Pressure Changes Across a Membrane Formed by Coacervation of Oppositely Charged Polymer-Surfactant Systems.

We investigate the mass transfer and membrane growth processes during capsule formation by the interaction of the biopolymer xanthan gum with CnTAB surfactants. When a drop of xanthan gum polymer solution is added to the surfactant solution, a membrane is formed by coacervation. It encapsulates the polymer drop in the surfactant solution. The underlying mechanisms and dynamic processes during capsule formation are not yet understood in detail. Therefore, we characterized the polymer-surfactant complex formation during coacervation by measuring the surface tension and surface elasticity at the solution-air interface for different surfactant chain lengths and concentrations. The adsorption behavior of the mixed polymer-surfactant system at the solution-air interface supports the understanding of observed trends during the capsule formation. We further measured the change in capsule pressure over time and simultaneously imaged the membrane growth via confocal microscopy. The cross-linking and shrinkage during the membrane formation by coacervation leads to an increasing tensile stress in the elastic membrane, resulting in a rapid pressure rise. Afterward, the pressure gradually decreases and the capsule shrinks as water diffuses out. This is not only due to the initial capsule overpressure but also due to osmosis caused by the higher ionic strength of the surfactant solution outside the capsule compared to the polymer solution inside the capsule. The influence of polymer concentration and surfactant type and concentration on the pressure changes and the membrane structure are studied in this work, providing detailed insights into the dynamic membrane formation process by coacervation. This knowledge can be used to produce capsules with tailored membrane properties and to develop a suitable encapsulation protocol in technological applications. The obtained insights into the mass transfer of water across the capsule membrane are important for future usage in separation techniques and the food industry and allow us to better predict the capsule time stability.

Evaluation of Interfacial Structure of Self-Assembled Nanoparticle Layers: Use of Standard Deviation between Calculated and Experimental Drop Profiles as a Novel Method.

The self-assembly of nanoparticles (NPs) at interfaces is currently a topic of increasing interest due to numerous applications in food technology, pharmaceuticals, cosmetology, and oil recovery. It is possible to create tunable interfacial structures with desired characteristics using tailored nanoparticles that can be precisely controlled with respect to shape, size, and surface chemistry. To address these functionalities, it is essential to develop techniques to study the properties of the underlying structure. In this work, we propose an experimental approach utilizing the standard deviation of drop profiles calculated by the Laplace equation from experimental drop profiles (STD), as an alternative to the Langmuir trough or precise microscopic methods, to detect the initiation of closely packed conditions and the collapse of the adsorbed layers of CTAB-nanosilica complexes. The experiments consist of dynamic surface/interfacial tension measurements using drop profile analysis tensiometry (PAT) and large-amplitude drop surface area compression/expansion cycles. The results demonstrate significant changes in STD values at the onset of the closely packed state of nanoparticle-surfactant complexes and the monolayer collapse. The STD trend was explained in detail and shown to be a powerful tool for analyzing the adsorption and interfacial structuring of nanoparticles. Different collapse mechanisms were reported for NP monolayers at the liquid/liquid and air/liquid interfaces. We show that the interfacial tension (IFT) is solely dependent on the extent of interfacial coverage by nanoparticles, while the surfactants regulate only the hydrophobicity of the self-assembled complexes. Also, the irreversible adsorption of nanoparticles and the increasing number of adsorbed complexes after the collapse were observed by performing consecutive drop surface compression/expansion cycles. In addition to a qualitative characterization of adsorption layers, the potential of a quantitative calculation of the parameter STD such as the number of adsorbed nanoparticles at the interface and the distance between them at different states of the interfacial layer was discussed.

Control of interfacial instabilities through variable injection rate in a radial Hele-Shaw cell: A nonlinear approach for late-time analysis.

In this paper, the nonlinear behavior of immiscible viscous fingering in a circular Hele-Shaw cell under the action of different time-dependent injection flow rate schemes is assessed numerically. Unlike previous studies which addressed the infinite viscosity ratio (inviscid-viscous flow), the problem is tackled by paying special attention to flows with finite viscosity ratio (viscous flow) in which the viscosity of the displacing and the displaced fluids can have any arbitrary value. Systematic numerical simulations based on a complex-variable formulation of Cauchy-Green barycentric coordinates are performed at different mobility ratios and capillary numbers with a focus on the late-time fully nonlinear regime. Additionally, numerical optimization is used to obtain the optimal flow rate schedule through a second-order weakly nonlinear stability analysis in contrast to previous studies in which the optimal flow rate was obtained entirely based on linear stability analysis. It is demonstrated that, irrespective of the values of the mobility ratio and/or the capillary number, for patterns whose constant injection counterpart exhibits linear flow regime, the curvature-driven relaxation time is comparable with the operational time of the time-dependent injection flow rate controlling schemes, and most of the controlling schemes work very well and suppress the fingering phenomenon remarkably with the maximum recovery improvement of 15%. As the nonlinearity of the system increases, the schemes may still perform well, but their effectiveness is more pronounced in patterns with less nonlinearity in their constant injection counterpart than those with higher nonlinearity. As the nonlinearity increases, the curvature-driven relaxation time becomes longer than the operational time of the schemes, leading to a reduction in their effectiveness. Additionally, it is shown that employment of the second-order weakly nonlinear stability analysis to formulate the objective function does not result in any remarkable variation in the obtained optimal flow rate schedule.

Dynamic monitoring of dielectric properties during two phase immiscible displacements in sand packs using frequency domain electromagnetic sweeps.

Electromagnetic heating is a promising soil remediation method especially in thin formations. The lack of a wide-spread adoption of this method stems from insufficient knowledge of how the complex dielectric properties, that govern propagation of the electromagnetic waves through porous media, change with changing frequency, water saturation, displacement types and flow regimes. To breach these gaps several sets of spontaneous deionized (DI) water imbibition experiments, followed by the primary drainage floods, that were followed by the secondary DI water imbibition floods in confined uniform sand packs were performed. The frequency domain relative dielectric constant and conductivities were extracted from the two-port complex S-parameter measurements taken with the vector network analyzer during these immiscible displacements at various water saturation levels at ambient conditions. A novel coaxial transmission line core holder was designed and commissioned, and a modified version of a plane-invariant dielectric extraction algorithm was developed for this purpose. Series, parallel and semi-disperse mixing models were applied to fit the water saturation dependent relative dielectric constant and conductivity values sampled at 500 MHz from the extracted frequency domain spectra. The Maxwell-Garnett parallel model was proved to be the most flexible because it could capture the sampled conductivity values in all secondary imbibition floods before and after the breakthroughs, where the inflection points were observed. These inflection points were attributed to silica production and a potential shear-stripping flow. This observation was further confirmed by conducting a single-phase Darcy's law analysis of two DI water imbibition floods.

On the Stability of Pickering and Classical Nanoemulsions: Theory and Experiments.

Emulsification is a crucial technique for mixing immiscible liquids into droplets in various industries, such as food, cosmetics, biomedicine, agrochemistry, and petrochemistry. Quantitative analysis of the stability is pivotal before the utilization of these emulsions. Differences in X-ray attenuation for emulsion components and surface relaxation of the droplets may contribute to X-ray CT imaging and low-field NMR spectroscopy as viable techniques to quantify emulsion stability. In this study, Pickering (stabilized solely by nanoparticles) and Classical (stabilized solely by low molecular weight polymers) nanoemulsions were prepared with a high-energy method. NMR and X-ray CT were employed to constantly monitor the two types of nanoemulsions until phase separation. The creaming rates calculated from NMR match well with the results obtained from X-ray CT. Furthermore, we show that Stokes' law coupled with the classical Lifshitz-Slyozov-Wagner theory underestimates the creaming rate of the nanoemulsions compared to the experimental results from NMR and X-ray CT imaging. A new theory is proposed by fully incorporating the effects of Pickering nanoparticles, hydrocarbon types, volume fraction, size distribution, and flocculation on the droplet coarsening. The theoretical results agree well with the experimentally measured creaming rates. It reveals that the attachment of nanoparticles onto a droplet surface decreases the mass transfer for hydrocarbon molecules to move from the bulk aqueous phase into other droplets, thus slowing the Ostwald ripening. Therefore, Pickering nanoemulsions show a better stability behavior compared to Classical nanoemulsions. The impacts of hydrocarbon and emulsification energy on the stability of nanoemulsions are reported. These findings demonstrate that the stability of the nanoemulsions can be manipulated and optimized for a specific application, setting the stage for subsequent investigations of these nanodroplets.

Break-up and mobilization of DNAPL by acoustic excitation: Experimental evidence and pore network modeling.

Dense non-aqueous phase liquids (DNAPLs) are long-term groundwater contaminants due to their high toxicity and slight solubility in water. The use of acoustic waves to remobilize trapped ganglia in subsurface porous systems have some advantages over pre-existing solutions including eliminating the bypassing effect and new environmental hazards. Designing an effective acoustically assisted remediation method for such purposes relies on understanding the underlying mechanisms and developing validated models. In this work, pore-scale microfluidic experiments were run to investigate the interplay between break-up and remobilization under sonication at different levels of flow rate and wettability conditions. Based on the experimental observation and pore-scale physical characteristics, a pore network model was developed and verified against the experimental results. Such a model was developed based on a two-dimensional network and scaled up to three-dimensional networks. In the experiments, processing of two-dimensional images showed that acoustic waves can remobilize trapped ganglia. The other observed effect of vibration is to break up blobs and reduce the mean ganglia size. Recovery enhancements were greater in hydrophilic micromodels as compared to hydrophobic system. A strong correlation was found between the remobilization and breakup indicating that the trapped ganglia are breaking up due to acoustic stimulation firstly and then a background viscous force may get them flowing under the new generated fluid distribution. In modeling, the simulation results of residual saturation reasonably matched with experimental observations. The differences between the prediction by the model and the experimental data at verification points is less than 2% for data before and after the acoustic excitation. The transitions from three-dimensional simulations were used to propose a modified capillary number. This study gives a better understanding of the mechanisms behind the effect of acoustic waves in porous media and provides a predictive tool for evaluating enhancement in fluid displacement.

Application of XGBoost model for in-situ water saturation determination in Canadian oil-sands by LF-NMR and density data.

Water saturation determination is among the most challenging tasks in petrophysical well-logging, which directly impacts the decision-making process in hydrocarbon exploration and production. Low-field nuclear magnetic resonance (LF-NMR) measurements can provide reliable evaluation. However, quantification of oil and water volumes is problematic when their NMR signals are not distinct. To overcome this, we developed two machine learning frameworks for predicting relative water content in oil-sand samples using LF-NMR spin-spin (T2) relaxation and bulk density data to derive a model based on Extreme Gradient Boosting. The first one facilitates feature engineering based on empirical knowledge from the T2 relaxation distribution analysis domain and mutual information feature extraction technique, while the second model considers whole samples' NMR T2-relaxation distribution. The NMR T2 distributions were obtained for 82 Canadian oil-sands samples at ambient and reservoir temperatures (164 data points). The true water content was determined by Dean-Stark extraction. The statistical scores confirm the strong generalization ability of the feature engineering LF-NMR model in predicting relative water content by Dean-Stark-root-mean-square error of 0.67% and mean-absolute error of 0.53% (R2 = 0.90). Results indicate that this approach can be extended for the improved in-situ water saturation evaluation by LF-NMR and bulk density measurements.

Electro-acoustic excitation of the interface.

Methods that use directed acoustic [14,128] and electric fields [104,115] have shown a promise in oil recovery in the past. These methods are great candidates to not only facilitate oil recovery, but also reduce CO2 emissions to a minimum. However, they have not found big commercial success due to poor understanding of the underlying mechanisms that facilitate the recovery. This paper is focused on breaching this gap by summarizing the main theories and experimental work done in the fields of acoustic and electric wave propagation though liquids, their interfaces and saturated porous media. The main theories of the acoustic and electric wave propagation through liquid and saturated porous media are outlined and discussed here. Key physical mechanisms that occur in the reservoir oil and water phases and at their interface during acoustic and electric wave propagation are identified. The development of the Maxwell stress theory of the liquid-liquid interface under the influence of the electric field by Melcher, Smith, Taylor and Lin et al. is shown to be a useful tool to estimate the critical voltage that disturbs a liquid-liquid interface [78,112,120]. Important aspects in wellbore acoustic transducer design and its selection to fit into the reservoir conditions are covered and scrutinized [66,101]. Characteristics of the magnetostrictive devices are shown to fit reservoir conditions the best.

An investigation into the effects of pore connectivity on T2 NMR relaxation.

Nuclear Magnetic Resonance (NMR) is a powerful technique used to characterize fluids and flow in porous media. The NMR relaxation curves are closely related to pore geometry, and the inversion of the NMR relaxometry data is known to give useful information with regards to pore size distribution (PSD) through the relative amplitudes of the fluids stored in the small and large pores. While this information is crucial, the main challenge for the successful use of the NMR measurements is the proper interpretation of the measured signals. Natural porous media patterns consist of complex pore structures with many interconnected or "coupled" regions, as well as isolated pores. This connectivity along the throats changes the relaxation distribution and in order to properly interpret this data, a thorough understanding of the effects of pore connectivity on the NMR relaxation distribution is warranted. In this paper we address two main points. The first pertains to the fact that there is a discrepancy between the relaxation distribution obtained from experiments, and the ones obtained from solving the mathematical models of diffusion process in the digitized images of the pore space. There are several reasons that may attribute to this such as the lack of a proper incorporation of surface roughness into the model. However, here we are more interested in the effects of pore connectivity and to understand why the typical NMR relaxation distribution obtained from experiments are wider, while the numerical simulations predict that a wider NMR relaxation distribution may indicate poor connectivity. Secondly, by not taking into account the pore coupling effects, from our experience in interpreting the data, we tend to underestimate the pore volume of small pores and overestimate the amplitudes in the large pores. The role of pore coupling becomes even more prominent in rocks with small pore sizes such as for example in shales, clay in sandstones, and in the microstructures of carbonates.

Parsimony and goodness-of-fit in multi-dimensional NMR inversion.

Multi-dimensional nuclear magnetic resonance (NMR) experiments are often used for study of molecular structure and dynamics of matter in core analysis and reservoir evaluation. Industrial applications of multi-dimensional NMR involve a high-dimensional measurement dataset with complicated correlation structure and require rapid and stable inversion algorithms from the time domain to the relaxation rate and/or diffusion domains. In practice, applying existing inverse algorithms with a large number of parameter values leads to an infinite number of solutions with a reasonable fit to the NMR data. The interpretation of such variability of multiple solutions and selection of the most appropriate solution could be a very complex problem. In most cases the characteristics of materials have sparse signatures, and investigators would like to distinguish the most significant relaxation and diffusion values of the materials. To produce an easy to interpret and unique NMR distribution with the finite number of the principal parameter values, we introduce a new method for NMR inversion. The method is constructed based on the trade-off between the conventional goodness-of-fit approach to multivariate data and the principle of parsimony guaranteeing inversion with the least number of parameter values. We suggest performing the inversion of NMR data using the forward stepwise regression selection algorithm. To account for the trade-off between goodness-of-fit and parsimony, the objective function is selected based on Akaike Information Criterion (AIC). The performance of the developed multi-dimensional NMR inversion method and its comparison with conventional methods are illustrated using real data for samples with bitumen, water and clay.

Nuclear magnetic resonance relaxometry as a spectroscopic probe of the coordination sphere of a paramagnetic metal bound to a humic acid mixture.

Protons on water molecules are strongly affected by paramagnetic ions. Since the acid-base properties of water facilitate rapid proton exchange, a single proton nuclear magnetic resonance (NMR) signal is seen in aqueous solutions of paramagnetic ions. Proton relaxation times are significantly affected by paramagnetic species and the readily detectable single signal serves as a powerful amplifier of the information contained concerning the protons in the paramagnetic environment. Where water molecules coordinated to free paramagnetic ions and to metal complexes of ligands that form non-labile (on the NMR time scale) complexes, the effects on water in the two environments can be distinguished. This can provide information on the nature of the ligand binding sites. The example of Cu2+ bound to the Laurentian humic acid mixture reported here using convenient low field NMR relaxometers shows that the information can enrich our understanding of complexation and speciation in the presence of complex mixture ligands characteristic of natural water systems. In this case, the data underline the role of aggregation and conformation in defining the complexation sites.

Soil wettability as determined from using low-field nuclear magnetic resonance.

The molarity of ethanol droplet and water drop penetration time methods are commonly used to determine soil wettability because these tests are quick and easy to perform. However, these tests do not provide reproducible results on the same sample. Low-field nuclear magnetic resonance (NMR) is shown as an alternative tool to determine soil wettability. Addition of small amounts of water in dry wettable porous media produces predominant amplitude peaks at transverse relaxation times (T2) of 100 ms or less while addition of water in dry water-repellent porous media with the same pore structure produce predominant amplitude peaks at T2 values near 1000 ms. The geometric mean of T2 (T(2gm)) from water-repellent samples immediately after the addition of water is greater than 1000 ms, which is close to that of bulk water, while T(2gm) from wettable samples immediately after the addition of water is significantly less than 1000 ms. Measurements over time show that water-repellent samples eventually reach the same equilibrium end point as its corresponding wettable sample when continually exposed to water. This paper will show that NMR can be used to formulate a screening criterion for quickly determining wettability. The advantage of using NMR is that the results are reproducible provided the sample is prepared and analyzed in a systematic manner.

Pore-scale redistribution of water during wetting of air-dried soils as studied by low-field NMR relaxometry.

The kinetics of water uptake and redistribution in several soils and their components are studied using NMR relaxometry. Unlike the normal behavior observed in stable porous media, entry into micropores in the soil is a slow process as compared to entry into macro- and mesopores. This indicates that soils air-dried at ambient temperature include gel phases that have collapsed or reoriented, closing micropores, during drying. Wetting must then include the swelling processes that re-open micropores. This can even exhibit temperature dependence giving an "apparent activation energy" comparable to that of a chemical reaction, for example, ester hydrolysis. The processes of micropore opening may play a role in slow uptake of contaminants into soils.

Low-field NMR relaxometry: a study of interactions of water with water-repellant soils.

Petroleum-induced water repellency in soils is a problem that has been thought to develop randomly following contamination and then remediation of a site with petroleum. The emergence of the phenomenon can occur within months or years of original contamination and with seemingly no warning. Low-field NMR has been used to study these soils and, specifically, the processes of water uptake that occur in them. Critical aspects in the development of this phenomenon have been identified as well--specifically, a dependence on climatic events in the area and contamination levels that contribute are suggested.