Dewetting dynamics of heavy crude oil droplet in low-salinity fluids at elevated pressures and temperatures.

HYPOTHESIS: Improved oil recovery by low-salinity injection correlates to the optimal brine concentration to achieve maximum dewetting of oil droplets on rock surfaces. While interfacial tension and electrical double layer forces are often cited as being determinant properties, we hypothesize that other structural/interfacial forces are more prominent in governing the system behavior. EXPERIMENTS: The sessile droplet technique was used to study the receding dynamics of oil droplets from flat hydrophilic substrates in brines of different salt type (NaCl and CaCl2) and concentration, and were studied at both low and elevated temperatures (60 and 140 °C) and pressures (1, 10, 100 and 200 bar). FINDINGS: At 1 bar and 60 °C, the minimum oil droplet-substrate adhesion force (FA) was determined at 34 mM NaCl and 225 mM CaCl2. For NaCl this strongly correlated to strengthening hydration forces, which for CaCl2 were diminished by long-range hydrophobic forces. These results highlight the importance of other non-DLVO forces governing the dewetting dynamics of heavy crude oil droplets. At 140 °C and 200 bar, the optimal brine concentrations were found to be much higher (1027 mM NaCl and 541 mM CaCl2), with higher concentrations likely attributed to weakening hydration forces at elevated temperatures.

Investigating Adsorbing Viscoelastic Fluids Using the Quartz Crystal Microbalance.

There is little research on using the quartz crystal microbalance (QCM) with adsorbing viscoelastic fluids. These fluids are widely encountered but often difficult to study as many are opaque and highly viscous. Since the QCM does not involve any scattering or reflection of input radiation, it has the potential to study these complex fluids to determine the relative viscoelasticity of the bulk fluid and surface adsorption of active species onto different substrates. In the current study, both Newtonian (sucrose) and viscoelastic (sodium polystyrene sulfonate (NaPSS)) fluids were introduced into the QCM, and the sensor responses were compared. QCM responses of Newtonian sucrose solutions matched the Kanazawa and Gordon model (KG model), as expected. The QCM responses with viscoelastic NaPSS solutions were well below those described by the KG model. A viscoelastic model was used to determine the fluid viscosity and shear modulus at a very high frequency. It was found that the viscosity of NaPSS did not change much compared with low-frequency rheometer measurements, but a significant increase in the shear modulus of several orders of magnitude was found at the QCM frequencies. Modifying the KG model frequency shifts by multiplying by the QCM shear wave decay length ratio, X = δV/δN, we were able to match the measured QCM values in viscoelastic NaPSS solutions. The QCM dissipation values for NaPSS were matched in a similar way by multiplying the KG model by X 1/3. By changing the QCM sensor from silica (no NaPSS adsorption) to alumina (NaPSS adsorption), it was shown that the adsorption isotherm of NaPSS on alumina could be recovered and fitted with a Langmuir isotherm despite the frequency response being only a small fraction of the total measured QCM signal.

Bio-Inspired Preparation of Clay-Hexacyanoferrate Composite Hydrogels as Super Adsorbents for Cs.

A facile and low-cost fabrication route, inspired by the adhesive proteins secreted by mussels, has been developed to prepare a clay-based composite hydrogel (DHG(Cu)) containing hexacyanoferrate (HCF) nanoparticles for the selective removal of Cs+ from contaminated water. Initially, montmorillonite was exfoliated prior to coating with a thin layer of polydopamine (PDOPA) via the self-polymerization of dopamine. Mixing the composite (D-clay) with the HCF precursor, followed by the addition of copper ions, led to the self-assembly of the polymer-coated exfoliated clay nanosheets into a three-dimensional network and in situ growth of KCuHCF nanoparticles embedded within the gel structure. Analytical characterization verified the fabrication route and KCuHCF immobilization by a copper-ligand complexation. Rheology testing revealed the composite hydrogel to be elastic under low strain and exhibited reversible, self-healing behavior following high strain deformation, providing a good retention of KCuHCF nanoparticles in the membrane. The adsorbent DHG(Cu) showed a superior Cs+ adsorption capacity (∼173 mg/g), with the performance maintained over a wide pH range, and an excellent selectivity for Cs+ when dispersed in seawater at low concentrations of 0.2 ppm. On the basis of its excellent mechanico-chemical properties, the fabricated hydrogel was tested as a membrane in column filtration, showing excellent removal of Cs+ from Milli-Q water and seawater, with the performance only limited by the fluid residence time. For comparison, the study also considered other composite hydrogels, which were fabricated as intermediates of DHG(Cu) or fabricated with Fe3+ as the cross-linker and reactant for HCF nanoparticle synthesis.

Comment on "Patterns in Drying Drops Dictated by Curvature-Driven Particle Transport".

In a recent article, Mondal et al. (Mondal, R.; Semwal, S.; Kumar, P. L.; Thampi, S. P.; Basavaraj, M. G. Langmuir 2018, 34, 11473-11483) demonstrated different patterns (coffee-rings and coffee-eyes) in dry deposits from solutions of concentrated well-stabilized nanofluids. Coffee rings created from dried sessile droplets result mainly from internal radial flow as proposed by Deegan et al. (Deegan, R. D.; Bakajin, O.; Dupont, T. F.; Huber, G.; Nagel, S. R.; Witten, T. A. Nature 1997, 389, 827-829). To generate coffee-eyes from pendent droplets, Mondal et al. have proposed a new particle transport route involving particle adsorption at the interface and its consequent curvature-driven settling along the interface due to gravity acting on the droplet. In this comment, we demonstrate that coffee-eyes can also be formed from pendent droplets by increasing the nanoparticle size to destabilize the colloidal liquid, causing nanoparticle accumulation at the water droplet apex without particle adsorption at the interface.

The influence of nanoparticle shape on the drying of colloidal suspensions.

Dried deposits of spherical Ludox silica and disk-like laponite clay nanoparticles have been examined by dark-field optical microscopy and atomic force microscopy (AFM) to investigate the effects of nanoparticle shape on the deposit structure. Dark-field optical images indicated that a higher concentration of Ludox nanoparticles was required, compared to laponite, for an optically visible deposit to be formed. Compared with the relatively simple ring-like features observed at the edges of Ludox deposits, the laponite deposits were more complex, with dendritic features appearing below 10ppm that disappeared at higher laponite concentrations. AFM images revealed that whilst the Ludox rim deposit structure gradually increased in height and width with increasing nanoparticle concentration, the laponite rim deposits increased steadily in height up to 1ppm, above which the rim height suddenly decreased and the deposit structure became smoother. The widths of the rim deposits were observed to increase in a similar manner for both nanoparticle types. Nanoparticle shape is suggested as the main reason for differences in the structural features of the rim for each nanoparticle type. The disk-like laponite forms tall thin rim profiles at low concentrations, before creating a more uniform rim profile at higher concentrations. We suggest that a critical laponite rim height is reached before partial collapse of the nanoparticle stack at the rim takes place as the particle concentration is further increased. This produces much thinner and smoother films of laponite at high particle concentrations than is found for similar concentrations of Ludox. Our work suggests that both the shape and the concentration of the nanoparticles themselves are crucial in determining the structure of the final dried nanoparticle deposit.

Complex adsorption behavior of rodlike polyelectrolyte-surfactant aggregates.

A quartz crystal microbalance (QCM) and an optical reflectometer have been used to quantify the long-term adsorption behavior of polyelectrolyte-surfactant aggregates of alkyltrimethylammonium and poly(4-vinylbenzoate) or pCnTVB at the silica-water interface. In solution, these polyelectrolyte-surfactant aggregates exist as weakly anionic semiflexible rodlike structures of several nanometers in radius and hundreds of nanometers in length. The optical reflectivity (OR) data confirmed our earlier proposed model of a two-stage adsorption process (Biggs, S.; Kline, S. R.; Walker, L. M. Langmuir, 2004, 20 (4), 1085-1094) where free CTA+ ions initially adsorb and charge reverse the silica surface, thus allowing the weakly anionic aggregates to adsorb. Combining data from the two techniques allows a distinction to be made between contributions to the measured signal from the bulk and the interface. The isotherm determined by OR showed a clear plateau at higher concentrations, whereas the isotherm obtained by QCM continues to increase across all concentrations tested. This indicates a significant influence of the bulk fluid on the measured signals from the QCM as the concentration is increased. Slow changes in the apparent adsorbed mass observed with the QCM were not reproduced in the OR data, suggesting that these effects were also caused by the bulk and were not a densification of the adsorbed layer. The combination of techniques clarifies the adsorption kinetics and mechanism of adsorption in polyelectrolyte-surfactant aggregate systems.

Behavior of thin films of poly(oxyethylene)-poly(oxybutylene) copolymers studied by brewster angle microscopy and atomic force microscopy.

Surface films of two copolymers of ethylene oxide (E) and butylene oxide (B), namely E23B8 and E87B18, have been examined by Brewster angle microscopy (BAM) and atomic force microscopy (AFM). Isotherms taken on unsupported films of these copolymers at the air-water interface showed a clear gas to liquid phase transition for E57B18 and a barely discernible phase transition for E23B8. The BAM studies showed a gradual brightening of the films as the surface pressure was increased, which was associated with a film thickening and/or a film densification. Several bright spots were also observed within the films, with the number of spots increasing gradually as the film surface pressure was increased. AFM studies of these films did not show any localized ordering, which fits in with the results from our previous X-ray study of these copolymers [Hodges, C. S.; Neville, F.; Konovalov, O.; Gidalevitz, D.; Hamley, I. W.; Langmuir 2006, 22 (21), 8821-8825], where no long-range ordering was observed. AFM imaging showed two sizes of particulates that were irregularly spaced across the film. The larger particulates were associated with silica contaminants from the copolymer synthesis, whereas the smaller particulates were assumed to be aggregated copolymer. An analysis of the semidilute region of the isotherm showed that while both copolymers had intermixed ethylene oxide and butylene oxide units, the lower molecular weight E23B8 copolymer manifested significantly more intermixing than E87B18.

Protegrin interaction with lipid monolayers: Grazing incidence X-ray diffraction and X-ray reflectivity study.

Interactions of the antimicrobial peptide protegrin-1 (PG-1) with phospholipid monolayers have been investigated by using grazing incidence X-ray diffraction (GIXD) and specular X-ray reflectivity (XR). The structure of a PG-1 film at the air-aqueous interface was also investigated by XR for the first time. Lipid A, dipalmitoyl-phosphatidylglycerol (DPPG) and dipalmitoyl-phosphatidylcholine (DPPC) monolayers were formed at the air-aqueous interface to mimic the surface of the bacterial cell wall and the outer leaflet of the erythrocyte cell membrane, respectively. Experiments were carried out under constant area conditions where the pressure changes upon insertion of peptide into the monolayer. GIXD data suggest that the greatest monolayer disruption produced by PG-1 is seen with the DPPG system at 20 mN/m since the Bragg peaks completely disappear after introduction of PG-1 to the system. PG-1 shows greater insertion into the lipid A system compared to the DPPC system when both films are held at the same initial surface pressure of 20 mN/m. The degree of insertion lessens at 30 mN/m with both DPPC and DPPG monolayer systems. XR data further reveal that PG-1 inserts primarily in the head group region of lipid monolayers. However, only the XR data of the anionic lipids suggest the existence of an additional adsorbed peptide layer below the head group of the monolayer. Overall the data show that the extent of peptide/lipid interaction and lipid monolayer disruption depends not only on the lipid composition of the monolayer, but the packing density of the lipids in the monolayer prior to the introduction of peptide to the subphase.

Structural analysis of PEO-PBO copolymer monolayers at the air-water interface.

X-ray reflectivity (XR) and grazing incidence X-ray diffraction (GIXD) have been used to examine an oxyethylene-b-oxybutylene (E(23)B(8)) copolymer film at the air-water interface. The XR data were fitted using both a one- and a two-layer model that outputted the film thickness, roughness, and electron density. The best fit to the experimental data was obtained using a two-layer model (representing the oxyethylene and oxybutylene blocks, respectively), which showed a rapid thickening of the copolymer film at pressures above 7 mN/m. The large roughness values found indicate a significant degree of intermixing between the blocks and back up the GIXD data, which showed no long range lateral ordering within the layer. It was found from the electron density model results that there is a large film densification at 7 mN/m, possibly suggesting conformational changes within the film, even though no such change occurs on the pressure-area isotherm at the same surface pressure.

In situ characterization of lipid A interaction with antimicrobial peptides using surface X-ray scattering.

Lipid A structure at the air-aqueous interface has been studied using pressure-area isotherm methods coupled with the surface X-ray scattering techniques of X-ray reflectivity (XR) and grazing incidence X-ray diffraction (GIXD). Lipid A monolayers were formed at the air-aqueous interface to represent the lipid moiety of the outer membrane of Gram-negative bacteria. Lipid A structure was characterized at surface pressures between 10 and 35 mN/m. Interactions of alpha-helical antimicrobial peptides LL-37, SMAP-29 and D2A22 with lipid A monolayers were subsequently studied. Although insertion into the lipid A monolayers was observed with the alpha-helical peptides, little change was seen from the X-ray data, suggesting that the lipid A hydrocarbon chains are involved in reorientation during insertion and that the hydrocarbon chains have a relatively rigid structure.

Use of the JKR model for calculating adhesion between rough surfaces.

A simple method for using the JKR model to determine interfacial adhesion between two ideal rough surfaces is demonstrated for individual asperity-asperity and asperity-flat contacts both in air and in water. The model takes into account the effect of a modified contact area at separation due to viscoelastic effects. The equilibrium version of the model significantly underestimates the measured adhesion, whereas the viscoelastic version of the model is much closer to the measured data. The asperity-flat geometry used with the viscoelastic version of the model seems to fit the experimental results best. This was thought to be due to the unlikely occurrence of direct asperity-asperity contacts. Instead, it would seem that the asperities have a far higher chance of fitting between each other on opposing surfaces, leading to correspondingly higher pull-off forces measured on separation. Many possible extensions to the roughness model described here may be made, allowing a much-improved understanding of the contact mechanics between two rough surfaces.