Interfacial rheology and structure of tiled graphene oxide sheets

The hydrophilic nature of graphene oxide sheets can be tailored by varying the carbon to oxygen ratio. Depending on this ratio, the particles can be deposited at either a water-air or a water-oil interface. Upon compression of thus-created Langmuir monolayers, the sheets cover the entire interface, assembling into a strong, compact layer of tiled graphene oxide sheets. With further compression, the particle layer forms wrinkles that are reversible upon expansion, resembling the behavior of an elastic membrane. In the present work, we investigate under which conditions the structure and properties of the interfacial layer are such that free-standing films can be obtained. The interfacial rheological properties of these films are investigated using both compressional experiments and shear rheometry. The role of surface rheology in potential applications of such tiled films is explored. The rheological properties are shown to be responsible for the efficiency of such layers in stabilizing water-oil emulsions. Moreover, because of the mechanical integrity, large-area monolayers can be deposited by, for example, Langmuir-Blodgett techniques using aqueous subphases. These films can be turned into transparent conductive films upon subsequent chemical reduction.     

Interfacial properties of water + alcohol mixtures

Mixtures of water with alcohol are important in numerous engineering applications. Caused by the polarity of water and alcohol self-association of water and alcohol as well cross-association between water and alcohol appear in such complex mixtures. These features show significant impact on physical and chemical properties, especially phase equilibrium behaviour and hence interfacial properties. The Cahn–Hilliard theory was combined with original statistical associated fluid theory equation of states (SAFT EOS) in order to describe both the phase behaviour and interfacial properties with respect of association. The paper focuses on theoretical investigations of surface tension, density profiles, surface thickness in vapour–liquid or vapour–liquid–liquid equilibrium of mixtures of water with ethanol or 1-butanol. Results of vapour–liquid equilibrium surface tension calculations were compared with experimental data taken from the literature.     

Interfacial rheology of food emulsifiers and proteins

The scientific literature from 1997 (inclusive) to the present on the interfacial rheology of emulsifiers and proteins of relevance to food has been reviewed. Both shear and dilatational rheology of oil–water and air–water interfaces have been covered and the main factors affecting interfacial rheology have been tabulated. Special attention is paid to: the sensitivity of interfacial rheology to film composition and structure; the growing viewpoint of treating proteins films as a two-dimensional gel state; recent theoretical modelling of interfacial rheological effects; those few publications that attempt to relate interfacial rheology to bulk stability. It is concluded that there have been few major advances in the last 4 or 5 years, but the heterogeneity of such adsorbed films seems to be better recognised, both spatially and rheologically, with the challenge remaining to connect this picture to the stability of the corresponding bulk systems.     

Interfacial shear rheology of protein-surfactant layers

The shear rheology of adsorbed or spread layers at air/liquid and liquid/liquid phase boundaries is relevant in a wide range of technical applications such as mass transfer, monolayers, foaming, emulsification, oil recovery, or high speed coating. Interfacial shear rheological properties can provide important information about interactions and molecular structure in the interfacial layer. A variety of measuring techniques have been proposed in the literature to measure interfacial shear rheological properties and have been applied to pure protein or mixed protein adsorption layers at air/water or oil/water interfaces. Such systems play for example an important role as stabilizers in foams and emulsions. The aim of this contribution is to give a literature overview of interfacial shear rheological studies of pure protein and protein/surfactant mixtures at liquid interfaces measured with different techniques. Techniques which utilize the damping of waves, spectroscopic or AFM techniques and all micro-rheological techniques will not discuss here.     

Effect of interfacial rheology on model emulsion coalescence I. Interfacial rheology

Interfacial elasticity and "dynamic" surface pressure isotherms were measured for interfaces between a dispersed water phase and a continuous phase of asphaltenes, toluene, and heptane. The interfacial modulus is a function of asphaltene concentration and in all cases reached a maximum at an asphaltene concentration of approximately 1 kg/m(3). The modulus increased significantly as the interface aged and slightly as the heptane content increased to a practical limit of 50 vol%. The modulus was approximately the same at 23 and 60 degrees C. The modulus correlated with the inverse of the initial compressibility determined from surface pressure isotherms. The surface pressure isotherms also indicated that a phase transition occurred as the interface was compressed leading to the formation of low compressibility films. Crumpling was observed upon further compression. The phase transition shifted to a higher film ratio with an increase in heptane content and interface age. Asphaltene concentration and temperature (23 and 60 degrees C) has little effect on the surface pressure isotherms. The surface pressure and elasticity measurements are consistent with the gradual formation of a cross-linked asphaltene network on the interface.     

Interfacial properties of colloid-polymer mixtures

Density functional theory and a virial approach are used to calculate the surface tension and bending rigidity of the interface between demixed fluid phases for a colloid-polymer mixture. The calculated surface tension compares well with results from computers simulations and experiments. The bending rigidity obtained from both theoretical approaches is negative (approximately equal to -0.1k(B)T), its magnitude increases away from the critical point and it is in reasonable agreement with computer simulations.     

Interfacial rheology of stable and weakly aggregated two-dimensional suspensions

The interfacial rheological properties of stable and weakly aggregated two-dimensional suspensions are studied experimentally using a magnetic rod interfacial rheometer. Particle monolayers with well controlled structures were prepared. Charged polystyrene particles create two-dimensional colloidal crystals at the water-decane interface over a wide range of concentrations. Under similar conditions a predominantly liquid structure is obtained at the water-air interface for the same particles. The addition of appropriate combinations of the anionic surfactant sodiumdodecylsulfate (SDS) and sodium chloride (NaCl) to the aqueous subphase leads to a destabilization of these monolayers with the formation of fractal aggregates at low concentrations and a heterogeneous gel forming as the surface coverage is increased. After the structures have been built up a reproducible structure can be obtained, of which the interfacial rheological properties can be investigated using a magnetic rod stress rheometer. In all cases, numerical calculations were used to assess the importance of instrumental artifacts and the effect of the coupling between surface and subphase flows. The rheology of aggregated suspensions was compared to the reference case of a colloidal crystal. The two-dimensional aggregated suspensions display rheological features which are similar to their three-dimensional counterparts. These include an elastic response with small linearity limits, a power law dependence on surface coverage and a dependence on the strength of attraction. The results shed some light on the possible role of interfacial rheology on the stability of particle laden high interface systems. Additionally, the 2D suspensions could present fundamental insights in the rheological properties of dense colloidal suspensions.     

Interfacial rheology of mixed layers of food proteins and surfactants

Mixed protein–surfactant adsorption layers at liquid interfaces are described including the thermodynamic basis, the adsorption kinetics and the shear and dilational interfacial rheology. It is shown that due to the protrusion of hydrophobic protein parts into the oil phase the adsorption layers at the water–hexane interface are stronger anchored as compared to the water-air surface. Based on the different adsorption protocols, a sequential and a simultaneous scheme, the peculiarities of complexes between proteins and added surfactants are shown when formed in the solution bulk or at a liquid interface. The picture drawn from adsorption studies is supported by the findings of interfacial rheology.     

Interfacial tension and wetting in colloid-polymer mixtures

We calculate the interfacial tension and the wetting behavior in phase separated colloid-polymer mixtures both for ideal and excluded volume interacting polymers. Within the recently developed extension of the free volume theory to include polymer interactions the interfacial tension of the free interface is calculated by adding a van der Waals squared gradient term. The wetting behavior at a hard wall is calculated following a Cahn-Fisher-Nakanishi approach taking the one- and two-body colloid-wall interactions into account. Comparing results for interacting polymers with those for ideal polymers we find that for interacting polymers the interfacial tension does not increase as steeply as a function of the gas-liquid colloid density difference. Furthermore, the wetting transition shifts to higher polymer concentrations, even to above the triple line. The predictions for both the interfacial tension and the wetting are compared to recent experiments.     

Interfacial rheology of petroleum asphaltenes at the oil-water interface

A biconical bob interfacial shear rheometer was used to study the mechanical properties of asphaltenic films adsorbed at the oil-water interface. Solutions of asphaltenes isolated from four crude oils were dissolved in a model oil of heptane and toluene and allowed to adsorb and age in contact with water. Film elasticity (G') values were measured over a period of several days, and yield stresses and film masses were determined at the end of testing. The degree of film consolidation was determined from ratios of G'/film mass and yield stress/G'. Asphaltenes with higher concentrations of heavy metals (Ni, 330-360 ppm; V, 950-1000 ppm), lower aromaticity (H/C, 1.24-1.29), and higher polarity (N, 1.87-1.99) formed films of high elasticity, yield stress, and consolidation. Rapid adsorption kinetics and G' increases were seen when asphaltenes were near their solubility limit in heptane-toluene mixtures (approximately 50% (v/v) toluene). In solvents of greater aromaticity, adsorption kinetics and film masses were reduced at comparable aging times. Poor film forming asphaltenes had yield stress/G' values ((1.01-1.21) x 10(-2)) more than 4-fold lower than those of good film forming asphaltenes. n-heptane asphaltenes fractionated by filtering solutions prepared at low aromaticity (approximately 40% toluene in mixtures of heptane and toluene) possessed higher concentrations of heavy metals and nitrogen and higher aromaticity. The less soluble fractions of good film forming asphaltenes exhibited enhanced adsorption kinetics and higher G' and yield stress values in pure toluene. Replacing the asphaltene solutions with neat heptane-toluene highlighted the ability of films to consolidate and become more elastic over several hours. Adding resins in solution to a partially consolidated film caused a rapid reduction in elasticity followed by gradual but modest consolidation. This study is among the first to directly relate asphaltene chemistry to adsorption kinetics, adsorbed film mechanical properties, and consolidation kinetics.     

Interfacial dynamics and rheology of polymer-grafted nanoparticles at air-water and xylene-water interfaces

Particle-stabilized emulsions and foams offer a number of advantages over traditional surfactant-stabilized systems, most notably a greater stability against coalescence and coarsening. Nanoparticles are often less effective than micrometer-scale colloidal particles as stabilizers, but nanoparticles grafted with polymers can be particularly effective emulsifiers, stabilizing emulsions for long times at very low concentrations. In this work, we characterize the long-time and dynamic interfacial tension reduction by polymer-grafted nanoparticles adsorbing from suspension and the corresponding dilatational moduli for both xylene-water and air-water interfaces. The dilatational moduli at both types of interfaces are measured by a forced sinusoidal oscillation of the interface. Surface tension measurements at the air-water interface are interpreted with the aid of independent ellipsometry measurements of surface excess concentrations. The results suggest that the ability of polymer-grafted nanoparticles to produce significant surface and interfacial tension reductions and dilatational moduli at very low surface coverage is a key factor underlying their ability to stabilize Pickering emulsions at extremely low concentrations.     

Interfacial rheology and conformations of triblock copolymers adsorbed onto the water-oil interface

The conformation and the dilatational properties of three non-ionic triblock PEO-PPO-PEO (where PEO is polyethyleneoxide and PPO is polypropyleneoxide) copolymers of different hydrophobicity and molecular weight were investigated at the water-hexane interface. The interfacial behavior of the copolymers was studied by combining dilatational rheology using the oscillating drop method and ellipsometry. From the dilatational rheology measurements the limiting elasticity values, E(0), of the Pluronics as function of surface pressure, Π, and adsorption time were obtained, i.e. E(0)(t) and E(0)(Π). Here, it is shown that E(0)(t) depends on the number of PEO units and on the bulk concentration, showing maximum and minimum surface elasticity values which indicate conformational changes in the interfacial layer. Furthermore, in the framework of the polymer scaling law theory, conformational transitions were discussed in E(0) vs. Π plots. In a dilute regime (Π<14 mN m(-1)) at the water-hexane interface, E(0)=2Π fits well all the data, which indicates a two-dimensional "stretched chain" conformation. Increasing Π, two other interfacial transitions could take place. The different behavior of Pluronic copolymers could be also described by the local minima of E(0), which depends on the hydrophobicity of the copolymers. Conformational transitions observed by interfacial rheology were compared to ellipsometric data. Experimental results were discussed and explained on the basis of two- and three-dimensional copolymer structure taking into account that PPO chains could be partially immersed in hexane and water.     

Effect of temperature and concentration on the structure of sec-butyl alcohol and isobutyl alcohol/water mixtures: near-infrared spectroscopic study

The effect of temperature and concentration on the structure of sec-butyl alcohol and isobutyl alcohol/water binary mixtures in the alcohol-rich region (mole fraction of water X(H2O) < 0.3) has been studied using Fourier transform (FT) near-infrared (NIR) spectroscopy. The experimental data were analyzed by a two-dimensional (2D) correlation approach and chemometric methods. It was found that molecules of both alcohols in the mixture with water are in the same environment as those in the pure alcohols. Even at very low water content (X(H2O) = 0.001) we did not observe water free from any specific interactions. The molecules of water are attached to the end free OH groups in the open chain associates of alcohol. In this way the structure of neat alcohol remains intact by addition of water. The water-alcohol interactions in sec-butyl alcohol and isobutyl alcohol/water mixtures are stronger than those in bulk water. The results obtained at higher water content or elevated temperatures indicate the possibility of water-water interaction. In the alcohol-rich region the hydrophobic effects are of minor importance and the structure and properties of these systems are determined by hydrogen bonding through the hydroxyl groups. Both alcohols behave similarly on the temperature or water content variation; the minor difference results from a different degree of self-association for sec-butyl alcohol and isobutyl alcohol.     

N2O5 reactive uptake on aqueous sulfuric acid solutions coated with branched and straight-chain insoluble organic surfactants

A flow reactor coupled to a chemical ionization mass spectrometer was used to study the reactive uptake coefficients at 273 K of N2O5 on aqueous 60 wt % sulfuric acid solutions coated with insoluble organic monolayers. Both straight-chain surfactants (1-hexadecanol, 1-octadecanol, and stearic acid) and a branched surfactant (phytanic acid) were studied. The reactive uptake coefficient decreased dramatically for straight-chain surfactants. The decrease ranged from a factor of 17 to a factor of 61 depending on the type of straight-chain surfactant. In contrast to the straight-chain data, the presence of phytanic acid did not have a significant effect on the N2O5 reactive uptake coefficient (the decrease was less than the uncertainty in the data) compared to the uncoated solution. In addition to measuring the reactive uptake coefficients, we also investigated the relationship between properties of the monolayers and the reactive uptake coefficients. The reactive uptake coefficients measured on aqueous sulfuric acid subphases showed a relationship to the surface area occupied by the surfactant molecules. However, data obtained with other subphases did not overlap with this trend.     

Structure, rheology and shear alignment of Pluronic block copolymer mixtures

The structure and flow behaviour of binary mixtures of Pluronic block copolymers P85 and P123 is investigated by small-angle scattering, rheometry and mobility tests. Micelle dimensions are probed by dynamic light scattering. The micelle hydrodynamic radius for the 50/50 mixture is larger than that for either P85 or P123 alone, due to the formation of mixed micelles with a higher association number. The phase diagram for 50/50 mixtures contains regions of cubic and hexagonal phases similar to those for the parent homopolymers, however the region of stability of the cubic phase is enhanced at low temperature and concentrations above 40 wt%. This is ascribed to favourable packing of the mixed micelles containing core blocks with two different chain lengths, but similar corona chain lengths. The shear flow alignment of face-centred cubic and hexagonal phases is probed by in situ small-angle X-ray or neutron scattering with simultaneous rheology. The hexagonal phase can be aligned using steady shear in a Couette geometry, however the high modulus cubic phase cannot be aligned well in this way. This requires the application of oscillatory shear or compression.     

Interfacial dilational rheological property and lamella stability of branched alkyl benzene sulfonates solutions

The dynamic dilational properties of branched alkyl benzene sulfonates at the air–water and decane–water interfaces were investigated by drop shape analysis, and their lamella stability was measured. The influences of time, dilational frequency, and bulk concentration on surface dilational elasticity and dilational viscosity were expounded. The results show that the molecular interaction controls the nature of adsorption film during lower concentration range and the film behaves elastic in nature. During higher concentration range, the diffusion-exchange process controls the dynamic dilational properties and the surface film shows remarkable viscoelasticity. An increase in hydrophobic chain length enhances the molecular interaction, which results in the increase of dilational parameters and lamella stability. The data correlation suggests that the ability to form a stable lamella is linked to the intrinsic surface dilational elasticity.     

Interfacial rheology of polyelectrolytes and polymer monolayers at the air–water interface

In this review, we describe interfacial rheology studies of polymer monolayers at the air–water interface. Since polyelectrolytes are usually soluble in water, the formation of surface monolayers requires the presence of a surfactant of opposite charge. The first part of the review is dedicated to these mixed monolayers. The second part is related to neutral monolayers that can be either adsorbed or deposited at the interface. Interfacial rheology studies of these systems are still scarce, despite a considerable interest: insoluble polymer monolayers in two dimensions are suitable model systems for the tests of polymer theories in two dimensions, such as and glass transition. The rheology of soluble polymer monolayers has important connections with the dynamic properties of dispersions stabilized with these polymers.     

Interfacial interactions and structure of polyolefins

The elucidation of structural aspects of polyolefins (isotactic and syndiotactic polypropene and isotactic poly(1-butene)) oriented by epitaxial crystallization is briefly described. Investigations are performed by a combination of electron and Atomic Force Microscopy. AFM helps assess submolecular details in well defined crystallographic planes selected via the epitaxial crystallization.