We investigate the structure and interactions of a model anionic/amphoteric mixed surfactant micellar system, namely, sodium dodecyl sulfate (SDS) and ,-dimethyldodecylamine -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 ( ∼ 25-40 Å), accompanied by up to a 6-fold increase in micellar charge.
View Article and Find Full Text PDFErucamide 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.
View Article and Find Full Text PDFWe 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), 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.
View Article and Find Full Text PDFPhys Chem Chem Phys
December 2022
We investigate the phase behavior of model ternary triacylglycerol blends, comprising triolein (CHO, OOO), tripalmitin (CHO, PPP) and tristearin (CHO, 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 β' + β ternary surface, reflecting the roles of unsaturation and polymorphism of its constituents.
View Article and Find Full Text PDFUsually, 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.
View Article and Find Full Text PDFACS Appl Mater Interfaces
July 2022
We investigate the effect of micrometer-scale surface wrinkling on the attachment and proliferation of model bacteria (, , and K12) and fungi (). 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.
View Article and Find Full Text PDFWe examine the solution structures in a mixed surfactant system of sodium dodecyl sulfate (SDS) and ,-dimethyldodecylamine -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.
View Article and Find Full Text PDFHypothesis: 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.
View Article and Find Full Text PDFUnderstanding 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 , here we evaluate its nanostructure on a . 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.
View Article and Find Full Text PDFThe 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.
View Article and Find Full Text PDFLinear 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 H NMR techniques.
View Article and Find Full Text PDFHypothesis: 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.
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.
View Article and Find Full Text PDFHypothesis: 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.
View Article and Find Full Text PDFWe 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.
View Article and Find Full Text PDFMeasurement 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 ≡ T - T (≲100 °C), volumetric flow rate Q ≡ ΔV/Δt (≲50 μl/min), which implicitly set the thermal gradient ΔT/Δt (≃0.
View Article and Find Full Text PDFHypothesis: 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.
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.
View Article and Find Full Text PDFThe interactions between supported cationic surfactant bilayers were measured by colloidal probe atomic force spectroscopy, and the effect of different halide salts was investigated. Di(alkylisopropylester)dimethylammonium methylsulfate (DIPEDMAMS) bilayers were fabricated by the vesicle fusion technique on muscovite mica. The interactions between the bilayers were measured in increasing concentrations of NaCl, NaBr, NaI, and CaCl.
View Article and Find Full Text PDFThe 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 (T) of SDS in water: glycerol mixtures, across the full composition range, and in NaCl solutions within 0.005-0.
View Article and Find Full Text PDFRecent advances in high resolution X-ray tomography (μCT) technology have enabled in-situ dynamic μCT imaging (4D-μCT) of time-dependent processes inside 3D structures, non-destructively and non-invasively. This paper illustrates the application of 4D-μCT for visualizing the removal of fatty liquids from kitchen sponges made of polyurethane after rinsing (absorption), squeezing (desorption) and cleaning (adding detergents). For the first time, time-dependent imaging of this type of system was established with sufficiently large contrast gradient between water (with/without detergent) and olive oil (model fat) by the application of suitable fat-sensitive X-ray contrast agents.
View Article and Find Full Text PDFIn complex colloidal systems, particle-poor regions can develop within particle-rich phases during sedimentation or creaming. These particle-poor regions are overlooked by 1D profiles, which are typically used to assess particle distributions in a sample. Alternative methods to visualise and quantify these regions are required to better understand phase separation, which is the focus of this paper.
View Article and Find Full Text PDFThe structure and flow behavior of a concentrated aqueous solution (45 wt %) of the ubiquitous linear sodium alkylbenzenesulfonate (NaLAS) surfactant is investigated by microfluidic small-angle X-ray scattering (SAXS) at 70 °C. NaLAS is an intrinsically complex mixture of over 20 surfactant molecules, presenting coexisting micellar (L1) and lamellar (Lα) phases. Novel microfluidic devices were fabricated to ensure pressure and thermal resistance, ability to handle viscous fluids, and low SAXS background.
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