Supramolecular Strategy Effects on Chitosan Bead Stability in Acidic Media: A Comparative Study.

Chitosan beads attract interest in diverse applications, including drug delivery, biocatalysis and water treatment. They can be formed through several supramolecular pathways, ranging from phase inversion in alkaline solutions, to the ionic crosslinking of chitosan with multivalent anions, to polyelectrolyte or surfactant/polyelectrolyte complexation. Many chitosan bead uses require control over their stability to dissolution. To help elucidate how this stability depends on the choice of supramolecular gelation chemistry, we present a comparative study of chitosan bead stability in acidic aqueous media using three common classes of supramolecular chitosan beads: (1) alkaline solution-derived beads, prepared through simple precipitation in NaOH solution; (2) ionically-crosslinked beads, prepared using tripolyphosphate (TPP); and (3) surfactant-crosslinked beads prepared via surfactant/polyelectrolyte complexation using sodium salts of dodecyl sulfate (SDS), caprate (NaC10) and laurate (NaC12). Highly variable bead stabilities with dissimilar sensitivities to pH were achieved using these methods. At low pH levels (e.g., pH 1.2), chitosan/SDS beads were the most stable, requiring roughly 2 days to dissolve. In weakly acidic media (at pH 3.0⁻5.0), however, chitosan/TPP beads exhibited the highest stability, remaining intact throughout the entire experiment. Beads prepared using only NaOH solution (i.e., without ionic crosslinking or surfactant complexation) were the least stable, except at pH 5.0, where the NaC10 and NaC12-derived beads dissolved slightly faster. Collectively, these findings provide further guidelines for tailoring supramolecular chitosan bead stability in acidic media.

Phase behavior and interfacial properties of a switchable ethoxylated amine surfactant at high temperature and effects on CO2-in-water foams.

The interfacial properties for surfactants at the supercritical CO2-water (C-W) interface at temperatures above 80°C have very rarely been reported given limitations in surfactant solubility and chemical stability. These limitations, along with the weak solvent strength of CO2, make it challenging to design surfactants that adsorb at the C-W interface, despite the interest in CO2-in-water (C/W) foams (also referred to as macroemulsions). Herein, we examine the thermodynamic, interfacial and rheological properties of the surfactant C12-14N(EO)2 in systems containing brine and/or supercritical CO2 at elevated temperatures and pressures. Because the surfactant is switchable from the nonionic state to the protonated cationic state as the pH is lowered over a wide range in temperature, it is readily soluble in brine in the cationic state below pH 5.5, even up to 120°C, and also in supercritical CO2 in the nonionic state. As a consequence of the affinity for both phases, the surfactant adsorption at the CO2-water interface was high, with an area of 207Å(2)/molecule. Remarkably, the surfactant lowered the interfacial tension (IFT) down to ∼5mN/m at 120°C and 3400 psia (23MPa), despite the low CO2 density of 0.48g/ml, indicating sufficient solvation of the surfactant tails. The phase behavior and interfacial properties of the surfactant in the cationic form were favorable for the formation and stabilization of bulk C/W foam at high temperature and high salinity. Additionally, in a 1.2 Darcy glass bead pack at 120°C, a very high foam apparent viscosity of 146 cP was observed at low interstitial velocities given the low degree of shear thinning. For a calcium carbonate pack, C/W foam was formed upon addition of Ca(2+) and Mg(2+) in the feed brine to keep the pH below 4, by the common ion effect, in order to sufficiently protonate the surfactant. The ability to form C/W foams at high temperatures is of interest for a variety of applications in chemical synthesis, separations, materials science, and subsurface energy production.

Steric stabilization of nanoparticles with grafted low molecular weight ligands in highly concentrated brines including divalent ions.

Whereas numerous studies of stabilization of nanoparticles (NPs) in electrolytes have examined biological fluids, the interest has grown recently in media with much higher ionic strengths including seawater and brines relevant to environmental science and subsurface oil and gas reservoirs. Given that electrostatic repulsion is limited at extremely high ionic strengths due to charge screening, we have identified ligands that are well solvated in concentrated brine containing divalent cations and thus provide steric stabilization of silica nanoparticles. Specifically, the hydrodynamic diameter of silica nanoparticles with grafted low molecular weight ligands, a diol ether, [3-(2,3-dihydroxypropoxy)propyl]-trimethoxysilane, and a zwitterionic sulfobetaine, 3-([dimethyl(3-trimethoxysilyl)propyl]ammonio)propane-1-sulfonate, is shown with dynamic light scattering to remain essentially constant, indicating lack of aggregation, at room temperature and up to 80 °C for over 30 days. An extended DLVO model signifies that steric stabilization is strongly dominant against van der Waals attraction for ∼10 nm particles given that these ligands are well solvated even in highly concentrated brine. In contrast, polyethylene glycol oligomers do not provide steric stabilization at elevated temperatures, even at conditions where the ligands are soluble, indicating complicating factors including bridging of the ether oxygens by divalent cations.

Ultradry Carbon Dioxide-in-Water Foams with Viscoelastic Aqueous Phases.

For foams with ultra low water contents, the capillary pressure is very large and induces rapid drainage that destabilizes the aqueous lamellae between the gas bubbles. However, we show that high-pressure CO2-in-water foams can be stabilized with a viscoelastic aqueous phase composed of entangled wormlike micelles, even for extremely high CO2 volume fractions ϕ of 0.95 to 0.98; the viscosity of these ultradry foams increased by up to 3-4-fold, reaching more than 100 cP relative to foams formed with conventional low viscosity aqueous phases. The foam morphology consisted of fine ∼20 µm polyhedral-shaped CO2 bubbles that were stable for hours. The wormlike micelles were formed by mixing anionic sodium lauryl ether sulfate (SLES) with salt and a protonated cationic surfactant, as shown by cryogenic transmission electron microscopy (cryo-TEM) and large values of the zero-shear viscosity and the dynamic storage and loss moduli. With the highly viscous continuous aqueous phases, the foam lamella drainage rates were low, as corroborated by confocal microscopy. The preservation of viscous thick lamellae resulted in lower rates of Ostwald ripening relative to conventional foams as shown by high-pressure optical microscopy. The ability to stabilize viscous ultra high internal phase foams is expected to find utility in various practical applications, including nearly "waterless" fracturing fluids for recovery of oil and gas in shale, offering the possibility of a massive reduction in the amount of wastewater.

High interfacial activity of polymers "grafted through" functionalized iron oxide nanoparticle clusters.

The mechanism by which polymers, when grafted to inorganic nanoparticles, lower the interfacial tension at the oil-water interface is not well understood, despite the great interest in particle stabilized emulsions and foams. A simple and highly versatile free radical "grafting through" technique was used to bond high organic fractions (by weight) of poly(oligo(ethylene oxide) monomethyl ether methacrylate) onto iron oxide clusters, without the need for catalysts. In the resulting ∼1 µm hybrid particles, the inorganic cores and grafting architecture contribute to the high local concentration of grafted polymer chains to the dodecane/water interface to produce low interfacial tensions of only 0.003 w/v % (polymer and particle core). This "critical particle concentration" (CPC) for these hybrid inorganic/polymer amphiphilic particles to lower the interfacial tension by 36 mN/m was over 30-fold lower than the critical micelle concentration of the free polymer (without inorganic cores) to produce nearly the same interfacial tension. The low CPC is favored by the high adsorption energy (∼10(6) kBT) for the large ∼1 µm hybrid particles, the high local polymer concentration on the particles surfaces, and the ability of the deformable hybrid nanocluster cores as well as the polymer chains to conform to the interface. The nanocluster cores also increased the entanglement of the polymer chains in bulk DI water or synthetic seawater, producing a viscosity up to 35,000 cP at 0.01 s(-1), in contrast with only 600 cP for the free polymer. As a consequence of these interfacial and rheological properties, the hybrid particles stabilized oil-in-water emulsions at concentrations as low as 0.01 w/v %, with average drop sizes down to 30 µm. In contrast, the bulk viscosity was low for the free polymer, and it did not stabilize the emulsions. The ability to influence the interfacial activity and rheology of polymers upon grafting them to inorganic particles, including clusters, may be expected to be broadly applicable to stabilization of emulsions and foams.

Modified montmorillonite clay microparticles for stable oil-in-seawater emulsions.

Environmentally benign clay particles are of great interest for the stabilization of Pickering emulsions. Dodecane-in-synthetic seawater (SSW) emulsions formed with montmorillonite (MMT) clay microparticles modified with bis(2-hydroxyethyl)oleylamine were stable against coalescence, even at clay concentrations down to 0.1% w/v. Remarkably, as little as 0.001% w/v surfactant lowered the hydrophilicity of the clay to a sufficient level for stabilization of oil-in-SSW emulsions. The favorable effect of SSW on droplet size reduction and emulsion stability enhancement is hypothesized to be due to reduced electrostatic repulsion between adsorbed clay particles and a consequent increase in the continuous phase (an aqueous clay suspension) viscosity. Water/oil (W/O) emulsions were inverted to O/W either by decreasing the mass ratio of surfactant-to-clay (transitional inversion) or by increasing the water volume fraction (catastrophic inversion). For both types of emulsions, coalescence was minimal and the sedimentation or creaming was highly correlated with the droplet size. For catastrophic inversions, the droplet size of the emulsions was smaller in the case of the preferred curvature. Suspensions of concentrated clay in oil dispersions in the presence of surfactant were stable against settling. The mass transfer pathways during emulsification of oil containing the clay particles were analyzed on the droplet size/stability phase diagrams to provide insight for the design of dispersant systems for remediating surface and subsurface oceanic oil spills.

Synergistic formation and stabilization of oil-in-water emulsions by a weakly interacting mixture of zwitterionic surfactant and silica nanoparticles.

Oil-in-water emulsions were formed and stabilized at low amphiphile concentrations by combining hydrophilic nanoparticles (NPs) (i.e., bare colloidal silica) with a weakly interacting zwitterionic surfactant, caprylamidopropyl betaine, to generate a high hydrophilic-lipophilic balance. The weak interaction of the NPs with surfactant was quantified with contact angle measurements. Emulsions were characterized by static light scattering to determine the droplet size distributions, optical photography to quantify phase separation due to creaming, and both optical and electron microscopy to determine emulsion microstructure. The NPs and surfactant acted synergistically to produce finer emulsions with a greater stability to coalescence relative to the behavior with either NPs or surfactant alone. As a consequence of the weak adsorption of the highly hydrophilic surfactant on the anionic NPs along with the high critical micelle concentration, an unusually large surfactant concentration was available to adsorb at the oil-water interface and lower the interfacial tension. The synergy for emulsion formation and stabilization for the two amphiphiles was even greater in the case of a high-salinity synthetic seawater aqueous phase. Here, higher NP adsorption at the oil-water interface was caused by electrostatic screening of interactions between (1) NPs and the anionic oil-water interface and (2) between the NPs. This greater adsorption as well as partial flocculation of the NPs provided a more efficient barrier to droplet coalescence.

Adsorption of iron oxide nanoclusters stabilized with sulfonated copolymers on silica in concentrated NaCl and CaCl2 brine.

Transport of metal oxide nanoparticles in porous rock is of interest for imaging and oil recovery in subsurface reservoirs, which often contain concentrated brine. Various copolymers composed of acrylic acid and either 2-acrylamido-2-methylpropanesulfonate or styrenesulfonate were synthesized and adsorbed on iron oxide nanoclusters to provide colloidal stability and to achieve low adsorption on silica in high salinity brine composed of 8%wt. NaCl+2%wt. CaCl2. Furthermore, the degree of adsorption of the nanoparticles on silica was controlled by modifying the acrylic acid groups in the copolymers with a series of diamines and triamines to add hydrophobicity. The adsorption on colloidal silica microparticles ranged from <1 mg/m(2) for highly charged hydrophilic surfaces on the iron oxide nanoparticles to 22 mg/m(2) for the most hydrophobic amine-modified surfaces, corresponding to monolayer coverages that ranged from 0.2% to 11.5%, respectively. The specific adsorption (mg-IO/m(2)-silica), monolayer coverage, and parameters for Langmuir isotherms were evaluated for various IO nanoclusters as a function of the properties of the copolymers on their surfaces.

Iron oxide nanoparticles grafted with sulfonated copolymers are stable in concentrated brine at elevated temperatures and weakly adsorb on silica.

Magnetic nanoparticles that can be transported in subsurface reservoirs at high salinities and temperatures are expected to have a major impact on enhanced oil recovery, carbon dioxide sequestration, and electromagnetic imaging. Herein we report a rare example of steric stabilization of iron oxide (IO) nanoparticles (NPs) grafted with poly(2-acrylamido-2-methylpropanesulfonate-co-acrylic acid) (poly(AMPS-co-AA)) that not only display colloidal stability in standard American Petroleum Institute (API) brine (8% NaCl + 2% CaCl2 by weight) at 90 °C for 1 month but also resist undesirable adsorption on silica surfaces (0.4% monolayer NPs). Because the AMPS groups interacted weakly with Ca(2+), they were sufficiently well solvated to provide steric stabilization. The PAA groups, in contrast, enabled covalent grafting of the poly(AMPS-co-AA) chains to amine-functionalized IO NPs via formation of amide bonds and prevented polymer desorption even after a 40,000-fold dilution. The aforementioned methodology may be readily adapted to stabilize a variety of other functional inorganic and organic NPs at high salinities and temperatures.

Stabilization of iron oxide nanoparticles in high sodium and calcium brine at high temperatures with adsorbed sulfonated copolymers.

A series of sulfonated random and block copolymers were adsorbed on the surface of ~100 nm iron oxide (IO) nanoparticles (NPs) to provide colloidal stability in extremely concentrated brine composed of 8% wt NaCl + 2% wt CaCl2 (API brine; 1.4 M NaCl + 0.2 M CaCl2) at 90 °C. A combinatorial materials chemistry approach, which employed Ca(2+)-mediated adsorption of anionic acrylic acid-containing sulfonated polymers to preformed citrate-stabilized IO nanoclusters, enabled the investigation of a large number of polymer coatings. Initially a series of poly(2-methyl-2-acrylamidopropanesulfonate-co-acrylic acid) (poly(AMPS-co-AA)) (1:8 to 1:1 mol:mol), poly(styrenesulfonate-block-acrylic acid) (2.4:1 mol:mol), and poly(styrenesulfonate-alt-maleic acid) (3:1 mol:mol) copolymers were screened for solubility in API brine at 90 °C. The ratio of AMPS to AA groups was varied to balance the requirement of colloid dispersibility at high salinity (provided by AMPS) against the need for anchoring of the polymers to the iron oxide surface (via the AA). Steric stabilization of IO NPs coated with poly(AMPS-co-AA) (1:1 mol:mol) provided colloidal stability in API brine at room temperature and 90 °C for up to 1 month. The particles were characterized before and after coating at ambient and elevated temperatures by a variety of techniques including colloidal stability experiments, dynamic light scattering, zeta potential, and thermogravimetric analysis.

Nanoparticle-stabilized carbon dioxide-in-water foams with fine texture.

The concept of hydrophilic/CO(2)-philic balance (HCB) was extended to describe stabilization of carbon dioxide-in-water (C/W) foams (also called emulsions) with silica nanoparticles adsorbed at the CO(2)-water interface. Opaque, white C/W foams (bubble diameter <100 µm) were generated with either PEG-coated silica or methylsilyl modified silica nanoparticles in a beadpack with CO(2) densities between 0.2 and 0.9 g mL(-1). For methylsilyl modified silica nanoparticles, 50% SiOH modification provided an optimal HCB for generation and stabilization of viscous C/W foams with high stability. The apparent viscosity measured with a capillary tube viscometer reached 120-fold that of a CO(2)-water mixture without nanoparticles, a consequence of the small bubble size and the energy required to deform a high density of aqueous lamellae between CO(2) bubbles. Air-in-water (A/W) foams stabilized with nanoparticles were used to gain insight into the relationship between nanoparticle surface properties and adsorption of the nanoparticles at various types of interfaces. With suitable nanoparticles, A/W foams were stable for at least 7 days and C/W foams were stable for at least 23 h. The ability to achieve long term stability for nanoparticle stabilized C/W foams could offer an alternative to conventional surfactants, which are known to have much lower adsorption energies.