Search Results (15)

Water injection is the most widely used secondary recovery method, but its low viscosity limits sweep efficiency in heterogeneous carbonate reservoirs, especially when displacing heavy crude oils. Polymer flooding overcomes this by increasing the viscosity of the injected fluid and improving the mobility ratio. In this work, we compare three biopolymers (i.e., Xanthan Gum, Scleroglucan, and Guar Gum) using a core flood test on Indiana Limestone with 16–19% porosity and 180–220 mD permeability at 60 °C and 30,905 mg/L of salinity. We injected solutions at 100–1500 ppm and 0.5–6 cm³/min to measure the Resistance Factor (RF), Residual Resistance Factor (RRF), in situ viscosity, and relative injectivity. All polymers behaved as pseudoplastic fluids with no shear thickening. The RF rose from ~1.1 in the dilute regime to 5–16 in the semi-dilute regime, and the RRF spanned 1.2–5.8, indicating moderate, reversible permeability impairment. In-site viscosity reached up to eight times that of brine, while relative injectivity remained 0.5. Xanthan Gum delivered the highest viscosity boost and strongest shear thinning, Scleroglucan offered a balance of stable viscosity and a moderate RF, and Guar Gum gave predictable but lower viscosity enhancement. These results establish practical guidelines for selecting polymer types, concentration, and flow rate in reservoir-condition polymer flood designs. Full article

The viscosity and viscoelasticity of polyelectrolyte solutions with a single electrostatic interaction have been carefully studied experimentally and theoretically. Despite some theoretical models describe experimental results well, the influence of multiple interactions (electrostatic and hydrophobic) on rheological scaling is not yet fully resolved. Herein, we systematically study the microstructures and rheological properties of short-side-chain perfluorosulfonic acid (S-PFSA), the most promising candidate of a proton exchange membrane composed of a hydrophobic backbone with hydrophilic side-chains, in water/2-propanol. Small-angle X-ray scattering confirms that semiflexible S-PFSA colloidal particles with a length of ~38 nm and a diameter of 1–1.3 nm are formed, and the concentration dependence of the correlation length (ξ) obeys the power law ξ~c^−0.5 consistent with the prediction of Dobrynin et al. By combining macrorheology with diffusing wave spectroscopy microrheology, the semidilute unentangled, semidilute entangled, and concentrated regimes corresponding to the scaling relationships η_sp~c^0.5, η_sp~c^1.5, and η_sp~c^4.1 are determined. The linear viscoelasticity indicates that the entanglement concentration (c_e) obtained from the dependence of η_sp on the polymer concentration is underestimated owing to hydrophobic interaction. The true entanglement concentration (c_te) is obtained by extrapolating the plateau modulus (G_e) to the terminal modulus (G_t). Furthermore, G_e and the plateau width, τ_r/τ_e (τ_r and τ_e denote reptation time and Rouse time), scale as G_e~c^2.4 and τ_r/τ_e~c^4.2, suggesting that S-PFSA dispersions behave like neutral polymer solutions in the concentrated regime. This work provides mechanistic insight into the rheological behavior of an S-PFSA dispersion, enabling quantitative control over the flow properties in the process of solution coating. Full article

Nonconventional luminescent materials (NLMs) which do not contain traditional aromatic chromophores are of great interest due to their unique chemical structures, optical properties, and their potential applications in various areas, such as cellular imaging and chemical sensing. However, most reported NLMs show weak or no emission in dilute solutions, which severely limits their applications. In this work, dynamic hydrogen bonds were utilized to design NLMs with efficient emission in dilute solutions. To further validate the results, polymers P1 and P2 were successfully prepared and investigated. It was found that the luminescence quantum efficiency of P1 and P2 at a concentration of 0.1 mg/mL in water solution was 8.9 and 0.6%, respectively. The high efficiency can be attributed to the fact that polymer P1 has more intra- or intermolecular dynamic hydrogen bonds and other short interactions than P2 in dilute solutions, allowing P1 to achieve the through-space conjugation effect to increase the degree of system conjugation, restrict molecular motion, and decrease nonradiative transitions, which can effectively improve luminescence. In addition, polymer P2 exhibits the characteristics of clustering-triggered emission, excitation wavelength-dependent and concentration-dependent fluorescence properties, excellent photobleaching resistance, low cytotoxicity, and selective recognition of Fe³⁺. The present study investigates the manipulation of luminescence properties of NLMs in dilute solutions through the modulation of dynamic hydrogen bonds. This approach can serve as a semi-empirical technique for designing and building innovative NLMs in the times ahead. Full article

Heat-resistant polymers with an intense, visible photoluminescence (PL) functionality are presented. A polybenzoxazole (PBO) containing hexafluoroisopropylidene (HFIP) side groups exhibited an intense purple PL with a quantum yield, Φ_PL, of 0.22 (22%), owing to the effectively disturbed concentration quenching (CQ) in the fluorophore units by the bulky HFIP side groups. The chain ends of a wholly cycloaliphatic polyimide (PI), derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and 4,4′-methylenebis(cyclohexylamine) (MBCHA), were modified with conjugated monoamines. The PI derived from 2,3,6,7-naphthalenetetracarboxylic dianhydride (2,3,6,7-NTDA) and MBCHA exhibited a very high glass transition temperature (T_g = 376 °C) and purple fluorescence from the S₁(π,π*) state. However, its Φ_PL value was lower than expected. A pronounced effect of fluorophore dilution using CBDA on the PL enhancement was observed. This is closely related to the planar structure of the 2,3,6,7-NTDA-based diimide units. By contrast, the counterpart using an 2,3,6,7-NTDA isomer, 1,4,5,8-NTDA, was virtually non-fluorescent, despite its sufficient dilution using CBDA. The PI film obtained using 3,3″,4,4″-p-terphenyltetracarboxylic dianhydride (TPDA) with a non-coplanar structure and MBCHA exhibited an intense blue fluorescence spectrum (Φ_PL = 0.26) peaking at 434 nm. The dilution approach using CBDA enhanced its fluorescence up to a high Φ_PL value of 0.41. Even when TPDA was combined with an aromatic diamine, 2,2′-bis(trifluoromethyl)benzidine (TFMB), the intense blue fluorescence was observed without charge-transfer fluorescence. A semi-cycloaliphatic PI derived from TFMB and a novel cycloaliphatic tetracarboxylic dianhydride, which was obtained from a hydrogenated trimellitic anhydride derivative and 4,4′-biphenol, was used as another host polymer for 9,10-bis(4-aminophenyl)anthracene (BAPA). The BAPA-incorporating PI film resulted in a significant PL enhancement with a considerably high Φ_PL of 0.48. This PI film also had a relatively high T_g (265 °C). A reactive dye, N,N′-bis[4-(4-amino-3-methylbenzyl)-2-methylphenyl]-3,4,9,10-perylenetetracarboxydiimide, was harnessed as a fluorescence probe to explore transamidation between polyimide precursors in solution. Full article

Films formed by dip coating brass wires with dilute and semi-dilute solutions of polyvinyl butyral in benzyl alcohol were studied in their liquid and solid states. While dilute and semi-dilute solutions behaved as Maxwell viscoelastic fluids, the thickness of the liquid films followed the Landau-Levich-Derjaguin prediction for Newtonian fluids. At a very slow rate of coating, the film thickness was difficult to evaluate. Therefore, the dynamic contact angle was studied in detail. We discovered that polymer additives preserve the advancing contact angle at its static value while the receding contact angle follows the Cox–Voinov theory. In contrast, the thickness of solid films does not correlate with the Landau-Levich-Derjaguin predictions. Only solutions of high-molecular-weight polymers form smooth solid films. Solutions of low-molecular-weight polymers may form either solid films with an inhomogeneous roughness or solid polymer domains separated by the dry substrate. In technological applications, very dilute polymer solutions of high-molecular-weight polymers can be used to avoid inhomogeneities in solid films. These solutions form smooth solid films, and the film thickness can be controlled by the experimental coating conditions. Full article

Application of polymer-flooding systems in secondary and tertiary oil recovery represents a real challenge for oil industry. In this work, our main objective is to explore possibilities of making use of xanthan-g-polyacrylamide for polymer flooding in a particular Devonian oilfield of medium salinity. The graft polymer was synthesized by using microwave-assisted graft copolymerization reaction of acrylamide on xanthan. The synthesized copolymer with optimized grafting parameters has been characterized by Infrared Spectroscopy and Thermal Analysis (DSC). Rheological analysis by steady shear and oscillatory flow experiments have been subsequently performed for xanthan and grafted xanthan under reservoir conditions. In steady shear, as expected the grafted polymer solutions flow as shear-thinning materials and apparent viscosity showed good fits with Cross’s model. The viscosity losses due to salinity or temperature are more controlled for the grafted xanthan compared to pristine xanthan. When the grafted polymer concentration is increased to 2000 ppm the losses were halved. In oscillatory shear, the copolymer solutions followed a global behavior of semi-dilute entangled systems; furthermore, all dynamic properties were influenced by the brine salinity. Compared to xanthan, the elastic properties of xanthan-g-polyacrylamide solutions have been significantly improved in saline media and the losses in elasticity of grafted polymer solutions are lower. Full article

This paper uses a combination of approaches to evaluate the viscoelastic phenomenon in high-molecular-weight polymers (24–28 M Daltons) used for enhanced oil recovery (EOR) applications. Rheological data were cross-analyzed with single- and two-phase polymer flooding experiments in outcrop cores and micromodels, respectively. First, the impact of semi-harsh conditions (salinity, hardness, and temperature) was evaluated. Second, the impact of polymer degradation (sand face flow), focusing on the viscoelastic properties, was investigated. Finally, polymer viscoelastic properties were characterized, proposing a threefold rheological approach of rotational, oscillatory, and elongational behavior. Data from the rheological approaches were cross-analyzed with core flooding experiments and performed at a room temperature of 22 °C and at a higher temperature of 55 °C. The change in polymer viscoelastic properties were analyzed by investigating the effluents from core flooding experiments. Oil recovery experiments in micromodel helped our understanding of whether salinity or hardness has a dominating impact on in situ viscoelastic polymer response. These approaches were used to study the impact of mechanical degradation on polymer viscoelasticity. The brines showed notable loss in polymer viscoelastic properties, specifically with the hard brine and at higher temperature. However, the same polymer solution diluted in deionized water exhibited stronger viscoelastic properties. Multiple flow-behaviors, such as Newtonian, shear thinning, and thickening dominated flow, were confirmed through pressure drop analysis against interstitial velocity as already reported by other peer researchers. Turbulence-dominated excessive pressure drop in porous media was calculated by comparing core flood pressure drop data against pressure data in extensional viscometer–rheometer on a chip (eVROC^®). In addition, a significant reduction in elastic-dominated flow was confirmed through the mechanical degradation that happened during core flood experiments, using various approaches. Finally, reservoir harsh conditions (high temperature, hardness, and salinity) resulted in a significant reduction in polymer viscoelastic behavior for all approaches. Full article

Droplet microfluidics involving non-Newtonian fluids is of great importance in both fundamental mechanisms and practical applications. In the present study, breakup dynamics in droplet generation of semi-dilute polymer solutions in a microfluidic flow-focusing device were experimentally investigated. We found that the filament thinning experiences a transition from a flow-driven to a capillary-driven regime, analogous to that of purely elastic fluids, while the highly elevated viscosity and complex network structures in the semi-dilute polymer solutions induce the breakup stages with a smaller power-law exponent and extensional relaxation time. It is elucidated that the elevated viscosity of the semi-dilute solution decelerates filament thinning in the flow-driven regime and the incomplete stretch of polymer molecules results in the smaller extensional relaxation time in the capillary-driven regime. These results extend the understanding of breakup dynamics in droplet generation of non-Newtonian fluids and provide guidance for microfluidic synthesis applications involving dense polymeric fluids. Full article

The behavior of a polymer in a passive crowded medium or in a very dilute active bath has been well studied, while a polymer immersed in an environment featured by both crowding and activity remains an open problem. In this paper, a systematic Langevin simulation is performed to investigate the conformational change of a semi-flexible chain in a concentrated solution packed with spherical active crowders. A very novel shrinkage-to-swelling transition is observed for a polymer with small rigidity. The underlying phase diagram is constructed in the parameter space of active force and crowder size. Moreover, the variation of the polymer gyration radius demonstrates a non-monotonic dependence on the dynamical persistence length of the active particle. Lastly, the activity-crowding coupling effect in different crowder size baths is clarified. In the case of small crowders, activity strengthens the crowding-induced shrinkage to the chain. As crowder size increases, activity turns out to be a contrasting factor to crowding, resulting in a competitive shrinkage and swelling. In the large size situation, the swelling effect arising from activity eventually becomes dominant. The present study provides a deeper understanding of the unusual behavior of a semi-flexible polymer in an active and crowded medium, associated with the nontrivial activity-crowding coupling and the cooperative crowder size effect. Full article

We study shear banding in a planar 4:1 contraction flow using our recently developed two-fluid model for semidilute entangled polymer solutions derived from the generalized bracket approach of nonequilibrium thermodynamics. In our model, the differential velocity between the constituents of the solution allows for coupling between the viscoelastic stress and the polymer concentration. Stress-induced migration is assumed to be the triggering mechanism of shear banding. To solve the benchmark problem, we used the OpenFOAM software package with the viscoelastic solver RheoTool v.2.0. The convection terms are discretized using the high-resolution scheme CUBISTA, and the governing equations are solved using the SIMPLEC algorithm. To enter into the shear banding regime, the uniform velocity at the inlet was gradually increased. The velocity increases after the contraction due to the mass conservation; therefore, shear banding is first observed at the downstream. While the velocity profile in the upstream channel is still parabolic, the corresponding profile changes to plug-like after the contraction. In agreement with experimental data, we found that shear banding competes with flow recirculation. Finally, the profile of the polymer concentration shows a peak in the shear banding regime, which is closer to the center of the channel for larger inlet velocities. Nevertheless, the increase in the polymer concentration in the region of flow recirculation was significantly larger for the inlet velocities studied in this work. With our two-fluid finite-volume solver, localized shear bands in industrial applications can be simulated. Full article

The critical overlap concentration C* is an important concept in polymer solutions and is defined as the boundary between dilute and semidilute regimes. In this study, the chain conformational changes of polystyrene (PS) with both high (M_n = 200,000 Da) and low (M_n = 13,000 Da) molecular weights in cis-decalin were compared by intrachain fluorescence resonance energy transfer (FRET). The random labeling of donor and acceptor chromophores strategy was employed for long PS chains, whereas chain-end labeling was used for short PS chains. By monitoring the spectroscopic intensity ratio between acceptor and donor, the concentration dependence on chain conformation from dilute to semidilute solutions was determined. Both long and short chains exhibit a conformational transition concentration, above which the polymer chains begin to collapse with concentration significantly. Interestingly, for randomly labeled polymer long chains, such concentration is consistent with C* determined from the viscosity result, below which only slight conformational change of polymer chain takes place. However, for the chain-end labeled short chain, the conformational transition concentration takes place earlier than C*, below which no significant polymer conformation change is observed. Full article

The structure and mechanical properties of model polymer networks consisting of alternating tetra-functional poly(ethylene glycol)s (PEGs) and bis-functional linear PEGs were investigated by dynamic light scattering and rheological measurements. The sizes of the correlation blob ( ${\xi }_c$ ) and the elastic blob ( ${\xi }_{el}$ ) were obtained from these measurements and compared to the theoretical mesh size, the geometric blob ( ${\xi }_g$ ), calculated by using the tree-like approximation. By fixing the concentration of tetra-PEGs and tuning the molecular weight of linear-PEGs, we systematically compared these blob sizes in two cases: complete network (Case A) and incomplete network (Case B). The correlation blob, ${\xi }_c$ , obtained by dynamic light scattering (DLS) was found to obey the well-known concentration dependence for polymer solutions in semidilute regime ( ${\xi }_c~{\varphi }^{-3/4}$ ) irrespective of the Cases. On the other hand, the $G^{\prime }$ was strongly dependent on the Cases: For Case A, $G^{\prime }$ was weakly dependent on the molecular weight of linear-PEGs ( $G^{\prime }~M_c{}^{0.69}$ ) while $G^{\prime }$ for Case B was a strong increasing function of $M_c$ ( $G^{\prime }~M_c{}^{1.2}$ ). However, both of them are different from the geometric blob (theoretical mesh) of the gel networks. In addition, interesting relationships between $G^{\prime }$ and ${\xi }_c$ , $G^{\prime }~{\xi }_c$ , $G^{\prime }~{\xi }_C^{-2}$ , were obtained for Cases A and B, respectively. Full article

We present a hierarchical coarse-graining framework for modeling semidilute polymer solutions, based on the wavelet-accelerated Monte Carlo (WAMC) method. This framework forms a hierarchy of resolutions to model polymers at length scales that cannot be reached via atomistic or even standard coarse-grained simulations. Previously, it was applied to simulations examining the structure of individual polymer chains in solution using up to four levels of coarse-graining (Ismail et al., J. Chem. Phys., 2005, 122, 234901 and Ismail et al., J. Chem. Phys., 2005, 122, 234902), recovering the correct scaling behavior in the coarse-grained representation. In the present work, we extend this method to the study of polymer solutions, deriving the bonded and non-bonded potentials between coarse-grained superatoms from the single chain statistics. A universal scaling function is obtained, which does not require recalculation of the potentials as the scale of the system is changed. To model semi-dilute polymer solutions, we assume the intermolecular potential between the coarse-grained beads to be equal to the non-bonded potential, which is a reasonable approximation in the case of semidilute systems. Thus, a minimal input of microscopic data is required for simulating the systems at the mesoscopic scale. We show that coarse-grained polymer solutions can reproduce results obtained from the more detailed atomistic system without a significant loss of accuracy. Full article

Using many-body dissipative particle dynamics (MDPD), polymer solutions with concentrations spanning dilute and semidilute regimes are modeled. The parameterization of MDPD interactions for systems with liquid–vapor coexistence is established by mapping to the mean-field Flory–Huggins theory. The characterization of static and dynamic properties of polymer chains is focused on the effects of hydrodynamic interactions and entanglements. The coil–globule transition of polymer chains in dilute solutions is probed by varying solvent quality and measuring the radius of gyration and end-to-end distance. Both static and dynamic scaling relations for polymer chains in poor, theta, and good solvents are in good agreement with the Zimm theory with hydrodynamic interactions considered. Semidilute solutions with polymer volume fractions up to 0.7 exhibit the screening of excluded volume interactions and subsequent shrinking of polymer coils. Furthermore, entanglements become dominant in the semidilute solutions, which inhibit diffusion and relaxation of chains. Quantitative analysis of topology violation confirms that entanglements are correctly captured in the MDPD simulations. Full article

In this review, we focus on the electrical conductivity of aqueous polyelectrolyte solutions in the light of the dynamic scaling laws, recently proposed by Dobrynin and Rubinstein, to take into account the polymer conformations in different concentration regimes, both in good and poor solvent conditions. This approach allows us to separate contributions due to polymer conformation from those due to the ionic character of the chain, and offers the possibility to extend the validity of the Manning conductivity model to dilute and semidilute regimes. The electrical conductivity in the light of the scaling approach compares reasonably well with the observed values for different polyelectrolytes in aqueous solutions, over an extended concentration range, from the dilute to the semidilute regime. Full article