Enhanced oil recovery (EOR) processes aim to recover trapped oil left in reservoirs after primary and secondary recovery methods. New materials and additives are needed to make EOR economical in challenging reservoirs or harsh environments. Nanoparticles have been widely studied for EOR, but nanoparticles with polymer chains grafted to the surface-known as polymercoated nanoparticles (PNPs)-are an emerging class of materials that may be superior to nanoparticles for EOR due to improved solubility and stability, greater stabilization of foams and emulsions, and more facile transport through porous media. Here, we review prior research, current challenges, and future research opportunities in the application of PNPs for EOR. We focus on studies of PNPs for improving mobility control, altering surface wettability, and for investigating their transport through porous media. For each case, we highlight both fundamental studies of PNP behavior and more applied studies of their use in EOR processes. We also touch on a related class of materials comprised of surfactant and nanoparticle blends. Finally, we briefly outline the major challenges in the field, which must be addressed to successfully implement PNPs in EOR applications. V C 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40576.

We explore the phase behaviour, solution conformation, and interfacial properties of bottlebrush polymers with side-chains comprised of poly(N-isopropylacrylamide) (PNIPAAM), a thermally responsive polymer that exhibits a lower critical solution temperature (LCST) in water. PNIPAAM bottlebrush polymers with controlled side-chain length and side-chain end-group structure are prepared using a "grafting-through" technique. Due to reduced flexibility of bottlebrush polymer side-chains, side-chain end-groups have a disproportionate effect on bottlebrush polymer solubility and phase behaviour. Bottlebrush polymers with a hydrophobic end-group have poor water solubilities and depressed LCSTs, whereas bottlebrush polymers with thiol-terminated side-chains are fully water-soluble and exhibit an LCST greater than that of PNIPAAM homopolymers. The temperature-dependent solution conformation of PNIPAAM bottlebrush polymers in D2O is analyzed by small-angle neutron scattering (SANS), and data analysis using the Guinier-Porod model shows that the bottlebrush polymer radius decreases as the temperature increases towards the LCST for PNIPAAM bottlebrush polymers with relatively long 9 kg mol(-1) side-chains. Above the LCST, PNIPAAM bottlebrush polymers can form a lyotropic liquid crystal phase in water. Interfacial tension measurements show that bottlebrush polymers reduce the interfacial tension between chloroform and water to levels comparable to PNIPAAM homopolymers without the formation of microemulsions, suggesting that bottlebrush polymers are unable to stabilize highly curved interfaces. These results demonstrate that bottlebrush polymer side-chain length and flexibility impact phase behavior, solubility, and interfacial properties.

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An important economical factor affecting Enhanced Oil Recovery (EOR) is the adsorption of surfactants on the rocks. Sacrificial agents may be used to reduce the adsorption of surfactants. An alkali (traditionally, sodium carbonate or sodium hydroxide) is often used as sacrificial adsorption agent; however, sodium carbonate is not an effective sacrificial agent in the presence of anhydrite in the rocks due to the reaction between sodium carbonate and sparingly-soluble anhydrite. Therefore, it is essential to develop a sacrificial adsorption agent that can act effectively in the presence of anhydrite. In this work, sodium polyacrylate is evaluated as a sacrificial agent, and is compared to many other conventional or recentlyrecommended sacrificial agents, and has shown advantage over all of them for the case of presence of anhydrite. Some experiments have been conducted to demonstrate the ineffectiveness of sodium carbonate as sacrificial agent in the presence of anhydrite. Effect of molecular weight of sodium polyacrylate is tested, and it is found that increase in molecular weight results in decrease in adsorption of surfactant until a certain molecular weight of polyacrylate is reached after which molecular weight has no further effect on reducing adsorption of surfactant. Addition of polyacrylate was shown to reduce adsorption of a selected anionic surfactant on different outcrop minerals, including Carlpool dolomite, industrial calcite, kaolinite, Berea sandstone, and Indiana limestone. To prove the point further, application of polyacrylate was tested with two different anionic surfactants. Adsorption of polyacrylate itself is measured in the presence and absence of surfactant and showed to be independent of the presence of surfactant. The effect of concentration of divalent ions and salinity in the brine on effectiveness of sodium polyacrylate as sacrificial agent has been evaluated on different minerals/rocks. Finally, dynamic adsorption data has been presented in different concentrations of sodium polyacrylate. All these experiments demonstrate the advantage of using sodium polyacrylate as sacrificial adsorption agent for anionic surfactants even in the presence of anhydrite in the rock.

Polymer-coated nanoparticles are interfacially active and have been shown to stabilize macroscopic emulsions of oil and water, also known as Pickering emulsions. However, prior work has not explored the phase behavior of amphiphilic nanoparticles in the presence of bicontinuous microemulsions. Here, we show that properly designed amphiphilic polymercoated nanoparticles spontaneously and preferentially segregate to the bicontinuous microemulsion phases of oil, water, and surfactant. Mixtures of hydrophilic and hydrophobic chains are covalently grafted onto the surface of oxidized carbon black nanoparticles. By sulfating hydrophilic chains, the polymer-coated nanoparticles are stable in the aqueous phase at salinities up to 15 wt % NaCl. These amphiphilic, negatively charged polymer-coated nanoparticles segregate to the bicontinuous microemulsion phases. We analyzed the equilibrium phase behavior of the nanoparticles, measured the interfacial tension, and quantified the domain spacing in the presence of nanoparticles. This work shows a novel route to the design of polymer-coated nanoparticles which are stable at high salinities and preferentially segregate to bicontinuous microemulsion phases.

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