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Adsorption of asphaltenes at the water-oil interface contributes to the stability of petroleum emulsions by forming a networked film that can hinder drop-drop coalescence. The interfacial microstructure can either be liquid-like or solid-like, depending on: i) initial bulk concentration of asphaltenes, ii) interfacial aging time, and iii) solvent aromaticity. Two techniques: interfacial shear rheology and integrated thin film drainage apparatus provided equivalent interface aging conditions, enabling direct correlation of the interfacial rheology and droplet stability. The shear rheological properties of the asphaltene film were found to be critical to the stability of contacting droplets. With a viscous dominant interfacial microstructure, the coalescence time for two drops in intimate contact was rapid, on the order of seconds. However, as the elastic contribution develops and the film microstructure begins to be dominated by elasticity, the two drops in contact do not coalescence. Such step-change transition in coalescence is thought to be related to the high shear yield stress (~10 4 Pa), which is a function of the film shear yield point and the film thickness (as measured by quartz crystal microbalance), and the increased elastic stiffness of the film that prevents mobility and rupture of the asphaltene film which when in a solid-like state provides an energy barrier for the droplets to coalescence.

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Drainage kinetics, thickness, and stability of water-in-oil thin liquid emulsion films obtained from asphaltenes, heavy oil (bitumen), and deasphalted heavy oil (maltenes) diluted in toluene are studied. The results show that asphaltenes stabilize thin organic liquid films at much lower concentrations than maltenes and bitumen. The drainage of thin organic liquid films containing asphaltenes is significantly slower than the drainage of the films containing maltenes and bitumen. The films stabilized by asphaltenes are much thicker (40-90 nm) than those stabilized by maltenes (∼10 nm). Such significant variation in the film properties points to different stabilization mechanisms of thin organic liquid films. Apparent aging effects, including gradual increase of film thickness, rigidity of oil/water interface, and formation of submicrometer size aggregates, were observed for thin organic liquid films containing asphaltenes. No aging effects were observed for films containing maltenes and bitumen in toluene. The increasing stability and lower drainage dynamics of asphaltene-containing thin liquid films are attributed to specific ability of asphaltenes to self-assemble and form 3D network in the film. The characteristic length of stable films is well beyond the size of single asphaltene molecules, nanoaggregates, or even clusters of nanoaggregates reported in the literature. Buildup of such 3D structure modifies the rheological properties of the liquid film to be non-Newtonian with yield stress (gel like). Formation of such network structure appears to be responsible for the slower drainage of thin asphaltenes in toluene liquid films. The yield stress of liquid film as small as ∼10(-2) Pa is sufficient to stop the drainage before the film reaches the critical thickness at which film rupture occurs.

Eighteen crude oils and condensates have been investigated by means of infrared (IR) and near-infrared spectroscopy (NIR) and high-performance liquid chromatography (HPLC). By means of HPLC the samples have been separated into four chemical group classes, namely saturates, aromatics, resins, and asphaltenes, the so-called SARA fractions. Using multivariate analysis techniques such as principal component analysis (PCA) and partial least-squares analysis (PLS), the predictive ability of the spectroscopic techniques with regard to the SARA components have been explored. The results show that the SARA distribution of crude oils and related materials can be determined both from infrared and near-infrared spectroscopy. The uncertainties in the prediction models based on IR spectroscopy have been found to be 2.5, 2.2, 1.4, and 1.3 wt % for the saturate, aromatic, resin, and asphaltene fraction, respectively. For NIR the equivalent uncertainties are 2.8, 2.4, 1.4, and 1.0 wt %. These values are in the same range as the reported uncertainty in the direct determination by HPLC. Spectroscopic determination of SARA values, especially using NIR, offers the possibility of rapid SARA determinations of these values. The determinations could be done at high pressure and temperature.

Four synthetic perylene bisimide-based polyaromatic (PA) surfactants with a structural or functional group difference in their attached hydrophilic/hydrophobic substituent side chains were used to probe structure-nanoaggregation relations in organic media by molecular dynamics simulations and dynamic light scattering. The results from the simulated radial distribution functions and light scattering experiments indicate that variation in the structure of side chains and polarity of functional groups leads to significant variations in molecular association, dynamics of molecular nanoaggregation and structure of nanoaggregates. The aggregates of PA surfactant molecules grow to much larger sizes in heptane than in toluene. The aromatic solvent is shown to hinder molecular association by weakening π-π stacking, demonstrating the control of molecular aggregation by tuning solvent properties. In aliphatic solvent, the aggregates formed from PA surfactants of aliphatic alkyl groups and phenylalanine derivatives as a side chain usually have a higher solvent accessible surface area to accessible volume ratio (SASA:AV) than that of tryptophan derivatives in their side chains. PA surfactants with an aliphatic functional group in both side chains does not form polyaromatic π-π stacking (T-stacking) due to its strong steric hindrance in both solvents. Depending on the nature of the side chains attached, various stacking distributions, aggregation sizes, and SASA:AV ratios were obtained. In PA surfactant nanoaggregates, all of the solvent molecules were found to be excluded from the interstices of the stacked polyaromatic cores, regardless of whether the solvent molecules are aliphatic or aromatic. Although the change in the structure of side chain substituent in polyaromatic surfactants has a negligible impact on their self-diffusivity, it can strongly influence their intermolecular interactions, leading to different aggregate diffusion coefficients.