Concentration Dependent Asymmetric Synergy in SDS-DDAO Mixed Surfactant Micelles.

We investigate the structure and interactions of a model anionic/amphoteric mixed surfactant micellar system, namely, sodium dodecyl sulfate (SDS) and N,N-dimethyldodecylamine N-oxide (DDAO), employing SANS, FTIR, DLS, and pH measurements, in the range 0.1-100 mM total surfactant concentration and 0-100% DDAO. Increasing surfactant concentration is found to elongate the prolate ellipsoid micelles (RPolar ∼ 25-40 Å), accompanied by up to a 6-fold increase in micellar charge. The surfactant synergy, in terms of micellar charge and size, diffusion coefficient, solution pH, and headgroup interactions, was found to vary with concentration. At lower concentrations (≤50 mM), the SDS-DDAO ratio of maximum synergy is found to be asymmetric (at 65-85% DDAO), which is rationalized using regular solution theory, suggesting an equilibrium between Na+ dissociation, DDAO protonation, and counterion concentration. At higher concentrations, maximum synergy shifts toward the equimolar ratio. Overall, our study expands and unifies previous reports, providing a comprehensive understanding for this model, synergetic mixed micellar system.

Effects of Erucamide on Fiber "Softness": Linking Single-Fiber Crystal Structure and Mechanical Properties.

Erucamide is known to play a critical role in modifying polymer fiber surface chemistry and morphology. However, its effects on fiber crystallinity and mechanical properties remain to be understood. Here, synchrotron nanofocused X-ray Diffraction (nXRD) revealed a bimodal orientation of the constituent polymer chains aligned along the fiber axis and cross-section, respectively. Erucamide promoted crystallinity in the fiber, leading to larger and more numerous lamellae crystallites. The nXRD nanostructual characterization is complemented by single-fiber uniaxial tensile tests, which showed that erucamide significantly affected fiber mechanical properties, decreasing fiber tensile strength and stiffness but enhancing fiber toughness, fracture strain, and ductility. To correlate these single-fiber nXRD and mechanical test results, we propose that erucamide mediated slip at the interfaces between crystallites and amorphous domains during stress-induced single-fiber crystallization, also decreasing the stress arising from the shear displacement of microfibrils and deformation of the macromolecular network. Linking the single-fiber crystal structure with the single-fiber mechanical properties, these findings provide the direct evidence on a single-fiber level for the role of erucamide in enhancing fiber "softness".

Microfluidic in-line dynamic light scattering with a commercial fibre optic system.

We report the coupling of dynamic light scattering (DLS) in microfluidics, using a contact-free fibre-optic system, enabling the under-flow characterisation of a range of solutions, dispersions, and structured fluids. The system is evaluated and validated with model systems, specifically micellar and (dilute) polymer solutions, and colloidal dispersions of different radii (∼1-100 nm). A systematic method of flow-DLS analysis is examined as a function of flow velocity (0-16 cm s-1), and considerations of the relative contribution of 'transit' and 'Brownian' terms enable the identification of regions where (i) a quiescent approximation suffices, (ii) the flow-DLS framework holds, as well as (iii) where deviations are found, until eventually (iv) the convection dominates. We investigate practically relevant, robust setups, namely that of a capillary connected to microdevice, as well as direct measurement on a glass microdevice, examining the role of capillary dimensions and challenges of optical alignment. We conclude with a demonstration of a continuous flow measurement of a binary surfactant/salt solution, whose micellar dimensions vary with composition, characterised with hundreds of data points (every ∼5 s) and adequate statistics, within a few minutes.

Phase behaviour of model triglyceride ternary blends: triolein, tripalmitin and tristearin.

We investigate the phase behavior of model ternary triacylglycerol blends, comprising triolein (C57H104O6, OOO), tripalmitin (C51H98O6, PPP) and tristearin (C57H110O6, SSS), building upon extensive characterisation of single and binary mixtures, in order to rigorously map the thermal transitions of model natural 'fats'. A combination of calorimetry, X-ray diffraction, and FTIR spectroscopy is employed to determine crystallisation and melting temperatures and identify the corresponding phases in the complex ternary system. We recover the eutectic behaviour of SSS-PPP blends and the invariability of OOO neat transitions, and resolve the complex ß' + ß ternary surface, reflecting the roles of unsaturation and polymorphism of its constituents. Our results provide a representation of the OOO:PPP:SSS:temperature phase behaviour into a triangular prism, consistent with binary pair-wise data, which can inform a range of food science, cosmetic, pharmaceutical and cleaning applications that depend strongly on the physical-chemistry of such multicomponent 'triglycerides'.

Ultra-/Small Angle X-ray Scattering (USAXS/SAXS) and Static Light Scattering (SLS) Modeling as a Tool to Determine Structural Changes and Effect on Growth in S. epidermidis.

Usually, to characterize bacterial cells' susceptibility to antimicrobials, basic microbiology techniques such as serial dilutions or disk assays are used. In this work, we present an approach focused on combining static light scattering (SLS) and ultra-/small angle X-ray scattering (USAXS/SAXS). This approach was used to support microbiology techniques, with the aim of understanding the structural changes caused to bacteria when they are exposed to different stresses like pH, oxidation, and surfactants. Using USAXS/SAXS and SLS data, we developed a detailed multiscale model for a Gram-positive bacterium, S. epidermidis, and we extracted information regarding changes in the overall size and cell thickness induced by different stresses (i.e., pH and hydrogen peroxide). Increasing the concentration of hydrogen peroxide leads to a progressive reduction in cell wall thickness. Moreover, the concomitant use of pH and hydrogen peroxide provides evidence for a synergy in inhibiting the S. epidermidis growth. These promising results will be used as a starting base to further investigate more complex formulations and improve/refine the data modeling of bacteria in the small angle scattering regime.

Microbial Response to Micrometer-Scale Multiaxial Wrinkled Surfaces.

We investigate the effect of micrometer-scale surface wrinkling on the attachment and proliferation of model bacteria (Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli K12) and fungi (Candida albicans). Specifically, sinusoidal (1D), checkerboard (C), and herringbone (H) patterns were fabricated by mechanical wrinkling of plasma-oxidized polydimethylsiloxane (PDMS) bilayers and contrasted with flat (F) surfaces. Microbial deformation and orientation were found to correlate with the aspect ratio and commensurably with surface pattern dimensions and local pattern order. Significantly, the proliferation of P. aeruginosa could be described by a linear scaling between bacterial area coverage and available surface area, defined as a fraction of the line integral along each profile with negative curvature. However, in the early stages of proliferation (up to 6 h examined), that C and H patterns disrupt the spatial arrangement of bacteria, impeding proliferation for several hours and reducing it (by ∼50%) thereafter. Our findings suggest a simple framework to rationalize the impact of micrometer-scale topography on microbial action and demonstrate that multiaxial patterning order provides an effective strategy to delay and frustrate the early stages of bacterial proliferation.

Solution Structures of Anionic-Amphoteric Surfactant Mixtures near the Two-Phase Region at Fixed pH.

We examine the solution structures in a mixed surfactant system of sodium dodecyl sulfate (SDS) and N,N-dimethyldodecylamine N-oxide (DDAO) in water, on both sides of the two-phase boundary, employing dynamic light scattering, small-angle neutron scattering, and Fourier transform infrared spectroscopy. The precipitate phase boundary was accessed by lowering pH to 8, from its floating pH 9.5 value, and was experimentally approached from the monomeric and micellar regions in three ways: at fixed DDAO or SDS concentrations and at a fixed (70:30) SDS:DDAO molar ratio. We characterize the size, shape, and interactions of micelles, which elongate approaching the boundary, leading to the formation of disk-like aggregates within the biphasic region, coexisting with micelles and monomers. Our data, from both monomeric and micellar solutions, indicate that the two phase structures formed are largely pathway-independent, with dimensions influenced by both pH and mixed surfactant composition. Precipitation occurs at intermediate stoichiometries with a similar SDS:DDAO ratio, whereas asymmetric stoichiometries form a re-entrant transition, returning to the mixed micelle phase. Overall, our findings demonstrate the effect of stoichiometry and solution pH on the synergistic interaction of mixed surfactants and their impact on phase equilibrium and associated micellar and two-phase structures.

Interfacial complexation of a neutral amphiphilic 'tardigrade' co-polymer with a cationic surfactant: Transition from synergy to competition.

HYPOTHESIS: Neutral amphiphilic PEG-g-PVAc co-polymer (a "tardigrade" polymer consisting of a hydrophilic polyethylene glycol, PEG, backbone with hydrophobic polyvinyl acetate, PVAc, grafts) can form complexes at the air-water interface with cationic dodecyltrimethylammonium bromide (DTAB) via self-assembly. Compared to anionic SDS, cationic DTAB headgroups are expected to interact strongly with the negatively charged OH- groups from the partial dissociation of the PVAc grafts. We anticipate a transition from synergistic to competitive behaviour, which is expected to be dependent on the surfactant structural characteristics and concentration. EXPERIMENTS: DTAB/PEG-g-PVAc mixtures were investigated using a combination of dynamic and equilibrium surface tension measurements, neutron reflectivity (NR) at the air-water interface, and foaming tests. We varied the concentrations of both the DTAB (0.05 to 5 critical micelle concentration, cmc) and that of PEG-g-PVAc (0.2 and 2 critical aggregation concentration, cac). FINDINGS: Our results show that the interfacial interactions between DTAB and PEG-g-PVAc were both synergistic and antagonistic, depending sensitively on the surfactant concentration. At DTAB concentrations below its cmc, a pronounced cooperative adsorption behaviour was likely driven by the hydrophobic interactions between the DTAB tail and the PVAc grafts and the attraction between the DTAB headgroups and the partially dissociated -O- groups in the partially hydrolysed PVAc grafts, forming a mixed layer. This synergistic adsorption behaviour transitioned to a competitive adsorption behaviour at DTAB concentrations above its cmc, leading to polymer-surfactant partition, forming a "hanging" polymer layer underlying a surfactant monolayer at the interface. We postulate that DTAB/PEG-g-PVAc complexation in the bulk contributed to partial depletion of the mixture from the interface. We therefore consider this polymer/surfactant system to be a moderately interacting system at the air-water interface. No discernible differences in the foaming behaviour were observed between the DTAB/PEG-g-PVAc systems and the pure surfactant. Our results suggest that surfactant headgroup characteristics (particularly charges) were crucial in determining the structure and composition of polymer-surfactant complexes at the air-water interface, as well as the foamability and foam stability, whilst the coexistence of the synergistic and competitive adsorption behaviour is attributed to the unique architecture of the tardigrade polymer with amphiphilicity and partial charge, facilitating different surfactant-polymer interactions at different DTAB concentrations.

Structure, Nanomechanical Properties, and Wettability of Organized Erucamide Layers on a Polypropylene Surface.

Understanding the nanostructure and nanomechanical properties of surface layers of erucamide, in particular the molecular orientation of the outermost layer, is important to its widespread use as a slip additive in polymer materials. Extending our recent observations of nanomorphologies of erucamide layers on a hydrophilic silica substrate, here we evaluate its nanostructure on a more hydrophobic polypropylene surface. Atomic force microscopy (AFM) imaging revealed the molecular packing, thickness, and surface coverage of the erucamide layers, while peak force quantitative nanomechanical mapping (QNM) showed that erucamide reduced the adhesive response on polypropylene. Synchrotron X-ray reflectivity (XRR) was used to probe the out-of-plane structure of the surface layers. Static contact angle measurements further corroborated on the resulting wettability, also demonstrating the efficacy of erucamide physisorption in facilitating control over polypropylene surface wetting. The results show the formation of erucamide monolayers, bilayers and multilayers, depending on the concentration in the spin-cast solution. Correlation of AFM, XRR and wettability results consistently points to the molecular orientation in the outermost layer, i.e. with the erucamide tails pointing outward for the surface nanostructures with different morphologies (i.e., bilayers and multilayers). Rare occurrence of monolayers with exposed hydrophilic head groups were observed only at the lowest erucamide concentration. Compared with our previous observations on the hydrophilic surface, the erucamide surface coverage was much higher on the more hydrophobic propylene surface at similar erucamide concentrations in the spin-cast solution. Furthermore, the structure, molecular orientation and nanomechanical properties of the spin-cast erucamide multilayers atop polypropylene were also similar to those on industrially relevant polypropylene fibers coated with erucamide via blooming. These findings shed light on the nanostructural features of the erucamide surface layer underpinning its nanomechanical properties, relevant to many applications in which erucamide is commonly used as a slip additive.

Aqueous Phase Behavior of a NaLAS-Polycarboxylate Polymer System.

Linear alkylbenzene sulfonate (NaLAS) surfactant is often combined with polycarboxylate polymers in detergent formulations. However, the behavior of these aqueous surfactant-polymer systems in the absence of an added electrolyte is unreported. This work investigates the behavior of such systems using polarized light microscopy, small-angle X-ray scattering (SAXS), centrifugation, and 2H NMR techniques. A phase diagram at 50 °C is reported for 0-50 wt % NaLAS concentrations and 0-10 wt % polycarboxylate concentrations. The NaLAS-water system is micellar at concentrations <35 wt %, and a 2-phase micellar-lamellar system is seen at higher NaLAS levels, consistent with that reported by previous studies. As polymers are added at low surfactant concentrations (∼10 to 20 wt % NaLAS), a second optically isotropic phase is formed; this is thought to be a polymer-rich phase. Further addition of polycarboxylate leads to the formation of a lamellar phase. At high surfactant concentrations (>20 wt % NaLAS), the addition of a polymer induces a second lamellar phase. These observed behaviors are thought to arise as a result of depletion flocculation and salting-out effects. The observed lamellar phases adopt colloidal multilamellar vesicle (MLV) structures, and the average MLV radii were estimated using 2H NMR by probing the diffusion and anisotropy of D2O within the bilayers of the vesicles. The NMR results show that as the polymer concentration was increased from 0 to 10 wt %, an increase in the average multilamellar vesicle size from ∼200 to ∼500 nm was observed. This increase in the calculated average MLV radius likely results from depletion flocculation-induced MLV fusion.

Characterization of Open-Cell Sponges via Magnetic Resonance and X-ray Tomography.

The applications of polymeric sponges are varied, ranging from cleaning and filtration to medical applications. The specific properties of polymeric foams, such as pore size and connectivity, are dependent on their constituent materials and production methods. Nuclear magnetic resonance imaging (MRI) and X-ray micro-computed tomography (µCT) offer complementary information about the structure and properties of porous media. In this study, we employed MRI, in combination with µCT, to characterize the structure of polymeric open-cell foam, and to determine how it changes upon compression, µCT was used to identify the morphology of the pores within sponge plugs, extracted from polyurethane open-cell sponges. MRI T2 relaxation maps and bulk T2 relaxation times measurements were performed for 7° dH water contained within the same polyurethane foams used for µCT. Magnetic resonance and µCT measurements were conducted on both uncompressed and 60% compressed sponge plugs. Compression was achieved using a graduated sample holder with plunger. A relationship between the average T2 relaxation time and maximum opening was observed, where smaller maximum openings were found to have a shorter T2 relaxation times. It was also found that upon compression, the average maximum opening of pores decreased. Average pore size ranges of 375-632 ± 1 µm, for uncompressed plugs, and 301-473 ± 1 µm, for compressed plugs, were observed. By determining maximum opening values and T2 relaxation times, it was observed that the pore structure varies between sponges within the same production batch, as well as even with a single sponge.

Heads or tails: Nanostructure and molecular orientations in organised erucamide surface layers.

HYPOTHESIS: Despite the widespread industrial usage of erucamide as a slip additive to modify polymer surface properties, a controversy appears to have persisted regarding the nanostructure of erucamide surface layers, particularly the molecular orientation at the outermost layer. The erucamide nanostructure and molecular orientation, along with its surface coverage, hydrophobicity, and adhesive response, can be tuned by simply varying the erucamide concentration in the solution from which the spin coated layer is prepared. EXPERIMENTS: Synchrotron X-ray reflectivity (XRR) allowed a comprehensive characterisation of the out-of-plane structural parameters (e.g. molecular packing and thickness) of the erucamide layers prepared via spin coating from nonaqueous solution on silica. Complementary Atomic Force Microscopy (AFM) imaging with high lateral resolution revealed localised in-plane structures. Contact angle measurements provided information on the wettability of erucamide-coated surfaces. Peak Force Quantitative Nanomechanical Mapping (QNM) allowed a correlation between the erucamide nanostructure with the surface nanomechanical properties (i.e. adhesive response). FINDINGS: Our results reveal erucamide surface nanostructures on silica as patchy monolayers, isolated circular bilayers/rounded rectangle-like aggregates and overlapping plate-like multilayers as the erucamide concentration in the spin coating solution was varied. In all the cases, XRR and AFM results were consistent with the picture that the erucamide tails were oriented outwards. The QNM adhesion force mapping of all the observed morphologies also supported this molecular orientation at the outermost erucamide monolayer. The wettability study further confirmed this conclusion with the observed increase in the surface hydrophobicity and coverage upon increasing erucamide concentration, with the macroscopic water contact angle θ = 92.9° ± 2.9° at the highest erucamide concentration of 2 wt%.

Phase separation and collapse in almost density matched depletion induced colloidal gels in presence and absence of air bubbles: An MRI imaging study.

HYPOTHESIS: Vesicle-polymer dispersions are found in drug-delivery systems and consumer products but undergo phase separation. Previous studies of phase separation have focussed on systems with high density differences between continuous and vesicular phases. In this study, we investigate phase separation in vesicle-polymer mixtures with very small density differences, in the presence and absence of air bubbles. EXPERIMENTS: Magnetic resonance (MR) imaging, X-ray Computed Tomography and rheological measurements are reported which characterise the properties and stability of vesicle suspensions composed of the cationic surfactant, diethylesterdimethyl ammonium chloride, mixed with non-adsorbing polymer. 1H T2 MR relaxation images are employed to observe phase separation, for a range of vesicle-polymer mixtures, which are analysed using Moran's I spatial autocorrelation to quantify the extent and rate of phase separation. FINDINGS: It was found that in presence of air bubbles, phase separation follows a compression/collapse mechanism, typical of colloidal gels with large density differences between the phases. Without air bubbles, phase separation develops through the formation of tiny cracks and fractures in the samples. MRI enabled visualisation of the evolution of phase separation inside highly turbid samples. The rate of phase separation was found to generally increase with increasing polymer concentration and decrease with increasing vesicle volume fraction.

Pure and mixed aqueous micellar solutions of Sodium Dodecyl sulfate (SDS) and Dimethyldodecyl Amine Oxide (DDAO): Role of temperature and composition.

Aqueous mixtures of anionic and nonionic/cationic surfactants can form non-trivial self-assemblies in solution and exhibit macroscopic responses. Here, we investigate the micellar phase of pure and mixed aqueous solutions of Sodium Dodecyl Sulfate (SDS) and Dimethyldodecyl Amine Oxide (DDAO) using a combination of Small Angle Neutron Scattering (SANS), Fourier-Transform Infrared Spectroscopy (FTIR) and rheological measurements. We examine the effect of temperature (0-60 °C), on the 20 wt% SDS micellar solutions with varying DDAO (⩽5 wt%), and seek to correlate micellar structure with zero-shear solution viscosity. SANS establishes the formation of prolate ellipsoidal micelles in aqueous solutions of pure SDS, DDAO and SDS/DDAO mixtures, whose axial ratio is found to increase upon cooling. Elongation of the ellipsoidal micelles of pure SDS is also induced by the introduction of the non-anionic DDAO, which effectively reduces the repulsive interactions between the anionic SDS head-groups. In FTIR measurements, the formation of elongated mixed ellipsoidal micelles is confirmed by the increase of ordering in the hydrocarbon chain tails and interaction between surfactant head-groups. We find that the zero-shear viscosity of the mixed surfactant solutions increases exponentially with decreasing temperature and increasing DDAO content. Significantly, a master curve for solution viscosity can be obtained in terms of micellar aspect ratio, subsuming the effects of both temperature and DDAO composition in the experimental range investigated. The intrinsic viscosity of mixed micellar solutions is significantly larger than the analytical and numerical predictions for Brownian suspensions of ellipsoidal colloids, highlighting the need to consider interactions of soft micelles under shear, especially at high concentrations.

Micellar structure and transformations in sodium alkylbenzenesulfonate (NaLAS) aqueous solutions: effects of concentration, temperature, and salt.

We investigate the shape, dimensions, and transformation pathways of micelles of linear sodium alkylbenzenesulfonate (NaLAS), a common anionic surfactant, in aqueous solution. Employing Small Angle Neutron Scattering (SANS) and surface tensiometry, we quantify the effects of surfactant concentration (0.6-15 wt%), temperature (5-40 °C) and added salt (≤0.35 M Na2SO4). Spherical micelles form at low NaLAS (≤2.6 wt%) concentration in water, and become elongated with increasing concentration and decreasing temperature. Addition of salt reduces the critical micelle concentration (CMC) and thus promotes the formation of micelles. At fixed NaLAS concentration, salt addition causes spherical micelles to grow into cylindrical micelles, and then multilamellar vesicles (MLVs), which we examine by SANS and cryo-TEM. Above a threshold salt concentration, the MLVs reach diameters of 100 s of nm to few µm, eventually causing precipitation. While the salt concentrations associated with the micelle-to-cylinder transformation increase only slightly with temperature, those required for the cylinder-to-MLV transformation exhibit a pronounced, linear temperature dependence, which we examine in detail. Our study establishes a solution structure map for this model anionic surfactant in water, quantifying the combined roles of concentration, temperature and salt, at practically relevant conditions.

A microfluidic-multiwell platform for rapid phase mapping of surfactant solutions.

Measurement of the phase behavior and (meta)stability of liquid formulations, including surfactant solutions, is required for the understanding of mixture thermodynamics, as well as their practical utilization. We report a microfluidic platform with a stepped temperature profile, imposed by a dual Peltier module, connected to an automated multiwell plate injector and optical setup, for rapid solution phase mapping. The measurement protocol is defined by the temperature step ΔT ≡ T1 - T2 (≲100 °C), volumetric flow rate Q ≡ ΔV/Δt (≲50 µl/min), which implicitly set the thermal gradient ΔT/Δt (≃0.1-50 °C/min), and measurement time (which must exceed the intrinsic timescale of the relevant phase transformation). Furthermore, U-shaped microchannels can assess the reversibility of such transformations, yielding a facile measurement of the metastable zone width of the phase diagram. By contrast with traditional approaches, the platform precisely controls the cooling and heating rates by tuning the flow rate, and the absolute temperature excursion by the hot and cold thermal profile, which remain stationary during operation, thus allowing the sequential and reproducible screening of large sample arrays. As a model system, we examined the transition from the micellar (L1) to the liquid crystalline lamellar phase (Lα), upon cooling, of aqueous solutions of sodium linear alkylbenzene sulfonate, a biodegradable anionic surfactant extensively employed in industry. Our findings are validated with quiescent optical microscopy and small angle neutron scattering data.

Multiscale characterisation of single synthetic fibres: Surface morphology and nanomechanical properties.

HYPOTHESIS: Thermal through-air bonding process and slip additive treatment affect fibre surface structure and nanomechanical properties, which is extremely difficult to characterise on a single-fibre level. EXPERIMENTS: Optical microscopy (OM) was applied to study the effect of air-through bonding, spunbonding, and crimping on fibre geometry and general appearance. A "spray-on" method developed here using a custom-designed fibre holder allowed a direct measurement of static contact angles of water droplets on single fibres. Scanning electron microscopy (SEM) showed different morphological features on the fibre due to the nonwoven fabric-making process and additive treatment. Synchrotron X-ray diffraction (XRD) was applied to study the effect of erucamide presence on polypropylene (PP) fibre crystal structure. Atomic force microscopy (AFM) imaging provided complementary characterization of fibre topographic features such as average surface roughness, along with adhesion force mapping by quantitative nanomechanical (QNM) AFM imaging. FINDINGS: Our results show the effect of nonwoven making process and surfactant additive treatment on the fibre surface structure and nanomechanical properties. Wettability experiment on the single fibre revealed the hydrophobic nature of all the synthetic fibres. For polyethylene/polyethylene terephthalate (PE/PET) bicomponent single fibres, the polyethylene sheath was found to possess fibrillar microstructure - typical for drawn fibres, whereas the fibres entangled in nonwoven fabrics exhibited a uniform, porous surface morphology attributed to the through-air process. Adhesion force mapping allowed us to correlate fibre nanomechanical properties with its topography, with surface pore interiors showing higher adhesion than the flat polyethylene region. Furthermore, on the polypropylene (PP) fibre surface treated with erucamide (13-cis-docosenamide; a common slip additive used in polyolefin film processing), we observed overlapping multilayers consisting of 4 nm erucamide bilayers, attributed to the slip additive migration onto the fibre surface. XRD measurements of the fibres did not detect the presence of erucamide; however, AFM imaging provided evidence for its migration to the fibre surface, imparting influence on the surface structure and adhesive properties of the fibre. Single-fibre AFM imaging also allowed a detailed analysis of different surface roughness parameters, revealing that both through-air bonding in the nonwoven making process and the slip additive (erucamide) treatment affected the fibre surface roughness. The wettability, surface morphology, and adhesion properties from this study, obtained with unprecedented resolution and details on single fibres, are valuable to informing rational design of fibre processing for fibre optimal properties, critically important in many industrial applications.

Synergy, competition, and the "hanging" polymer layer: Interactions between a neutral amphiphilic 'tardigrade' comb co-polymer with an anionic surfactant at the air-water interface.

Understanding the structure of polymer/surfactant mixtures at the air-water interface is of fundamental importance and also of relevance to a variety of practical applications. Here, the complexation between a neutral 'tardigrade' comb co-polymer (consisting of a hydrophilic polyethylene glycol backbone with hydrophobic polyvinyl acetate grafts, PEG-g-PVAc) with an anionic surfactant (sodium dodecyl sulfate, SDS) at the air-water interface has been studied. Contrast-matched neutron reflectivity (NR) complemented by surface tension measurements allowed elucidation of the interfacial composition and structure of these mixed systems, as well as providing physical insights into the polymer/surfactant interactions at the air-water interface. For both polymer concentrations studied, below and above its critical aggregation concentration, cac, (0.2 cac and 2 cac, corresponding to 0.0002 wt% or 0.013 mM and 0.002 wt% or 0.13 mM respectively), we observed a synergistic cooperative behaviour at low surfactant concentrations with a 1-2 nm mixed interfacial layer; a competitive adsorption behaviour at higher surfactant concentrations was observed where the polymer was depleted from the air-water interface, with an overall interfacial layer thickness ~1.6 nm independent of the polymer concentration. The weakly associated polymer layer "hanging" proximally to the interface, however, played a role in enhancing foam stability, thus was relevant to the detergency efficacy in such polymer/surfactant mixtures in industrial formulations.

Spontaneous formation of multilamellar vesicles from aqueous micellar solutions of sodium linear alkylbenzene sulfonate (NaLAS).

We report the spontaneous formation of multilamellar vesicles (MLVs) from low concentration (<30 wt%) aqueous micellar solutions of sodium linear alkylbenezene sulfonate (NaLAS) upon cooling, employing a combination of optical microscopy (OM), Small Angle Neutron Scattering (SANS), and Cryo-TEM. Upon cooling, MLVs grow from, and coexist with, the surfactant micelles, attaining diameters ranging from hundreds of nanometers to a few micrometers depending on the cooling rate, whilst the d-spacing of internal lamellae remains unchanged, at ≃ 3 nm. While microscale fluid and flow properties of the mixed MLVs and micellar phase depend on rate of cooling, the corresponding nanoscale structure of the surfactant aggregates, resolved by time-resolved SANS, remains unchanged. Our data indicate that the mixed MLV and micellar phases are in thermodynamic equilibrium with a fixed relative volume fraction determined by temperature and total surfactant concentration. Under flow, MLVs aggregate and consequently migrate away from the channel walls, thus reduce the overall hydrodynamic resistance. Our findings demonstrate that the molecular and mesoscopic structure of ubiquitous, low concentration NaLAS solutions, and in turn their flow properties, are dramatically influenced by temperature variation about ambient conditions.

Effect of glycerol with sodium chloride on the Krafft point of sodium dodecyl sulfate using surface tension.

The effect of glycerol with sodium chloride (NaCl) on the phase behaviour of sodium dodecyl sulfate (SDS) near the Krafft point was studied by surface tension analysis using the pendant drop method. The critical micelle concentration (CMC) and Krafft Temperature (TK) of SDS in water: glycerol mixtures, across the full composition range, and in NaCl solutions within 0.005-0.1 M were obtained. The pendant drop method successfully allowed us to determine the Krafft point of SDS in high glycerol systems where other traditional methods (e.g. conductivity) have been ineffective. Overall the addition of glycerol increases the CMC and the TK, thus shifting the Krafft point of SDS to higher temperatures (increasing crystallisation temperatures) and higher SDS content in the presence of glycerol, which is interpreted as a result of the reduction in solvent polarity which opposes micellization. The addition of NaCl to the SDS - water-glycerol systems brings the CMC back down, while having no significant effect on the TK. Our results establish a robust route for tuning the Krafft point of model surfactant SDS by adjusting solvent quality and salt content.