Rosangela de Carvalho Balaban

New Insights Into Polymer Rheology in Porous Media

This paper (SPE 129200) was accepted for presentation at the SPE Symposium on Improved Oil Recovery, Tulsa, 24–28 April 2010, and revised for publication. Original manuscript received for review 18 January 2010. Revised manuscript received for review 15 June 2010. Paper peer approved 21 June 2010. Summary This paper clarifies the rheology of xanthan and partially hydrolyzed polyacrylamide (HPAM) solutions in porous media, especially at low velocities. Previous literature reported resistance factors (effective viscosities in porous media) and an apparent shear thinning at low fluxes that were noticeably greater than what is expected on the basis of viscosity measurements. The polymer component that causes the latter behavior is shown to propagate quite slowly and generally will not penetrate deep into a formation. Particularly for HPAM solutions, this behavior can be reduced or eliminated for solutions that experience mechanical degradation or flow through a few feet of porous rock. Under practical conditions where HPAM is used for enhanced oil recovery (EOR), the degree of shear thinning is slight or nonexistent, especially compared to the level of shear thickening that occurs at high fluxes.

Development of dual-sensitive smart polymers by grafting chitosan with poly (N-isopropylacrylamide): an overview

A great deal of research on polymers over the past two decades has been focused on the development of stimuli-responsive polymers to obtain materials able to respond to specific surroundings. In this paper, an overview is presented of the concepts, behavior and applicability of these “smart polymers”. Polymers that are temperature- or pH-sensitive are discussed in detail, including the response mechanisms and types of macromolecules, because they are easy to handle and have a wide range of applications. Finally, the combination of pH and temperature responsive properties by means of graft copolymerization of chitosan with poly (N-isopropylacrylamide) (PNIPAM) was chosen to represent some synthetic routes and properties of dual-sensitive polymeric systems developed currently.

PNIPAM-based graft copolymers prepared using potassium persulfate as free-radical initiator: synthesis reproducibility

The use of free radicals has been considered an easy way to get grafted polymers. However, its reproducibility has not yet been evaluated. In this paper, the synthesis reproducibility of copolymers obtained by combining carboxymethylcellulose with N-isopropylacrylamide, in a free-radical copolymerization with potassium persulfate, was investigated. Poly(N-isopropylacrylamide) (PNIPAM) homopolymer and a PNIPAM/CMC blend were also prepared, in order to confirm the success of the synthesis. The polymers were characterized by infrared spectroscopy, thermogravimetry, and rheology. Copolymers and PNIPAM/CMC spectra exhibited characteristic absorptions of the precursor polymers. TGA analyses showed that the copolymers had better thermal stability than CMC and blend. The rheological studies demonstrated that the copolymers exhibited, at low temperatures, an improved thermosensitive performance, higher viscosity, and greater shear thinning behavior, in comparison with PNIPAM and PNIPAM/CMC. The copolymers solutions also exhibited greater thermal stability with increasing temperature. The spectroscopic and rheological properties confirmed the reproducibility of the chemical modification.

Solution properties of a hydrophobically associating polyacrylamide and its polyelectrolyte derivatives determined by light scattering, small angle x-ray scattering and viscometry

A hydrophobically-modified polyacrylamide and two partially hydrolyzed derivatives containing hydrophobic and carboxylic groups were prepared by micellar polymerization and post-hydrolysis. The molecular weight, second virial coefficient and radius of gyration were determined by static light scattering (SLS). Dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) were employed to determine the aggregate formation and type of chain packing in the semidilute regime, respectively. The behavior of solutions in dilute and semidilute regimes was also studied by viscometry and rheology. The hydrophobically-modified polyacrylamide showed a tendency to form aggregates due to the hydrophobic groups, but not enough to increase apparent viscosity. The partially hydrolyzed derivatives did not show the same aggregate-forming tendency. Rather, they exhibited anisotropic behavior, due to the charge density introduced into the polymer chain, which led to a more elongated macromolecular conformation and higher viscosity.

Solution properties of poly(acrylamide-co-3,5,5-trimethylhexane methacrylate) and its polyelectrolyte derivative

The physicochemical properties of hydrophobically modified polyacrylamide (HAPAM) containing a small amount of hydrophobic groups (3,5,5-trimethylhexane methacrylate) and its partially hydrolyzed derivative (HAPAM-10N500) were investigated. The 13C spectrum was used to establish the degree of hydrolysis of HAPAM-10N500. Small-angle X-ray scattering (SAXS) was employed to highlight the polyelectrolyte character of HAPAM-10N500, estimate the chain conformation in the semidilute regime, and evaluate the influence of the ionic strength and the type of salt. The weight average molecular weight, the second virial coefficient, and radius of gyration were determined by static light scattering (SLS). The polymers showed different rheological properties in aqueous solution, with significant increase in viscosity due to partial hydrolysis of HAPAM, however, with strong dependence on ionic strength of the medium. Results showed that the polymers HAPAM and HAPAM-10N500 are suitable for application in processes of moderate temperatures and salinities.

Polyelectrolyte and non-polyelectrolyte polyacrylamide copolymer solutions: the role of salt on the intra- and intermolecular interactions

Poly(acrylamide-co-dihexylacrylamide) (PAHM-0) and poly(acrylamide-co-sodium acrylate-co-dihexylacrylamide) (PAHM-21) were studied through small-angle X-ray scattering (SAXS), light scattering (LS) and rheology. SAXS results highlighted the polyelectrolyte character of PAHM-21, with highly extended conformation in aqueous solution owing to charge repulsion, while the PAHM-0 has a coil conformation. LS measurements indicated that PAHM-0 makes intermolecular clusters in solution, in presence and absence of salt, even with a lower hydrophobic content than that described in the literature to the associative polyacrylamides. However, the rheological results showed that there is not an enhancement of the viscosity although hydrophobic association takes place. LS results for PAHM-21 suggest that this polymer makes intramolecular associations mainly in the presence of salts. Furthermore, the viscosity measurements show that its viscosity decreases due to screening of the charges by the addition of salts.

Effect of carboxymethylcellulose on colloidal properties of calcite suspensions in drilling fluids

Drilling fluids are multicomponent systems used to aid the removal of cuttings from a borehole, and subject to a number of requirements to ensure a safe drilling operation. One of the most important is to form a low permeability cake on the walls of the hole penetrated by the bit, to avoid excessive filtrate loss. To that end, carboxymethylcellulose (CMC) associated with calcite (CaCO3) can be used. In this paper, the effect of carboxymethylcellulose on the colloidal properties of calcite suspensions in brine was systematically evaluated by rheological properties, filtrate volume and zeta potential. Higher viscosity fluids, lower filtrate loss and less negative zeta potential were obtained using small calcite particles with wide size distribution and CMC with high average molecular weight (Mw) and low average degree of substitution (DS), highlighting the importance of effective interactions between CMC and calcite to improve drilling fluid properties.

Application of guar gum in brine clarification and oily water treatment

The increasing amount of oil wastewater is causing serious damage to the environment. Oily water is a worrisome by-product of the oil industry due to its growing volume in mature basins and complex chemical composition. Low-cost polymers are being used as alternative materials to treat oily waters after treatment by conventional methods, oil and grease (O&G) concentration being the primary parameter for final disposal. In this respect, guar gum can be used to treat petroleum-contaminated waters, with the advantage of being a low-cost, highly-hydrophilic natural polymer. In this study, guar gum, under specific conditions, shapes itself into three-dimensional structures with interesting physicochemical properties. The salting out effect occurs with reticulation of the polymeric chains by borate ions and in the presence of electrolytes, reducing the solubility of the polymeric network in the solution and leading to an electrolyte- and polymer-rich phase. When the guar gum gel was prepared in situ in the produced water, after the salting out effect, the oil was imprisoned in the interstices of the collapsed gel. The gelling guar gum was highly efficient in synthetic oily waters. In the case of initial O&G above 100ppm, the oil removal percentage was above 90%.

Synthesis and characterization of carboxymethylcellulose grafted with thermoresponsive side chains of high LCST: The high temperature and high salinity self-assembly dependence

Graft copolymers based on carboxymethylcellulose (CMC) and thermosensitive polyetheramines (ethylene oxide/propylene oxide = 33/10 and 1/9) were prepared in water, at room temperature, by using a carbodiimide and N-hydroxysuccinimide as activators. SLS was applied to obtain Mw, A2 and Rg of CMC and its derivatives. Amide linkages were evidenced by FTIR and grafting percentage was determined by 1H NMR. TGA demonstrated that copolymers were thermally more stable than their precursors. DLS, UV-vis and rheological measurements revealed that properties were salt- and thermo-responsive and linked to the polysaccharide/polyetheramine ratio and the hydrophobicity of the graft. None of the copolymers showed cloud point temperature (Tcp) in water, but they turned turbid in saline media when heated. Copolymers exhibited thermothickening behaviour at 60 °C (>Tcp) in saline media. Below their Tcp, they showed the ability of keeping constant viscosity or even slight increase it, which was interpreted in terms of intermolecular hydrophobic associations.

Water-soluble carboxymethylchitosan used as corrosion inhibitor for carbon steel in saline medium

Biodegradability and ecotoxicity of products used in oil industry are of great relevance and corrosion inhibitor could not be an exception. In earlier reports, chitosan and some derivatives were evaluated as corrosion inhibitors at acid pH, mainly due to polymer solubility. An eco-friendly corrosion inhibitor with water solubility in all pH range should be ideal, as well as that could act under the high salinity of oil field environment. Thus, herein is presented the performance of a water-soluble carboxymethylchitosan (CMC) as corrosion inhibitor in presence of chlorides (3.5% NaCl) in 1020 carbon steel, without any addition of acid or base. CMC showed good properties as corrosion inhibitor in media containing Cl-, and behaved as an anodic inhibitor. CMC exhibited inhibitory efficiency of about 80% and 67%, according to Tafel curve and electrochemical impedance, respectively, which was attributed to chemisorption mechanism (ΔGads ≈ -45 kJ/mol).