Gel-like Phase Research Articles

Delamination of graphite oxide in a liquid upon cooling.

Graphite oxide (GO) in liquid acetonitrile undergoes a transition from an ordered phase around ambient temperature to a gel-like disordered phase at temperatures below 260 K, as demonstrated by in situ X-ray diffraction. The stacking order of GO layers is restored below the freezing point of acetonitrile (199 K). The reversible swelling transition between a stacked crystalline phase and an amorphous delaminated state observed upon cooling provides an unusual example of increased structural disorder at lower temperatures. The formation of the gel-like phase is attributed to the thermo-responsive conformational change of individual GO flakes induced by stronger solvation. Scanning force microscopy demonstrates that GO flakes deposited onto a solid substrate from acetonitrile dispersions at a temperature below 260 K exhibit corrugations and wrinkling which are not observed for the flakes deposited at ambient temperature. The thermo-responsive transition between the delaminated and stacked phases reported here can be used for sonication-free dispersion of graphene oxide, micro-container applications, or the preparation of new composite materials.

Rheological properties of graphene oxide liquid crystal

We report the rheological properties of liquid crystalline graphene oxide (GO) aqueous dispersion. GO dispersions exhibit typical shear thinning behaviors of liquid crystals, which is described by power law or simple Curreau model. Irrespective of the shear rate, shear viscosity exhibits sudden decrease with the increase of GO composition around a critical volume fraction, ϕc=0.33%, demonstrating typical colloidal isotropic–nematic phase transition. Dynamic measurements reveal the liquid-like (isotropic phase, G′>G″) behavior at a low GO composition (ϕ∼0.08%) and solid-like (liquid crystalline) behavior at higher compositions (ϕ∼0.45%), where G′ exceeds over G″. Nematic gel-like phase is confirmed at a higher GO composition over ϕ>0.83%, where both G′ and G″ moduli are nearly independent of frequency (ω). Simple power law scaling arguments are introduced to model the dependence of yield stress and viscoelastic moduli on the GO composition. We also observed the yield stress and rigidity percolation transition above phase transition composition ϕc>0.33% with a percolation exponent of 1.3±0.1. These rheological insights provide valuable information for the liquid crystalline processing of GO based materials including fibers, sheets and other complex structures for electronic/optoelectronic and energy storage/conversion applications.

NATURAL AND CALCINED CLAYEY DIATOMITE AS CEMENT REPLACEMENT MATERIALS: MICROSTRUCTURE AND PORE STRUCTURE STUDY

This manuscript introduces clayey diatomite from Jelsovec deposit in Slovakia intended for use in cement and concrete industry. Jelsovec deposit contains 3350 kilotons of clayey diatomite to be easily mined. Natural clayey diatomite (CD) and calcined clayey diatomite (CCD) were used to substitute 5 to 15 % by wt. of CEM I according to EN 197-1 Standard. CCD was prepared from CD by calcination at 900 °C for 1 hour. Frattini test was applied for the estimations of pozzolanic activity. Pozzolanic activity of CCD is found to be comparable to that of traditional natural and industrial pozzolans. The pozzolanic activity of the CD is only slightly lower opposite to that of CCD. Both clayey diatomites are behaving as high-efficient pozzolans when partially substituting the Portland cement. Cement composites of Water/Solid ratio of 0.5 with a substitution rate of CEM I between 5 and 15 wt. % CD and CCD were used for the tests. The specimens were studied by X-ray diffraction and thermal analysis as well as mercury intrusion porosimetry after 28- and 365-days test on compressive strength. The composites consumed a larger amount of Ca(OH)2. They had a higher volume of gel-like hydrate phase and finer pore structure relative to the reference cement paste. The present findings indicate that Slovak diatomite from Jelsovec can be considered as a suitable pozzolan for use in cement-based materials. The results show that the microstructural properties of the respective materials are comparable to those of the traditional natural and industrial cement modifiers. Moreover, the substitution of CEM I by CD and CCD save energy and protect the environment by reducing the CO2 emissions.

Chemical and spectroscopic characterization of insoluble and soluble humic acid fractions at different pH values

BackgroundHumic acids (HA) are organic molecules with complex structure and function and variable properties. They are insoluble in strongly acid pH conditions. At present, it is not clear how much is the amount of HA in solution at the pH of natural soils nor are known the characteristics of the different soluble fractions and their possible association with the inorganic phase of soil. The scope of this work was to characterize the soluble and insoluble fractions obtained by acidifying Na humate solution at pH values 3, 5, and 7 and to compare these fractions with the HA obtained at pH 1. At each pH, the precipitate and the soluble fractions were separated and characterized by elemental analysis, total acidity and carboxylic group content, infrared, and 13C NMR and 1H NMR spectroscopy.ResultsThe HA fraction insoluble at pH 1 had a high acid group content and aromaticity but a low content of O- and N-containing groups. At pH 3, a fraction with nearly the same characteristics was obtained. At pH 1 and pH 3, the inorganic phase bound to the insoluble humic material was largely constituted by clay minerals and some Al and Fe hydroxides. The soluble fractions at pH values 1 and 3 were very poor and they were composed of a silica gel-like phase associated with polar organic material rich in carboxylic and metal-carboxylate groups. At pH values 5 and 7, only a small fraction of the Na humates precipitated. The fractions remaining in the solution were mainly composed of organic material particularly rich in aromatic and aliphatic groups, while the inorganic phase contained phyllosilicates. The fractions insoluble at pH values 5 and 7 contained a large amount of inorganic material that consisted mainly of phyllosilicates.ConclusionsThe soluble fractions obtained at pH values 5 and 7 represent the humic component that in environmental situations would be dissolved in the soil solution. Our findings could be very useful for a more detailed investigation into the way HA influence plant metabolism under environmental-like conditions, both as regards pH conditions and interaction with the mineral fraction.

Garnets within geode-like serpentinite veins: Implications for element transport, hydrogen production and life-supporting environment formation

Geochemical micro-environments within serpentinizing systems can abiotically synthesize hydrocarbons and provide the ingredients required to support life. Observations of organic matter in microgeode-like hydrogarnets found in Mid-Atlantic Ridge serpentinites suggest these garnets possibly represent unique nests for the colonization of microbial ecosystems within the oceanic lithosphere. However, little is known about the mineralogical and geochemical processes that allow such unique environments to form. Here we present work on outcrop-scale vein networks from an ultramafic massif in Norway that contain massive amounts of spherulitic garnets (andradite), which help to constrain such processes. Vein andradite spherulites are associated with polyhedral serpentine, brucite, Ni–Fe alloy (awaruite), and magnetite indicative of low temperature (<200°C) alteration under low fO2 and low aSiO2,aq geochemical conditions. Together with the outcrop- and micro-scale analysis geochemical reaction path modeling shows that there was limited mass transport and fluid flow over a large scale. Once opened the veins remained isolated (closed system), forming non-equilibrium microenvironments that allowed, upon a threshold supersaturation, the rapid crystallization (seconds to weeks) of spherulitic andradite. The presence of polyhedral serpentine spheres indicates that veins were initially filled with a gel-like protoserpentine phase. In addition, massive Fe oxidation associated with andradite formation could have generated as much as 600mmol H2,aq per 100cm3 vein. Although no carboneous matter was detected, the vein networks fulfill the reported geochemical criteria required to generate abiogenic hydrocarbons and support microbial communities. Thus, systems similar to those investigated here are of prime interest when searching for life-supporting environments within the deep subsurface.

Coaggregation of Two Anionic Azo Dyestuffs: A Combined Static Light Scattering and Small-Angle X-ray Scattering Study.

The formation of azo dyestuff aggregates in dilute aqueous solution induced by the addition of Mg2+, Ca2+, Sr2+, or Ba2+ ions is followed by time-resolved static light scattering (SLS) and time-resolved small-angle X-ray scattering (SAXS). Time-dependent molar mass data of the growing aggregates is interpreted by means of a kinetic model introduced by Lomakin et al. ( Proc. Natl. Acad. Sci. U.S.A. 1996 , 93 , 1125 ) for the description of β-amyloid aggregation. This interpretation reveals significant trends within the homologous series of alkaline earth cations. The trends refer to the nucleation and the growth rate of the dyestuff fibers. Time-resolved SAXS experiments indicate that these first two stages are followed by a third one during which a network forms by partial lateral alignment of fibers. At high enough dyestuff concentrations, this network formation even leads to a gel-like phase. Anomalous SAXS (ASAXS) on such a gel phase formed upon the addition of Sr2+ revealed the extent of neutralization of the dyestuff molecules within the gel by the specifically interacting alkaline earth cations.

Elastic fingering in rotating Hele-Shaw flows.

The centrifugally driven viscous fingering problem arises when two immiscible fluids of different densities flow in a rotating Hele-Shaw cell. In this conventional setting an interplay between capillary and centrifugal forces makes the fluid-fluid interface unstable, leading to the formation of fingered structures that compete dynamically and reach different lengths. In this context, it is known that finger competition is very sensitive to changes in the viscosity contrast between the fluids. We study a variant of such a rotating flow problem where the fluids react and produce a gellike phase at their separating boundary. This interface is assumed to be elastic, presenting a curvature-dependent bending rigidity. A perturbative weakly nonlinear approach is used to investigate how the elastic nature of the interface affects finger competition events. Our results unveil a very different dynamic scenario, in which finger length variability is not regulated by the viscosity contrast, but rather determined by two controlling quantities: a characteristic radius and a rigidity fraction parameter. By properly tuning these quantities one can describe a whole range of finger competition behaviors even if the viscosity contrast is kept unchanged.

A Nacre Protein, n16.3, Self-Assembles To Form Protein Oligomers That Dimensionally Limit and Organize Mineral Deposits

The mollusk shell is a complex biological material that integrates mineral phases with organic macromolecular components such as proteins. The role of proteins in the formation of the nacre layer (aragonite mineral phase) is poorly understood, particularly with regard to the organization of mineral deposits within the protein extracellular matrix and the identification of which proteins are responsible for this task. We report new experiments that provide insight into the role of the framework nacre protein, n16.3 (Pinctada fucata), as an organizer or assembler of calcium carbonate mineral clusters. Using a combination of biophysical techniques, we find that recombinant n16.3 (r-n16.3) oligomerizes to form amorphous protein films and particles that possess regions of disorder and mobility. These supramolecular assemblies possess an intrinsically disordered C-terminal region (T64-W98) and reorganize in the presence of Ca(2+) ions to form clustered protein oligomers. This Ca(2+)-induced reorganization leads to alterations in the molecular environments of Trp residues, the majority of which reside in putative aggregation-prone cross-β strand regions. Potentiometric Ca(2+) titrations reveal that r-n16.3 does not significantly affect the formation of prenucleation clusters in solution, and this suggests a role for this protein in postnucleation mineralization events. This is verified in subsequent in vitro mineralization assays in which r-n16.3 demonstrates its ability to form gel-like protein phases that organize and cluster nanometer-sized single-crystal calcite relative to protein-deficient controls. We conclude that the n16 nacre framework proteome creates a protein gel matrix that organizes and dimensionally limits mineral deposits. This process is highly relevant to the formation of ordered, nanometer-sized nacre tablets in the mollusk shell.

Nanoscale Packing Differences in Sphingomyelin and Phosphatidylcholine Revealed by BODIPY Fluorescence in Monolayers: Physiological Implications

Phosphatidycholines (PC) with two saturated acyl chains (e.g., dipalmitoyl) mimic natural sphingomyelin (SM) by promoting raft formation in model membranes. However, sphingoid-based lipids, such as SM, rather than saturated-chain PCs have been implicated as key components of lipid rafts in biomembranes. These observations raise questions about the physical packing properties of the phase states that can be formed by these two major plasma membrane lipids with identical phosphocholine headgroups. To investigate, we developed a monolayer platform capable of monitoring changes in surface fluorescence by acquiring multiple spectra during measurement of a lipid force–area isotherm. We relied on the concentration-dependent emission changes of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-labeled PC to detect nanoscale alterations in lipid packing and phase state induced by monolayer lateral compression. The BODIPY-PC probe contained an indacene ring with four symmetrically located methyl (Me) substituents to enhance localization to the lipid hydrocarbon region. Surface fluorescence spectra indicated changes in miscibility even when force–area isotherms showed no deviation from ideal mixing behavior in the surface pressure versus cross-sectional molecular area response. We detected slightly better mixing of Me4-BODIPY-8-PC with the fluid-like, liquid expanded phase of 1-palmitoyl-2-oleoyl-PC compared to N-oleoyl-SM. Remarkably, in the gel-like, liquid condensed phase, Me4-BODIPY-8-PC mixed better with N-palmitoyl-SM than dipalmitoyl-PC, suggesting naturally abundant SMs with saturated acyl chains form gel-like lipid phase(s) with enhanced ability to accommodate deeply embedded components compared to dipalmitoyl-PC gel phase. The findings reveal a fundamental difference in the lateral packing properties of SM and PC that occurs even when their acyl chains match.

Vapor-crystal phase transition in synthesis of paracetamol films by vacuum evaporation and condensation

We report on the structural and technological investigations of the vapor-crystal phase transition during synthesis of paracetamol films of the monoclinic system by vacuum evaporation and condensation in the temperature range 220–320 K. The complex nature of the transformation accompanied by the formation of a gel-like phase is revealed. The results are interpreted using a model according to which the vapor-crystal phase transition is not a simple first-order phase transition, but is a nonlinear superposition of two phase transitions: a first-order transition with a change in density and a second-order phase transition with a change in ordering. Micrographs of the surface of the films are obtained at different phases of formation.

The French SON68 Glass Vapor Hydration under Different Atmospheres

We investigated the role of pH in the vapor hydration at 175oC of the French SON68 glass using controlled atmospheres. Hence, experiments were conducted under ammonia and hydrogen sulfide to respectively simulate high and low pH conditions. Results were compared with those obtained under air. Glass hydration and surface analysis were conducted by FTIR, SEM and μ-Raman spectrometry. The glass hydration is ten times higher under NH3 than under H2S. Under ammonia the main corrosion products were analcime and a smectite, and incidentally calcite, apatite and tobermorite while under hydrogen sulfide only a gel-like phase was identified. The precipitation of silica-consuming secondary phases at high pH involves high hydration rates under ammonia atmosphere.

Advection of shear-induced surfactant threads and turbulent drag reduction

Surfactant solutions containing wormlike micelles often show complex structural changes in laminar shear flow. These structural changes produce anomalous rheological phenomena in which the shear induced structure (hereafter SIS) increases the viscosity of surfactant solutions. In turbulent shear flow, dilute solutions of 5 nm diameter and micron length wormlike micelles reduce frictional drag. It has been speculated that this drag reduction is related to wormlike micelles or SIS, although to date there have been no studies that have made their direct link to drag reduction in turbulent flow. The mechanism of drag reduction and the role of the micellar structure remain unclear. Here, we identify SIS with a long (several centimeters), threadlike structure. The threads form a gel-like phase under shear, which is clearly separated from the surrounding fluid. The threads breakdown at high shear stresses and disappear at the same time as the drag reduction does. The correlation between the existence of surfactant threads and turbulent drag reduction is discussed.

New Phases Found in Reverse Micelle Systems with High Concentrations of AOT

This paper discusses the phase behavior, rheology, and structure of self-assembled sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reverse micelle systems at high AOT concentrations. When the amount of AOT and w(o) (the molar ratio of water to AOT) were changed, many different phases were found, a fact which is not discussed in the literature. Opaque gel-like phase (phase separation) occurred with high concentrations of AOT in organic solvents without water. When the AOT concentration and w(o) were increased to 18-72 m and 2, respectively, the samples were gel-like and translucent. Dynamic rheological results indicate that the viscoelastic transition agreed with a multirelaxation time model. Small-angle X-ray scattering (SAXS) results imply that these samples showed a hexagonally close-packed cylindrical structure in which the diameter of a cylinder was ~2.5-3.0 nm, depending on the water contents. Moreover, these AOT cylinders self-assembled into fiber bundles with a diameter of 1-10 μm, as determined using a polarized optical microscope. As w(o) was increased to 2-6 in 72 m AOT samples, similar rheological and SAXS results were obtained. However, a different type of viscoelastic transition occurred, from multirelaxation to single-relaxation, when w(o) was increased to 7-11. The samples were in the transparent gel-like phase, and the structures determined by SAXS were a combination of hexagonally packed cylindrical and lamellar structure. The close-packed cylindrical structures had larger radii and shorter lengths with increasing w(o). Furthermore, when w(o) was increased to 12, the gel-like phase disappeared and a highly viscous solution was observed. This is because all the cylindrical structures collapsed and transformed into lamellar structures when the amount of water was further increased.

Recovery of poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) from Ralstonia eutropha cultures with non‐halogenated solvents

Reduced downstream costs, together with high purity recovery of polyhydroxyalkanoate (PHA), will accelerate the commercialization of high quality PHA-based products. In this work, a process was designed for effective recovery of the copolymer poly(hydroxybutyrate-co-hydroxyhexanoate) (P(HB-co-HHx)) containing high levels of HHx (>15 mol%) from Ralstonia eutropha biomass using non-halogenated solvents. Several non-halogenated solvents (methyl isobutyl ketone, methyl ethyl ketone, and butyl acetate and ethyl acetate) were found to effectively dissolve the polymer. Isoamyl alcohol was found to be not suitable for extraction of polymer. All PHA extractions were performed from both dry and wet cells at volumes ranging from 2 mL to 3 L using a PHA to solvent ratio of 2% (w/v). Ethyl acetate showed both high recovery levels and high product purities (up to 99%) when using dry cells as starting material. Recovery from wet cells, however, eliminates a biomass drying step during the downstream process, potentially saving time and cost. When wet cells were used, methyl isobutyl ketone (MIBK) was shown to be the most favorable solvent for PHA recovery. Purities of up to 99% and total recovery yields of up to 84% from wet cells were reached. During polymer recovery with either MIBK or butyl acetate, fractionation of the extracted PHA occurred, based on the HHx content of the polymer. PHA with higher HHx content (17-30 mol%) remained completely in solution, while polymer with a lower HHx content (11-16 mol%) formed a gel-like phase. All PHA in solution could be precipitated by addition of threefold volumes of n-hexane or n-heptane to unfiltered PHA solutions. Effective recycling of the solvents in this system is predicted due to the large differences in the boiling points between solvent and precipitant. Our findings show that two non-halogenated solvents are good candidates to replace halogenated solvents like chloroform for recovery of high quality PHA.

Different hyaluronic acid morphology modulates primary articular chondrocyte behavior in hyaluronic acid‐coated polycaprolactone scaffolds

Scaffolds for cartilage tissue engineering should promote both adequate biomechanical environment and chondrogenic stimulation. Hyaluronic acid (HA) has been used in cartilage engineering for its chondrogenic and chondroprotective properties, nevertheless its mechanical properties are limited. Influence of HA microstructure in chondrocyte response has not been addressed yet. In this work, polycaprolactone (PCL) scaffolds were modified using HA following two coating strategies: coating in one step (PCL-HA1s) yields a gel-like phase within the scaffold, whereas a two-step reaction (PCL-HA2s) yields a thin HA layer coating internal surfaces of PCL structure. Chondrocytes were seeded in the scaffolds and cultured in dedifferentiating conditions up to 3 weeks and analyzed using a total DNA assay and sulfated glycosaminoglycan (sGAG) determination assay; cell morphology and extracellular matrix secretion were assessed by electron microscopy as well as immunofluorescent imaging (collagen I, collagen II, aggrecan, CD44). Cells proliferate in all samples and no cytotoxicity is observed. PCL-HA1s shows higher sGAG production per cell than PCL and PCL-HA2s at all times. Presence of hyaluronic acid promotes qualitative expression of CD44 surface markers and aggrecan (more visible in PCL-HA1s than PCL-HA2s), whereas in dedifferentiating conditions, expression of CD44 and aggrecan can hardly be detected in pure PCL scaffolds. Collagen type II seems more prominent in PCL-HA2s; although PCL-HA2s shows markers for COL II, aggrecan and CD44, quantitative ECM production is not improved with respect to PCL. It is thus likely that CD44 activation is not sufficient for explaining the better response in PCL-HA1s.

Formation of semi-solid lipid phases by aggregation of protein microspheres in water-in-oil emulsions

Controlled aggregation of protein microspheres in water-in-oil (W/O) emulsions was used to form semi-solid lipid materials. The aqueous phase consisted of 10wt% whey protein isolate (WPI) in buffer solution (pH 7.0, 100mM NaCl). The oil phase consisted of a lipophilic nonionic surfactant (8 wt % polyglycerol polyricinoleate, PGPR) dispersed in a liquid oil (soybean oil). Lipid phases containing protein microspheres were formed by homogenization of the oil and aqueous phases to form a W/O emulsion followed by heating (90°C for 30min) to promote gelation of the WPI in the aqueous phase. Temperature-scanning dynamic shear measurements showed that the W/O emulsions underwent an irreversible liquid-to-solid transition when heated above the thermal denaturation temperature of WPI, which was attributed to protein gelation and microsphere aggregation. Optical microscopy indicated that a three-dimensional network of aggregated protein microspheres was formed at high aqueous phase contents (>30 wt %). Shear rheology measurements (shear stress versus shear rate) indicated that these structured emulsions were non-ideal plastic-like materials. The apparent shear viscosity increased with thermal treatment, increasing aqueous phase content, and decreasing shear rate. The structured W/O emulsions developed in this study may be useful materials for the development of foods with highly viscous or gel-like lipid phases, but low saturated or trans-fat contents.

N-Butanol Partitioning and Phase Behavior in DPPC/DOPC Membranes

Membrane phase behavior and fluidization have been examined in heterogeneous membranes composed of dipalmitoylphosphatidylcholine (DPPC, a saturated lipid) and dioleoylphosphatidylcholine (DOPC, an unsaturated lipid) at n-butanol concentrations below and above the interdigitation threshold of DPPC. Our results show that the presence of DOPC did not influence the interdigitation concentration of n-butanol on DPPC (0.1-0.13 M) despite the fact that DOPC increased n-butanol partitioning into the membranes. When DPPC was the continuous phase, up to equimolar DPPC:DOPC, n-butanol partitioning into gel or interdigitated DPPC was only slightly affected by the presence of DOPC. In this case a "cooperative effect" of DOPC + n-butanol eliminated the DPPC pretransition phase and yielded an untilted gel-like phase. When DOPC was the continuous phase, more n-butanol was needed to cause DPPC interdigitation (0.2 M), which was attributed to n-butanol residing at the interface between DOPC and DPPC domains. To our knowledge, this is the first study to examine the effects of n-butanol partitioning on membranes composed of saturated and unsaturated lipids that exhibit coexisting phase states.

Modeling and Simulation of Aggregation of Membrane Protein LAT with Molecular Variability in the Number of Binding Sites for Cytosolic Grb2-SOS1-Grb2

The linker for activation of T cells (LAT), the linker for activation of B cells (LAB), and the linker for activation of X cells (LAX) form a family of transmembrane adaptor proteins widely expressed in lymphocytes. These scaffolding proteins have multiple binding motifs that, when phosphorylated, bind the SH2 domain of the cytosolic adaptor Grb2. Thus, the valence of LAT, LAB and LAX for Grb2 is variable, depending on the strength of receptor activation that initiates phosphorylation. During signaling, the LAT population will exhibit a time-varying distribution of Grb2 valences from zero to three. In the cytosol, Grb2 forms 1∶1 and 2∶1 complexes with the guanine nucleotide exchange factor SOS1. The 2∶1 complex can bridge two LAT molecules when each Grb2, through their SH2 domains, binds to a phosphorylated site on a separate LAT. In T cells and mast cells, after receptor engagement, receptor phosphoyrlation is rapidly followed by LAT phosphorylation and aggregation. In mast cells, aggregates containing more than one hundred LAT molecules have been detected. Previously we considered a homogeneous population of trivalent LAT molecules and showed that for a range of Grb2, SOS1 and LAT concentrations, an equilibrium theory for LAT aggregation predicts the formation of a gel-like phase comprising a very large aggregate (superaggregate). We now extend this theory to investigate the effects of a distribution of Grb2 valence in the LAT population on the formation of LAT aggregates and superaggregate and use stochastic simulations to calculate the fraction of the total LAT population in the superaggregate.

Modeling an Elastic Fingering Instability in a Reactive Hele-Shaw Flow

In this paper we develop a mathematical model of Hele-Shaw flows in which two immiscible fluids react and form a gel-like phase at the interface, a phenomenon which has been observed in recent experiments. This phase significantly stiffens the interface. The interface is modeled as an elastic membrane which has a bending rigidity dependent on the local curvature. A dispersion relation is derived using an energy variational method. Several types of instabilities are categorized, and how various physical parameters affect the instability is investigated. Our model is able to account for some of the anomalous fingering instabilities observed in experiments by Podgorski et al. [Phys. Rev. E, 76 (2007), 016202]. Consistent with the experimental observations, the fingering instability in a reactive system is shown to be greater than in a nonreactive system.

Recent Advances in Surfactant EOR

Summary In this paper, recent advances in surfactant enhanced oil recovery (EOR) are reviewed. The addition of alkali to surfactant flooding in the 1980s reduced the amount of surfactant required, and the process became known as alkaline/surfactant/polymer flooding (ASP). It was recently found that the adsorption of anionic surfactants on calcite and dolomite can also be significantly reduced with sodium carbonate as the alkali, thus making the process applicable for carbonate formations. The same chemicals are also capable of altering the wettability of carbonate formations from strongly oil-wet to preferentially water-wet. This wettability alteration in combination with ultralow interfacial tension (IFT) makes it possible to displace oil from preferentially oil-wet carbonate matrix to fractures by oil/water gravity drainage. The alkaline/surfactant process consists of injecting alkali and synthetic surfactant. The alkali generates soap in situ by reaction between the alkali and naphthenic acids in the crude oil. It was recently recognized that the local ratio of soap/surfactant determines the local optimal salinity for minimum IFT. Recognition of this dependence makes it possible to design a strategy to maximize oil recovery with the least amount of surfactant and to inject polymer with the surfactant without phase separation. An additional benefit of the presence of the soap component is that it generates an oil-rich colloidal dispersion that produces ultralow IFT over a much wider range of salinity than in its absence. It was once thought that a cosolvent such as alcohol was necessary to make a microemulsion without gel-like phases or a polymer-rich phase separating from the surfactant solution. An example of an alternative to the use of alcohol is to blend two dissimilar surfactants: a branched alkoxylated sulfate and a double-tailed, internal olefin sulfonate. The single-phase region with NaCl or CaCl2 is greater for the blend than for either surfactant alone. It is also possible to incorporate polymer into such aqueous surfactant solutions without phase separation under some conditions. The injected surfactant solution has underoptimum phase behavior with the crude oil. It becomes optimum only as it mixes with the in-situ-generated soap, which is generally more hydrophobic than the injected surfactant. However, some crude oils do not have a sufficiently high acid number for this approach to work. Foam can be used for mobility control by alternating slugs of gas with slugs of surfactant solution. Besides effective oil displacement in a homogeneous sandpack, it demonstrated greatly improved sweep in a layered sandpack.