Rheo-optical characterization of dilute polymer mixtures under shear flow

Optical properties can estimate morphological changes of polymer chains under flow. This work proposes a rheo-optical procedure to determine turbidity and both flow and form birefringence of diluted polymer mixtures of polystyrene (PS) and polypropylene (PP) during a controlled shear flow, by measuring the transmitted light intensity with and without crossed polarizers via an own built optical sensor. The turbidity in these dilute mixtures decreased with the increase of the shear rate due to deformation of the dispersed phase droplets, which reduces their cross-sections. The presence of PP as the dispersed phase in the PS matrix caused a decrease in the total birefringence measured, whereas PS as the dispersed phase in the PP matrix caused an increase in it. Both effects are associated to the positive contribution of the form birefringence, produced by the shear-induced elongated morphology of the dispersed phase.     

Jetting of dilute polymer solutions

Light emitting devices containing conjugated polymers are conveniently fabricated using ink-jet printing. A common problem in the processing of these materials is that the Newtonian viscosity of the polymer solution is not sufficient to describe the jetting performance because the molecular weights and concentrations employed are such that the resulting solutions are elastic. These differences in fluid elasticity levels cannot be measured using traditional techniques like dynamic mechanical experiments or the first normal stress difference in shear, but strongly impact the jetting behavior of the liquid. In this study, a variety of polystyrene solutions in DECALIN having a shear viscosity of ~5 mPa s but different elasticity levels were examined for their jetting behavior. The jetting behavior of these solutions was studied visually using drop-on-demand jetting equipment and their rheology was characterized using a custom extensional rheometer designed for measuring the elasticity of such low viscosity liquids. If elasticity effects are absent as in Newtonian liquids (corresponding to a Trouton ratio of 3) satellite drops are formed resulting in loss of liquid and poor positioning. On the other hand, if elasticity effects are very large (Trouton ratios ≫4) separation problems occur at the nozzle with undesirable “tailing.” The optimum range for stable, efficient jetting occurs at Trouton ratios in a narrow band between 3 and ~5. A very slight degree of elasticity corresponding to a Trouton Ratio around four thus seems to be optimum for the jetting process. This appears to be the first time that such a design criterion has been outlined for this process. Such an approach complements thermal techniques for elucidating the role of molecular and flow properties on the processing behavior of polymeric systems.     

Determination of molecular parameters from polymer solutions in shear flow

A light scattering photometer with a double cylinder shear cell has been developed which allows detection not only in one plane as usual, but in a half-spherical range around the scattering volume. The anisotropic scattering behavior of oriented and deformed polymer molecules in dilute solution was investigated. All measurements were performed on polystyrene in several viscous solvents. From measurements in the plane of flow the average orientation angle was determined. By variation of detector position and wavelength of the primary beam, the determination of all three axes of the molecular gyration space of polymer coils was possible. Compared to predictions of the well-known dynamic theories by Kuhn, Rouse and Zimm, corresponding orientation data were found while the molecular deformation ratio shows much lower values than expected.     

Shear thinning in dilute polymer solutions

We use bead-spring models for a polymer coupled to a solvent described by multiparticle collision dynamics to investigate shear thinning effects in dilute polymer solutions. First, we consider the polymer motion and configuration in a shear flow. For flexible polymer models we find a sharp increase in the polymer radius of gyration and the fluctuations in the radius of gyration at a Weissenberg number approximately 1. We then consider the polymer viscosity and the effect of solvent quality, excluded volume, hydrodynamic coupling between the beads, and finite extensibility of the polymer bonds. We conclude that the excluded volume effect is the major cause of shear thinning in polymer solutions. Comparing the behavior of semiflexible chains, we find that the fluctuations in the radius of gyration are suppressed when compared to the flexible case. The shear thinning is greater and, as the rigidity is increased, the viscosity measurements tend to those for a multibead rod.     

Viscosities of dilute polymer solutions in nematic liquids

A nematic fluid is characterized by five friction coefficients. When dilute polymer coils are added to the fluid, all these coefficients are modified. Three Miesowicz viscosities (measured under an aligning magnetic field) and two coupling coefficients between orientation and flow are discussed. In our calculation, elastic dumbbells are used to model the flexible polymer chains. The results are written in terms of two size parameters R_∥ and R_⊥ and two chain friction coefficients λ_∥ and λ_⊥ (the label ∥ refers to a direction parallel to the nematic axis). This could be compared to other experiments (such as translational diffusion) which measure λ_∥ and _⊥ directly. They may give useful estimates of coil conformation in nematic solvents.     

Thermodtnamics of surfactant-polymer interactions in dilute aqueous solutions

A thermodynamic model for suffactant binding to polymers in dilute aqueous solution is present. It assumes that the inter- molecular contacts between the polar and the non-polar polymer segment resemble the macroscopic hydrocarbon-water interface ,where preferential accumulation of surfactant accurs. The model also considers the competitive surfactant micelization.     

Transient entanglements and clusters in dilute polymer solutions

A convenient method to monitor polymer dissolution is to measure the pressure drop created by passing a polymer solution through a capillary constriction rheometer. In this work, we studied the dissolution of polyethylene oxide (PEO) and cationic starch (C‐starch). We found that for freshly dissolved and entangled PEO, the main contribution to the overall pressure drop is due to the contraction and expansion of PEO entanglements at the entrance and exit of the capillary, and that the friction in the capillary plays a minor role. On the other hand, for well‐dissolved PEO, because of the absence of PEO entanglements, the loss of pressure is mainly due to friction. At high velocities the contraction and expansion coefficient for freshly dissolved PEO was more than 20 times higher than for well‐dissolved PEO, resulting in a three times higher overall pressure drop. C‐starch consists of amylopectin (～ 85%) and amylose and is known to contain clusters when freshly dissolved, likely formed from the globular amylopectin molecules. For C‐starch, the main contribution to the overall pressure drop is due to friction. Entrance and exit effects contribute only 10% to the overall pressure drop, which might be due to the linear amylose molecules in C‐starch. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 253–262, 2008     

Kinetic effects of excluded volume and selective adsorption in macromolecule solutions

Kinetic effects of excluded volume and selective adsorption in macromolecule solutions have been studied for an arbitrary position of reacting groups along the chain. It has been shown that the reactivities of similar functional groups can depend upon their location along the chain and also upon the nature of the solvent.     

Effect of excluded volume interactions on the interfacial properties of colloid-polymer mixtures

We report a numerical study of equilibrium phase diagrams and interfacial properties of bulk and confined colloid-polymer mixtures using grand canonical Monte Carlo simulations. Colloidal particles are treated as hard spheres, while the polymer chains are described as soft repulsive spheres. The polymer-polymer, colloid-polymer, and wall-polymer interactions are described by density-dependent potentials derived by Bolhuis and Louis [Macromolecules 35, 1860 (2002)]. We compared our results with those of the Asakura-Oosawa-Vrij model [J. Chem. Phys. 22, 1255 (1954); J. Polym Sci 33, 183 (1958); Pure Appl. Chem. 48, 471 (1976)] that treats the polymers as ideal particles. We find that the number of polymers needed to drive the demixing transition is larger for the interacting polymers, and that the gas-liquid interfacial tension is smaller. When the system is confined between two parallel hard plates, we find capillary condensation. Compared with the Asakura-Oosawa-Vrij model, we find that the excluded volume interactions between the polymers suppress the capillary condensation. In order to induce capillary condensation, smaller undersaturations and smaller plate separations are needed in comparison with ideal polymers.     

Application of the porous-sphere hydrodynamic model to dilute polymer solutions

The porous-sphere model of Debye–Brinkman–Bueche is applied to predict the limiting frictional coefficient f₀ and intrinsic viscosity [η] of polystyrene fractions in tetrahydrofuran and random protein coils in 6M guanidine hydrochloride. Following the formulation of Wiegel and Mijnlieff, the molecular permeability is modeled to increase exponentially as the square of the distance from the center of the molecule. A method is developed to obtain this permeability from the translational diffusion coefficient. The experimental values of f₀ and [η] are in satisfactory agreement with the calculated values. Also, this analysis predicts values of the Mandelkern–Flory–Scheraga parameter for flexible coils which are significantly smaller than the minimum values permitted by the Kirkwood–Riseman theory. This is in accord with the experimental evidence.     

Polymers in an external periodic field: the effect of the excluded volume interactions

By developing and making use of the "transfer operator" formalism, we calculate the number density and average Flory end-to-end distance of the polymers placed in an external periodic field. The considered mathematical problem is of immediate relevance for such realistic physical systems as the homopolymers immersed in the host structure of alternating layers that have different affinities for homopolymers (e.g., lamellar microphases of copolymers, ripple morphology of the mixed brush, and lipidwater systems). In contrast to the conventional ground state dominance approximation, the developed method makes it possible to calculate the characteristic size (Flory radius R(F)) of the polymers in the direction of applied external periodic field, with the effect of the excluded volume taken into account. The excluded volume interactions are shown to qualitatively change the behavior of R(F) as a function of the reduced field strength theta relative to the case of ideal Gaussian polymers. In particular, in the limit of strong fields theta>1 the average Flory radius R(F) is found to saturate to its minimal value, which is calculated as a function of the excluded volume parameter u. This finding is in distinct contrast to the result for the Flory radius R(F) in the case of ideal polymers where R(F) approaches zero as the interaction parameter theta increases.