The CSF concentrations were elevated in both cases, whereas patients with meningitis demonstrated significantly higher CSF concentrations of soluble ICAM-1, VCAM-1, E-selectin, and TNF-alpha ( p<0.001), with higher corresponding CSF/serum ratios. Correlations between CSF and serum concentrations were found only in meningitis. These correlations were strong for soluble ICAM-1 (r(2)=0.7, p<0.001) and E-selectin (r(2)=0.9, p<0.001), but weaker for VCAM-1. VCAM-1 CSF/serum ratios were increased, in comparison with ICAM-1 and E-selectin CSF/serum ratios, despite similar molecular weights. Serum and CSF levels of cytokines and adhesion molecules were not predictive of death for the whole population, except concentrations of ICAM-1 significantly increased in non-surviving patients ( p<0.05). CONCLUSIONS: The CSF soluble adhesion molecules are increased in sepsis, SIRS and meningitis. In meningitis, the correlation between CSF and serum concentrations of adhesion molecules and the presence of a discrepancy of CSF/serum ratios for molecules of the same molecular weight may suggest intrathecal shedding in addition to diffusion through blood-CSF barrier.

Shear-induced phase transitions in sucrose ester surfactant.

The behavior of a commercial sucrose stearate blend has been examined by means of various experimental techniques (differential scanning calorimetry, light polarization and electron microscopy, and rotational rheometry). A partial phase diagram in water has been established. It shows that the binary system forms a lamellar lyotropic mesophase and that the melting behavior is characterized by a lamellar gel-lamellar liquid crystalline phase transition. The identification of the liquid crystalline phase has been carried out from textural observation using polarization microscopy and freeze-fracture electron microscopy. At low surfactant concentrations, the phase transition has been followed through rheological experiments. Furthermore, a shear-induced transition, from the lamellar phase (sheets of surfactant bilayers including a few large multilamellar vesicles) to an onion phase, has been observed above a critical temperature of 43 degrees C. The vesicles so obtained did not relax over more than 3 weeks. The presence of a small ratio of distearate in the sugar ester blend seems to be the key to vesicle formation at low surface-active material concentration.