The synthesis of polymer grafted nanoparticles that are stable at high salinities and high temperature with low retention in porous media is of paramount importance for subsurface applications including electromagnetic imaging, enhanced oil recovery and environmental remediation. Herein, we present an improved approach to synthesize and purify sub-100 nm IONPs grafted with a random copolymer poly(AMPS-co-AA) (poly(2-acrylamido-3-methylpropanesulfonate-co-acrylic acid)) by means of catalyzed amide bond formation at room temperature. The improved and uniform polymer grafting of magnetic nanoparticles led to colloidal stability of IONPs at high temperature (120 °C) in API for a month. The transport behavior of the polymer grafted IONPs was investigated in crushed and in consolidated Berea sandstone. The high poly (AMPS-co-AA) polymer level on the surface (∼34%) provided electrosteric stabilization between the NPs and weak interactions of the NPs with anionic silica and sandstone surfaces. This behavior was enabled by low affinity of Ca2+ towards the highly acidic AMPS monomers thus enabling strong solvation in API brine. In crushed Berea sandstone, the retention was reduced by three fold and nine fold relative to our earlier studies, given the improvements in the grafted polymer layer. For intact core flood experiments in Berea sandstone carried out at elevated temperature (65 °C) and pressure (1000 psi net confining stress), the retention was 519 μg/g, comparable to the value for crushed Berea sandstone. Furthermore, the addition of a relatively small amount (0.1% v/v) of commercially available sacrificial polymer (e.g., HEC-10) further reduced IONP retention to 252 μg/g or 0.17 mg/m2 by blocking retentive sites
Ultralow water content carbon dioxide-in-water (C/W) foams with gas phase volume fractions (ϕ) above 0.95 (that is <0.05 water) tend to be inherently unstable given that the large capillary pressures that cause the lamellar films to thin. Herein, we demonstrate that these C/W foams may be stabilized with viscoelastic aqueous phases formed with a single zwitterionic surfactant at a concentration of only 1% (w/v) in DI water and over a wide range of salinity. Moreover, they are stable with a foam quality ϕ up to 0.98 even for temperatures up to 120 °C. The properties of aqueous viscoelastic solutions and foams containing these solutions are examined for a series of zwitterionic amidopropylcarbobetaines, R-ONHC3H6N(CH3)2CH2CO2, where R is varied from C12–14 (coco) to C18 (oleyl) to C22 (erucyl). For the surfactants with long C18 and C22 tails, the relaxation times from complex rheology indicate the presence of viscoelastic wormlike micelles over a wide range in salinity and pH, given the high surfactant packing fraction. The apparent viscosities of these ultralow water content foams reached more than 120 cP with stabilities more than 30-fold over those for foams formed with the non-viscoelastic C12–14 surfactant. At 90 °C, the foam morphology was composed of ∼35 μm diameter bubbles with a polyhedral texture. The apparent foam viscosity typically increased with ϕ and then dropped at ϕ values higher than 0.95–0.98. The Ostwald ripening rate was slower for foams with viscoelastic versus non-viscoelastic lamellae as shown by optical microscopy, as a consequence of slower lamellar drainage rates. The ability to achieve high stabilities for ultralow water content C/W foams over a wide temperature range is of interest in various technologies including polymer and materials science, CO2 enhanced oil recovery, CO2 sequestration (by greater control of the CO2flow patterns), and possibly even hydraulic fracturing with minimal use of water to reduce the requirements for wastewater disposal.
We report a new way of storing CO2 in a highly porous hydrate structure, stabilized by silica nanoparticles (NPs). Such a porous CO2 hydrate structure was generated either by cooling down NP-stabilized CO2-in-seawater foams, or by gently mixing CO2 and seawater that contains silica NPs under CO2 hydrate-generating conditions. With the highly porous structure, enhanced desalination was also achievable when the partial meltdown of CO2 hydrate was allowed
Three techniques to measure and understand the contact angle, θ, of a CO2/brine/rock system relevant to geologic carbon storage were performed with Mount Simon sandstone. Traditional sessile drop measurements of CO2/brine on the sample were conducted and a water-wet system was observed, as is expected. A novel series of measurements inside of a Mount Simon core, using a micro X-ray computed tomography imaging system with the ability to scan samples at elevated pressures, was used to examine the θ of residual bubbles of CO2. Within the sandstone core the matrix appeared to be neutrally wetting, with an average θ around 90°. A large standard deviation of θ (20.8°) within the core was also observed. To resolve this discrepancy between experimental measurements, a series of Lattice Boltzmann model simulations were performed with differing intrinsic θ values. The model results with a θ=80° were shown to match the core measurements closely, in both magnitude and variation. The small volume and complex geometry of the pore spaces that CO2 was trapped in is the most likely explanation of this discrepancy between measured values, though further work is warranted.
Recently, N,N-trans Re(O)(LN–O)2X (LN–O = monoanionic N–O chelates; X = Cl or Br prior to being replaced by solvents or alkoxides) complexes have been found to be superior to the corresponding N,N-cis isomers in the catalytic reduction of perchlorate via oxygen atom transfer. However, reported methods for Re(O)(LN–O)2X synthesis often yield only the N,N-cis complex or a mixture of trans and cis isomers. This study reports a geometry-inspired ligand design rationale that selectively yields N,N-trans Re(O)(LN–O)2Cl complexes. Analysis of the crystal structures revealed that the dihedral angles (DAs) between the two LN–O ligands of N,N-cis Re(O)(LN–O)2Cl complexes are less than 90°, whereas the DAs in most N,N-trans complexes are greater than 90°. Variably sized alkyl groups (−Me, −CH2Ph, and −CH2Cy) were then introduced to the 2-(2′-hydroxyphenyl)-2-oxazoline (Hhoz) ligand to increase steric hindrance in the N,N-cis structure, and it was found that substituents as small as −Me completely eliminate the formation of N,N-cisisomers. The generality of the relationship between N,N-trans/cis isomerism and DAs is further established from a literature survey of 56 crystal structures of Re(O)(LN–O)2X, Re(O)(LO–N–N–O)X, and Tc(O)(LN–O)2X congeners. Density functional theory calculations support the general strategy of introducing ligand steric hindrance to favor synthesis of N,N-trans Re(O)(LN–O)2X and Tc(O)(LN–O)2X complexes. This study demonstrates the promise of applying rational ligand design for isomeric control of metal complex structures, providing a path forward for innovations in a number of catalytic, environmental, and biomedical applications.
A novel ultrafast reflective grating-imaging technique has been developed to measure ambipolar carrier diffusion in GaAs/AlAs quantum wells and bulk GaAs. By integrating a transmission grating and an imaging system into the traditional pump–probe setup, this technique can acquire carrier diffusion properties conveniently and accurately. The fitted results of the diffusion coefficient and diffusion length in bulk GaAs agree well with the literature values obtained by other techniques. The diffusion coefficient and diffusion length of GaAs/AlAs quantum wells are found to increase with the well layer thickness, which suggests that interface roughness scattering dominates carrier diffusion in GaAs/AlAs quantum wells. With the advantages of simple operation, sensitive detection, rapid and nondestructive measurement, and extensive applicability, the ultrafast reflective grating-imaging technique has great potential in experimental study of carrier diffusion in various materials.