Molecular Interactions between a Biodegradable Demulsifier and Asphaltenes in an Organic Solvent

A surface forces apparatus (SFA) was used to measure the intermolecular forces between a biodegradable demulsifier (ethyl cellulose, EC) and asphaltenes immobilized individually on molecularly smooth mica surfaces in an organic solvent. A steric repulsion on approach between the immobilized EC layers and asphaltenes was measured despite strong adhesion (Fad/R ≈ −2 mN/m; Wad = 0.42 mJ/m2) during retraction. The measured adhesion was attributed to the interpenetration and tangling of aliphatic branches of swollen asphaltenes and solvated chains of EC macromolecules. Competitive adsorption of EC on/in immobilized asphaltene layers was confirmed by combining SFA force measurements and atomic force microscopy (AFM) imaging. Following the injection of EC-in-toluene solution, an immediate (<5 min) increase in the confined layer thickness of the immobilized asphaltene layers was measured. Irreversibly adsorbed asphaltenes were displaced by EC macromolecules through binding with unoccupied surface sites on mica, followed by the spreading of EC across the mica substrate due to increased surface activity governed by the higher number of hydroxyl groups per EC molecule. AFM imaging confirmed that the increase in confined layer thickness resulted from the formation of larger asphaltene aggregates/clusters protruding from the mica substrate. Molecular level topographical images showed that the asphaltenes were not resolvated in the organic phase but self-associated as the EC macromolecules spread across the hydrophilic mica substrate. The results from this study provide not only fundamental insights into the basic interaction mechanisms of asphaltenes with EC macromolecules as a demulsifier in organic media but also directions toward enhancing demulsification of water-in-oil emulsions

An X-ray Tomography Study of Gas Retention in Nuclear Legacy Waste

The retention and release of flammable gases from corroded Magnox sludge waste at Sellafield, UK and secondary reprocessing waste at Hanford, USA has significant economic and safety implications for decommissioning various nuclear legacy buildings. Magnesium hydroxide is the primary precipitation product from the corrosion of first generation nuclear fuel in the UK, with hydrogen gas produced as a reaction by-product. Depending on the bed microstructure, wettability and shear yield stress behaviour, some consolidated sediments of these corrosion products are able to trap a substantial volume of gas, sufficient in some instances to become buoyant with respect to a water supernatant, resulting in an undesirable upward transfer of radioactive material from the consolidated bed. These phenomena are investigated using the decomposition of hydrogen peroxide to produce oxygen bubbles within magnesium hydroxide soft sediments at laboratory scale. X-ray tomography analysis showed that high strength sediments of 1112 Pa shear yield stress supported much larger bubbles up to 20 mm equivalent spherical diameter than beds in the 7-234 Pa range, which demonstrated almost identical bubble size distributions across the range. The largest retained bubbles became progressively more distorted with increased sediment strength until the lateral cracks consistent with tensile fracture became apparent in the 1112 Pa bed. These cracks significantly limited the capacity for bed swell as gas diffusion along the cracks to the container walls provided a continuous escape route. The capacity for gas retention was also substantially reduced when gas generation was not homogeneous through the bed as localised gas generation promoted the formation of low density pathways, rich with micro-bubbles, which enable gas transport through the bed

Yield stress dependency on the evolution of bubble populations generated in consolidated soft sediments

Retention of hydrogen bubbles within consolidated soft sediments represents an important safety consideration for the management of legacy nuclear wastes due to the potential for acute gas release. Gas retention sufficiently reduced the bulk density of intermediate yield stress (< 800 Pa) sediments for the bed to become buoyant with respect to an aqueous supernatant, potentially inducing Rayleigh-Taylor instabilities. X-ray computed tomography revealed that beds of 7-234 Pa yield stress retained very similar, steady state size distributions of mature bubbles, limited to 9 mm equivalent spherical diameter, for long residence times. This implied a dominant gas release mechanism dictated by the pore to millimeter scale bubble population, not previously identified in such weak sediments and unrelated to the bubbles' buoyant force. At 1112 Pa yield stress, large bubbles of up to 20 mm diameter were observed to grow through induction of lateral cracks, facilitating gas transport to the bed periphery, thereby limiting the maximum void fraction, while non-homogeneous gas generation promoted the formation of low density regions rich with micro-bubbles which similarly provide pathways for gas release

Probing Mechanical Properties of Water-Crude Oil Interfaces and Colloidal Interactions of Petroleum Emulsions using Atomic Force Microscopy

Atomic force microscopy (AFM) is frequently used to elucidate complex interactions in emulsion systems. However, comparing results obtained with “model” planar surfaces to curved emulsion interfaces often proves unreliable, because droplet curvature can affect adsorption and arrangement of surface-active species, while droplet deformation affects the net interaction force. In the current study, AFM was used to study the interactions between a colloidal probe and water droplet. Force magnitude and water droplet deformation were measured in toluene solutions of asphaltene or bitumen at different concentrations and varying droplet aging time. Interfacial stiffening and an increase in particle–droplet adhesion force were observed upon droplet aging in bitumen solution. As reported in our previous study (Kuznicki, N. P., Harbottle, D., Masliyah, J., and Xu, Z.Dynamic Interactions between a Silica Sphere and Deformable Interfaces in Organic Solvents Studied by Atomic Force Microscopy. Langmuir 2016, 32 (38), 9797−9806), a viscoelasticity parameter should be included in the high-force Stokes–Reynolds–Young–Laplace (SRYL) equations to account for the interfacial stiffening and non-Laplacian response of the water droplet at longer aging times. However, following the addition of a biodegradable demulsifier, ethyl cellulose (EC), an immediate reduction in both the particle–droplet adhesion force and the rigidity of the water droplet occurred. Following EC addition, the interface reverted back to a Laplacian response and droplet deformation was once again accurately predicted by the classical SRYL model. These changes in both droplet deformation and particle–droplet adhesion, tracked by AFM, imply a rapid asphaltene/bitumen film displacement by EC molecules. The colloidal probe technique provides a convenient way to quantify forces at deformable oil/water interfaces and characterize the in situ effectiveness of competing surface-active species

Synthesis and Physical Property Characterisation of Spheroidal and Cuboidal Nuclear Waste Simulant Dispersions

This study investigated dispersions analogous to highly active nuclear waste, formed from the reprocessing of Spent Nuclear Fuel (SNF). Non-radioactive simulants of spheroidal caesium phosphomolybdate (CPM) and cuboidal zirconium molybdate (ZM-a) were successfully synthesised; confirmed via Scanning Electron Microscopy (SEM), powder X-ray diffraction (PXRD) and Fourier transform infrared (FTIR) spectroscopy. In addition, a supplied ZM (ZM-b) with a rod-like/wheatsheaf morphology was also analysed along with titanium dioxide (TiO2). The simulants underwent thermal gravimetric analysis (TGA) and size analysis, where CPM was found to have a D50 value of 300 nm and a chemical formula of Cs3PMo12O40·13H2O, ZM-a a D50 value of 10 μm and a chemical formula of ZrMo2O7(OH)2·3H2O and ZM-b to have a D50 value of 14 μm and a chemical formula of ZrMo2O7(OH)2·4H2O. The synthesis of CPM was tracked via Ultraviolet-visible (UV-Vis) spectroscopy at both 25 °C and 50 °C, where the reaction was found to be first order with the rate constant highly temperature dependent. The morphology change from spheroidal CPM to cuboidal ZM-a was tracked via SEM, reporting to take 10 days. For the onward processing and immobilisation of these waste dispersions, centrifugal analysis was utilised to understand their settling behaviours, in both aqueous and 2 M nitric acid environments (mimicking current storage conditions). Spheroidal CPM was present in both conditions as agglomerated clusters, with relatively high settling rates. Conversely, the ZM were found to be stable in water, where their settling rate exponents were related to the morphology. In acid, the high effective electrolyte resulted in agglomeration and faster sedimentation