Associative Polymer Solutions Research Articles

Effects of Hydrophobic Groups Content and Micro-block Length on the Elasticity of Associative Polymer Solution

Effects of Hydrophobic Groups Content and Micro-block Length on the Elasticity of Associative Polymer Solution

Influence of hydrophobe fraction content on the rheological properties of hydrosoluble associative polymers obtained by micellar polymerization

AbstractThe synthesis, characterization and rheological properties in aqueous solutions of water-soluble associative polymers (AP’s) are reported. Polymer chains consisting of water-soluble polyacrylamides, hydrophobically modified with low amounts of N,N-dihexylacrylamide (1, 2, 3 and 4 mol%) were prepared via free radical micellar polymerization. The properties of these polymers, with respect to the concentration of hydrophobic groups, using steady-flow and oscillatory experiments were compared. An increase of relaxation time (TR) and modulus plateau (G0) was observed in all samples studied. Two different regimes can be clearly distinguished: a first unentangled regime where the viscosity increase rate strongly depends on hydrophobic content and a second entangled regime where the viscosity follows a scaling behavior of the polymer concentration with an exponent close to 4.

Effect of distribution of stickers along backbone on temperature-dependent structural properties in associative polymer solutions

Effect of distribution of stickers along the backbone on structural properties in associating polymer solutions is studied using self-consistent field lattice model. Only two inhomogeneous morphologies, i.e., microfluctuation homogenous (MFH) and micelle morphologies, are observed. If the system is cooled, the solvent content within the aggregates decreases. When the spacing of stickers along the backbone is increased the temperature-dependent range of aggregation in MFH morphology and half-width of specific heat peak for homogenous solutions-MFH transition increase, and the symmetry of the peak decreases. However, with increasing spacing of stickers, the above three corresponding quantities related to micelles behave differently. It is demonstrated that the broad nature of the observed transitions can be ascribed to the structural changes which accompany the replacement of solvents in aggregates by polymer, which is consistent with the experimental conclusion. It is found that different effect of spacing of stickers on the two transitions can be interpreted in terms of intrachain and interchain associations.

Concentration dependence of rheological properties of telechelic associative polymer solutions

We consider concentration dependence of rheological properties of associative telechelic polymer solutions. Experimental results for model telechelic polymer solutions show rather strong concentration dependence of rheological properties. For solutions with relatively high concentrations, linear viscoelasticity deviates from the single Maxwell behavior. The concentration dependence of characteristic relaxation time and moduli is different in high- and low-concentration cases. These results suggest that there are two different concentration regimes. We expect that densely connected (well percolated) networks are formed in high-concentration solutions, whereas sparsely connected (weakly percolated) networks are formed in low-concentration solutions. We propose single chain type transient network models to explain experimental results. Our models incorporate the spatial correlation effect of micellar cores and average number of elastically active chains per micellar core (the network functionality). Our models can reproduce nonsingle Maxwellian relaxation and nonlinear rheological behavior such as the shear thickening and thinning. They are qualitatively consistent with experimental results. In our models, the linear rheological behavior is mainly attributable to the difference of network structures (functionalities). The nonlinear rheological behavior is attributable to the nonlinear flow rate dependence of the spatial correlation of micellar core positions.

1108 アルカリ溶解性会合高分子溶液中を特異な形状で上昇する気泡の詳細観察(OS11 非ニュートン流体の流動現象,オーガナイズドセッション)

1108 アルカリ溶解性会合高分子溶液中を特異な形状で上昇する気泡の詳細観察(OS11 非ニュートン流体の流動現象,オーガナイズドセッション)

Size effect on the rheological behavior of nanoparticle suspensions in associating polymer solutions

Associating polymers are hydrophilic long-chain molecules containing a small amount of hydrophobic groups and tend to create bonds between chains by reversible associating interactions. The effects of associating polymer on the steady-shear viscosity and dynamic viscoelasticity are studied for suspensions of silica nanoparticles with diameters of 8, 18, and 25 nm. The silica particles of 8 nm are entrapped in the transient network of associating polymer by reversible adsorption. The enhancement of network results in the high viscosity with a Newtonian flow profile in the limit of zero shear rate. In suspensions of 25 nm silica, the hydrophobes extending from the chains adsorbed onto different particles can form a micelle by association interactions. The multichain bridging gave rise to the shear-thinning flow and high storage modulus at low frequencies. The suspensions of 25 nm silica are characterized as flocculated systems. Because of intermediate curvature, the flexible bridges are formed between silica particles of 18 nm. When the flexible bridges are highly extended within the lifetime in shear fields, the suspensions show shear-thickening flow. The shear-thickening flow can be attributed to the elastic effect of flexible bridges.

Micellar polymerization, characterization, and viscoelasticity of combined thermally insensitive terpolyacrylamides

AbstractPolymer chains consisting of water‐soluble polyacrylamides and N‐isopropylacrylamide (NIPAM), hydrophobically modified with low amounts of N,N‐dialkylacrylamides (N,N‐dioctylacrylamide) have been prepared via free radical micellar polymerization, using a hydrophobic initiator derived from 4,4′‐azobis(4‐cyanopentanoic acid) containing a long linear chain of 16 (C16) carbon atoms. This procedure resulted in polyacrylamides containing hydrophobic groups along the chain as well as at the chain ends. These polymers are named “combined associative polymers” and include within their structure a water‐soluble monomer (acrylamide), a thermosensitive monomer (NIPAM) and a hydrophobic monomer. The polymers were characterized by different techniques, also studying the effect of adding a surfactant anion such as sodium dodecylsulfate. The viscoelastic properties as a function of temperature of these associative polymers were investigated using steady‐flow and oscillatory experiments considering the relaxation time (TR) and the plateau modulus (G0). The effect of concentration of acrylamide and NIPAM on the viscosity of the associative polymer solutions was investigated. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers

Effects of polymer concentration and chain length on aggregation in physically associating polymer solutions

The effects of polymer concentration and chain length on aggregation in associative polymer solutions, are studied using self-consistent field lattice model. Only two inhomogenous morphologies, i.e. microfluctuation homogenous (MFH) and micelle morphologies, are observed in the systems with different chain lengths. The temperatures at which the above two inhomogenous morphologies first appear, which are denoted by T_MFH and T_m, respectively, are dependent on polymer concentration and chain length. The variation of the logarithm of critical MFH concentration with the logarithm of chain length fulfils a linear-fitting relationship with a slope equaling -1. Furthermore, the variation of the average volume fraction of stickers at the micellar core (AVFSM) with polymer concentration and chain length is focused in the system at T_m. It is founded by calculations that the above behavior of AVFSM, is explained in terms of intrachain and interchain associations.

Rheological properties of three different microstructures of water-soluble polymers prepared by solution polymerization

Polymer chains consisting of water-soluble polyacrylamides hydrophobically modified with low amount of hydrophobic groups, with varying hydrophobic chain structure (C16 and Cdi8) and with varying localization of the hydrophobe along the chain (telechelic, multisticker, and combined polymers) were investigated. The viscoelastic behavior of these associative polymers has been studied in semidilute solutions using steady-flow and oscillatory experiments. The effect of type and localization of the hydrophobic groups on the viscosity of the associative polymer solution was investigated. It can be inferred that the high viscosity presented by these polymers, is due largely to G0, which represents the number of associations in the medium at any given time and less so on TR, which represents the duration time of any given association. On all studied samples, TR as well as G0, were affected by the type (di-substituted or linear) and localization of the hydrophobic groups (telechelic, multisticker, or combined).

Necessity and feasibility of improving the residual resistance factor of polymer flooding in heavy oil reservoirs

The efficiency of water flooding in heavy oil reservoirs would be improved by increasing the viscosity of the displacing phase, but the sweep efficiency is not of significance due to the low mobility of the vicious oil. On the basis of mobility control theory, increasing the residual resistance factor not only reduces the water-oil mobility ratio but also decreases the requirement for viscosity enhancement of the polymer solution. The residual resistance factor caused by hydrophobic associating polymer solution is higher than that caused by polyacrylamide solution in brine containing high concentrations of calcium and magnesium ions. The results of numerical simulations show that the polymer flooding efficiency improved by increasing the residual resistance factor is far better than that by only increasing solution viscosity. The recovery factor of heavy oil reservoirs (70 mPa·s) can be enhanced by hydrophobic associating polymer solution of high residual resistance factor (more than 3) and high effective viscosity (24 mPa·s). Therefore, increasing the residual resistance factor of the polymer solution not only decreases the requirement for the viscosity of polymer solution injected into heavy oil reservoirs but also is favorable to enhanced oil recovery during polymer flooding.

Self-consistent field lattice model study on the phase behavior of physically associating polymer solutions

The phase behavior of physically associating polymer solutions, where the polymer chain contains a small fraction of "stickers" regularly placed along the backbone, is studied using self-consistent field lattice model. Two inhomogenous morphologies are observed. One is a microfluctuation homogenous (MFH) morphology, where the mean-field values of the local average concentrations of polymers phi(P)(r) and stickers phi(st)(r) slightly fluctuate around their respective bulk average values phi(P) and phi(st) and regularly from site to site. The other is a randomly close-packed micelle (RCPM) morphology. The structure of the micelle in RCPM morphology is similar to that of the "flower micelle" in the telechelic associative polymer system, where stickers are located in the core of the micelle and nonsticky groups in the corona. When phi(P) approximately or > 0.08, if homogenous associating polymer solutions are cooled, MFH morphology appears, and the system entirely changes from homogenous solutions (HS) to MFH morphology; If the solutions are cooled further, RCPM morphology appears. When phi(P) < 0.08, however, RCPM morphology appears immediately. If phi(P) < 0.53, a macroscopic phase separation, where the polymer rich phase is RCPM morphology, occurs. If phi(P) approximately or > 0.53, only RCPM morphology is found in the system. A peak appears in the temperature-dependent specific-heat curve C(V)(chi) at each transition point. For the HS-MFH transition, C(V)(chi) has an abrupt increase and a slow decrease, whereas for the MFH-RCPM transition, both the increase and the decrease in C(V)(chi) are slow. Furthermore, the system with only MFH morphology may be trapped in one of the two energy basins in a experimental time scale. However, the appearance of RCPM morphology means that the system is trapped in one of a series of "deeper" energy basins, and it is very difficult to jump off this deep basin into the one of MFH morphology or one of the other RCPM morphologies through thermal fluctuations.

Rheology and phase behavior of dense casein micelle dispersions

Casein micelle dispersions have been concentrated through osmotic stress and examined through rheological experiments. In conditions where the casein micelles are separated from each other, i.e., below random-close packing, the dispersions have exactly the flow and dynamic properties of the polydisperse hard-sphere fluid, demonstrating that the micelles interact only through excluded volume effects in this regime. These interactions cause the viscosity and the elastic modulus to increase by three orders of magnitude approaching the concentration of random-close packing estimated at C(max) approximately 178 g/l. Above C(max), the dispersions progressively turn into "gels" (i.e., soft solids) as C increases, with elastic moduli G(') that are nearly frequency independent. In this second regime, the micelles deform and/or deswell as C increases, and the resistance to deformation results from the formation of bonds between micelles combined with the intrinsic mechanical resistance of the micelles. The variation in G(') with C is then very similar to that observed with concentrated emulsions where the resistance to deformation originates from a set of membranes that separate the droplets. As in the case of emulsions, the G(') values at high frequency are also nearly identical to the osmotic pressures required to compress the casein dispersions. The rheology of sodium caseinate dispersions in which the caseins are not structured into micelles is also reported. Such dispersions have the behavior of associative polymer solutions at all the concentrations investigated, further confirming the importance of structure in determining the rheological properties of casein micelle systems.

Droplet formation in quickly stretched liquid filaments

Film splitting necessarily occurs in roll coating and unwanted droplets can occur at high machine speeds when the resulting filaments break up. To study this ‘misting’ problem, an apparatus was designed and built to simulate filament fluid mechanics. The device creates a filament by elongating a liquid bridge and stretches the filament at a high and constant rate of acceleration to mimic coating machine kinematics. Filament breakup was observed using a high-speed video camera and the images were analyzed to yield droplet size and number. With Newtonian fluids, a single droplet formed at Ohnesorge (Oh) numbers less than 0.1 and more and smaller droplets were produced at Oh numbers above 0.1. Associative polymer solutions, prepared as weakly elastic fluids to represent industrial coatings, produced even more and smaller droplets, but only for Ohnesorge numbers in the range of 0.01 to 0.1.

Surfactant-Mediated Modulation of Hydrophobic Interactions in Associative Polymer Solutions Containing Cyclodextrin

The ability of nonionic surfactants to modulate the rheological characteristics of comblike hydrophobically modified associative polymer solutions containing cyclodextrin (CD) is examined. Addition of either alpha- or beta-CD to these polymers results in a marked decrease in solution viscosity and viscoelastic properties because of the encapsulation of the polymer hydrophobes by CD. Nonionic surfactants, introduced to such a system, alter the hydrophobic interactions by competing with the polymer hydrophobes for complexation with the CDs. In this regard, nonylphenol ethoxylates (NPe) with different ethylene oxide chain lengths, which determine the hydrophilic-lipophilic balance (HLB) of the surfactant, are used. Our results reveal that the extent and rate of recovery of zero shear viscosity as well as dynamic moduli are strongly influenced by the type of CD (alpha versus beta) as well as the HLB of the surfactant. For polymer solutions containing alpha-CD, recovery is observed solely in the presence of a low-HLB surfactant (NP6 and NP8). Additionally, in the case of NP6, the viscosity increases monotonically above the original hydrophobically modified alkali-soluble emulsion viscosity with surfactant addition, whereas for that of a higher HLB surfactant (NP15), the viscosity shows no appreciable change. In the case of beta-CD, on the other hand, a complete recovery as well as further enhancement of rheological properties is achieved using the above surfactants. However, the trends of viscosity modulation are dissimilar for different surfactants as we witness a monotonous increase in the case of NP6 while a maximum in viscosity is observed in the presence of NP8 and NP15. The contrasting observations can be explained in terms of varying affinities of alpha- and beta-CDs to bind with NP surfactants and the existence of different micellar structures in solution as governed by surfactant HLB. These results are further confirmed by UV/vis spectroscopy and cloud point measurements.

Simultaneous Acid Diversion and Water Control in Carbonate Reservoirs: A Case History From Saudi Arabia

Summary Matrix acidizing and water control are usually addressed as two separate issues. Associative polymers can be used to simultaneously achieve effective acidizing and water control during a single treatment. A polymer-based treatment was applied in an offshore, perforated vertical well with two sets of perforations in a carbonate reservoir in Saudi Arabia. The acid treatment was needed to restore the productivity of the upper set of perforations and reduce water production from the lower set of perforations. Experimental studies were carried out to investigate the potential use of associative polymers to control water mobility and act as an acid diverter. Coreflood experiments were conducted on reservoir cores at downhole conditions (temperature of 200°F and pressure of 3,500 psi). Extensive laboratory testing showed that associative polymers had no significant effect on the relative permeability to oil. However, the relative permeability to water was significantly reduced. This paper presents a case history where an associative polymer was applied during matrix acid treatment of a damaged well. The treatment included two stages of associative polymer solutions and 20 wt% HCl with additives. Post-stimulation treatment production data showed that oil rate increased 11.18-fold, whereas water rate decreased 1.7-fold, resulting in a reduction in the water cut from 75 to 14 vol%. The production logging tool (PLT) results indicated that the associative polymer was effective in diverting the acid into the oil producing zone. The upper set of perforations was producing most of the fluid, which further confirmed that the associative polymer significantly reduced water production from the lower zone.

Influence of Binary Surfactant Mixtures on the Rheology of Associative Polymer Solutions

Hydrophobically modified alkali-soluble emulsion polymers (HASE) are a class of comblike associative polymers that can impart high viscosities to aqueous solutions. The rheology of HASE solutions can be tuned by the addition of surfactants, such as nonylphenol ethoxylates (NP e), where e is the length of the hydrophilic (ethoxylate) chain. While previous studies have considered individual surfactants, our focus here is on binary surfactant mixtures. We find that equimolar NP4-NP12 mixtures significantly enhance the zero-shear viscosities of HASE solutions as compared to equivalent amounts of NP8, especially at high overall surfactant concentrations. Dynamic rheological measurements suggest that the higher viscosities are due to increases in the lifetime of hydrophobic junctions in the polymer-surfactant network. In contrast to the above results, equimolar NP4-NP8 mixtures are rheologically identical to equivalent solutions of NP6. The differences between the two sets of mixtures are further correlated with cloud point measurements and thereby with the overall hydrophilic-lipophilic balance (HLB) of the surfactant system.

Hierarchical Structures in Amphiphilic Random Copolymer Solutions

Surveying the theory of associating polymer solutions, we have applied the theory to aqueous solution systems of two amphiphilic random copolymers to reveal the hierarchical structure in the solutions. The two random copolymers form uni-core flower micelles comprising of 2 and 8 copolymer chains in dilute solution. However, a part of hydrophobic groups are outside the micellar core and act as binding sites for higher-order aggregation of micelles progressing with increasing the copolymer concentration. The aggregates of flower micelles are bimodal: the major fast relaxation mode component with mw (the weight average aggregation number) of the order of 10 and the minor slow relaxation mode component with mw of order of 10 3 . The viscosity enhancement of the copolymer solutions with increasing the concentration mostly arises from the growth of the major fast mode aggregate.

Equilibrium Capillary Forces with Atomic Force Microscopy

We present measurements of equilibrium forces resulting from capillary condensation. The results give access to the ultralow interfacial tensions between the capillary bridge and the coexisting bulk phase. We demonstrate this with solutions of associative polymers and an aqueous mixture of gelatin and dextran, with interfacial tensions around 10 microN/m. The equilibrium nature of the capillary forces is attributed to the combination of a low interfacial tension and a microscopic confinement geometry, based on nucleation and growth arguments.

Cyclodextrin-hydrophobe complexation in associative polymers.

We develop a new rheology-based method to study the complexation of cyclodextrins with hydrophobes in hydrophobically modified associative polymer solutions. The associative polymers have comb-like structure with hydrophobic groups randomly attached to the polymer backbone. Intermolecular interactions between the hydrophobic groups form a transient network resulting in thickening of the polymer solutions. On addition of cyclodextrins (CD) to the solution, the hydrophobes are encapsulated within the hydrophobic cavity of the cyclodextrins. This reduces viscoelastic properties of the polymer solution by several orders of magnitude. We exploit the existence of a dynamic equilibrium between CD adsorbed to the hydrophobes and free CD in the solution, to develop a rheology-based Langmuir-type adsorption isotherm for estimating the binding constant for molecular complexation. The model is based on the assumption that the amount of CD adsorbed is proportional to the reduction in elastic modulus of the polymer solution due to the encapsulation of the network junctions by CD. The effects of temperature on binding constant are studied to estimate the enthalpy and entropy of complexation. Experiments are conducted with both α-and β-CD at different polymer concentrations and temperatures to estimate the relative strength of binding of the CDs. At a given temperature and a polymer concentration, α-CD has a lower binding constant compared to that of β-CD, indicating higher affinity of α-CD to adsorb onto the hydrophobes. Since α-CDs have a smaller ring size, they can snugly fit to the hydrophobes and the association leads to higher enthalpy and entropy change.

Rheological properties of binary associating polymers

Dynamics of associating polymer solutions above the reversible gelation point are studied. Each macromolecule consists of a soluble backbone (B) and a small fraction of specific strongly interacting groups (A or C stickers) attached to B. A mixture of B–A and B–C associating polymers with 1:1 stoichiometric ratio is considered. As a result of AC association, the polymers reversibly gelate above the overlap concentration. It is shown that (1) the network strands are linear complexes (double chains) of B–A and B–C; (2) “diffusion” of the network junction points is characterized by an apparent activation energy, which can be significantly higher than the energy of one AC bond; (3) most importantly, the randomness of sticker distribution along the chain can significantly slow down the network relaxation leading to a markedly non-Maxwellian viscoelastic behavior. The theory elucidates the most essential features of rheological behavior of polysaccharide associating systems (with A = adamantyl moiety, C = β-cyclodextrin, B = either chitosan or hyaluronan) including similar behavior of G ′ and G ″ in a wide frequency range, strong temperature dependence of the characteristic frequency ω x , and an extremely strong effect of added free stickers (fC) on the dynamics.