Salt-Induced Linker Dehydration Modulates Micellar Structure in Ether-Linked Sulfate Surfactants.

Ether-linked surfactants are widely used in formulations such as liquid soaps, but despite their ubiquity, it is unclear how n-ethylene glycol linkers in surfactants, such as sodium lauryl n-(ethylene glycol) sulfate (SLEnS), influence micellar packing in the presence of NaCl. In the present work, we probe the structure and hydration of ether linkers in micelles comprising monodisperse SLEnS surfactants using contrast-variation small-angle neutron scattering (CV-SANS) and small-angle X-ray scattering (SAXS). Using SAXS, changes in micellar structure were observed for SLEnS (n = 1, 2, or 3) arising from the extent of ethoxylation. Scattering profiles indicated a clear transition from elongated cylindrical micelles to shorter ellipsoidal micelles with increasing ethoxylation. With CV-SANS, micellar structure and linker geometries of SLE3S were able to be resolved, indicating that a change in micellar architecture is modulated by dehydration of the tri(ethylene glycol) linker, offering new insights into the role of water and ions in the self-assembly of this key class of surfactants.

Small-angle scattering of complex fluids in flow.

Complex fluids encompass a significant proportion of the materials that we use today from feedstocks such as cellulose fibre dispersions, materials undergoing processing or formulation, through to consumer end products such as shampoo. Such systems exhibit intricate behaviour due to their composition and microstructure, particularly when analysing their texture and response to flow (rheology). In particular, these fluids when flowing may undergo transitions in their nano- to microstructure, potentially aligning with flow fields, breaking and reassembling or reforming, or entirely changing phase. This manifests as macroscopic changes in material properties, such as core-annular flow of concentrated emulsions in pipelines or the favourable texture of liquid soaps. Small-angle scattering provides a unique method for probing underlying changes in fluid nano- to microstructure, from a few angströms to several microns, of complex fluids under flow. In particular, the alignment of rigid components or shape changes of soft components can be explored, along with local inter-particle ordering and global alignment with macroscopic flow fields. This review highlights recent important developments in the study of such complex fluid systems that couple flow or shear conditions with small-angle scattering measurements, and highlights the physical insight obtained by these experiments. Recent results from neutron scattering measurements made using a simple flow cell are presented, offering a facile method to explore alignment of complex fluids in an easily accessible geometry, and contextualised within existing and potential future research questions.

Influence of Surfactant Structure on Polydisperse Formulations of Alkyl Ether Sulfates and Alkyl Amidopropyl Betaines.

Surfactants provide detergency, foaming, and texture in personal care formulations, yet the micellization of typical industrial primary and cosurfactants is not well understood, particularly in light of the polydisperse nature of commercial surfactants. Synergistic interactions are hypothesized to drive the formation of elongated wormlike self-assemblies in these mixed surfactant systems. Small-angle neutron scattering, rheology, and pendant drop tensiometry are used to examine surface adsorption, viscoelasticity, and self-assembly structure for wormlike micellar formulations comprising cocoamidopropyl betaine, and its two major components laurylamidopropyl betaine and oleylamidopropyl betaine, with sodium alkyl ethoxy sulfates. The tail length of sodium alkyl ethoxy sulfates was related to their ability to form wormlike micelles in electrolyte solutions, indicating that a tail length greater than 10 carbons is required to form wormlike micelles in NaCl solutions, with the decyl homologue unable to form elongated micelles and maintaining a low viscosity even at 20 wt % surfactant loading with 4 wt % NaCl present. For these systems, the incorporation of a disperse ethoxylate linker does not enable shorter chain surfactants to elongate into wormlike micelles for single-component systems; however, it could increase the interactions between surfactants in mixed surfactant systems. For synergy in surfactant mixing, the nonideal regular solution theory is used to study the sulfate/betaine mixtures. Tail mismatch appears to drive lower critical micelle concentrations, although tail matching improves synergy with larger relative reductions in critical micelle concentrations and greater micelle elongation, as seen by both tensiometric and scattering measurements.

Shear-induced nanostructural changes in micelles formed by sugar-based surfactants with varied anomeric configuration.

HYPOTHESIS: The self-assembly of long tail sugar-based surfactants into worm-like micelles has recently been demonstrated, and the rheological properties of such systems have been shown to be tuneable through subtle modifications of the molecular characteristics of the surfactant monomer. In particular, the anomeric configuration of the hexadecylmaltoside headgroup was shown to induce profound changes in the nanostructure and rheology of the system. The origin of such changes is hypothesised to arise from differences in the structure and relaxation of the micellar networks in the semi-dilute regime. EXPERIMENTS: Here we explore the molecular background to the flow properties of the two anomers of hexadecylmaltoside (α- and ß-C16G2) by directly connecting their rheological behaviour to the micelle morphology. For this purpose, 1-3 plane rheo-small-angle neutron scattering measurements, using a Couette cell geometry, probed the structural changes in the micellar phase under shear. The effect of surfactant anomeric configuration, surfactant concentration, temperature and mixing ratio of the two anomers were investigated. The static micelle structure in the semi-dilute regime was determined using the polymer reference interaction site model. FINDINGS: The segmental alignment of the micellar phase was studied under several flow conditions, showing that the shear-thinning behaviour relates to the re-arrangement of ß-C16G2 worm-like micelles, whilst shorter α-C16G2 micelles are considerably less affected by the flow. The results are rationalised in terms of micelle alignment and disruption of the entangled network, providing a detailed mechanism by which sugar-based surfactants control the rheology of the fluid. To further enable future studies, we provide the complete code for modelling micelle structure in the semi-dilute regime using the polymer reference interaction site model.

Heads or tails? The synthesis, self-assembly, properties and uses of betaine and betaine-like surfactants.

Betaines are a key class of zwitterionic surfactant that exhibit particularly favorable properties, making them indispensable in modern formulation. Due to their composition, betaines are readily biodegradable, mild on the skin and exhibit some antimicrobial activity. Vital to their function, these surfactants self-assemble into diverse micellar geometries, some of which contribute to increased solution viscosity, and their surface activity results in strong detergency and foaming. As such, their behavior has been exploited in various applications from personal care (including shampoos and liquid soaps) to specific industrial fields (such as enhanced oil recovery). This review aims to inform the reader of the diverse range of different betaine and betaine-like surfactants that have been actively researched over the past three decades. Synthesis as well as both chemical and physical characterization of betaine surfactants are discussed, including small-angle scattering studies that indicate self-assembly structures and rheological data that demonstrates texture and flow. Stimulus responsive systems and exotic betaine analogs with enhanced functionality are also covered. Crucially, the connection between surfactant molecular architecture and function are highlighted, exemplifying precisely why zwitterionic betaine and related surfactants are so uniquely functional.

In Situ Nanostructural Analysis of Concentrated Wormlike Micellar Fluids Comprising Sodium Laureth Sulfate and Cocamidopropyl Betaine Using Small-Angle Neutron Scattering.

Concentrated wormlike micellar fluids form the basis for a vast array of formulated products, from liquid soaps and shampoos to drag reduction and drilling fluids. Typically, these systems are analyzed using bulk rheological measurements to determine their flow properties and cryo-microscopy to detect their nanostructure. Small-angle neutron scattering provides an opportunity to directly and nonperturbatively analyze nanostructure in situ but is complicated for concentrated systems by correlations from interparticle volume exclusion. Here, we use small-angle and ultra-small-angle neutron scattering to probe directly for the first time the nanostructure of concentrated wormlike micellar fluids composed of the widely used surfactant pair sodium laureth sulfate and cocamidopropyl betaine in aqueous electrolytes. Obtained data are analyzed using different approaches to determine scattering contributions from the wormlike particles themselves and interactions between them. It is found that approximating worms as locally rigid cylinders offers some insight into their aggregation dimensions at short length scales, and both volume exclusion and screened Coulombic interaction potentials describe interactions reasonably well. Using the semi-empirical polymer reference interaction site model (PRISM) gives excellent agreement with observed scattering, and physical insight obtained using this approach is discussed in detail. A drawback of this method is the significant complexity in coding the model in order to fit data, so to facilitate this for future researchers, we provide with this paper a fully operational, open-source code to utilize this model.