Karsten Vogtt

Scattering Function for Branched Wormlike Chains.

Wormlike or threadlike structures with local cylindrical geometry are abundantly found in nature and technical products. A thorough structural characterization in the bulk for a whole ensemble, however, is difficult. The inherent semiordered nature of the tortuous large-scale structure and especially the quantification of branching renders an assessment difficult. In the present work we introduce a hybrid function expressing the scattering intensities for X-rays, neutrons, or light in the small-angle regime for this system. The function is termed hybrid because it employs terms from different approaches. The large-scale structure is described via a Guinier term as well as a concomitant power-law expression in momentum transfer q taken from the so-called unified function. The local cylindrical shape, however, is taken into account through a form factor for cylinders from rigid-body modeling. In principle, the latter form factor can be replaced by an expression for any other regular body so that the new hybrid function is a versatile tool for studying hierarchical structures assembled from uniform subunits. The appropriateness and capability of the new function for cylindrical structures is exemplified using the example of a wormlike micellar system.

Free Energy of Scission for Sodium Laureth-1-Sulfate Wormlike Micelles

Wormlike micelles (WLMs) are nanoscale, self-assembled components of many products from shampoos to fracking fluids due to their viscoelasticity. Their rheological behavior is largely governed by the contour length of the micelles and the concomitant propensity of the micelles to overlap and entangle. The large contour lengths, on the order of micrometers, is the result of a delicate balance between the scission enthalpy of the wormlike micelles on the one hand and entropic factors such as the mixing entropy of dispersion, the ordering of water molecules and counterions, and the mobility of branch points on the other hand. The structure and contour length of wormlike micelles assembled from sodium laureth-1-sulfate was determined at various temperatures using small-angle neutron scattering. The results allow the calculation of the enthalpy and entropy as well as the free energy of scission and are employed to critically evaluate the common methods to determine micellar scission energy from mean-field theory. Interesting behavior is observed when comparing branched and unbranched WLMs that may reflect on mechanistic differences in chain scission.

Structural Emergence in Particle Dispersions

Particle dispersions, such as pigment-based inks, comprise weakly bound, milled nanoparticles. The properties of these pigments depend on both their chemical composition and a rather complex structural hierarchy which emerges from these dispersions. The emergence of structure under semidilute conditions is related to the structure of the dilute particles, the particle spacing (mesh size), processing history, and the interaction potential. Kinetic simulations could predict such emergence using these input parameters. In this paper, organic pigments are studied as an example of the importance of emergent structure to predict properties such as brilliance and opacity. Organic pigments are used to impart color to commercial inks, plastics, coatings, and cosmetics. In many cases, dilute pigments are mass fractal structures consisting of aggregated nanoparticles held together by weak van der Waals forces. In water, surfactant is added to create a pigment dispersion (an ink). The final properties of a pigment emerge from a complex interplay between aggregation and dispersion of aggregates as a function of concentration. Samples of the organic pigment yellow 14, PY14, were milled to four primary particle sizes to study the effect on structural emergence. The interaction between surfactant-stabilized PY14 aggregates in an aqueous medium was quantified by the second virial coefficient, A2, which reflects long-range interactions. The degree of aggregation is associated with short-range attractive interactions between primary particles. In this series of pigments, the degree of aggregation increases dramatically with reduction in primary particle size. Concurrently, the second-order virial coefficient, A2, increases reflecting stronger long-range repulsive interactions with particle size. Structural emergence can be understood through the percolation concentration and the filler mesh size. A2 is translated into a repulsive interaction potential for use in dissipative particle dynamics simulations to enable predictive modeling. This description of the interactions between dispersed pigment aggregates allows for a more scientific and predictive approach to understand structural emergence.

Enthalpy and Entropy of Scission in Wormlike Micelles

The free scission energy is the thermodynamic parameter that governs the contour length of wormlike micelles (WLMs). It is the contour length and the propensity to coil and entangle that determine the viscoelastic properties of this commercially important substance class. The free scission energy Δ Fsc and the associated change in enthalpy Δ Hsc and entropy Δ Ssc on scission have been determined for a mixed anionic/zwitterionic surfactant system (sodium laureth sulfate and cocamidopropyl betaine) at various salt concentrations (3-5 wt % NaCl). Both enthalpy Δ Hsc and entropy Δ Ssc changes decrease linearly with increasing NaCl concentration. At NaCl concentrations above 4 wt %, Δ Ssc even adopts negative values. The term TΔ Ssc decreases more rapidly than Δ Hsc around room temperature and causes the observed elongation of WLMs upon addition of NaCl. It is suggested that Δ Ssc is initially positive due to fewer bound counterions per surfactant molecule at end caps compared to the intact, cylindrical parts before scission, leading to a net release of ions upon scission. Negative values of Δ Ssc are attributed to hydrophobic hydration occurring at the end caps at high salt concentrations. 23Na NMR measurements indicate the presence of immobilized ions, supporting a previously proposed ion-cloud model based on neutron scattering results.

The effect of solvent polarity on wormlike micelles using dipropylene glycol (DPG) as a cosolvent in an anionic/zwitterionic mixed surfactant system

HYPOTHESISnThe behavior/properties of micellar solutions are governed by Coulombic interactions that are influenced by the polarity of the surfactant head groups, hydrophobic tails, and solvent molecules. The addition of co-solvent should have a direct impact on solvent polarity and the size of the micelles are expected to decrease accordingly.nnnEXPERIMENTSnIn this study, a mixed surfactant system is studied composed of a common anionic surfactant, sodium laureth sulfate-1, modified by a zwitterionic surfactant, cocamidopropyl betaine in deuterated water. In this system, worm-like micelles (WLMs) are formed. The influence of a co-solvent, dipropylene glycol (DPG) in the present of high salt content, is investigated. DPG primarily modifies the dielectric constant of the solvent.nnnFINDINGSnIt was found that the addition of DPG slightly decreased the micelle radius, but dramatically reduced the persistence length as well as the contour length of the micelles. The relative dependence of contour length on salt concentration is not significantly changed. Thus, it is shown that the self-assembled structure can be tuned by adjusting solvent polarity without affecting the relative tunability of the WLM/ellipsoidal structure through counter ion concentration.