Mechanical Properties and Flow Behavior of Polymers for Enhanced Oil Recovery

The mechanical properties and flow behavior in porous media of three different polymer systems including a hydrophobically modified acrylamide-based copolymer (HMSPAM), a partially hydrolyzed polyacrylamide (HPAM), and a polysaccharide (xanthan gum) were evaluated to establish their functional differentiation as mobility control agents in enhanced oil recovery (EOR). The rheological properties of the polymers were described by the power-law model to investigate their non-Newtonian behavior. The first normal stress difference (N₁) and Weissenberg number (W_e) were also used to compare their elastic properties. The experimental results showed that, at comparable shear viscosity, HMSPAM exhibited significant elasticity compared to HPAM and xanthan gum. Shear resistance tests indicated that all of the polymers experienced an extra stress when converging into a capillary tube due to the “entrance effect.” Xanthan gum was the most mechanically stable polymer. Moreover, HMSPAM showed the superior reformability which was quantified by the regained viscosity with relaxation time. This could be explained by the rapid re-association of the hydrophobic interactions. Sandpack flood tests indicated that HMSPAM rendered extremely high mobility control ability during polymer flooding suggesting its potential in EOR. However, this polymer also experienced significant retention within the porous media (potential injectivity and plugging problems), which may be attributed to the formation of bulky associative polymer networks. In this work, UV spectrometry was employed to monitor the concentration of the produced polymer solutions and quantify the polymer retention within porous media. This analytical approach offers great reliability and simplicity. It was concluded that the use of a particular polymer system depends on the oil reservoir conditions and the target EOR application.     

Study on Steady Shear Rheological Behavior of Concentrated Suspensions of Sulfonated Polyacrylamide/Na-Montmorillonite Nanoparticles

Concentrated suspensions of sulfonated polyacrylamide (SPA)/Na⁺-montmorillonite (Na-MMT) were prepared and their stability and steady shear rheological properties were described as a function of nanoparticle and polymer concentration and temperature. The results showed that the Na-MMT nanoparticles suspensions were stable in the absence and presence of SPA and no sedimentation was seen. The Z-average particle sizes for the SPA/Na-MMT suspensions increased in the presence of SPA. Rheological investigations showed that the SPA solutions and SPA/Na-MMT suspensions displayed non-Newtonian behavior in almost the whole range of shear rate. All the suspensions exhibited a shear-thinning flow character as shear rate increased. The flow curves indicated the shear viscosity and stress of the samples were decreased with increasing nanoparticles concentration up to 1.5 wt%, but for Na-MMT loading greater than 1.5 wt% there was an increase in shear viscosity and stress of the suspensions. Increasing of SPA concentration had more effect on increasing the rheological properties of SPA/Na-MMT suspensions than increasing of nanoclay content. Shear viscosity and stress of the suspensions increased with increasing SPA concentration and decreased with increasing temperature from 50°C to 70°C.     

Flow Characteristics of Partially Hydrolyzed Polyacrylamides during Converging into a Capillary

Partially hydrolyzed polyacrylamides (HPAMs) are the most widely used polymers in enhanced oil recovery (EOR). This study presents capillary flow measurements of three different molecular weight HPAMs in synthetic brine. Polymer solutions having similar viscoelasticity were forced to flow through a 0.23 mm (radius) stainless steel capillary to investigate their flow characteristics including mobility reduction (apparent viscosity) and mechanical stability, represented by the extent of mechanical degradation (DR). The results indicated that the apparent viscosity of the polymer solutions markedly dropped with increasing flow rate until 5 mL/min, corresponding to the shear rate of 8,730s^?1; after that a slight viscosity decrease was observed. The high-molecular-weight HPAMs (6.5 and 8.0 × 10⁶ g/mol) began to have slightly greater apparent viscosity than the low-molecular-weight HPAM (1.0×10⁶ g/mol) above the shear rate of 26,180 s^?1; this might result from the occurrence of the coil-stretch transition. All the HPAMs experienced very similar percentages of mechanical degradation (10%) at shear rates between 1750 and 8730 s^?1; however, above 8730s^?1 the high-molecular-weight HPAMs exhibited a steep increase in mechanical degradation (DR). On the other hand, in the case of the low-molecular-weight HPAM, the DR curve almost leveled off at 12%. Therefore, low-molecular-weight HPAMs are generally suggested for EOR applications. These results, we suggested, should be useful to improve the efficiency of polymer EOR by minimizing mechanical degradation.     

Steady Shear Rheological Behavior,Mechanical Properties,and Morphology of the Polypropylene/Carbon Nanotube Nanocomposites

Nanocomposites based on polypropylene (PP) and multiwall carbon nanotubes (MWNT) have been prepared through melt blending. Scanning electron microscopy (SEM) observations indicate that nanotubes were dispersed almost homogeneously throughout the matrix; however, some aggregates were also observed at high nanotubes loading. Rheological studies showed that at low shear rates, there is an increase in steady shear viscosity and shear stress of samples with increasing of nanotubes concentration. However, at high shear rates nanocomposites behave like pure PP. The activation energy of flow showed an increasing trend and has a maximum at 1wt% MWNT content. It was found that incorporation of nanotubes causes a remarkable decrease in surface and volume resistivity values of the polymeric matrix. The presence of CNTs improved the tensile and flexural properties of the polymeric matrix.     

Viscosity of Collagen Solutions: Influence of Concentration,Temperature, Adsorption,and Role of Intermolecular Interactions

An investigation of the influences of the adsorption, electrolyte, shear rate, and temperature on the viscometric behavior of collagen solutions was performed using a photoelectric viscometer. The experimental results showed an abnormal behavior of the reduced viscosity (η_sp/C) of dilute collagen solutions measured by a viscometer with or without a hydrophobic surface treatment; the reduced viscosity increased with decreasing concentration. This phenomenon can be completely eliminated by increasing the concentration of an added salt. It indicated that the abnormal viscosity resulted from a long-ranged, inter-molecular electrostatic force. The reduced viscosity decreased as the shear rate increased. The shear-thinning cavitation phenomenon resulted from the high aspect ratio of the collagen molecules. The reduced viscosity of the collagen solutions increased with an increase in temperature, which was due to the association of collagen molecules at high temperature.     

A Rheological Study of Xanthan Polymer for Enhanced Oil Recovery

This study explored the potential application of xanthan gum as a polymer-flooding agent for oil recovery applications in a specific Devonian oil field. Rheological measurements using oscillatory and steady shear were carried out to examine the change in shear viscosity when the polymer was applied under reservoir conditions. The xanthan rheological properties were described by the Herschel–Bulkley and Ostwald models to characterize its non-Newtonian behavior. As expected, the results showed that higher xanthan concentrations raised the polymer viscosity and increased the degree of shear thinning. Addition of alkalis caused the viscosity of the xanthan solutions to decrease, but they maintained their shear-thinning properties. Polymer solutions in typical oil field brine increased in viscosity by ca. 400% for 720 hours storage time. On the other hand, as expected, the solutions lost their viscosity gradually with increasing temperature. However, at reservoir temperature (68°C), the polymer solutions kept more than 60% of their initial viscosity. In oscillatory deformation tests it was observed that all the measured viscoelastic properties were influenced by temperature and confirmed that xanthan solution behaved as a weak-gel. An order-disorder transition exists within the xanthan-brine solutions which responds to changes in solution concentration, temperature and alkalis.     

Gelation and Swelling Behavior of Semi-Interpenetrating Polymer Network Hydrogels Based on Polyacrylamide and Poly(vinyl alcohol)

Novel semi-Interpenetrating Polymer Network (semi-IPN) hydrogels based on partially Hydrolyzed Polyacrylamide (HPAM) and Poly(Vinyl Alcohol) (PVA) were prepared by solution crosslinking using chromium triacetate. Effects of PVA content on the gelation process and swelling behavior in tap water and different electrolyte solutions were investigated. Study of the gelation behavior using dynamic rheometery showed that the limiting storage modulus of the semi-IPN gels decreased with increasing PVA content. It was also found that increasing the PVA content increases the loss factor, indicating that the viscous properties of this gelling system increase more strongly than the elastic properties. The swelling ratio of the semi-IPN gels in tap water decreased as the concentration of the PVA increased. However, the semi-IPN gels showed lower salt sensitivity factor in synthetic oil reservoir water as compared with HPAM gels. Therefore, they are potentially good candidates for enhanced oil recovery applications.     

Solution Behavior of Hydrophobic Cationic Hydroxyethyl Cellulose

The hydrophobic cationic hydroxyethyl cellulose (HEC-g-DA) was prepared by grafting HEC with various alkyl ammonium chlorides (DA) in order to improve the thickening properties of cationic hydroxyethyl cellulose. The solution behavior of HEC-g-DA was studied, and showed that the apparent viscosity of HEC-g-DA increased with polymer concentration, and there existed a critical association concentration (Cp*). The alkyl chain length of DA had a great influence on Cp*, which decreased with increasing alkyl chain length; however, too long an alkyl chain of DA reduced the water solubility of the polymer, resulting in a slight increase of Cp*. The effect of temperature and electrolyte concentration on the thickening properties of HEC-g-DA was investigated; the value of viscous flow activation energy (E_a) was minimum for the sample of HEC-g-DA16 (glycidyl-N-hexadecyl–N,N-dimethyl-ammonium chloride), indicating the weakest sensitivity of the viscosity to temperature. In the whole range of shear rate investigated, the solutions of HEC-g-DA displayed the shear thinning behavior of a pseudoplastic fluid. The values of viscous index (n) from the Ostwald model simulation decreased with polymer concentration, indicating an improvement of the shear thinning property of the solution, whereas the increase of the consistency coefficient (k) indicated the enhancement of the thickening behavior of the polymer. With increasing polymer concentration, the molecular association of HEC-g-DA16 became strong, and high-shear stress was required to remove the association, while the difference between G′ and G″ became small, indicating that the elasticity of the system was enhanced at high polymer concentration. The amphiphilic structure of the HEC-g-DA16 molecules contributed to the low surface tension of the polymer.     

Morphological Aspects of In-Situ Compatiblized Binary Polymer Blends With Variable Viscosity Ratios of Components

The in-situ compatiblized binary polymer blend polypropylene(PP)/polystyrene(PS)/ anhydrous aluminum chloride(AlCl₃) was selected as a model system of a reactive polymer blend to investigate the effect of viscosity ratio of components at a constant shear rate on the phase morphological behavior in in-situ compatibilized systems. The results showed that the well-known interfacial compatibilization effect was related to variations of viscosity ratios of components in the reactive PP/PS blends with different contents of AlCl₃ catalyst. The phase morphology evolution of the in-situ compatiblized reactive blend was determined by both the interfacial compatibilization and the variation of the viscosity ratio of components under the fixed mixing conditions, which showed characteristics obviously different from and much more complex than those in binary polymer blends generally compatiblized by added compatiblizers. The results implied that the variation of the viscosity ratio of components should be checked carefully and taken into account if necessary, when the phase morphology of binary polymer blends is investigated, especially in complex in-situ compatiblized reactive polymer blends.     

Shear Effect on Morphology of Poly(Butylene Terephthalate)/Poly(Styrene‐co‐Acrylonitrile) Blends

Abstract

The shear flow effect on the morphology of poly(butylene terephthalate)(PBT)/poly(styrene‐co‐acrylonitrile)(SAN) was studied by a parallel plate type shear apparatus. In PBT/SAN = 20/80 blend, particle size of dispersed domains was governed by both break‐up and coalescence processes, and it was much affected by shear rate. The minimum particle size was observed at a certain shear rate. This phenomenon can be explained by the shear matching effect of PBT and SAN; that is, the viscosity ratio of PBT to SAN changed with shear rate and the finest morphology was obtained at the appropriate viscosity ratio. Similar behavior was also observed for PBT/SAN = 70/30 (PBT was the matrix), even though the particle size was larger than that of PBT/SAN = 20/80. For PBT/SAN = 10/90 blend, the sample showed a complicated appearance during shearing. A translucent region correlated to the fine morphology was observed more than twice with increasing shear rate. This phenomenon could not be explained by the viscosity matching effect only. It was affected by small changes in the balance of breaking‐up and coalescence effects.     

Corresponding states principle for newtonian viscosities-temperature effects

In the first part of the paper a superposition method for the polymer solution zero shear rate viscosity η_o as a function of concentration c is reviewed. The method was successful in numerous systems, but it partially failed in four, the worst case being polyisobutene in isooctane, where data were available over the full concentration range and molecular weights (MW) ranged from 900 to 2.5 × 10⁶. It was postulated that the possible cause for this is either MW dependence of T_g which would result in a faster than expected increase in η_o for higher MW samples, or a difference in flow mechanism between the solutions at low and high concentration. In the second part, a new theory for the temperature effect on η_o is proposed. The theory permits linearization of η_o (T) results both for small molecules and for polymeric liquids. In systems where a transition occurs, the linearized plot shows a sharp break. The theory was extended to the concentration dependence of the polymer solution viscosity.

It permits linearization of η_o (c) data, compensates for the MW dependence of T_g, and allows detection of transition points. The theory was tested on solutions of polyisobutene and polydimethyl-siloxane. In both cases, the data were superimposed on a single master curve.     

Flow birefringence,stress optical rule and rheology of four micellar solutions with the same low shear viscosity

The flow birefringence and the rheological properties of four viscoelastic solutions having nearly the same zero shear viscosity and subjected to shear flows are investigated in the linear and non-linear domains. The surfactant used for the samples is the cetyltrimethylammonium chloride in water at the concentration of 100 mmol/l with an organic salt, the sodium salicylate. The low shear viscosity curve versus the salt concentration is non-monotonic and has two maxima separated by a minimum forming four domains in which the salt concentration is chosen. For the two solutions belonging to the inner branch, i.e. between the two maxima, a simple Maxwellian behaviour is observed and shear banding occurs as confirmed by the flow birefringence pictures. Contrary to the results of P. Fisher (1996) where the unstable flow regime is restricted to the first decreasing part of the low shear viscosity curve of a cetylpyridinium chloride solution, we show that shear banding exits in a wider domain of the salt concentration. Received 18 November 2002 / Published online: 1 April 2003 RID="a" ID="a"e-mail: Decruppe@lpli.sciences.univ-metz.fr     

Transport coefficients of hard sphere fluids

New calculations have been made of the self-diffusion coefficient D, the shear viscosity η_s, the bulk viscosity η_b and thermal conductivity λ of the hard sphere fluid, using molecular dynamics (MD) computer simulation. A newly developed hard sphere MD scheme was used to model the hard sphere fluid over a wide range up to the glass transition (～0.57 packing fraction). System sizes of up to 32 000 hard spheres were considered. This set of transport coefficient data was combined with others taken from the literature to test a number of previously proposed analytical formulae for these quantities together with some new ones given here. Only the self-diffusion coefficient showed any substantial N dependence for N < 500 at equilibrium fluid densities (ε 0.494). D increased with N, especially at intermediate densities in the range ε ～ 0.3–0.35. The expression for the packing fraction dependence of D proposed by Speedy, R. J., 1987, Molec. Phys., 62, 509 was shown to fit these data well for N ～ 500 particle systems. We found that the packing fraction ε dependence of the two viscosities and thermal conductivity, generically denoted by X, were represented well by the simple formula X/X ₀ = 1/[1 ? (ε/ε₁)]^m within the equilibrium fluid range 0 > ε > 0.493. This formula has two disposable parameters, ε and m, and X ₀ is the value of the property X in the limit of zero density. This expression has the same form as the Krieger-Dougherty formula (Kreiger, I. M., 1972, Adv. Colloid. Interface Sci., 3, 111) which is used widely in the colloid literature to represent the packing fraction dependence of the Newtonian shear viscosity of monodisperse colloidal near-hard spheres. Of course, in the present case, X _o was the dilute gas transport coefficient of the pure liquid rather than the solvent viscosity. It was not possible to fit the transport coefficient normalized by their Enskog values with such a simple expression because these ratios are typically of order unity until quite high packing fractions and then diverge rapidly at higher values over a relatively narrow density range. At the maximum equilibrium fluid packing fraction ε = 0.494 for both the hard sphere fluid and the corresponding colloidal case a very similar value was found for η_s/η_o ?30–40, suggesting that the ‘crowding’ effects and their consequences for the dynamics in this region of the phase diagram in the two types of liquid have much in common. For the hard sphere by MD, D_o/D ～ 11 at the same packing fraction, possibly indicating the contribution from ‘hydrodynamic enhancement’ of this transport coefficient, which is largely absent for the shear viscosity. Interestingly the comparable ratio for hard sphere colloids is the same.     

Mechanical Properties and Rheological Behavior of Dynamically Vulcanized Trans-Polyisoprene/Polypropylene Blends

The degree of dynamic vulcanization, mechanical properties, rheological behavior, and the ageing-resistant performance of thermoplastic vulcanizates (TPVs) based on Trans 1,4-polyisoprene/polypropylene (TPI/PP) blends with the blend ratios of 70/30, 60/40, and 50/50 were investigated. The results showed that TPI fully dynamically vulcanized in the Haake mixer chamber when mixed with PP, and the specimen with the blend ratio 70/30, for the same sulfur content in all samples, had the lowest cross-linking degree of the TPI phase. The shear viscosity of TPI/PP-TPVs dropped as the shear rate increased and the specimen with the blend ratio 70/30 had a relatively greater shear viscosity in the region of shear rates less than 1000 s^?1. With the antiageing agent Vulkanox 4020 NA (Bayer) added, all the TPI/PP-TPVs showed good ageing characteristics, and the specimen with the blend ratio 70/30 possessed the best mechanical properties.     

Influence of High-Density Polyethylene and Nano-Calcium Carbonate of Various Content Ratios on the Crystallization of Polypropylene

The influence of high-density polyethylene (HDPE) and nano-CaCO₃ of various content ratios on the crystallization of polypropylene (PP) was investigated by differential scanning calorimetry, dynamic rheology, wide angle X-ray diffraction (WAXD), and Izod impact strength measurements. The results showed that HDPE and PP were phase separated in their blends and the additive CaCO₃ filler mainly dispersed in the PP phase, acting as a nucleation agent to promote the crystallization of PP. For the samples HDPE/ nano-CaCO₃ 30/0 and 25/5, the β crystals content was much higher than the other samples. The reason is that the viscosity difference between HDPE and PP led to a velocity difference, which could induce shear stress at the interfaces of HDPE and PP during injection molding. The intensive shear stress at their phase interfaces is advantageous for orientation of the chains, inducing the formation of β crystals. However, with the increment of CaCO₃ content, there were dual effects of CaCO₃ on the crystallization of PP: at low CaCO₃ content, it would hamper the orientation of PP chains, thus leading to a decrease of β crystals; at high CaCO₃ content, it would induce β crystals by itself.     

High Pressure High Temperature Dynamic Rheometry of Sulfonated Polyacrylamide Solutions in Electrolyte Media as Used for Oil Recovery Applications

Sulfonated polyacrylamide (SPAA) solutions were prepared and the effects of pressure, polymer concentration, and water temperature, pH and salinity on their rheological behavior were investigated using a concentric cylinder dynamic rheometer equipped with a high pressure cell. According to the rheological flow curves the shear stress of SPAA solutions increased less than in proportion to their shear rates; that is, a shear thinning effect occurred. For polymer solutions containing 15,000 ppm of SPAA, shear viscosity, and stress were nearly insensitive to pressure. However, the shear viscosity and stress of SPAA solutions were affected by temperature and this effect was more evident at lower pressure. The flow curves indicated the shear viscosity and stress of the samples increased with increasing SPAA concentration and pH of the water, but were decreased with increasing water salinity and temperature.     

液晶N相→SA相转变点附近的反常粘滞系数

本文由粘滞系数的时间关联函数表达式,得到了实验观察到的现象:在液晶N相→S_A相转变点附近(T→T_(sA)),体粘滞系数的反常发散比切变粘滞系数反常发散要大得多。说明了Brochard等人的理论中,不能解释此实验的原因。 关键词：     

Synergic effects of ultrasound and ionic liquids on fluconazole emulsion

The aim of this work was to evaluate the influence of US on the properties of the fluconazole emulsions prepared using imidazolium-based ILs ([C_n C₁im]Br). The effects of the preparation method (mechanical stirring or US), US amplitude, alkyl chain length (of [C₁₂C₁im]Br or [C₁₆C₁im]Br), and IL concentration on the physicochemical properties were evaluated. Properties such as droplet size, span index, morphology, viscosity encapsulation efficiency, and drug release profile were determined. The results showed that US-prepared emulsions had a smaller droplet size and smaller polydispersity (Span) than those prepared by mechanical stirring. Additionally, the results showed that emulsions prepared with [C₁₆C₁im]Br and US had spherical shapes and increased stability compared to emulsions prepared by MS, and also depended on the IL concentration. The emulsion prepared by US at 40% amplitude had increased encapsulation efficiency. US provided a decrease in the viscosity of emulsions containing [C₁₂C₁im]Br; however, in general, all emulsions had viscosity close to that of water. Emulsions containing [C₁₆C₁im]Br had the lowest viscosities of all the emulsions. The emulsions containing the IL [C₁₆C₁im]Br had more controlled release and a lower cumulative percentage of drug release. The IL concentration required to prepare these emulsions was lower than the amount of conventional surfactant required, which highlights the potential synergic effects of ILs and US in preparing emulsions of hydrophobic drugs.     

Optimized atomistic force fields for aqueous solutions of Magnesium and Calcium Chloride: Analysis,achievements and limitations

Molecular simulations are an important tool in the study of aqueous salt solutions. To predict the physical properties accurately and reliably, the molecular models must be tailored to reproduce experimental data. In this work, a combination of recent global and local optimization tools is used to derive force fields for MgCl₂ (aq) and CaCl₂ (aq). The molecular models for the ions are based on a Lennard-Jones (LJ) potential with a superimposed point charge. The LJ parameters are adjusted to reproduce the bulk density and shear viscosity of the different solutions at 1 bar and temperatures of 293.15, 303.15, and 318.15 K. It is shown that the σ-value of chloride consistently has the strongest influence on the system properties. The optimized force field for MgCl₂ (aq) provides both properties in good agreement with the experimental data over a wide range of salt concentrations. For CaCl₂ (aq), a compromise was made between the bulk density and shear viscosity, since reproducing the two properties requires two different choices of the LJ parameters. This is demonstrated by studying metamodels of the simulated data, which are generated to visualize the correlation between the parameters and observables by using projection plots. Consequently, in order to derive a transferable force field, an error of ～3% on the bulk density has to be tolerated to yield the shear viscosity in satisfactory agreement with experimental data.     

Ultrasound-assisted extraction of polysaccharides from Rhododendron aganniphum: Antioxidant activity and rheological properties

In this study, we aimed to optimize the extraction of polysaccharides from the leaves of Rhododendron aganniphum and investigate its rheological properties and antioxidant activity. After optimizing the operating parameters using a Box-Behnken design (BBD), the results showed that the optimal ultrasound-assisted extraction conditions were as follows: extraction temperature, 55 °C; liquid-solid ratio, 25:1; extraction time, 2.2 h; and ultrasound treatment power, 200 W. The optimized experimental yield of polysaccharides by ultrasound-assisted extraction (PUAE) was 9.428%, higher than that obtained by hot water extraction (PHWE) for 12 h at the same liquid-solid ratio and extraction temperature. In the in vitro antioxidant activity tests, PUAE had higher positive radical scavenging activity for hydroxyl, superoxide and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radicals than PHWE. However, PUAE and PHWE solutions had similar intermolecular interactions in the steady-shear flow and dynamic viscoelasticity tests, resulting in similar macroscopic behaviour. With respect to the apparent viscosity, storage modulus (G′) and loss modulus (G″) of PUAE were lower at the same shear rate or angular frequency. All PUAE solutions exhibited non-Newtonian shear-thinning pseudoplastic behaviour that was accurately described by the Carreau model but was better fit by the power-law model at high shear rates (≥1/s), which demonstrated that the variation in the apparent viscosity dependence was greater at higher concentrations and shear rates. The G′ and G″ of the solutions increased as the experimental frequency increased from 0.05 to 500 rad/s under all experimental concentrations, and the modulus crossover point decreased gradually with increasing PUAE concentration. The above results demonstrated that the ultrasound-assisted extraction methods gave a higher yield of polysaccharides from the leaves of R. aganniphum with a shorter extraction time than the hot water extraction method, which could affect the apparent viscosity and dynamic viscoelasticity. PUAE presented good radical scavenging activity for DPPH, superoxide and hydroxyl radicals in vitro and could be used as a natural antioxidant in the food and medical industries.