skip to main content


The NSF Public Access Repository (NSF-PAR) system and access will be unavailable from 5:00 PM ET until 11:00 PM ET on Friday, June 21 due to maintenance. We apologize for the inconvenience.

Title: Polyelectrolyte Complex Stabilized CO2 Foam Systems for Hydraulic Fracturing Application

Hydraulic fracturing of oil and gas wells is a water intensive process. Limited availability, cost and increasing government regulations restraining the use and disposal of fresh water have led to the need for alternative fracturing fluids. Using CO2 foam as a fracturing fluid can drastically reduce the need for water in hydraulic fracturing. We address the addition of polyelectrolyte complex nanoparticles (PECNP) to surfactant solutions to improve foam stability, durability and rheological properties at high foam qualities. Polyelectrolyte pH and polyanion/polycation ratios were varied to minimize particle size and maximize absolute zeta potential of the resulting nanoparticles. Rheological tests were conducted on foam systems of varying surfactant/PECNP ratios and different foam quality to understand the effect of shear on viscosity under simulated reservoir conditions of 40°C and 1300 psi. The same foam systems were tested for stability and durability in a view cell at reservoir conditions. Supercritical CO2 foam generated by surfactant alone resulted in short lived, low viscosity foam because of surfactant drainage from foam lamellae. However, addition of PECNP strengthens the foam film by swelling the film due to increased osmotic pressure and electrostatic forces. Electrostatic interactions reduce dynamic movement of surfactant micelles, thereby stabilizing the foam lamellae, which imparts high durability and viscosity to supercritical CO2 foams. From the rheology test results, it was concluded that increasing foam quality and the presence of PECNP resulted in improved viscosity. Also, foam systems with PECNP showed promising results compared with foam generated using surfactant alone in the view cell durability test. The addition of optimized polyelectrolyte nanoparticles to the surfactant can improve viscosity and durability of supercritical CO2 foam during hydraulic fracturing, which can lead to large reductions in water requirements.

more » « less
Award ID(s):
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
SPE Liquids-Rich Basins Conference- North America
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. In spite of their high surface charge (zeta potential ζ = +34 mV), aqueous suspensions of portlandite (calcium hydroxide: Ca(OH) 2 ) exhibit a strong tendency to aggregate, and thereby present unstable suspensions. While a variety of commercial dispersants seek to modify the suspension stability and rheology ( e.g. , yield stress, viscosity), it remains unclear how the performance of electrostatically and/or electrosterically based additives is affected in aqueous environments having either a high ionic strength and/or a pH close to the particle's isoelectric point (IEP). We show that the high native ionic strength (pH ≈ 12.6, IEP: pH ≈ 13) of saturated portlandite suspensions strongly screens electrostatic forces (Debye length: κ −1 = 1.2 nm). As a result, coulombic repulsion alone is insufficient to mitigate particle aggregation and affect rheology. However, a longer-range geometrical particle–particle exclusion that arises from electrosteric hindrance caused by the introduction of comb polyelectrolyte dispersants is very effective at altering the rheological properties and fractal structuring of suspensions. As a result, comb-like dispersants that stretch into the solvent reduce the suspension's yield stress by 5× at similar levels of adsorption as compared to linear dispersants, thus enhancing the critical solid loading ( i.e. , at which jamming occurs) by 1.4×. Significantly, the behavior of diverse dispersants is found to be inherently related to the thickness of the adsorbed polymer layer on particle surfaces. These outcomes inform the design of dispersants for concentrated suspensions that present strong charge screening behavior. 
    more » « less
  2. ConspectusGold nanoparticles (AuNPs) exhibit unique size- and shape-dependent properties not obtainable at the macroscale. Gold nanorods (AuNRs), with their morphology-dependent optical properties, ability to convert light to heat, and high surface-to-volume ratios, are of great interest for biosensing, medicine, and catalysis. While the gold core provides many fascinating properties, this Account focuses on AuNP soft surface coatings, which govern the interactions of nanoparticles with the local environments. Postmodification of AuNP surface chemistry can greatly alter NP colloidal stability, nano-bio interactions, and functionality. Polyelectrolyte coatings provide controllable surface-coating thickness and charge, which impact the composition of the acquired corona in biological settings. Covalent modification, in which covalently bound ligands replace the original capping layer, is often performed with thiols and disulfides due to their ability to replace native coatings. N-heterocyclic carbenes and looped peptides expand the possible functionalities of the ligand layer.The characterization of surface ligands bound to AuNPs, in terms of ligand density and dynamics, remains a challenge. Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for understanding molecular structures and dynamics. Our recent NMR work on AuNPs demonstrated that NMR data were obtainable for ligands on NPs with diameters up to 25 nm for the first time. This was facilitated by the strong proton NMR signals of the trimethylammonium headgroup, which are present in a distinct regime from other ligand protons’ signals. Ligand density analyses showed that the smallest AuNPs (below 4 nm) had the largest ligand densities, yet spin–spin T2 measurements revealed that these smallest NPs also had the most mobile ligand headgroups. Molecular dynamics simulations were able to reconcile these seemingly contradictory results.While NMR spectroscopy provides ligand information averaged over many NPs, the ligand distribution on individual particles’ surfaces must also be probed to fully understand the surface coating. Taking advantage of improvements in electron energy loss spectroscopy (EELS) detectors employed with scanning transmission electron microscopy (STEM), a single-layer graphene substrate was used to calibrate the carbon K-edge EELS signal, allowing quantitative imaging of the carbon atom densities on AuNRs with sub-nanometer spatial resolution. In collaboration with others, we revealed that the mean value for surfactant-bilayer-coated AuNRs had 10–30% reduced ligand density at the ends of the rods compared to the sides, confirming prior indirect evidence for spatially distinct ligand densities.Recent work has found that surface ligands on nanoparticles can, somewhat surprisingly, enhance the selectivity and efficiency of the electrocatalytic reduction of CO2 by controlling access to the active site, tuning its electronic and chemical environment, or denying entry to impurities that poison the nanoparticle surface to facilitate reduction. Looking to the future, while NMR and EELS are powerful and complementary techniques for investigating surface coatings on AuNPs, the frontier of this field includes the development of methods to probe the surface ligands of individual NPs in a high-throughput manner, to monitor nano-bio interactions within complex matrices, and to study structure–property relationships of AuNPs in biological systems. 
    more » « less

    The chemo-mechanical loading of rocks causes the dissolution and precipitation of multiple phases in the rock. This dissolution and precipitation of load-bearing mineral phases lead to the stress redistribution in neighboring phases, which in turn results in deformational changes of the sample composite. The aim of this study is to investigate the link between microstructural evolution and creep behavior of shale rocks subjected to chemo-mechanical loading through modeling time-dependent deformation induced by the dissolution-precipitation process. The model couples the microstructural evolution of the shale rocks with the stress/strain fields inside the material as a function of time. The modeling effort is supplemented with an experimental study where shale rocks were exposed to CO2-rich brine under high temperature and pressure conditions. 3D snapshots of the sample microstructure were generated using segmented micro-CT images of the shale sample. The time-evolving microstructures were then integrated with the Finite element-based mechanical model to simulate the creep induced by dissolution and precipitation processes independent of the intrinsic viscoelasticity/viscoplasticity of the mineral phases. After computation of the time-dependent viscoelastic properties of the shale composite, the combined microstructure model and finite element model were utilized to predict the time-dependent stress and strain fields in different zones of reacted shale.


    Determination of viscous behavior of shale rocks is key in wide range of applications such as stability of reservoirs, stability of geo-structures subjected to environmental forcing, underground storage of hazardous materials and hydraulic fracturing. Short-term creep strains in hydraulic fracturing can change stress fields and in turn can impact the hydraulic fracturing procedures(H. Sone & Zoback, 2010; Hiroki Sone & Zoback, 2013). While long-term creep strains can hamper the reservoir performance due to the reduction in permeability of the reservoir by closing of fractures and fissures(Du, Hu, Meegoda, & Zhang, 2018; Rybacki, Meier, & Dresen, 2016; Sharma, Prakash, & Abedi, 2019; Hiroki Sone & Zoback, 2014). Owing to these significance of creep strain, it is important to understand the viscoelastic/viscoplastic behavior of shales.

    more » « less
  4. Aqueous foams are ubiquitous; they appear in products and processes that span the cosmetics, food, and energy industries. The versatile applicability of foams comes as a result of their intrinsic viscous and elastic properties; for example, foams are exploited as drilling fluids in enhanced oil recovery for their high viscosity. Recently, so-called capillary foams were discovered: a class of foams that have excellent stability under static conditions and whose flow properties have so far remained unexplored. The unique architecture of these foams, containing oil-coated bubbles and a gelled network of oil-bridged particles, is expected to affect foam rheology. In this work, we report the first set of rheological data on capillary foams. We study the viscoelastic properties of capillary foams by conducting oscillatory and steady shear tests. We compare our results on the rheological properties of capillary foams to those reported for other aqueous foams. We find that capillary foams, which have low gas volume fractions, exhibit long lasting rheological stability as well as a yielding behavior that is reminiscent of surfactant foams with high gas volume fractions. 
    more » « less
  5. We use diamond nanoparticles (DNPs) wrapped in the cationic polyelectrolyte poly(allylamine) hydrochloride (PAH) and bilayers composed of either pure DOPC or a mixture of DOPC/DOPG to investigate the influence of membrane phospholipid composition and net surface charge on nanoparticle-membrane interactions and the extent of nanoparticle adhesion to supported phospholipid bilayers. Our results show that in all cases electrostatic attractions between the negatively charged bilayer and cationic PAH-DNP were responsible for the initial attachment of particles, and the lateral electrostatic repulsion between adsorbed particles on the bilayer surface determined the final extent of PAH-DNP attachment. Upon attachment, NPs attract lipids by the contact ion pairing between the ammonium groups on PAH and phosphate and glycerol groups on the lipids and acquire a lipid corona. Lipid corona formation on the PAH-DNP reduces the effective charge density of the particle and is in fact a key factor determining the final extent of NP attachment to the bilayer. Incorporation of DOPG to the bilayer leads to a decrease in efficiency and final extent of attachment compared to DOPC alone. The reduction in PAH-DNP attachment in the presence of DOPG is attributed to the adsorption of free PAH in equilibrium with bound PAH in the nanoparticle solution, thus reducing electrostatic attraction between PAH-DNPs and SLBs. This leads to an increase in hydrogen bonding interactions between lipid headgroups that limits extraction of phospholipids from the bilayer by PAH-DNP, lessening the reduction in interparticle repulsion achieved by acquisition of a lipid corona. Our results indicate that the inclusion of charged phospholipids in SLBs changes bilayer rigidity and stability and hinders the attachment of PAH-DNPs by preventing lipid extraction from the bilayer. 
    more » « less