Dilute Polymer Solutions Research Articles

Definitions of terms relating to individual macromolecules, macromolecular assemblies, polymer solutions, and amorphous bulk polymers (IUPAC Recommendations 2014)

Abstract This document defines terms relating to the properties of individual macromolecules, macromolecular assemblies, polymer solutions, and amorphous bulk polymers. In the section on polymer solutions and amorphous bulk polymers, general and thermodynamic terms, dilute solutions, phase behaviour, transport properties, scattering methods, and separation methods are considered. The recommendations are a revision and expansion of the IUPAC terminology published in 1989 dealing with individual macromolecules, macromolecular assemblies, and dilute polymer solutions. New terms covering the principal theoretical and experimental developments that have occurred over the intervening years have been introduced. Polyelectrolytes are not included.

Pullback attractors for the model of motion of dilute aqueous polymer solutions

Изучается качественная динамика слабых решений неавтономной модели движения слабо концентрированных водных растворов полимеров на основании теории pullback-аттракторов пространств траекторий. Для рассматриваемой модели устанавливается существование слабых решений, определяется семейство пространств траекторий, вводится понятие траекторного и минимального pullback-аттракторов и доказывается существование этих аттракторов. Библиография: 15 наименований.

0611 曲がり部を有する微小管内流れにおける希薄高分子水溶液の流動特性

0611 曲がり部を有する微小管内流れにおける希薄高分子水溶液の流動特性

The impact of graphene oxide particles on viscosity stabilization for diluted polymer solutions using in enhanced oil recovery at HTHP offshore reservoirs

Over 60% of the original oil in a place (OOIP) is retained in a reservoir after conventional methods have been exploited. Application of enhanced oil recovery (EOR) technology gives an additional chance to get out possibly about 20% more oil from the reservoir. The use of water-soluble polymers improves the water–oil mobility ratio, therefore, the displacement efficiency increased, and leads to enhanced oil recovery. High-molecular-weight polyacrylamide group is widely and successfully used in EOR. But no commercial polymer composition can be used in conditions of high temperature and hardness brine offshore reservoirs yet. To avoid the time consumption and high expense for selection and synthesis of the appropriate-structural polymer for EOR application, we attempt to find additives to enhance the thermal stability of polymer solutions. In this paper, we report the results of improved viscosity stability of diluted polymer/seawater solutions aged at reservoir conditions for 31days by adding graphite-oxide particles (GOs). In the presence of 300 ppm of GOs, the viscosity stability of 1700 ppm acrylamide-based polymer in sea water solution increases from 92 °C to 135 °C. FESEM pictures show good distribution of GOs in polymer network, which is a result of integration of functional groups in GOs surfaces and hydrophilic polymer chains.

Macromolecular motions and hydrodynamic radius variation in dilute solutions under shear action

Understanding the dynamics of single polymer chains and rheological mechanism in dilute polymer solutions under shear stress is essential for fields such as the petroleum and food industries, biomedical materials and drug delivery. Here we present an experimental method for measuring the viscosity of polymer solutions and studying the variation of single polymer chain conformation and the mechanism of molecular motions according to the relationship between the intrinsic viscosity, [η], and the shear rate. Of striking interest is that we find that [η] changing with the shear rate presents three stages which may explain the nature of the viscoelastic performance of polymer solutions and the isolated molecular motions. The significance of these results is the finding of the polymer chain deformation to match the pore throat which has enormous potential implications in drug delivery, genetics and biomedicine © 2014 Society of Chemical Industry.

Clear antismudge unimolecular coatings of diblock copolymers on glass plates.

Two poly[3-(triisopropyloxysilyl)propyl methacrylate]-block-poly[2-(perfluorooctyl)ethyl methacrylate] (PIPSMA-b-PFOEMA) samples and one poly(perfluoropropylene oxide)-block-poly-[3-(triisopropyloxysilyl)propyl methacrylate] (PFPO-b-PIPSMA) sample were synthesized, characterized, and used to coat glass plates. These coatings were formed by evaporating a dilute polymer solution containing HCl, which catalyzed PIPSMA's sol-gel chemistry. Polymer usage was minimized by targeting at diblock copolymer unimolecular (brush) layers that consisted of a sol-gelled grafted PIPSMA layer and an oil- and water-repellant fluorinated surface layer. Investigated is the effect of varying the catalyst amount, polymer amount, as well as block copolymer type and composition on the structure, morphology, and oil- and water-repellency of the coatings. Under optimized conditions, the prepared coatings were optically clear and resistant to writing by a permanent marker. The marker's trace was the faintest on PFPO-b-PIPSMA coatings. In addition, the PFPO-b-PIPSMA coatings were far more wear-resistant than the PIPSMA-b-PFOEMA coatings.

Rheological properties of a vesicle suspension.

The rheological behavior of a dilute suspension of vesicles in linear shear flow at a finite concentration is analytically examined. In the quasispherical limit, two coupled nonlinear equations that describe the vesicle orientation in the flow and its shape evolution were derived [Phys. Rev. Lett. 96, 028104 (2006)PRLTAO0031-900710.1103/PhysRevLett.96.028104] and serve here as a starting point. Of special interest is to provide, for the first time, an exact analytical prediction of the time-dependent effective viscosity η_{eff} and normal stress differences N_{1} and N_{2}. Our results shed light on the effect of the viscosity ratio λ (defined as the inner over the outer fluid viscosities) as the main controlling parameter. It is shown that η_{eff},N_{1}, and N_{2} either tend to a steady state or describe a periodic time-dependent rheological response, previously reported numerically and experimentally. In particular, the shear viscosity minimum and the cusp singularities of η_{eff},N_{1}, and N_{2} at the tumbling threshold are brought to light. We also report on rheology properties for an arbitrary linear flow. We were able to obtain a constitutive law in a closed form relating the stress tensor to the strain rate tensor. It is found that the resulting constitutive markedly contrasts with classical laws known for other complex fluids, such as emulsions, capsule suspensions, and dilute polymer solutions (Oldroyd B model). We highlight the main differences between our law and classical laws.

Cyano azobenzene polymer films: Photo-induced reorientation and birefringence behaviors with linear and circular polarized light

Photo-induced behavior of polymethacrylate polymer, with cyano azobenzene side group, was studied. The photoisomerization process occurs in cyano azo polymer, by illumination of a film with polarized and unpolarized light. The illumination of the polymer film with light results in color change, the color of film gets darker. This is in opposition to common azo polymers in which the result of illumination is a photo-bleaching. Study of spectrum changes of a dilute polymer solution shows that the color change under pump beam illumination is not due to interaction between dye molecules. Time evaluation of probe beam absorption induced by Ar+laser pump beam shows the fast change in population of isomers at higher light powers. Light induced birefringence (LIB) experiments with high power pump beams shows uncommon new features. A high long-term stability of LIB is demonstrated when the polymer film is kept in the dark. Not only a circular polarized light cannot erase the birefringence but it also induces anisotropy in polymer film. It appears that this is relevant of a phase transition in the polymer film.

Nonequilibrium thermodynamics of dilute polymer solutions in flow.

Modern materials processing applications and technologies often occur far from equilibrium. To this end, the processing of complex materials such as polymer melts and nanocomposites generally occurs under strong deformations and flows, conditions under which equilibrium thermodynamics does not apply. As a result, the ability to determine the nonequilibrium thermodynamic properties of polymeric materials from measurable quantities such as heat and work is a major challenge in the field. Here, we use work relations to show that nonequilibrium thermodynamic quantities such as free energy and entropy can be determined for dilute polymer solutions in flow. In this way, we determine the thermodynamic properties of DNA molecules in strong flows using a combination of simulations, kinetic theory, and single molecule experiments. We show that it is possible to calculate polymer relaxation timescales purely from polymer stretching dynamics in flow. We further observe a thermodynamic equivalence between nonequilibrium and equilibrium steady-states for polymeric systems. In this way, our results provide an improved understanding of the energetics of flowing polymer solutions.

Molecular characteristics of an exopolysaccharide from Lactobacillus rhamnosus KF5 in solution

The molecular weight and chain conformation of an exopolysaccharide (EPS), S2, from Lactobacillus rhamnosus KF5 were determined by size-exclusion chromatography combined with multi-angle laser light scattering (SEC-MALLS), dynamic light scattering (DLS), viscometry and atomic force microscopy (AFM). The weight-average molecular weight (Mw), intrinsic viscosity [ƞ], radii of gyration (Rg) and hydrodynamic radii (Rh) were 7.5×105Da, 2.331dL/g, 44.3nm and 29.4nm, respectively. The conformational parameters were calculated from the above data according to the theory of dilute polymer solutions. The Mark–Houwink–Sakurada exponent α was found to be 0.687, and the value of the structure-sensitive parameter ρ (Rg/Rh) was 1.51. The results revealed that the EPS S2 existed as a random coil conformation in 0.1M NaNO3 aqueous solution. AFM further confirmed the random coil morphology of this molecule in aqueous solution. EPS S2 present extended chains (fibrous morphology), with circular side chains, dispersed in SDS solution.

Viscosity Radius of Polymers in Dilute Solutions: Universal Behavior from DNA Rheology and Brownian Dynamics Simulations

The swelling of the viscosity radius, αη, and the universal viscosity ratio, UηR, have been determined experimentally for linear DNA molecules in dilute solutions with excess salt, and numerically by Brownian dynamics simulations, as a function of the solvent quality. In the latter instance, asymptotic parameter free predictions have been obtained by extrapolating simulation data for finite chains to the long chain limit. Experiments and simulations show a universal crossover for αη and UηR from θ to good solvents in line with earlier observations on synthetic polymer–solvent systems. The significant difference between the swelling of the dynamic viscosity radius from the observed swelling of the static radius of gyration is shown to arise from the presence of hydrodynamic interactions in the nondraining limit. Simulated values of αη and UηR are in good agreement with experimental measurements in synthetic polymer solutions reported previously and with the measurements in linear DNA solutions reported here.

Hydrodynamic correlations and diffusion coefficient of star polymers in solution.

The center-of-mass dynamics of star polymers in dilute solution is analyzed by hybrid mesoscale simulations. The fluid is modeled by the multiparticle collision dynamics approach, a particle-based hydrodynamic simulation technique, which is combined with molecular dynamics simulations for the polymers. Star polymers of various functionalities are considered. We determine the center-of-mass velocity correlation functions, the corresponding mean square displacements, and diffusion coefficients. The velocity correlation functions exhibit a functionality-dependent and structure-specific intermediate time regime, with a slow decay. It is followed by the long-time tail t(-3/2), which is solely determined by the fluid. Infinite-system-size diffusion coefficients are determined from the velocity correlation function by a combination of simulation and analytical results, as well as from the center-of-mass mean square displacement for various systems sizes and extrapolation. In terms of the hydrodynamic radius, the star polymer hydrodynamic diffusion coefficient exhibits the same universal system-size dependence as a spherical colloid. The functionality dependence of the ratio of hydrodynamic radii and the radii of gyration agrees well with experimental predictions.

Radical-triplet pair interactions as probes of long-range polymer motion in solution.

Radical-triplet pair interactions are used to investigate the dynamics of acrylic polymers in dilute solution. Methyl methacrylate was randomly copolymerized with a small amount of an amine-containing monomer to create the polymers. The amine subunits were then oxidized to nitroxide moieties (stable free radicals). Using time-resolved electron paramagnetic resonance (TREPR) spectroscopy on the sub-microsecond time scale, competition is observed between two deactivation processes of the ester side chain photoexcited triplet state: (1) Norrish I α-cleavage, leading to a 21-line main chain polymeric free radical TREPR spectrum with emissive triplet mechanism spin polarization, and (2) spin polarization transfer or quenching by a nearby stable nitroxide radical, which gives a 3-line spectrum exhibiting emissive radical-triplet pair spin polarization. The main chain polymer radical signal dominates the TREPR spectrum if the probability of radical-triplet pair encounters is low. These competing reactions show a strong dependence on nitroxide incorporation (mol %), temperature, solvent, and acrylic polymer ester side chain structure. A comparison of steady state EPR and TREPR signals from inter- vs intramolecular processes clearly demonstrates the influence of polymer chain dynamics on the observed phenomena.

Dispersity and spinnability: Why highly polydisperse polymer solutions are desirable for electrospinning

We develop new criteria that describe the minimum concentration limits controlling the spinnability of dilute and semi-dilute flexible polymer solutions with high molecular weight and varying polydispersity. By asserting that the finite and bounded extensional viscosity of the solution is the key material property determining the stability of a filament during spinning, we propose a new scaling relating the minimum necessary concentration of a polymer cspin to its molecular weight M and the quality of the solvent (through the excluded volume exponent ν) of the form cspin∼M−(ν+1). This new scaling differs from the classical interpretation of the coil overlap concentration c∗ or entanglement concentration ce as the minimum concentration required to increase the viscosity of the spinning dope, and rationalizes the surprising spinnability of high molecular weight polymers at concentrations much lower than ce. Furthermore, we introduce the concept of an extensibility average molecular weight ML as the appropriate average for the description of polydisperse solutions undergoing an extension-dominated spinning process. In particular it is shown that this extensibility average measure, and thus the solution spinnability, is primarily determined by the extensibility of the highest molecular weight fractions. For highly polydisperse systems this leads to an effective lowering of the minimum required concentration for successful fibre spinning (in comparison to narrowly distributed polymer solutions of similar weight average molecular weights). These predictions are validated with experimental observations of the electrospinnablity of mono- and polydisperse poly(methyl methacrylate) (PMMA) solutions as well as a model bimodal blend, and through comparison to published literature data on the minimum spinnable polymer concentration for a variety of flexible long chain polymers over a range of molecular weights.

Superhydrophobic nanocomposites from biodegradable thermoplastic starch composites (Mater-Bi®), hydrophobic nano-silica and lycopodium spores

Due to increasing environmental concerns related to bio-persistence of petroleum based polymers, research efforts have intensified towards developing biodegradable materials with equivalent performance properties. Among these properties liquid repellence is one of the most challenging to obtain due to the fact that most biopolymers such as polysaccharides or bio-polyesters are hygroscopic or hydrophilic. One possible approach is to formulate biopolymer nanocomposites with water repellent properties. Here, we demonstrate such an approach using a commercial thermoplastic starch composite, Materi-Bi®, hydrophobic fumed silica nanoparticles and lycopodium spores. We found that both hydrophobic fumed silica and Materi-Bi® have excellent colloidal stability and solubility in chloroform and they can be spray coated onto various surfaces like paper, metals and semiconductors. By varying the concentration ratio of biopolymer to hydrophobic fumed silica, the wetting properties of the nanocomposites could be tuned. Superhydrophobic nanocomposites displayed raspberry-like surface roughness with water contact angles exceeding 160° with very low water droplet roll-off angles (∼1°). On the other hand, composites of Materi-Bi® and lycopodium spores displayed sticky superhydrophobicity (rose petal effect). Superhydrophobic nanocomposites were found to withstand thermal aging at 250 °C without loss of properties. Due to the resultant micro-morphology of the nanocomposites, certain coatings were rendered superoleophobic by functionalizing with a dilute fluoroacrylic polymer solution in acetone. Oil droplet contact angles reached 166° with droplet roll-off angles of approximately 15°.

A statistical theory of cosolvent-induced coil-globule transitions in dilute polymer solution.

We present a statistical model of a dilute polymer solution in good solvent in the presence of low-molecular weight cosolvent. We investigate the conformational changes of the polymer induced by a change of the cosolvent concentration and the type of interaction between the cosolvent and the polymer. We describe the polymer in solution by the Edwards model, where the partition function of the polymer chain with a fixed radius of gyration is described in the framework of the mean-field approximation. The contributions of polymer-cosolvent and the cosolvent-cosolvent interactions in the total free energy are treated also within the mean-field approximation. For convenience we separate the system volume on two parts: the volume occupied by the polymer chain expressed through its gyration volume and the bulk solution. Considering the equilibrium between the two subvolumes we obtain the total free energy of the solution as a function of radius of gyration and the cosolvent concentration within gyration volume. After minimization of the total free energy with respect to its arguments we obtain a system of coupled equations with respect to the radius of gyration of the polymer chain and the cosolvent concentration within the gyration volume. Varying the interaction strength between polymer and cosolvent we show that the polymer collapse occurs in two cases--either when the interaction between polymer and cosolvent is repulsive or when the interaction is attractive. The reported effects could be relevant for different disciplines where conformational transitions of macromolecules in the presence of a cosolvent are of interest, in particular in biology, chemistry, and material science.

Dissipative particle dynamics simulation of dilute polymer solutions—Inertial effects and hydrodynamic interactions

We examine the accuracy of dissipative particle dynamics (DPD) simulations of polymers in dilute solutions with hydrodynamic interaction (HI), at the theta point, modeled by setting the DPD conservative interaction between beads to zero. We compare the first normal-mode relaxation time extracted from the DPD simulations with theoretical predictions from a normal-mode analysis for theta chains. We characterize the influence of bead inertia within the coil by a ratio Lm/Rg, where Lm is the ballistic distance over which bead inertia is lost, and Rg is the radius of gyration of the polymer coil, while the HI strength per bead h* is determined by the ratio of bead hydrodynamic radius (rH) to the equilibrium spring length. We show how to adjust h* through the spring length and monomer mass, and how to optimize the accuracy of DPD for fixed h* by increasing the friction coefficient (γ ≥ 9) and by incorporating a nonlinear distance dependence into the frictional interaction. Even with this optimization, DPD simulations exhibit deviations of over 20% from the theoretical normal-mode predictions for high HI strength with h* ≥ 0.20, for chains with as many as 100 beads, which is a larger deviation than is found for Stochastic rotation dynamics simulations for similar chains lengths and values of h*.

Stress-gradient induced migration of polymers in corrugated channels

We study the flow of a dilute polymer solution in a wavy channel under steady-state flow conditions by employing the nonequilibrium thermodynamics two-fluid model [Mavrantzas and Beris, Phys. Rev. Lett. 69, 273–276 (1992)], allowing for the coupling between polymer concentration and polymer stresses. The resulting highly complex system of partial differential equations describing inhomogeneous transport phenomena in the fluid are solved with an efficient implementation of the mixed finite-element method. We present numerical results for polymer concentration, stress, velocity, and fluxes of polymer as a function of the nondimensional parameters of the problem (the Deborah number De, the Peclet number Pe, the Reynolds number Re, the ratio of the solvent viscosity to the total fluid viscosity β, and the constriction ratio of the channel width cr). We find that the constricted part of the wall is depleted of polymer, when the polymer diffusion length scale, expressed by the ratio of De/Pe, increases. The migration is more pronounced for macromolecules characterized by longer relaxation times and takes place toward the expanding part of the channel or toward the centerplane. Migration is also enhanced by the width variability of the channel: The more corrugated the channel, the stronger the transfer of polymer to the centerplane. This increases the spatial extent of polymer depletion near the wall or induces a zone of sharp variation in polymer stress and concentration, which moves away from the channel wall, especially in lower polymer concentration. The development of a polymer-depleted layer smooths out the boundary layer which is known to arise with Boger fluids at the walls of such corrugated channels or tubes and gives rise to an “apparent” slip in the constricted section of the wall and to a very low value of the drag force on the wall. When and where boundary layers arise, they scale as (1/De) for the stresses and as (De/Pe)1/3 for the concentration.

Joint aqueous solutions of dextran and bovine serum albumin: coexistence of three liquid phases.

The phase diagram of the system water/dextran (DEX)/BSA was measured as well as modeled. On the experimental side, cloud points were determined and the coexisting phases were analyzed. The theoretical calculations use an approach capable of describing solutions of chain polymers and of globular proteins with the same formalism. The required thermodynamic input comes from experiments concerning the binary subsystems, except for the polymer blend for which one interaction parameter had to be adjusted. Both sources of information yield the same essential features: the existence of a large composition area of immiscibility, starting from the subsystem DEX/BSA and extending well into the region of dilute polymer solutions. This range is subdivided into three sections: one two-phase area at high polymer content, a two-phase area at low polymer content, and a three-phase region located in between. Measured and calculated phase diagrams match qualitatively; the reasons for the quantitative discrepancies are being discussed.

Thermophoresis of polymers: nondraining vs draining coil.

Present theories for the thermophoretic mobility of polymers in dilute solution without long-ranged electrostatic interaction are based on a draining coil model with short-ranged segment-solvent interaction. We show that the characteristic thermophoretic interaction decays as r(-2) with the distance from the chain segment, which is of much longer range than the underlying rapidly decaying binary van der Waals interaction (∝r(-6)). As a consequence, thermophoresis on the monomer level is governed by volume forces, resulting in hydrodynamic coupling between the chain segments. The inner parts of the nondraining coil do not actively participate in thermophoresis. The flow lines penetrate only into a thin surface layer of the coil and cause tangential stresses along the surface of the entire coil, not the individual segments. This model is motivated by recent experimental findings for thermoresponsive polymers and core-shell particles, and it explains the well-known molar mass independent thermophoretic mobility of polymers in dilute solution.