Colloidal Dynamics Research Articles

Immersed boundary method for dynamic simulation of polarizable colloids of arbitrary shape in explicit ion electrolytes.

We develop a computational method for modeling electrostatic interactions of arbitrarily shaped, polarizable objects on colloidal length scales, including colloids/nanoparticles, polymers, and surfactants, dispersed in explicit ion electrolytes and nonionic solvents. Our method computes the nonuniform polarization charge distribution induced in a colloidal particle by both externally applied electric fields and local electric fields arising from other charged objects in the dispersion. This leads to expressions for electrostatic energies, forces, and torques that enable efficient molecular dynamics and Brownian dynamics simulations of colloidal dispersions in electrolytes, which can be harnessed to accurately predict structural and transport properties. We describe an implementation in which colloidal particles are modeled as rigid composites of small spherical beads that tessellate the surface of the particle. The electrostatics calculations are accelerated using a spectrally accurate particle-mesh-Ewald technique implemented on a graphics processing unit and regularized such that the electrostatic calculations are well-defined even for overlapping bodies. We illustrate the effectiveness of this approach with a comprehensive set of calculations: the induced dipole moments and forces for individual, paired, and lattice configurations of spherical colloids in an electric field; the induced dipole moment and torque for anisotropic particles subjected to an electric field; the equilibrium ion distribution in the double layer surrounding charged colloids; the dynamics of charged colloids; and the behavior of ions in the double layer of a polarizable colloid under the influence of an electric field.

Brownian colloids in optothermal field: An experimental perspective

Colloidal matter undergoing Brownian motion serves as a model system to study various physical phenomena. Understanding the effect of external perturbation on the assembly and dynamics of “Brownian colloids” has emerged as a relevant research issue in soft matter and biological physics. Optical perturbation in the form of photonic forces and torques has added impetus to this exploration. In recent years, optothermal effects arising due to optical excitation of mesoscale matter have expanded the toolbox of light–colloidal matter interactions. In this perspective, we present an experimental viewpoint on some of the developments related to the assembly and dynamics of Brownian colloids driven by the optothermal field. Furthermore, we discuss some interesting prospects on driven colloidal matter that can have implications on soft matter physics and soft photonics.

Aqueous and Colloidal Dynamics in Size-Fractionated Paddy Soil Aggregates with Multiple Metal Contaminants under Redox Alternations.

Soil contamination by multiple metals is a significant concern due to the interlinked mobilization processes. The challenges in comprehending this issue arise from the poorly characterized interaction among different metals and the complexities introduced by spatial and temporal heterogeneity in soil systems. We delved into these complexities by incubating size-fractionated paddy soils under both anaerobic and aerobic conditions, utilizing a combination of techniques for aqueous and colloidal analysis. The contaminated paddy soil predominantly consisted of particles measuring <53, 250-53, and 2000-250 μm, with the <53 μm fractions exhibiting the highest concentrations of multiple metals. Interestingly, despite their higher overall content, the <53 μm fractions released less dissolved metal. Furthermore, glucose enhanced the release of arsenic while simultaneously promoting the sequestration of other metals, such as Pb, Zn, and Cu. Utilizing asymmetric flow field-flow fractionation, we unveiled the presence of both fine (0.3-130 kDa) and large (130-450 nm) colloidal pools, each carrying various metals with different affinities for iron minerals and organic matter. Our results highlighted the pivotal role of the <53 μm fraction as a significant reservoir for multiple metal contaminants in paddy soils, in which the colloidal metals were mainly associated with organic matter. These findings illuminated the size-resolved dynamics of soil metal cycling and provided insights for developing remediation strategies for metal-contaminated soil ecosystems.

Investigating reactive transport and precipitation patterns of calcium carbonate in fractured porous media

HypothesisUnderstanding calcium carbonate (CaCO3) precipitation in various polymorphs from nanoparticle size (amorphous calcium carbonate) to microparticle size (vaterite, aragonite, dendrite, calcite) is important for practical applications, including carbon geo-storage (e.g., basalt formations), hydrogen storage, groundwater management, and soil stabilization. Our hypothesis suggests that the interplay of Péclet numbers (Pe), Damköhler numbers (Da), and Supersaturation Index (SI) significantly impacts the evolution of CaCO3 precipitation in fractured porous media in terms of mixing patterns, spatiotemporal evolution, crystal morphology, crystal size, and clogging behavior. ExperimentsThis study takes a novel approach to explore the colloidal formation and precipitation dynamics of CaCO3 within a fractured microfluidic system. Here, calcium chloride (CaCl2) and sodium bicarbonate (NaHCO3) solutions were injected and reacted under varied Pe (0–11), Da (0–1), and SI (2–5). FindingsOur analysis revealed distinct precipitation patterns and mixing types, such as transverse, longitudinal, and incomplete mixing, providing insights into the behavior in fractured porous media. We systematically analyzed the temporal and spatial evolution of precipitation, demonstrating how Pe, Da, and SI dictate precipitation rates and spatial distribution. Additionally, the study uncovered a range of CaCO3 polymorphic forms, illustrating their evolution and coexistence. Morphological changes and crystal sizes were examined to decode nucleation and growth processes. Significantly, our findings highlight the relationship between precipitation and clogging in the fractured medium, offering a deeper understanding of reactive transport in complex porous environments. These insights are crucial for enhancing carbon containment security and storage efficiency in underground formations, improving groundwater remediation techniques, and developing novel construction materials through controlled precipitation processes.

Influence of natural organic matter on the aggregation dynamics of biochar colloids derived from various feedstocks

Abundant biochar colloids (BCs) produced from a wide range of feedstocks, resulting from forest fires, agricultural production, and environmental restoration, exhibit varying aggregation behaviors influenced by feedstock type and natural organic matter. However, the impact of natural organic matter on the colloidal stability of BCs derived from different feedstocks remains poorly understood. In this study, six selected biochars were derived from various feedstocks as follows: sewage sludge (SS), rice husk (RH), oil seed rape straw pellets (OSR), wheat straw pellets (WS), miscanthus straw pellets (MS) and softwood pellets (SW). The colloidal stability of BCs, with the exogenous addition of organic matter, was further determined. The order of critical coagulation concentrations (CCCs) of BCs with the presence of humic acid (HA) was as follows: RH (989.48 mM) < MS (1084.69 mM) < SS (1149.76 mM) < WS (1338.99 mM) < OSR (2402.98 mM) < SW (3151.32 mM). This order was significantly positively correlated with the specific surface area and negatively correlated with the ash content of the bulk biochar. Compared to HA, bovine serum albumin (BSA) more effectively inhibited the aggregation behavior of BCs due to steric hindrance. The initial aggregation rate constant (k) of BCs at 3000 mM NaCl was as follows: MS (0.238 nm/s) > OSR (0.142 nm/s) > WS (0.128 nm/s) > SS (0.126 nm/s) > RH (0.118 nm/s) > SW (0.112 nm/s). The stabilizing effects of BSA on biochar colloids were independent of the physicochemical properties of bulk biochar. In the presence of BSA, a thin layer of protein corona significantly enhanced the stability of biochar colloids, particularly the BCs derived from MS. Our results underscore the importance of considering feedstock resources and natural organic matter type when assessing the aggregation and potential risks of BCs in aquatic systems.

Rescaled mode-coupling scheme for the quantitative description of experimentally observed colloid dynamics.

We describe experimentally observed collective dynamics in colloidal suspensions of model hard-sphere particles using a modified mode coupling theory (MCT). This rescaled MCT is capable of describing quantitatively the wave-vector and time-dependent diffusion in these systems. Intermediate scattering functions of liquidlike structured dispersions are determined by means of static and dynamic light-scattering experiments. The structure and short-time dynamics of the systems can be described quantitatively employing a multicomponent Percus-Yevick ansatz for the partial structure factors and an effective, one-component description of hydrodynamic interactions based on the semianalytical δγ expansion. Combined with a recently proposed empirical modification of MCT in which memory functions are calculated using effective structure factors at rescaled number densities, the scheme is able to model the collective dynamics over the entire accessible time and wave-vector range and predicts the volume-fraction-dependence of long-time self-diffusion coefficients and the zero-shear viscosity quantitatively. This highlights the potential of MCT as a practical tool for the quantitative analysis and prediction of experimental observations.

Adsorption and distribution of heavy metals in aquatic environments: The role of colloids and effects of environmental factors

The study investigated the distributions of heavy metals (Cd, Cr, Cu, Mn, and Pb) between dissolved fraction (<0.7 µm) and particles (>0.7 µm) during the adsorption process. The dissolved fraction was further separated into truly dissolved (<3 kDa) and colloidal (3 kDa-0.7 µm) fractions. Significant metal adsorption occurred on the colloids, resulting in their aggregation into particles, which in turn influenced the particle adsorption kinetics. Colloids could either accelerate or inhibit the transformation of metal ions into particulates, depending on their stability. Competitive metals for colloids (Pb and Cr) were more susceptible to the effects of colloids than other elements. DOM was the predominant environmental factor influencing colloid behavior. The XDLVO theory showed that DOM enhanced the negative charge of colloids and made the colloid surface more hydrophilic, inhibiting the aggregation of colloids. DOM resulted in substantial increases in the concentrations of colloidal Pb and Cr from 0.31 μg/L and 4.58 μg/L to 20.52 μg/L and 43.51 μg/L, respectively, whereas the increment for less competitive metals (Cd and Mn) was smaller. These findings suggest that the distribution of heavy metals is influenced not only by adsorption from particles and ions but also by the complex dynamics of colloids.

Colloid phase separation dynamics driven by chiral turbulent flows

Hydrodynamic interactions significantly influence phase-ordering kinetics in complex fluids. While passive fluid phase separation is well studied, the impact of active components remains relatively unexplored. We examine pure- and quasi-two-dimensional mixtures of attractive colloids and self-rotating particles in a solvent. Varying rotor rotational speed and area fraction yield diverse dynamic patterns such as percolated networks and round droplets composed of passive colloids alone. At intermediate rotation speeds, inertial chiral flows, accompanied by the inverse energy cascade, lead to self-similar power-law coarsening with a growth exponent of 1/2. The flows spontaneously organize within fluid domains, exhibiting turbulent and chiral characteristics. Surprisingly, these turbulent flows can sustain hexatic order hydrodynamically stabilized by the Magnus force under certain conditions. Conversely, at higher speeds, nonlinear hydrodynamic interactions impede phase separation. Our findings illuminate the intriguing dynamic interplay between phase separation and chiral turbulence, effectively bridging the realms of phase ordering and turbulent physics. Published by the American Physical Society 2024

Dynamic density functional theory with inertia and background flow.

We present dynamic density functional theory (DDFT) incorporating general inhomogeneous, incompressible, time-dependent background flows and inertia, describing externally driven passive colloidal systems out of equilibrium. We start by considering the underlying nonequilibrium Langevin dynamics, including the effect of the local velocity of the surrounding liquid bath, to obtain the nonlinear, nonlocal partial differential equations governing the evolution of the (coarse-grained) density and velocity fields describing the dynamics of colloids. In addition, we show both with heuristic arguments, and by numerical solution, that our equations and solutions agree with existing DDFTs in the overdamped (high friction) limit. We provide numerical solutions that model the flow of hard spheres, in both unbounded and confined domains, and compare with previously derived DDFTs with and without the background flow.

Transmission Electron Microscopy and Dynamic Light Scattering-Fundamental Perspective

Transmission Electron Microscopy (TEM) and Dynamic Light Scattering (DLS) are fundamental tools in nanotechnology and materials science, providing information about the structural and dynamic properties of nanomaterials and colloidal systems. This review provides a thorough examination of TEM and DLS, beginning with a discussion of their fundamental principles. It discusses the interaction of electron beams in TEM and the dynamics of scattered light in DLS, followed by an examination of instrumentation and experimental setups, including recent advances for increased resolution and sensitivity. The article then discusses the numerous applications of TEM and DLS in nanomaterial characterization. It includes analyses of nanoparticle size, shape, morphology, and distribution, as well as research into colloidal system dynamics such as nanoparticle aggregation, diffusion, and stability. The review concludes with a forward-looking perspective on emerging trends and future directions in nanomaterial characterization. It emphasizes the potential of TEM and DLS to overcome current challenges and advance our understanding of nanoscale phenomena. Overall, this comprehensive review provides researchers and practitioners with a solid understanding of the TEM and DLS principles, methodologies, and applications, as well as valuable fundamental insights.

Recent advances in synchrotron scattering methods for probing the structure and dynamics of colloids

Recent progress in synchrotron based X-ray scattering methods applied to colloid science is reviewed. An important figure of merit of these techniques is that they enable in situ investigations of colloidal systems under the desired thermophysical and rheological conditions. An ensemble averaged simultaneous structural and dynamical information can be derived albeit in reciprocal space. Significant improvements in X-ray source brilliance and advances in detector technology have overcome some of the limitations in the past. Notably coherent X-ray scattering techniques have become more competitive and they provide complementary information to laboratory based real space methods. For a system with sufficient scattering contrast, size ranges from nm to several μm and time scales down to μs are now amenable to X-ray scattering investigations. A wide variety of sample environments can be combined with scattering experiments further enriching the science that could be pursued by means of advanced X-ray scattering instruments. Some of these recent progresses are illustrated via representative examples. To derive quantitative information from the scattering data, rigorous data analysis or modeling is required. Development of powerful computational tools including the use of artificial intelligence have become the emerging trend.

Dynamical arrest transition of a bidisperse two-patchy colloidal dispersion: A dynamic Monte Carlo study.

During the last few years, patchy colloidal dispersions have emerged as ideal candidates of glass-formers of systems composed of particles that interact with non-isotropic potentials. However, from the computational point of view, the characterization of their dynamical properties close to the glass transition via any kind of molecular dynamics simulation technique can be very difficult due to the slowing down of both the rotational and translational dynamics. Although a plethora of dynamical techniques have been developed to account for the dynamics of patchy colloids, new and complementary simulation techniques are required to explore, much faster and more efficiently, the dynamical arrest transition of patchy colloidal dispersions when computer simulation consists of a large number of particles and, due to the slow particle dynamics at the glass transition, an extended time window is explicitly required. Then, in this contribution, by means of the so-called dynamic-Monte Carlo method, we report on the dynamical arrest transition, both rotational and translational, of a bidisperse patchy colloidal dispersion, following three different paths along the density-temperature plane, including high densities and low temperatures. Although this method has not been extensively tested at extreme thermodynamic conditions, we show that even at the dynamical arrest transition, it allows us to extract good dynamical data from a complex system. Therefore, it turns out to be a promising technique to explore the onset of vitrification of anisotropic colloidal particles.

Chemical Micromotors Move Faster at Oil-Water Interfaces.

Many real-world scenarios involve interfaces, particularly liquid-liquid interfaces, that can fundamentally alter the dynamics of colloids. This is poorly understood for chemically active colloids that release chemicals into their environment. We report here the surprising discovery that chemical micromotors─colloids that convert chemical fuels into self-propulsion─move significantly faster at an oil-water interface than on a glass substrate. Typical speed increases ranged from 3 to 6 times up to an order of magnitude and were observed for different types of chemical motors and interfaces made with different oils. Such speed increases are likely caused by faster chemical reactions at an oil-water interface than at a glass-water interface, but the exact mechanism remains unknown. Our results provide valuable insights into the complex interactions between chemical micromotors and their environments, which are important for applications in the human body or in the removal of organic pollutants from water. In addition, this study also suggests that chemical reactions occur faster at an oil-water interface and that micromotors can serve as a probe for such an effect.

The dynamics of PEG‐coated nanoparticles in concentrated protein solutions up to the molecular crowding range

AbstractPolymer‐coated nanoparticles are widely studied in the context of nanomedicine and it is therefore of utmost importance to understand not only how their structure but also how their colloidal dynamics are affected by physiologically relevant conditions. A characteristic feature of the cytosol of cells is the very high concentration of proteins among other matrix components, often termed macromolecular crowding. Here, the structure and colloidal dynamics of poly(ethylene glycol) (PEG)‐coated gold nanoparticles in the presence of bovine serum albumin (BSA) concentrations ranging from 0 to 265 mg/mL are studied with X‐ray photon correlation spectroscopy. For protein–nanoparticle mixtures with high BSA concentrations, comparable to intracellular levels, a significant deviation of the apparent viscosity from expectations for pure BSA solutions is found. The findings strongly indicate that the nanoscopic viscous properties of the dense protein solutions are significantly affected by the nanoparticles. At these high concentrations, the colloidal stability of the samples depends on the molecular weight of the coating PEG–ligand, whereas at lower concentrations no differences are observed.

Dynamics of anisotropic colloidal systems: What to choose, DLS, DDM or XPCS?

Investigation of the dynamics of colloids in bulk can be hindered by issues such as multiple scattering and sample opacity. These challenges are exacerbated when dealing with inorganic materials. In this study, we employed a model system of Akaganeite colloidal rods to assess three leading dynamics measurement techniques: 3D-(depolarized) dynamic light scattering (3D-(D)DLS), polarized-differential dynamic microscopy (P-DDM), and x-ray photon correlation spectroscopy (XPCS). Our analysis revealed that the translational and rotational diffusion coefficients captured by these methods show a remarkable alignment. Additionally, by examining the q-ranges and maximum volume fractions for each approach, we offer insights into the best technique for investigating the dynamics of anisotropic systems at the colloidal scale.

Insights into controlling bacterial cellulose nanofiber film properties through balancing thermodynamic interactions and colloidal dynamics

Proposed mechanistic model: balancing electrokinetic and thermodynamic factors in CNF colloid to film transition.

Dual access to the fluid networks of colloid-stabilized bicontinuous emulsions through uninterrupted connections.

Large surface areas are important for enhancing mass and energy transfer in biological and technological processes. Bicontinuous interfacially jammed emulsion gels (bijels) increase the surface area between two fluids by intertwining them into particle stabilized networks. To facilitate efficient mass and energy exchange via the bijels' high surface area, the fluid networks need to be connected to their respective bulk phases. Here, we generate bijels between two bulk fluids and investigate the connections the bijel makes. We analyze these connections by investigating the colloidal stability, interfacial rheology and mass transfer dynamics during bijel formation. To this end, we employ confocal and electron microscopy, as well as dynamic light scattering, pendant drop analysis, electrophoretic mobility measurements and diffusion simulations. We find that the connections the bijel makes to the bulk fluid can be disrupted by severe colloidal aggregation and interruptions of the bicontinuous fluid network. However, the addition of alcohol to the bulk fluid moderates aggregation and allows undisturbed fluid network formation, facilitating open connections between bijel and bulk fluid. The unprecedented control of bijel pore connections from this research will be crucial for the application of bijels as separation membranes, electrochemical energy storage materials and chemical reactors.

Entangled nematic disclinations using multi-particle collision dynamics.

Colloids dispersed in nematic liquid crystals form topological composites in which colloid-associated defects mediate interactions while adhering to fundamental topological constraints. Better realising the promise of such materials requires numerical methods that model nematic inclusions in dynamic and complex scenarios. We employ a mesoscale approach for simulating colloids as mobile surfaces embedded in a fluctuating nematohydrodynamic medium to study the kinetics of colloidal entanglement. In addition to reproducing far-field interactions, topological properties of disclination loops are resolved to reveal their metastable states and topological transitions during relaxation towards ground state. The intrinsic hydrodynamic fluctuations distinguish formerly unexplored far-from-equilibrium disclination states, including configurations with localised positive winding profiles. The adaptability and precision of this numerical approach offers promising avenues for studying the dynamics of colloids and topological defects in designed and out-of-equilibrium situations.

Dynamic Light Scattering and Its Application to Control Nanoparticle Aggregation in Colloidal Systems: A Review.

Colloidal systems and their control play an essential role in daily human activities, but several drawbacks lead to an avoidance of their extensive application in some more productive areas. Some roadblocks are a lack of knowledge regarding how to influence and address colloidal forces, as well as a lack of practical devices to understand these systems. This review focuses on applying dynamic light scattering (DLS) as a powerful tool for monitoring and characterizing nanoparticle aggregation dynamics. We started by outlining the core ideas behind DLS and how it may be used to examine colloidal particle size distribution and aggregation dynamics; then, in the last section, we included the options to control aggregation in the chemically processed toner. In addition, we pinpointed knowledge gaps and difficulties that obstruct the use of DLS in real-world situations. Although widely used, DLS has limits when dealing with complicated systems, including combinations of nanoparticles, high concentrations, and non-spherical particles. We discussed these issues and offered possible solutions and the incorporation of supplementary characterization approaches. Finally, we emphasized how critical it is to close the gap between fundamental studies of nanoparticle aggregation and their translation into real-world applications, recognizing challenges in colloidal science.

Brownian-molecular dynamic correspondence in two-dimensional hard-disk fluids

It has been both experimentally and theoretically observed that the structural and dynamical properties of glass-forming fluids can be scaled and described within the dynamic universality class of hard spheres. One of the key predictions of this universality is the long-time dynamic equivalence between Brownian and Molecular dynamics systems governed by the same kind of interaction potential. However, the application and extent of this principle has not been validated for two-dimensional systems. To this end, we employ Brownian and Molecular Dynamics simulations to validate this principle in the two-dimensional case, analysing the long-time properties of systems made up of monodisperse hard disks. By introducing a suitable density-dependent scaling factor, we successfully extend the principle of dynamic equivalence to two dimensions. This dynamic correspondence will facilitate the interpretation of long-time molecular dynamic properties in the context of colloidal dynamics. For instance, this correspondence will allow us to establish the extension of the colloidal freezing criterion to the molecular case.