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.

Stratification and film ripping induced by structural forces in granular micellar thin films.

HYPOTHESIS: Interactions across incredibly thin layers of fluids, known as thin films, underpin many important processes involving colloids, such as wetting-dewetting phenomena. Often in these systems, thin films are composed of complex fluids that contain dispersed components, such as spherical micelles, giving rise to oscillatory structural forces due to preferential layering under confinement. Modelling of thin film dynamics involving Derjaguin-Landau-Verwey-Overbeek (DLVO) type forces has been widely reported using the Stokes-Reynolds-Young-Laplace (SRYL) model, and we hypothesize that this theory can be extended to a concentrated micellar system by including an oscillatory structural force term in the disjoining pressure. EXPERIMENTS: We study the drainage behaviour of thin films comprising sodium dodecyl sulfate (SDS) micelles across a range of concentrations and interaction conditions between an air bubble and a mica disk using a custom-built dual-wave interferometry apparatus. FINDINGS: Early-stage film behaviour is dominated by hydrodynamics, which can be well reproduced by the SRYL model. However, experimental profiles drain significantly faster than predicted, transitioning into a structural force dominated phase characterised by four types of film ripping instabilities that we term 'waving', 'ridging', 'webbing', and 'hole-sheeting'. These instabilities were mapped according to SDS concentration and approach velocity, providing insight into the interplay between structural forces and hydrodynamic conditions.

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.

Parametric Study of Colloidal Particle Confinement near a Surface in the Presence of DLVO and Structural Interactions Using Brownian Dynamic Simulations.

Total internal reflection microscopy (TIRM) has become a crucial technique for understanding the surface interactions and dynamics of Brownian colloidal particles near a surface. However, for select colloidal systems, experimental limitations associated with TIRM can occlude exploration of nano- and submicrometer colloids dispersed in complex or structured fluids. It should be possible to use Brownian dynamic simulations to quantify, explore, or circumvent these limitations to extend the TIRM technique further. A Brownian dynamics algorithm based on the Langevin equation was utilized to identify favorable colloidal systems for conducting TIRM experiments in electrolyte and nonadsorbing polyelectrolyte solutions. In electrolyte solution, the motion of polystyrene and silica particles of nanometer- and micrometer-sized radii was simulated near a glass slide in the presence of retarded van der Waals and electric double-layer forces to develop potential energy profiles. In the case of nonadsorbing polyelectrolyte solutions, a structural force was also implemented into the simulation, and the influence of structural interactions on particle confinement was explored as a function of particle size, particle density, and polyelectrolyte concentration. In electrolyte solutions, our results were able to identify the minimum particle size required for TIRM experiments as well as insight into particle selection based on material density. For structural or oscillatory forces, our results show that prior to conducting TIRM experiments, Brownian dynamics simulation can be used to select the appropriate particle size, material, and polyelectrolyte concentration range where the colloidal particle can sample multiple structural energy wells without confinement. These results provide insight into the colloidal system suitable to experimentally study near-surface particle diffusion dynamics for a range of separations in the presence of structural interactions.

Anisotropic Particle Fabrication Using Thermal Scanning Probe Lithography.

Size, shape, and chemical properties of nanoparticles are powerful tools to modulate the optical and physicochemical properties of a particle suspension. Despite having many methods to synthesize anisotropic nanoparticles, often there are challenges in terms of controlling the polydispersity, shape, size, or composition of anisotropic nanoparticles. This work has been inspired by the potential for developing a unique pathway to make different shaped monodispersed anisotropic nano- and microparticles with large flexibility in material choice. Compared to existing methods, this state-of-the-art nanolithographic method is fast, easy to prototype, and much simple in terms of its mechanical requirement. We show that this technique has been efficiently used to make a variety of anisotropic nano- and microparticles of different shapes, such as triangular prisms, ovals, disks, flowers, and stairs following the same pathway, at the same time showing the potential of being flexible with respect to the composition of the particles. The thermal scanning probe lithographic method in combination with dry reactive ion etching was used to make two-dimensional and three-dimensional templates for the fabrication of anisotropic nano- and microparticles. Deposition of different metal/metal oxides by the electron-beam evaporation method onto these templates allowed us to fabricate a range of nanomaterials according to the required functionality in potential applications. The particles were characterized by atomic force microscopy, He-ion microscopy, scanning electron microscopy, and dynamic light scattering to ensure that the developed method is reproducible, flexible, and robust in choosing the shapes for making monodispersed anisotropic nanoparticles with great control over shape and size.

Assembling Native Elementary Cellulose Nanofibrils via a Reversible and Regioselective Surface Functionalization.

Selective surface modification of biobased fibers affords effective individualization and functionalization into nanomaterials, as exemplified by the TEMPO-mediated oxidation. However, such a route leads to changes of the native surface chemistry, affecting interparticle interactions and limiting the development of potential supermaterials. Here we introduce a methodology to extract elementary cellulose fibrils by treatment of biomass with N-succinylimidazole, achieving regioselective surface modification of C6-OH, which can be reverted using mild post-treatments. No polymer degradation, cross-linking, nor changes in crystallinity occur under the mild processing conditions, yielding cellulose nanofibrils bearing carboxyl moieties, which can be removed by saponification. The latter offers a significant opportunity in the reconstitution of the chemical and structural interfaces associated with the native states. Consequently, 3D structuring of native elementary cellulose nanofibrils is made possible with the same supramolecular features as the biosynthesized fibers, which is required to unlock the full potential of cellulose as a sustainable building block.

Viscoelastic characterization of the crosslinking of ß-lactoglobulin on emulsion drops via microcapsule compression and interfacial dilational and shear rheology.

HYPOTHESIS: Interfacial rheology provides insight into the mechanical properties of adsorption layers on liquid-liquid interfaces, which mediates the stability of emulsion droplets. The use of capsule compression at the scale of an emulsion droplet to probe the interfacial rheology may open up the possibility of testing the interfacial rheological properties of droplets with complex histories and extremely small volumes found in many applications. EXPERIMENTS: The time dependent interfacial rheological behavior of ß-lactoglobulin adsorption layers on an oil/water interface in the native and crosslinked state was extracted using small oscillatory indentation with atomic force microscopy (AFM). The results of this novel model and experimental approach were compared to the well-established techniques of interfacial shear rheology (ISR) and dilational pendant drop tensiometry that were performed on analogous interfaces. FINDINGS: The tan δ measured between the ISR and AFM measurements provide similar results in an overlapping frequency range, but the viscoelastic moduli G' and G'' differ by several orders of magnitude. This is most likely the result of the different flow fields and the low deformation of the AFM measurements compared to dilational and shear flow fields.

Interfacial Properties of Chitosan in Interfacial Shear and Capsule Compression.

The time-dependent behavior of surface-active adsorption layers at the oil/water interface can dictate emulsion behavior at both the micro- and macroscale. In addition, self-healing behavior of the adsorption layer may benefit emulsion stability subject to large deformation under processing or during final application. We explore the behavior of chitosan, a known hydrophilic emulsifier, which forms nanoparticle aggregates when the concentration of acetate buffer exceeds 0.3 M. We observe a Pickering adsorption layer building and strain-dependent behavior of the chitosan at the medium chain triglyceride oil/water interface. We compare this to the behavior of identical chitosan layers coated on oil droplets via atomic force microscopy colloidal probe compression in both linear and oscillatory compressions. In both interfacial shear rheometry and the capsule compression, a thick, elastic layer with strong time-dependent recovery behavior is observed, suggesting that the layer has some self-healing capabilities.

Poroelastic properties of hydrogel microparticles.

Hydrogels can be formed in a number of different geometries depending upon desired function. However, due to the lack of appropriate models required to interpret experimental data, it remains unclear whether hydrogel microparticles have the same poroelastic properties as hydrogel films made with the same components. We perform numerical simulations to determine the universal force relaxation of a poroelastic hydrogel particle undergoing constant compression by a spherical probe, allowing analysis of experimental measurements of hydrogel particle material properties for the first time. In addition, we perform experimental measurements, using colloidal probe atomic force microscopy, of the force relaxation of polyacrylamide films and particles made with identical monomer and cross-linker concentrations. We fit our universal curve to the experimental data in order to extract material properties including shear modulus, Poisson's ratio and solvent diffusivity. Good agreement is found for the shear modulus and Poisson's ratio between the particles and the films. In contrast, the diffusivity of the polyacrylamide particles was found to be about half that of the films, suggesting that differences in the synthesis and homogeneity of the films and the particles play a role in determining transport and subsequent release of molecules in hydrogel particles.

Mass transfer between microbubbles.

HYPOTHESIS: The role of interfacial coatings in gas transport dynamics in foam coarsening is often difficult to quantify. The complexity of foam coarsening measurements or gas transport measurements between bubbles requires assumptions about the liquid thin film thickness profile in order to explore the effects of interfacial coatings on gas transport. It should be possible to independently quantify the effects from changes in film thickness and interfacial permeability by using both atomic force microscopy and optical microscopy to obtain time snapshots of this dynamic process. Further, it is expected that the surfactant and polymer interfacial coatings will affect the mass transfer differently. EXPERIMENTS: We measure the mass transfer between the same nitrogen microbubbles pairs in an aqueous solution using two methods simultaneously. First, we quantify the bubble volume changes with time via microscopy and second, we use Atomic Force Microscopy to measure the film thickness and mass transfer resistances using a model for the gas transport. FINDINGS: Modelling of the interface deformation, surface forces and mass transfer across the thin film agrees with independent measurements of changes in bubble size. We demonstrate that an anionic surfactant does not provide a barrier to mass transfer, but does enhance mass transfer above the critical micelle concentration. In contrast, a polymer monolayer at the interface does restrict mass transfer.

Effect of Orientation and Wetting Properties on the Behavior of Janus Particles at the Air-Water Interface.

The adhesion force and contact angle of gold-capped silica Janus particles and plain silica particles at an air-water interface are studied via colloidal atomic force microscopy. Particles are attached to cantilevers at various orientations, and wetting properties of the gold surface are varied through modification with dodecanethiol. Thiol modification increases the hydrophobicity of the gold surface, thereby increasing the difference between the contact angles of the gold hemisphere and the silica hemisphere and, thus, increasing the degree of amphiphilicity of the Janus particle. Subsequently, the colloidal probe is pushed into a stationary bubble from the water phase followed by retraction back into the water phase. Adhesion force is found to be higher for Janus particles than isotropic silica particles, regardless of orientation of the anisotropic hemisphere. Particles with their polar half oriented toward the water and apolar half facing the air show an increase in adhesion force and contact angle as the degree of amphiphilicity of the particles increases. For particles of the reverse orientation, no significant difference is observed as wetting properties change. Both adhesion force and contact angle display an inverse relationship with a cap angle for particles with a higher degree of amphiphilicity. These results are of importance for using Janus particles to stabilize interfaces as well as for understanding the equilibrium height of Janus particles at the interface, which will impact capillary interactions and thus self-assembly.

Use of microaspiration to study the mechanical properties of polymer gel microparticles.

The mechanical properties of polyacrylamide (PA) and polydimethylsiloxane (PDMS) microparticle populations have been measured using microaspiration, a recently developed experimental technique. Microaspiration is an augmented version of micropipette aspiration, in which optical microscopy data are obtained as individual soft particles pass through the tip of a micropipette. During microaspiration, the ion current passing through the pipette tip is also measured, and the synchronised optical and current data streams are used to study and quantify mechanical properties. Ion current signatures for the poroelastic PA particles were qualitatively different from those of the viscoelastic PDMS particles. For PA particles the current gradually reduced during each aspiration event, whereas for PDMS particles the current trace resembled a negative top hat function. For PA particles it was found that the maximum change in current during aspiration (ΔIh) increased with particle size. By considering the initial elastic response, a mean effective shear modulus (G') of 6.6 ± 0.2 kPa was found for aspiration of 115 PA particles of ∼10-20 µm diameter. Using a viscoelastic model to describe flow into the pipette, a mean initial effective elastic modulus (E0') of 3.5 ± 1.7 MPa was found for aspiration of 17 PDMS particles of ∼ 9-11 µm diameter. These moduli are consistent with previously reported literature values, providing initial validation of the microaspiration method.

Forces between oil drops in polymer-surfactant systems: Linking direct force measurements to microfluidic observations.

HYPOTHESIS: Linking atomic force microscopy and microfluidics opens up the possibility of probing adhesive interactions between drops in a high-throughput context. A microfluidic device designed to form, and subsequently break-up, chains of drops, where the drop break-up is sensitive to the underlying surface forces between drops, not hydrodynamic drainage forces, would play a key role in developing this link. EXPERIMENTS: Both techniques have been used to quantify the forces between oil drops in the presence of complexes formed with anionic surfactant, sodium dodecylsulphate, and neutral, water soluble polymer, poly(vinylpyrrolidone). Measurement and modelling of the interaction forces between both rigid and deformable surfaces demonstrated that the attraction between the drops is due to depletion forces, whereas the repulsive force is a combination of electrical double layer and steric forces, indicating complexes exist both in the bulk and at the drop interface. FINDINGS: The interaction behaviour between the force measurements and the microfluidic observations showed a strong correlation, where the observed adhesion between drops in the microfluidics is sensitive to the drop deformation and Laplace pressure. Correlation between the two techniques provides insight into the surface forces between drops in flowing systems and has potential utility in the formulation of emulsions.

Ultrasonically synthesized organic liquid-filled chitosan microcapsules: part 2: characterization using AFM (atomic force microscopy) and combined AFM-confocal laser scanning fluorescence microscopy.

Atomic Force Microscopy (AFM) is used to measure the stiffness and Young's modulus of individual microcapsules that have a chitosan cross-linked shell encapsulating tetradecane. The oil filled microcapsules were prepared using a one pot synthesis via ultrasonic emulsification of tetradecane and crosslinking of the chitosan shell in aqueous solutions of acetic acid. The concentration of acetic acid in aqueous solutions of chitosan was varied from 0.2% to 25% v/v. The effect of acetic acid concentration and size of the individual microcapsules on the strength was probed. The deformations and forces required to rupture the microcapsules were also measured. Three dimensional deformations of microcapsules under large applied loads were obtained by the combination of Laser Scanning Confocal Microscopy (LSCM) with Atomic Force Microscopy (AFM). The stiffness, and hence the modulus, of the microcapsules was found to decrease with an increase in size with the average stiffness ranging from 82 to 111 mN m-1 and average Young's modulus ranging from 0.4 to 6.5 MPa. The forces required to rupture the microcapsules varied from 150 to 250 nN with deformations of the microcapsules up to 62 to 110% relative to their radius, respectively. Three dimensional images obtained using laser scanning confocal microscopy showed that the microcapsules retained their structure and shape after being subjected to large deformations and subsequent removal of the loads. Based on the above observations, the oil filled chitosan crosslinked microcapsules are an ideal choice for use in the food and pharmaceutical industries as they would be able to withstand the process conditions encountered.

Ultrasonically synthesized organic liquid-filled chitosan microcapsules: part 1: tuning physical & functional properties.

This study reports the synthesis of tetradecane-filled chitosan microcapsules in acetic acid aqueous solutions using high intensity ultrasound at 20 kHz. The size, size distribution, and stability of microcapsules were tuned by varying the concentration of acetic acid from 0.2% to 25% v/v. After long-time storage at room temperature (more than 3 months), the microcapsules maintained their shell-core structure where the volume of the microcapsules at 0.2% acetic acid concentration increased by 8.3% due to leaking and coalescence. Microcapsules were consistently spherical and had a smooth shell surface, however, their shell thickness varied with acetic acid concentration. The relaxation behavior of individual microcapsules to an applied constant stress was measured by atomic force microscopy (AFM) to probe the shell strength and extent of crosslinking. The effect of acetic acid on the relative viscosity of chitosan aqueous solutions played a major role in microcapsule size control at low acid concentrations. With constant addition of acetic acid, amino groups in chitosan chains were acetylated partially under ultrasonic irradiation. This reduced the amphiphilicity of the shell material and therefore influenced the size, size distribution, stability and mechanical strength of the microcapsules. Apart from the acetylation effect, the counter-ion effect and the formation of covalent bond crosslinks also made contributions to the formation of stable chitosan microcapsules.

Dynamic forces between emulsified water drops coated with Poly-Glycerol-Poly-Ricinoleate (PGPR) in canola oil.

The dynamic collision of emulsified water drops in the presence of non-ionic surfactants plays a crucial role in many practical applications. Interaction force between water drops coated with non-ionic food grade surfactants is expected to exhibit rich dynamic behavior that is not yet explored. The collision forces between immobilized water drops in canola oil in the presence of a well-known food grade surfactant polyglycerol polyricinoleate (PGPR) are measured at concentrations well below typically used to form stable emulsions. An extension or kink, attributed to a short-range attractive interaction due to PGPR bridging between the drops, was observed in the retract portion of the force curves at higher applied forces or slower collision velocities. The Stokes-Reynolds-Young-Laplace (SRYL) model was used to calculate theoretical force curves. For higher collisions velocities, the agreement between the calculated and experiment data was acceptable, but the SRYL model failed to describe the extension or kink feature observed at slower velocities below. Both the AFM data and the comparison to the model calculation indicated the presence of a short-range attractive force, not of a hydrodynamic origin, attributed to the bridging and extension of PGPR molecules on the surface of water drops below saturation of the interface.

Charge tunable thin-film composite membranes by gamma-ray triggered surface polymerization.

Thin-film composite poly(amide) (PA) membranes have greatly diversified water supplies and food products. However, users would benefit from a control of the electrostatic interactions between the liquid and the net surface charge interface in order to benefit wider application. The ionic selectivity of the 100 nm PA semi-permeable layer is significantly affected by the pH of the solution. In this work, for the first time, a convenient route is presented to configure the surface charge of PA membranes by gamma ray induced surface grafting. This rapid and up-scalable method offers a versatile route for surface grafting by adjusting the irradiation total dose and the monomer concentration. Specifically, thin coatings obtained at low irradiation doses between 1 and 10 kGy and at low monomer concentration of 1 v/v% in methanol/water (1:1) solutions, dramatically altered the net surface charge of the pristine membranes from -25 mV to +45 mV, whilst the isoelectric point of the materials shifted from pH 3 to pH 7. This modification resulted in an improved water flux by over 55%, from 45.9 to up 70 L.m-2.h-1, whilst NaCl rejection was found to drop by only 1% compared to pristine membranes.

Charge and Film Drainage of Colliding Oil Drops Coated with the Nonionic Surfactant C12E5.

The interaction forces between colliding tetradecane drops were measured in the presence of the nonionic surfactant pentaethylene glycol monododecyl ether (C12E5). The force behavior was measured in the range of premicellar compositions of the nonionic surfactant in various salt solutions and was consistent with the presence of a surface charge even though the surfactant was nonionic in nature. The surface potential of oil drops was found to decrease with an increase in C12E5 concentration. The measured electrophoretic mobilities and ζ potentials of emulsified tetradecane drops also decreased with an increase in the C12E5 concentration. The surface potential decreased with an increase in the electrolyte at a constant C12E5 concentration, further confirming the presence of a charged oil-water interface. In addition to the charging behavior, the nonequilibrium film drainage between the tetradecane drops coated with C12E5 was also measured. In contrast to some existing experiments in the literature, it was found that oil drops coated with the nonionic surfactant were stable against coalescence, even when the drops were deformed on the order of their radii. These findings have significant implications on the stability of emulsions in food, personal care, and detergent industries.

Insights into Free Volume Variations across Ion-Exchange Membranes upon Mixed Solvents Uptake by Small and Ultrasmall Angle Neutron Scattering.

Ion-exchange membranes are composite separation materials increasingly used in a variety of electro-membranes and electrochemical processes. Although promising for solvent reclamation, to date, their main applications are limited to aqueous environments due to physicochemical and microstructural changes of the materials upon exposure to nonaqueous and mixed solvents solutions, affecting long-term stability and separation performance. In the present work, the structural changes of commercial and novel hybrid ion-exchange membranes in mixed methanol/water and ethanol/water solutions are assessed for the first time using ultra- and small-angle neutron scattering techniques. The interface between the ion-exchange functional layer and the mechanical support of the membranes is evaluated in the ultralow-q region, while a broad solvent-dependent peak at the mid-q region was correlated to the microstructural properties which are related to the free volume across the ion-exchange domains and to the materials electrical and nanoscale mechanical properties. The results of this study may offer new opportunities toward the development of an efficient separation process using ion-exchange membranes for the purification of fermentation broths toward biofuel generation.

Precise measurements of capsule mechanical properties using indentation.

Application of elastic theory to experimental data of capsule and particle compression under-predicts the value of material properties such as the Young's modulus by up to 100% when the effect of the rigid substrate is neglected, as is commonly done in the literature. Results of numerical simulations, spanning the range from thin-shelled capsules to solid particles, are presented in terms of correction factors that account for the substrate. In addition, the scaling relationship between indentation force and displacement is characterised for arbitrary shell thicknesses and indenter radii.