Chain conformation of polymers adsorbed to clay particles: effects of charge and concentration.

High molecular weight polymers are used in industrially important applications where the polymers adsorb onto surfaces of inorganic particles and facilitate dispersion, stabilization or flocculation of formulations. The surface conformation of these adsorbed polymers is key to their performance, yet an understanding of the effects of polymer charge, concentration and molecular weight on polymer conformation is incomplete. Here the adsorption behavior of high molecular weight, non-ionic, polyethylene oxide (PEO) and anionic partially hydrolyzed polyacrylamide (HPAM) polymers to a model clay, LAPONITE® (a trademark of BYK Additives, Inc.), was studied by small angle neutron scattering over a range of polymer concentrations. The adsorption of PEO was dependent on polymer concentration at all molecular weights, first adsorbing onto the radial edge of the clay particles and then to the clay faces as polymer concentration increased. While similar behavior was observed at low concentrations of HPAM, above a critical concentration, HPAM desorption results in large clay aggregates, which decrease in size at higher polymer loadings. The difference in adsorption properties as a function of polymer charge and concentration is interpreted in terms of conformational differences of adsorbed polymer at the clay surface. Changes in the volume fraction of adsorbed PEO with polymer concentration indicate changes in the relative amounts of adsorbed chain segments in trains, loops and tails, with no clay aggregation. In contrast, a constant volume fraction of adsorbed HPAM at low concentrations gives way to desorption at higher concentration due to charge repulsion, and depletion aggregation of the clay.

Oscillatory and Steady Shear Rheology of Model Hydrophobically Modified Ethoxylated Urethane-Thickened Waterborne Paints.

Hydrophobically modified ethoxylated urethane (HEUR) thickeners are widely used as rheology modifiers for waterborne paints. Although the rheology of HEUR solutions in water is fairly well-understood, their impact on the rheology of waterborne latex/pigment suspensions (formulated paints) is more complicated. We study the shear rheology of model HEUR/latex/TiO2 suspensions in water and investigate the dependence of both oscillatory and steady shear behaviors on the strength of the HEUR hydrophobes. We observe that in both oscillatory and steady shear experiments, rheological curves could be shifted onto a single master curve, demonstrating a "time-hydrophobe superposition". We also note that the oscillatory shear behavior exhibits a power-law spectrum of relaxation times, unlike the single-Maxwellian behavior of pure HEUR solutions. On the basis of these results and earlier experimental and theoretical findings, we propose that the rheology of the HEUR-thickened latex/TiO2 suspensions is mainly determined by the transient network of HEUR-bridged latex particles, with a broad distribution of the characteristic lifetimes of the bridge. The model is found to be in good qualitative and semiquantitative agreement with the experiments for both steady shear and oscillatory shear.

Formulation-Controlled Positive and Negative First Normal Stress Differences in Waterborne Hydrophobically Modified Ethylene Oxide Urethane (HEUR)-Latex Suspensions.

Hydrophobically modified ethylene oxide urethane (HEUR) associative thickeners are widely used to modify the rheology of waterborne paints. Understanding the normal stress behavior of the HEUR-based paints under high shear is critical for many applications such as brush drag and spreading. We observed that the first normal stress difference, N1, at high shear (large Weissenberg number) can be positive or negative depending on the HEUR hydrophobe strength and concentration. We propose that the algebraic sign of the N1 is primarily controlled by two factors: (a) adsorption of HEURs on the latex surface and (b) the ability of HEURs to form transient molecular bridges between latex particles. Such transient bridges are favored for dispersions with small interparticle distances and dense surface coverages; in these systems; HEUR-bridged latex microstructures flow-align in high shear and exhibit positive N1. In the absence of transient bridges (large interparticle distances, low surface coverage), the dispersion rheology is similar to that of weakly interacting spheres, exhibiting negative N1. The results are summarized in a simplified phase diagram connecting formulation, microstructure, and the N1 behavior.

On a different approach toward low-frequency dielectric spectroscopy measurements of conductive liquids.

Driven by recent interest in the low-frequency Debye-like relaxations in hydrogen bonding liquids, here we present an alternative method for measuring such relaxations without the detrimental effects of ionic conductivity or electrode polarization. Glycerol was chosen as a molecule of interest, and a fit for the α-transition using the Vogel-Fulcher-Tammann equation was found to be τ = 2.31 × 10(-14) exp(2110 K∕[T-135 K]). This method is easily adaptable by most laboratories with existing dielectric spectrometers, and could prove useful in the accurate measurement of relaxations in conductive media at low frequencies. A brief summary of comparable techniques is also presented.

Structure and properties of aqueous methylcellulose gels by small-angle neutron scattering.

Cold, semidilute, aqueous solutions of methylcellulose (MC) are known to undergo thermoreversible gelation when warmed. This study focuses on two MC materials with much different gelation performance (gel temperature and hot gel modulus) even though they have similar metrics of their coarse-grained chemical structure (degree-of-methylether substitution and molecular weight distribution). Small-angle neutron scattering (SANS) experiments were conducted to probe the structure of the aqueous MC materials at pre- and postgel temperatures. One material (MC1, higher gel temperature) exhibited a single almost temperature-insensitive gel characteristic length scale (ζ(c) = 1090 ± 50 Å) at postgelation temperatures. This length scale is thought to be the gel blob size between network junctions. It also coincides with the length scale between entanglement sites measured with rheology studies at pregel temperatures. The other material (MC2, lower gel temperature) exhibited two distinct length scales at all temperatures. The larger length scale decreased as temperature increased. Its value (ζ(c1) = 1046 ± 19 Å) at the lowest pregel temperature was indistinguishable from that measured for MC1, and reached a limiting value (ζ(c1) = 450 ± 19 Å) at high temperature. The smaller length scale (ζ(c2) = 120 to 240 Å) increased slightly as temperature increased, but remained on the order of the chain persistence length (130 Å) measured at pregel temperatures. The smaller blob size (ζ(c1)) of MC2 suggests a higher bond energy or a stiffer connectivity between network junctions. Moreover, the number density of these blobs, at the same reduced temperature with respect to the gel temperature, is orders of magnitude higher for the MC2 gels. Presumably, the smaller gel length scale and higher number density lead to higher hot gel modulus for the low gel temperature material.

Apparatus for Simultaneous Small Angle Neutron Scattering and Steady Shear Viscosity Studies of Polymer Melts and Solutions.

The design and construction of an apparatus for studying the simultaneous small angle neutron scattering (SANS) and steady shear viscosity behavior of polymer melts and concentrated solutions is discussed. Successful operation of the device is demonstrated on a blend of 20 weight percent deuterated polystyrene and 80 weight percent poly(vinylmethylether). The effects of shear on the critical behavior of the blend are observed in the SANS behavior as a function of temperature and shear rate and indicate shear induced mixing behavior for the range of shear rates examined. The steady shear viscosity results alone are insufficient for detecting the transition from one to two phases. The examination of shear effects in polymer blends is important for understanding the critical behavior of binary systems. Technologically, knowledge of the phase behavior of polymer blends under shear are important for the design and improvement of commercial blend processing.