Detection of Crude Oil in Subsea Environments Using Organic Electrochemical Transistors.

Current methods for detecting pipeline oil leaks depend primarily on optical detection, which can be slow and have deployment limitations. An alternative non-optical approach for earlier and faster detection of oil leaks would enable a rapid response and reduce the environmental impact of oil leaks. Here, we demonstrate that organic electrochemical transistors (OECTs) can be used as non-optical sensors for crude oil detection in subsea environments. OECTs are thin film electronic devices that can be used for sensing in a variety of environments, but they have not yet been tested for crude oil detection in subsea environments. We fabricated OECTs with poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) as the channel and showed that coating the channel with a polystyrene film results in an OECT with a large and measurable response to oil. Oil that comes in contact with the device will adsorb onto the polystyrene film and increases the impedance at the electrolyte interface. We performed electrochemical impedance spectroscopy measurements to quantify the impedance across the device and found an optimal thickness for the polystyrene coating for the detection of oil. Under optimal device characteristics, as little as 10 µg of oil adsorbed on the channel surface produced a statistically significant change in the source-drain current. The OECTs were operable in seawater for the detection of oil, and we demonstrated that the devices can be transferred to flexible substrates which can be easily implemented in vehicles, pipelines, or other surfaces. This work demonstrates a low-cost device for oil detection in subsea environments and provides a new application of OECT sensors for sensing.

Single Extracellular Vesicle Imaging and Computational Analysis Identifies Inherent Architectural Heterogeneity.

Evaluating the heterogeneity of extracellular vesicles (EVs) is crucial for unraveling their complex actions and biodistribution. Here, we identify consistent architectural heterogeneity of EVs using cryogenic transmission electron microscopy (cryo-TEM), which has an inherent ability to image biological samples without harsh labeling methods while preserving their native conformation. Imaging EVs isolated using different methodologies from distinct sources, such as cancer cells, normal cells, immortalized cells, and body fluids, we identify a structural atlas of their dominantly consistent shapes. We identify EV architectural attributes by utilizing a segmentation neural network model. In total, 7,576 individual EVs were imaged and quantified by our computational pipeline. Across all 7,576 independent EVs, the average eccentricity was 0.5366 ± 0.2, and the average equivalent diameter was 132.43 ± 67 nm. The architectural heterogeneity was consistent across all sources of EVs, independent of purification techniques, and compromised of single spherical, rod-like or tubular, and double shapes. This study will serve as a reference foundation for high-resolution images of EVs and offer insights into their potential biological impact.

Effects of velocity on N2 and CO2 foam flow with in-situ capillary pressure measurements in a high-permeability homogeneous sandpack.

The effects of velocity and gas type on foam flow through porous media have yet to be completely elucidated. Pressure drop and capillary pressure measurements were made at ambient conditions during a series of foam quality scan experiments in a homogenous sandpack while foam texture was simultaneously visualized. New insights into foam-flow behavior in porous media were discovered. Previously accepted "limiting" capillary pressure theory is challenged by the findings in this work, and the "limiting" terminology is replaced with the word "plateau" to reflect these novel observations. Plateau capillary pressure [Formula: see text] and transition foam quality were found to increase with velocity. Transition foam quality was found to depend mostly on liquid velocity rather than gas velocity and is physically linked to foam type (continuous vs. discontinuous) and texture (fine vs. coarse). Distinct rheological behaviors also arose in the low- and high-quality foam regimes as a function of velocity. Foam flow was found to be strongly shear thinning in the low-quality regime where foam texture was fine and discontinuous. In the high-quality regime, the rheology was weakly shear thinning to Newtonian for coarsely textured foam and continuous-gas flow respectively. When all other variables were held constant, at ambient conditions, CO2 foam was found to be weaker with also lower capillary pressures than N2 foam and the differences in gas solubility is a likely explanation.

Active Colloids as Models, Materials, and Machines.

Active colloids use energy input at the particle level to propel persistent motion and direct dynamic assemblies. We consider three types of colloids animated by chemical reactions, time-varying magnetic fields, and electric currents. For each type, we review the basic propulsion mechanisms at the particle level and discuss their consequences for collective behaviors in particle ensembles. These microscopic systems provide useful experimental models of nonequilibrium many-body physics in which dissipative currents break time-reversal symmetry. Freed from the constraints of thermodynamic equilibrium, active colloids assemble to form materials that move, reconfigure, heal, and adapt. Colloidal machines based on engineered particles and their assemblies provide a basis for mobile robots with increasing levels of autonomy. This review provides a conceptual framework for understanding and applying active colloids to create material systems that mimic the functions of living matter. We highlight opportunities for chemical engineers to contribute to this growing field.

Coiling of semiflexible paramagnetic colloidal chains.

Semiflexible filaments deform into a variety of configurations that dictate different phenomena manifesting at low Reynolds number. Harnessing the elasticity of these filaments to perform transport-related processes at the microfluidic scale requires structures that can be directly manipulated to attain controllable geometric features during their deformation. The configuration of semiflexible chains assembled from paramagnetic colloids can be readily controlled upon the application of external time-varying magnetic fields. In circularly rotating magnetic fields, these chains undergo coiling dynamics in which their ends close into loops that wrap inward, analogous to the curling of long nylon filaments under shear. The coiling is promising for the precise loading and targeted transport of small materials, however effective implementation requires an understanding of the role that field parameters and chain properties play on the coiling features. Here, we investigate the formation of coils in semiflexible paramagnetic chains using numerical simulations. We demonstrate that the size and shape of the initial coils are governed by the Mason and elastoviscous numbers, related to the field parameters and the chain bending stiffness. The size of the initial coil follows a nonmonotonic behavior with Mason number from which two regions are identified: (1) an elasticity-dependent nonlinear regime in which the coil size decreases with increasing field strength and for which loop shape tends to be circular, and (2) an elasticity-independent linear regime where the size increases with field strength and the shape become more elliptical. From the time scales associated to these regimes, we identify distinct coiling mechanisms for each case that relate the coiling dynamics to two other configurational dynamics of paramagnetic chains: wagging and folding behaviors.

Lab on a chip for a low-carbon future.

Transitioning our society to a sustainable future, with low or net-zero carbon emissions to the atmosphere, will require a wide-spread transformation of energy and environmental technologies. In this perspective article, we describe how lab-on-a-chip (LoC) systems can help address this challenge by providing insight into the fundamental physical and geochemical processes underlying new technologies critical to this transition, and developing the new processes and materials required. We focus on six areas: (I) subsurface carbon sequestration, (II) subsurface hydrogen storage, (III) geothermal energy extraction, (IV) bioenergy, (V) recovering critical materials, and (VI) water filtration and remediation. We hope to engage the LoC community in the many opportunities within the transition ahead, and highlight the potential of LoC approaches to the broader community of researchers, industry experts, and policy makers working toward a low-carbon future.

Single extracellular vesicle imaging and computational analysis identifies inherent architectural heterogeneity.

Evaluating the heterogeneity of extracellular vesicles (EVs) is crucial for unraveling their complex actions and biodistribution. Here, we identify consistent architectural heterogeneity of EVs using cryogenic transmission electron microscopy (cryo-TEM) which has an inherent ability to image biological samples without harsh labeling methods and while preserving their native conformation. Imaging EVs isolated using different methodologies from distinct sources such as cancer cells, normal cells, and body fluids, we identify a structural atlas of their dominantly consistent shapes. We identify EV architectural attributes by utilizing a segmentation neural network model. In total, 7,576 individual EVs were imaged and quantified by our computational pipeline. Across all 7,576 independent EVs, the average eccentricity was 0.5366, and the average equivalent diameter was 132.43 nm. The architectural heterogeneity was consistent across all sources of EVs, independent of purification techniques, and compromised of single spherical (S. Spherical), rod-like or tubular, and double shapes. This study will serve as a reference foundation for high-resolution EV images and offer insights into their potential biological impact.

Grain boundary dynamics driven by magnetically induced circulation at the void interface of 2D colloidal crystals.

The complexity of shear-induced grain boundary dynamics has been historically difficult to view at the atomic scale. Meanwhile, two-dimensional (2D) colloidal crystals have gained prominence as model systems to easily explore grain boundary dynamics at single-particle resolution but have fallen short at exploring these dynamics under shear. Here, we demonstrate how an inherent interfacial shear in 2D colloidal crystals drives microstructural evolution. By assembling paramagnetic particles into polycrystalline sheets using a rotating magnetic field, we generate a particle circulation at the interface of particle-free voids. This circulation shears the crystalline bulk, operating as both a source and sink for grain boundaries. Furthermore, we show that the Read-Shockley theory for hard-condensed matter predicts the misorientation angle and energy of shear-induced low-angle grain boundaries based on their regular defect spacing. Model systems containing shear provide an ideal platform to elucidate shear-induced grain boundary dynamics for use in engineering improved/advanced materials.

Extension of Kelvin's equation to dipolar colloids.

Vapor pressure refers to the pressure exerted by the vapor phase in thermodynamic equilibrium with either its liquid or solid phase. An important class of active matter is field-driven colloids. A suspension of dipolar colloids placed in a high-frequency rotating magnetic field undergoes a nonequilibrium phase transition into a dilute and dense phase, akin to liquid­vapor coexistence in a simple fluid. Here, we compute the vapor pressure of this colloidal fluid. The number of particles that exist as the dilute bulk phase versus condensed cluster phases can be directly visualized. An exponential relationship between vapor pressure and effective temperature is determined as a function of applied field strength, analogous to the thermodynamic expression between vapor pressure and temperature found for pure liquids. Additionally, we demonstrate the applicability of Kelvin's equation to this field-driven system. In principle, this appears to be in conflict with macroscopic thermodynamic assumptions due to the nonequilibrium and discrete nature of this colloidal system. However, the curvature of the vapor­liquid interface provides a mechanical equilibrium characterized by interfacial tension that connects the condensed clusters observed with these active fluids to classical colligative fluid properties.

Periodic deformation of semiflexible colloidal chains in eccentric time-varying magnetic fields.

Elastic filaments driven out of equilibrium display complex phenomena that involve periodic changes in their shape. Here, the periodic deformation dynamics of semiflexible colloidal chains in an eccentric magnetic field are presented. This field changes both its magnitude and direction with time, leading to novel nonequilibrium chain structures. Deformation into S-, Z-, and 4-mode shapes arises via the propagation and growth of bending waves. Transitions between these morphologies are governed by an interplay among magnetic, viscous, and elastic forces. Furthermore, the periodic behavior leading to these structures is described by four distinct stages of motion that include rotation, arrest, bending, and stretching of the chain. These stages correspond to specific intervals of the eccentric field's period. A scaling analysis that considers the relative ratio of viscous to magnetic torques via a critical frequency illustrates how to maximize the bending energy. These results provide new insights into controlling colloidal assemblies by applying complex magnetic fields.

Physicochemical Characterization of Asphaltenes Using Microfluidic Analysis.

Crude oils are complex mixtures of organic molecules, of which asphaltenes are the heaviest component. Asphaltene precipitation and deposition have been recognized to be a significant problem in oil production, transmission, and processing facilities. These macromolecular aromatics are challenging to characterize due to their heterogeneity and complex molecular structure. Microfluidic devices are able to capture key characteristics of reservoir rocks and provide new insights into the transport, reactions, and chemical interactions governing fluids used in the oil and gas industry. Understanding the microscale phenomena has led to better design of macroscale processes used by the industry. One area that has seen significant growth is in the area of chemical analysis under flowing conditions. Microfluidics and microscale analysis have advanced the understanding of complex mixtures by providing in situ imaging that can be combined with other chemical characterization methods to give details of how oil, water, and added chemicals interface with pore-scale detail. This review article aims to showcase how microfluidic devices offer new physical, chemical, and dynamic information on the behavior of asphaltenes. Specifically, asphaltene deposition and related flow assurance problems, interfacial properties and rheology, and evaluation of remediation strategies studied in microchannels and microfluidic porous media are presented. Examples of successful applications that address key asphaltene-related problems highlight the advances of microscale systems as a tool for advancing the physicochemical characterization of complex fluids for the oil and gas industry.

Combining ReaxFF Simulations and Experiments to Evaluate the Structure-Property Characteristics of Polymeric Binders in Si-Based Li-Ion Batteries.

High energy capacity silicon (Si) anodes in Li-ion batteries incorporate polymeric binders to improve cycle life, which is otherwise limited by large volume and stress fluctuations during charging/discharging cycles. Several properties of the polymeric binder play a role in achieving optimal battery performance, including interfacial adhesion strength, mechanical elasticity, and lithium-ion conduction rate. In this work, we utilize atomistic simulations with the ReaxFF force field and complementary experiments to investigate how these properties dictate the performance of Si/binder anodes. We study three C/N/H-based polymer binders with varying structures (pyrolyzed polyacrylonitrile (PPAN), polyacrylonitrile (PAN), and polyaniline (PANI)) to determine how the structure-property characteristics of the binder affect performance. The Si/binder adhesion analysis reveals some counter-intuitive results: although an individual PANI chain has a stronger affinity to Si compared to PPAN, the PANI bulk binds weaker to the Si surface. Interfacial structural analyses from simulations of the bulk phase show that PANI chains have poor stacking at the interface, while PPAN chains exhibit dense and highly ordered stacking behavior, leading to stronger adhesion. PPAN also has a lower Young's modulus compared to PANI and PAN owing to its ordered and less entangled bulk structure. This added elasticity better accommodates volume changes associated with cycling, making it a more suitable candidate for Si anodes. Finally, both simulations and experimental measurements of Li-ion diffusion rates show higher Li mobility through PPAN than PAN and PANI because the ordered stacking of PPAN chains creates channels that are favorable for Li diffusion to the Si surface. Galvanostatic charge-discharge cycling experiments show that PPAN is indeed a highly promising binder for Si anodes in Li-ion batteries, retaining a capacity of ∼1400 mAh g-1 for 150 cycles. This work demonstrates that the orientation and structure of the polymer at and near the interface are essential for optimizing binder performance as well as showcases the initial steps for binder evaluation, selection, and application for electrodes in Li-ion batteries.

Investigating the Compatibility of TTMSP and FEC Electrolyte Additives for LiNi0.5Mn0.3Co0.2O2 (NMC)-Silicon Lithium-Ion Batteries.

This study examines the compatibility of multielectrolyte additives for NMC-silicon lithium-ion batteries. Research studies with Si-based anodes have shown stable reversible cycling using electrolytes containing fluoroethylene carbonate (FEC). At the same time, the electrolyte additive, tris(trimethylsilyl) phosphite (TTMSP), has shown to improve the electrochemical performance of nickel-rich layered cathodes, such as LiNi0.5Mn0.3Co0.2O2 (NMC). However, the combination of these electrolyte additives for the realization of a full-cell NMC-Si lithium-ion battery has not been previously explored. Changes in the electrochemical performance (capacity retention, internal cell resistance, and electrochemical impedance) in half-cells are studied as the ratio of TTMSP and FEC is tuned. At the optimal TTMSP/FEC ratio of 0.33 (T1F3), the NMC-Si full-cells achieve a 2× longer cycle life when compared to the FEC-rich (T0F4) electrolyte. Moreover, T1F3 full-cells demonstrate 1.5 mAh/cm2 areal capacities and high-capacity retention (25% more than T0F4). A detailed investigation of the electrode-electrolyte interfaces is conducted by using time-of-flight secondary ion mass spectroscopy (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). The chemical species depth profiles and elemental analysis illustrate adequate hydrogen fluoride (HF) scavenging. These results demonstrate the synergistic effects of electrolyte additives in minimizing the capacity degradation in NMC-Si full-cells by effectively stabilizing the electrode-electrolyte interfaces.

Hierarchical assemblies of superparamagnetic colloids in time-varying magnetic fields.

Magnetically-guided colloidal assembly has proven to be a versatile method for building hierarchical particle assemblies. This review describes the dipolar interactions that govern superparamagnetic colloids in time-varying magnetic fields, and how such interactions have guided colloidal assembly into materials with increasing complexity that display novel dynamics. The assembly process is driven by magnetic dipole-dipole interactions, whose strength can be tuned to be attractive or repulsive. Generally, these interactions are directional in static external magnetic fields. More recently, time-varying magnetic fields have been utilized to generate dipolar interactions that vary in both time and space, allowing particle interactions to be tuned from anisotropic to isotropic. These interactions guide the dynamics of hierarchical assemblies of 1-D chains, 2-D networks, and 2-D clusters in both static and time-varying fields. Specifically, unlinked and chemically-linked colloidal chains exhibit complex dynamics, such as fragmentation, buckling, coiling, and wagging phenomena. 2-D networks exhibit controlled porosity and interesting coarsening dynamics. Finally, 2-D clusters have shown to be an ideal model system for exploring phenomena related to statistical thermodynamics. This review provides recent advances in this fast-growing field with a focus on its scientific potential.

Role of Wettability on the Adsorption of an Anionic Surfactant on Sandstone Cores.

We investigate the dynamic adsorption of anionic surfactant C14 - 16 alpha olefin sulfonate on Berea sandstone cores with different surface wettability and redox states under high temperature that represents reservoir conditions. Surfactant adsorption levels are determined by analyzing the effluent history data with a dynamic adsorption model assuming Langmuir isotherm. A variety of analyses, including surface chemistry, ionic composition, and chromatography, is performed. It is found that the surfactant breakthrough in the neutral-wet core is delayed more compared to that in the water-wet core because the deposited crude oil components on the rock surface increase the surfactant adsorption via hydrophobic interactions. As the surfactant adsorption is satisfied, the crude oil components are solubilized by surfactant micelles and some of the adsorbed surfactants are released from the rock surface. The released surfactant dissolves in the flowing surfactant solution, thereby resulting in an overshoot of the produced surfactant concentration with respect to the injection value. Furthermore, under water-wet conditions, changing the surface redox potential from an oxidized to a reduced state decreases the surfactant adsorption level by 40%. We find that the decrease in surfactant adsorption is caused not only by removing the iron oxide but also by changing the calcium concentration after the core restoration process (calcite dissolution and ion exchange as a result of using EDTA). Findings from this study suggest that laboratory surfactant adsorption tests need to be conducted by considering the wettability and redox state of the rock surface while recognizing how core restoration methods could significantly alter the ionic composition during surfactant flooding.

Characterizing the spatiotemporal evolution of paramagnetic colloids in time-varying magnetic fields with Minkowski functionals.

Phase separation processes are widely utilized to assemble complex fluids into novel materials. These separation processes can be thermodynamically driven due to changes in concentration, pressure, or temperature. Phase separation can also be induced with external stimuli, such as magnetic fields, resulting in novel nonequilibrium systems. However, how external stimuli influence the transition pathways between phases has not been explored in detail. Here, we describe the phase separation dynamics of superparamagnetic colloids in time-varying magnetic fields. An initially homogeneous colloidal suspension can transition from a continuous colloidal phase with voids to discrete colloidal clusters, through a bicontinuous phase formed via spinodal decomposition. The type of transition depends on the particle concentration and magnitude of the applied magnetic field. The spatiotemporal evolution of the microstructure during the nucleation and growth period is quantified by analyzing the morphology using Minkowski functionals. The characteristic length of the colloidal systems was determined to correlate with system variables such as magnetic field strength, particle concentration, and time in a power-law scaling relationship. Understanding the interplay between particle concentration and applied magnetic field allows for better control of the phases observed in these magnetically tunable colloidal systems.

Comparing the Coalescence Rate of Water-in-Oil Emulsions Stabilized with Asphaltenes and Asphaltene-like Molecules.

Asphaltenes are a significant contributor to flow assurance problems related to crude oil production. Because of their polydispersity, model molecules such as coronene and violanthrone-79 (VO-79) have been used as mimics to represent the physiochemical properties of asphaltenes. This work aims to evaluate the emulsion-stabilization characteristics of fractionated asphaltenes and these two model molecules. Such evaluation is expected to better characterize the stabilizing mechanisms of asphaltenes on water-in-oil emulsions. The coalescence process of water-in-oil emulsion droplets is visualized using a microfluidic flow-focusing geometry. The rate of coalescence events is used as the parameter to assess emulsion stability. Interfacial tension (IFT) and oil/brine zeta potential are measured to help explain the differences in the rates of coalescence. VO-79 is found to be better at stabilizing emulsions as compared to coronene. Although VO-79 and asphaltenes have similar interfacial tension and oil/brine zeta potential values, the rate of coalescence differs significantly. This highlights the difficulty in using model molecules to mimic the transport dynamics of asphaltenes.

Dislocation mechanisms in the plastic deformation of monodisperse wet foams within an expansion-contraction microfluidic geometry.

Densely packed wet foam was subjected to gradual expansion and contraction in a wide (1400-1800 µm) microfluidic channel to study localized plastic deformation events within the monodisperse bubble matrix. Dislocation glide, reflection, nucleation, and dipole transformations from extensional and compressive stresses were observed across a range of fluid flow rates and bubble packing densities. Disparate, cyclic reflections occur in two independent regions of the flowing foam, and the mechanisms of dislocation reflection under tension are expanded. The use of an asymmetric channel created a dichotomy in the model crystalline system between straighter, aligned bubble rows and curved, misaligned rows due to the corresponding streamlines within the channel. The resulting gradient in crystalline alignment had numerous effects on dislocation mobility and plastic deformation. 7/7 dipoles were found to rearrange to a more stable configuration aligned with the foam flow before dissociating. Dislocations comprising 5/5 dipoles (resembling the inverse-Stone-Wales defect in carbon nanostructures) were discovered to pass through one another via intermediate ring structures, which most commonly consisted of three dislocation pairs around a triangular-shaped central bubble.

Two-Step Adsorption of a Switchable Tertiary Amine Surfactant Measured Using a Quartz Crystal Microbalance with Dissipation.

The adsorption of a switchable cationic surfactant, N, N, N'-trimethyl- N'-tallow-1,3-diaminopropane (DTTM, Duomeen TTM), at the silica/aqueous solution interface is characterized using a quartz crystal microbalance with dissipation (QCM-D). The adsorption isotherms reveal that changes in the solution pH or salinity affect surfactant adsorption in competing ways. In particular, the combination of the degree of protonation of the surfactant and electrostatic interactions is responsible for surfactant adsorption. The kinetics of adsorption is carefully measured using the real-time measurement of a QCM-D, allowing us to fit the experimental data with analytical models. At pH values of 3 and 5, where the DTTM is protonated, DTTM exhibits two-step adsorption. This is representative of a fast step in which the surfactant molecules are adsorbed with head-groups orientated toward the surface, followed by a slower second step corresponding to formation of interfacial surfactant aggregates on the silica surface.

Bubble-bubble pinch-off in symmetric and asymmetric microfluidic expansion channels for ordered foam generation.

By incorporating the techniques of geometrically mediated splitting and bubble-bubble breakup, the present work offers a novel microfluidic foam generation system via production of segregated, mono- or bidisperse bubbles at capacities exceeding 10 000 bubbles per second. Bubble-bubble pinch-off is precise at high capillary numbers (Ca > 0.065), generating monodisperse or bidisperse daughter bubbles for a symmetric or an asymmetric expansion respectively. Bi- or tridisperse foam is produced as pinch-off perfectly alternates such that the system contains twice the number of fragmented bubbles as intact bubbles. A relationship between the upstream bubble extension and the capillary number demarcates the different regimes of pinch-off defined with respect to frequency and precision: non-splitting, irregular, polydisperse, and monodisperse (or bidisperse for an asymmetric expansion). For tridisperse foam generation via a fixed asymmetric expansion geometry, the wall bubble confinement can be tuned to adjust the pinch-off accuracy in order to access a spectrum of fragmented bubble size ratios. The simplicity in operating and characterizing our system will enable studies on dynamic bubble interactions and ordered, wet foam applications.