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At least 163 records · Page 9

Spontaneous shock waves in pulse-stimulated flocks of Quincke rollers

Active matter demonstrates complex spatiotemporal self-organization not accessible at equilibrium and the emergence of collective behavior. Fluids comprised of microscopic Quincke rollers represent a popular realization of synthetic active matter. Temporal activity modulations, realized by modulated external electric fields, represent an effective tool to expand the variety of accessible dynamic states in active ensembles. Here, we report on the emergence of shockwave patterns composed of coherently moving particles energized by a pulsed electric field. The shockwaves emerge spontaneously and move faster than the average particle speed. Combining experiments, theory, and simulations, we demonstrate that the shockwaves originate from intermittent spontaneous vortex cores due to a vortex meandering instability. They occur when the rollers’ translational and rotational decoherence times, regulated by the electric pulse durations, become comparable. The phenomenon does not rely on the presence of confinement, and multiple shock waves continuously arise and vanish in the system.

36 MATERIALS SCIENCE↗

Field-Driven Out-of-Equilibrium Collective Patterns for Swarm Micro-Robotics

Soft robotics has been rapidly advancing, offering significant improvements over traditional rigid robotic systems through the use of compliant materials that enhance adaptability and interaction with the environment. However, current approaches face critical challenges, including the reliance on complex “top-down” fabrication techniques and the difficulty of wireless powering and control at the microscale. Swarm robotics introduces a paradigm shift, leveraging collective dynamics to achieve cooperative and adaptable behaviors among multiple robotic units. Inspired by nature, this “bottom-up” approach enables swarm robots to execute task-specific reconfigurations, enhancing flexibility and robustness. Field-driven active colloids emerge as a promising platform for swarm microrobotics, capable of self-propulsion and self-organization into dynamic collective patterns under external field excitation and manipulation. These systems mimic biologically inspired swarm behaviors, such as flocking and vortex formation, providing a versatile foundation for designing innovative swarm microrobots. Here, this review discusses the principles of electric and magnetic field-driven collective self-organization, focusing on the particle dynamics, the emergence of collective swarm patterns, and illustrative examples of functional swarm microrobots. It concludes with future perspectives on harnessing these systems for adaptive, scalable, and multifunctional microrobotic applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Emergence and dynamics of unconfined self-organised vortices in active magnetic roller liquids

Actively driven colloids demonstrate complex out-of-equilibrium dynamics often rivaling self-organized patterns and collective behavior observed in living systems. Recent studies revealed the emergence of steady macroscopic states with multiple interacting vortices in an unconfined environment that emerge from the coupling between microscale particle rotation and translation. Yet, insights into the microscopic behavior during the vortex emergence, growth, and formation of a multi-vortical state remain lacking. Here, we investigate in experiments and simulations how the microscale magnetic roller behavior leads to the emergence of seed vortices, their aggregation or annihilation, and the formation of stable large-scale vortical structures. We reveal that the coupling of roller-induced hydrodynamic flows guides the local self-densifications and self-organization of the micro-rollers into seed vortices. Here, the resulting multi-vortical state is sensitive to the external magnetic field amplitude and allows tuning the rollers' number density in a vortex and its characteristic size.

36 MATERIALS SCIENCE↗

Scaling of Shear Rheology of Concentrated Charged Colloidal Suspensions across Glass Transition

Electrostatic interparticle interactions are a key component in controlling and designing rheological characteristics of concentrated charged colloidal suspensions. Herein, we investigate electroviscous effects on shear rheology using highly charged silica particles. By fixing the volume fraction but varying the salinity, the system undergoes a glass transition as evidenced by the evolution of the yield stress and zero-shear viscosity. We show that the steady shear viscosities obey a critical scaling relation that scales the flow curves into a super- and a sub-critical branch with glass transition salinity serving as the bifurcation point; we also demonstrate an isoviscosity scaling that collapses all isoviscosity lines into a single master curve that exhibits no singularity. Based on each scaling relation, in conjunction with common modeling equations, the quantitative relationships between the shear viscosity, stress, and salinity are established. This study demonstrates a new framework to model the steady shear rheology of concentrated charged colloids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Trace elements and their isotopes in streams and rivers

The occurrence and speciation of trace elements in streams and rivers are controlled by interconnected hydrogeological, biogeochemical, and anthropogenic factors that include rock weathering, climate, vegetation, and land use within the watershed. This chapter provides a broad overview of trace element abundance, speciation, and mobility in streams and rivers, including an assessment of how trace elements are partitioned into dissolved, colloidal, and particulate phases. We also discuss how trace elements are mobilized into stream networks and transformed during transport. Select isotopic systems are reviewed to provide examples of how isotopic analyses can be used to understand geochemical and anthropogenic processes.

Herndon, Elizabeth [ORNL] (ORCID:0000000291945493)↗

Active matter commensuration and frustration effects on periodic substrates

In this report we show that self-driven particles coupled to a periodic obstacle array exhibit active matter commensuration effects that are absent in the Brownian limit. As the obstacle size is varied for sufficiently large activity, a series of commensuration effects appear in which the motility induced phase separation produces commensurate crystalline states, while for other obstacle sizes we find frustrated or amorphous states. The commensuration effects are associated with peaks in the amount of sixfold ordering and the maximum cluster size. When a drift force is added to the system, the mobility contains peaks and dips similar to those found in transport studies for commensuration effects in superconducting vortices and colloidal particles.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Basal Plane Doping to Activate Colloidal MoS 2 Nanosheets for Catalytic Hydrodeoxygenation of para- Cresol

The valorization of biomass into biofuels is a critical process for producing renewable fuels. Hydrodeoxygenation (HDO), particularly over doped molybdenum disulfide (MoS 2 ), a transition metal dichalcogenide (TMD) material, is a common representative catalytic reaction system for converting biomass-derived materials into useful hydrocarbons. However, the location and role of dopants, such as Co, in HDO is not fully understood. The effects of dopant location and oxidation state are often precluded by inhomogeneity in the ensemble properties of nanosheet size and dopant dispersion, as well as difficulty in observing the behavior of atomic site behavior directly. Using a colloidal approach to synthesize cobalt-doped MoS 2 nanosheets with controlled dopant concentration, combined with X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations, we determine that basal plane doped Co (25% Co:Mo mole ratio) shows peak catalytic activity in HDO of para-cresol, a model biomass-derived compound, and that basal Co sites are demonstrably more active than edge sites. By observing these doping effects in MoS 2 catalysts for HDO, we can further optimize not only the production of carbon-neutral fuels but also direct the tailoring of doped TMD catalysts toward their intended applications.

36 MATERIALS SCIENCE↗

Active-noise-induced dynamic clustering of passive colloidal particles

Active fluids generate spontaneous, often chaotic mesoscale flows. Harnessing these flows to drive soft materials embedded within an active fluid into structures with controlled length scales and lifetimes is a key challenge at the interface between the fields of active matter and nonequilibrium self-assembly. Here, we present a simple and efficient computational approach to model soft materials advected by active fluids, by simulating particles moving in a spatiotemporally correlated noise field. To illustrate our approach, we simulate the dynamical self-organization of repulsive colloids within such an active noise field. The colloids form structures whose sizes and dynamics can be tuned by the correlation time and length of the active fluid, and range from small rotating droplets to clusters with internal flows and system-spanning sizes that vastly exceed the active correlation length. Our results explain how the interplay between active fluid time and length scales and emergent driven assembly can be used to rationally design functional assemblies. More broadly, our approach can be used to efficiently simulate diverse active fluids and other systems with spatiotemporally correlated noise.

Brownian dynamics↗

Prospects and challenges of colloidal quantum dot laser diodes

Colloidal quantum dots (QDs) combine the superior light-emission characteristics of quantum-confined semiconductors with the chemical flexibility of molecular systems. We find that these properties could, in principle, enable solution-processable laser diodes with an ultrawide range of accessible colours. However, the realization of such devices has been hampered by fast optical gain decay due to non-radiative Auger recombination and poor stability of QD solids at the high current densities required for the lasing regime. Recently, these problems have been resolved, which resulted in the development of electrically pumped optical gain devices operating at ultrahigh current densities of around 1,000 A cm -2 . The next step is the realization of a QD laser diode (QLD). Here we assess the status of the QD lasing field, examine the remaining challenges on the path to a QLD and discuss practical strategies for attaining electrically pumped QD lasing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Programming Function via Soft Materials (PFvSM) (Final Report)

The PFvSM cluster at the University of Illinois greatly deepened the science of soft materials and expanded the means for embedding within them unprecedented functionalities. We pioneered a mesoscopic approach to materials design that combined leading competencies in fundamental experimental and theoretical soft matter science and fabrication that powerfully establishes equilibrium and nonequilibrium assembly of novel and complex building blocks as a preeminent contributor to progress in materials chemistry. Our cluster’s vision was an integrated program of work centered on soft matter science with the ultimate goal of impacting important energy technologies. As elementary units we employed function-encoded colloids, nanoparticles, large mesh fibrillar gels, deterministically fabricated networks and hybrid objects. These materials were employed as building blocks for diverse model systems that allowed fundamental soft matter principles of wide relevance to be established. Their assembly into materials with useful functional behavior provided new approaches to challenging problems in basic energy science including energy harvesting, transport and storage. To achieve these goals the cluster brought together a team of recognized world-leaders in materials synthesis and processing, in-situ characterization, theory and modeling, and materials design, integration and fabrication

36 MATERIALS SCIENCE↗

Solution-processable integrated CMOS circuits based on colloidal CuInSe2 quantum dots

Abstract The emerging technology of colloidal quantum dot electronics provides an opportunity for combining the advantages of well-understood inorganic semiconductors with the chemical processability of molecular systems. So far, most research on quantum dot electronic devices has focused on materials based on Pb- and Cd chalcogenides. In addition to environmental concerns associated with the presence of toxic metals, these quantum dots are not well suited for applications in CMOS circuits due to difficulties in integrating complementary n - and p -channel transistors in a common quantum dot active layer. Here, we demonstrate that by using heavy-metal-free CuInSe 2 quantum dots, we can address the problem of toxicity and simultaneously achieve straightforward integration of complimentary devices to prepare functional CMOS circuits. Specifically, utilizing the same spin-coated layer of CuInSe 2 quantum dots, we realize both p - and n -channel transistors and demonstrate well-behaved integrated logic circuits with low switching voltages compatible with standard CMOS electronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Accelerated annealing of colloidal crystal monolayers by means of cyclically applied electric fields

Abstract External fields are commonly applied to accelerate colloidal crystallization; however, accelerated self-assembly kinetics can negatively impact the quality of crystal structures. We show that cyclically applied electric fields can produce high quality colloidal crystals by annealing local disorder. We find that the optimal off-duration for maximum annealing is approximately one-half of the characteristic melting half lifetime of the crystalline phase. Local six-fold bond orientational order grows more rapidly than global scattering peaks, indicating that local restructuring leads global annealing. Molecular dynamics simulations of cyclically activated systems show that the ratio of optimal off-duration for maximum annealing and crystal melting time is insensitive to particle interaction details. This research provides a quantitative relationship describing how the cyclic application of fields produces high quality colloidal crystals by cycling at the fundamental time scale for local defect rearrangements; such understanding of dynamics and kinetics can be applied for reconfigurable colloidal assembly.

36 MATERIALS SCIENCE↗

System with buffer for lateral flow on a porous membrane

Systems are described, based on a primary binding compound and a secondary binding compound used in combination with a support to detect a target in a sample. The systems includes at least one support structure, at least one small primary support portion containing at least one molecule covalently bound to a visual colloidal marker, a plurality of secondary support portions comprising secondary binding compounds that are covalently bound to the support portions and chemically active, at least one pH litmus indicator, at least one pH strip, a buffer for lateral flow on the porous membrane support that allows preservation and activity of binding compounds.

Bearinger, Jane P.↗

Electrical Switching of Nematic Plasmonic Nanocolloids for Infrared Solar Gain Control

Controlling solar gain is essential to reduce the energy consumption by residential and commercial buildings, which are responsible for ≈40% of all energy generated globally. However, the dynamic control of solar gain in the near-infrared that corresponds to ≈50% of the overall Sun's energy at the Earth's surface, separately from the visible spectral range has been a challenge, albeit commercial coatings provide passive control while retaining highly visible transmission. To address this problem, in this paper switchable silver colloids (SSCs) are demonstrated, colloidal analogs of the common silver coatings used for solar gain control. When dispersed in a nematic liquid crystal, orientations of such plasmonic silver nanoplates are controlled by ≈1 V low-voltage electric fields, allowing for sub-second switching of the near-infrared-based solar gain. Installed and retrofit products made from thin films of such nanoplate dispersions confined between glass and plastic substrates, respectively, exhibit electrically controlled infrared-based solar gain while retaining high visible-range transparency, low haze, and high color rendering index. Furthermore, this study's findings reveal a great potential of soft-matter systems in addressing energy-related problems.

36 MATERIALS SCIENCE↗

Applying colloidal silica suspensions injection and sequential gelation to block vertical water flow in well annulus: laboratory testing on rheology, gelation, and injection

We evaluated the application of silica suspension injection and sequential gelation to block vertical water flow in the annuli of long-screened wells. First, we studied the viscosity, rheological behavior, and gelation performance of colloidal silica suspensions in batch tests. Then, we tested the injection of silica suspensions and the water flow blocking efficiency of the later formed silica gel in column and bench-scale sandbox experiments. Micron-sized fumed powder silica suspensions and nanosized silica suspensions recovered from geothermal fluids were tested in this work. Fumed silica suspensions showed shear thinning, while nanosized silica suspensions exhibited Newtonian flow behavior. During the gelation process, the nanosized silica suspension changed from a Newtonian fluid to a shear thinning fluid while increasing its overall viscosity. At comparable concentrations, the nanosized silica suspensions have much lower viscosity than that of the fumed silica suspensions. Increases in the Na + concentration and silica particle concentration in these suspensions shortened the gelation time. Silica suspension gelation in sand columns completely blocked the water flow and sustained the injection pressure up to 50 psig (344.7 kPa). A silica suspension was successfully injected into the target zone in the annulus of a bench-scale sandbox mimicking long-screened wells in the field. The silica gel formed in the annulus effectively blocked chemical transport through the gelled zone. Our research reveals that a process using silica suspension injection and sequential gelation technology is promising for blocking the vertical water flow and chemical transport through the filter pack in targeted zones within the annulus of long-screened well systems.

54 ENVIRONMENTAL SCIENCES↗

Nonadditive Interactions Unlock Small-Particle Mobility in Binary Colloidal Monolayers

We examine the organization and dynamics of binary colloidal monolayers composed of micron-scale silica particles interspersed with smaller-diameter silica particles that serve as minority component impurities. These binary monolayers are prepared at the surface of ionic liquid droplets over a range of size ratios (σ = 0.16–0.66) and are studied with low-dose minimally perturbative scanning electron microscopy (SEM). The high resolution of SEM imaging provides direct tracking of all particle coordinates over time, enabling a complete description of the microscopic state. In these bidisperse size mixtures, particle interactions are nonadditive because interfacial pinning to the droplet surface causes the equators of differently sized particles to lie in separate planes. By varying the size ratio, we control the extent of nonadditivity in order to achieve phase behavior inaccessible to additive 2D systems. Across the range of size ratios, we tune the system from a mobile small-particle phase (σ < 0.24) to an interstitial solid (0.24 < σ < 0.33) and furthermore to a disordered glass (σ > 0.33). These distinct phase regimes are classified through measurements of hexagonal ordering of the large-particle host lattice and the lattice’s capacity for small-particle transport. Altogether, we explain these structural and dynamic trends by considering the combined influence of interparticle interactions and the colloidal packing geometry. Our measurements are reproduced in molecular dynamics simulations of 2D nonadditive disks, suggesting an efficient method for describing confined systems with reduced dimensionality representations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Selective Catalytic Behavior Induced by Crystal–Phase Transformation in Well–Defined Bimetallic Pt–Sn Nanocrystals

The Pt-Sn bimetallic system is a much studied and commercially used catalyst for propane dehydrogenation. The traditionally prepared catalyst, however, suffers from inhomogeneity and phase separation of the active Pt–Sn phase. Colloidal chemistry offers a route for the synthesis of Pt–Sn bimetallic nanoparticles (NPs) in a systematic, well-defined, tailored fashion over conventional methods. Here, the successful synthesis of well-defined ≈2 nm Pt, PtSn, and Pt 3 Sn nanocrystals with distinct crystallographic phases is reported; hexagonal close packing (hcp) PtSn and fcc Pt 3 Sn show different activity and stability depending on the hydrogen-rich or poor environment in the feed. Moreover, face centred cubic (fcc) Pt 3 Sn/Al 2 O 3 , which exhibited the highest stability compared to hcp PtSn, shows a unique phase transformation from an fcc phase to an L1 2 -ordered superlattice. Contrary to PtSn, H 2 cofeeding has no effect on the Pt 3 Sn deactivation rate. Finally, the results reveal structural dependency of the probe reaction, propane dehydrogenation, and provide a fundamental understanding of the structure–performance relationship on emerging bimetallic systems.

36 MATERIALS SCIENCE↗

Colloidal State Machines as Smart Tracers for Chemical Reactor Analysis

A widely utilized tool in reactor analysis is passive tracers that report the residence time distribution, allowing estimation of the conversion and other properties of the system. Recently, advances in microrobotics have introduced powered and functional entities with sizes comparable to some traditional tracers. This has motivated the concept of Smart Tracers that could record the local chemical concentrations, temperature, or other conditions as they progress through reactors. Herein, the design constraints and advantages of Smart Tracers by simulating their operation in a laminar flow reactor model conducting chemical reactions of various orders are analyzed. It is noted that far fewer particles are necessary to completely map even the most complex concentration gradients compared with their conventional counterparts. Design criteria explored herein include sampling frequency, memory storage capacity, and ensemble number necessary to achieve the required accuracy to inform a reactor model. Cases of severe particle diffusion and sensor noise appear to bind the functional upper limit of such probes and require consideration for future design. The results of the study provide a starting framework for applying the new technology of microrobotics to the broad and impactful set of problems classified as chemical reactor analysis.

97 MATHEMATICS AND COMPUTING↗