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Solvent exchange is a controlled process for dilution-induced phase separation. This work utilizes the solvent exchange method to reveal the effect of the mixing dynamics on the asphaltene precipitation process under 20 different mixing conditions using a model system of n-heptane and asphaltene in toluene. The external mixing between the asphaltene solution and the paraffinic solvent is strictly controlled. We employed a high-spatial-resolution total internal reflection fluorescence microscope to detect asphaltene precipitates with a resolution up to 200 nm. A multiphysics model is used to simulate the evolution of the oversaturation pulse in the solvent exchange process. Based on the simulation results, we predicted the effect of the flow rate, dimension, the orientation of the microfluidic chamber, and temperature on the surface coverage and size distribution of asphaltene precipitates. The model predictions of all factors corroborate with the experimental observations. Local concentration of the solvent and shear forces are found to be the two main reasons for the change of asphaltene precipitation caused by mixing dynamics. However, the influence of thermodynamics is more critical than the mixing dynamics as temperature changes. Through a combination of experimental and simulation studies, this work illuminates the significance of the transportation process for the final morphology of asphaltene precipitates and provides an in-depth insight into the mechanism of mixing dynamics on the asphaltene precipitation. A smart mixing may be to boost new phase formation without excessive solvent consumption., Comment: 34 pages, 13 figures

Asphaltene precipitation is a crucial phase separation phenomenon in the oil industry, especially in paraffinic froth treatment to extract bitumen from oil sands ores. This work reveals the formation of particles at 0.2 to 0.4 um in radius, defined as a primary sub-micron particle (PSMP), which is ubiquitous from diffusive mixing between asphaltene solution and any of 23 types of precipitants examined in our experiments. The yield and quantity of asphaltene particles are affected not only by the Hildebrand solubility parameter of the precipitants but also by the diffusion coefficients of the asphaltene solution and the precipitant. The Population Balance Model (PBM) with the Hildebrand solubility parameter has been used to model particle size distribution. Good agreement has been achieved between numerical predictions and the experimental data. It indicates that the colloid theory can describe the size distribution of PSMP and larger aggregates. Therefore, this study provides new insight into the mechanism for the dependence of yield and size distribution of the precipitated asphaltene particles on the composition of precipitants and adding inhibitors. Controlling of asphaltene yield and size distribution may be applied to the process of hydrocarbon separation or asphaltene precipitation prevention., Comment: Preprint submitted to Fuel

In situ observation of precipitation or phase separation induced by solvent addition is important in studying its dynamics. Combined with optical and fluorescence microscopy, microfluidic devices have been leveraged in studying the phase separation in various materials including biominerals, nanoparticles, and inorganic crystals. However, strong scattering from the subphases in the mixture is problematic for in situ study of phase separation with high temporal and spatial resolution. In this work, we present a quasi-2D microfluidic device combined with total internal reflection microscopy as an approach for in situ observation of phase separation. The quasi-2D microfluidic device comprises of a shallow main channel and a deep side channel. Mixing between a solution in the main channel (solution A) and another solution (solution B) in the side channel is predominantly driven by diffusion due to high fluid resistance from the shallow height of the main channel, which is confirmed using fluorescence microscopy. Moreover, relying on diffusive mixing, we can control the composition of the mixture in the main channel by tuning the composition of solution B. We demonstrate the application of our method for in situ observation of asphaltene precipitation and beta-alanine crystallization., Comment: Preprint submitted to The European Physical Journal E

Complex polar structures of incommensurate modulations (ICMs) are revealed in chemically modified PbZrO$_3$ perovskite antiferroelectrics using advanced transmission electron microscopy techniques. The Pb-cation displacements, previously assumed to arrange in a fully-compensated antiparallel fashion, are found to be either antiparallel but with different magnitudes, or in a nearly orthogonal arrangement in adjacent stripes in the ICMs. Ab initio calculations corroborate the low-energy state of these arrangements. Our discovery corrects the atomic understanding of ICMs in PbZrO$_3$-based perovskite antiferroelectrics.