Particle Surface Research Articles

Packing properties assessment of cement and alternative powders: Artefacts and protocols

This paper introduces three major recommendations for the assessment of the maximum packing fraction of mineral powders through compressive rheology. First, our results show that a minimum compressive stress is required for the measured solid volume fraction to tend towards a constant jamming fraction. Second, we show that the modification of the particles surface properties, especially their friction coefficient, by polymer adsorption, allows for this jamming fraction to get closer to the particle maximum packing fraction. Finally, we show that a minimal value of the initial solid volume fraction of a sample is necessary to prevent particle size separation during testing. We moreover show that the measured jamming fraction depends on the initial solid volume fraction of cement-based samples. We suggest that such a peculiar behavior finds its origin in the dependency of early hydrates volume or morphology on the initial supersaturation.

Experimental study on decarburization of fine fly ash by electric separation

ABSTRACT The effect of rotary triboelectric separation parameters on decarburization of fly ash was systematically studied to prove that the technology was an effective means to purify fly ash. The results showed that obvious mismatch of carbon particles occurs when separation voltage was greater than 25 kV, while mismatch of other mineral particles was generated when separation voltage was greater than 30kV; The decarburization effect of fly ash could be significantly reduced due to the decrease of particle surface charge density when the feed frequency was greater than 20 hz. The feed was also affected by the speed and direction of the particle feed, the closer to the middle of the feed port, the higher the probability of the particle being effectively separated; when rotation speed of the friction wheel exceeded 4000 r/min, the particle mismatch in the separation chamber becomes more and more obvious. In addition, the speed of the friction wheel also affected flow field in separation chamber, which may have an adverse effect on separation effect; Co-flow velocity affected retention time of particles in the separation chamber. 6 m/s is the best co-flow velocity for fly ash decarburization. In this case, the flow field generated by the co-flow is uniform to ensure stable transport of particles.

Engineering Functional Particles to Modulate T Cell Responses.

T cells play a critical role in adaptive immune responses. They work with other immune cells such as B cells to protect our bodies when the first line of defense, the innate immune system, is overcome by certain infectious diseases or cancers. Studying and regulating the responses of T cells, such as activation, proliferation, and differentiation, helps us understand not only their behavior in vivo but also their translation and application in the field of immunotherapy, such as adoptive T cell therapy and immune checkpoint therapy, the situations in which T cells cannot fight cancer alone and require external engineering regulation to help them. Nano- to micrometer-sized particulate biomaterials have achieved great progress in the assistance of T cell-based immunomodulation. For example, various types of microparticles decorated with T cell recognition and activation signals to mimic native antigen-presenting cells have shown successful ex vivo expansion of primary T cells and have been approved for clinical use in adoptive T cell therapy. Functional particles can also serve as vehicles for transporting cargos including small molecule drugs, cytokines, and antibodies. Especially for cargos with limited bioavailability and high repeat-dose toxicity, systemic administration in their free form is difficult. By using particle-assisted systems, the delivery can be tailored on demand, of which targeting and controlled release are two typical examples, ultimately aiding in the regulation of T cell responses. Furthermore, when T cells become overactive and behave in ways that contradict our expectations, such as attacking our own cells or innocuous foreign molecules, this can lead to a breakdown of immune tolerance. In such cases, particles to help reprogram those overactive T cells or suppress their activity are appreciated in vivo. The urgent need to introduce immune stimulation into the treatment of cancers, infectious diseases, and autoimmune diseases has driven recent advances in the engineering of functional particulate biomaterials that regulate T cell responses. In this Account, we will first cover a brief overview of the process of T cell-based immunomodulation from principle to development. It then outlines critical points in the design of functional particle platforms, including materials, size, morphology, surface engineering, and delivery of cargos, to modulate the features of T cells, and introduces selected work from our and other research groups with a focus on three major therapeutic applications: adoptive T cell therapy, immune checkpoint therapy, and immune tolerance restoration. Current challenges and future opportunities are also discussed.

Oxidation progress and inner structure during single micron-sized iron particles combustion in a hot oxidizing atmosphere

The present experimental study focuses on the determination of the oxidation progress and internal structures during the combustion of single iron particles using combined in-situ optical measurements and ex-situ material examination of rapidly quenched particles. Narrowly sieved iron particles with a mean diameter of 49µm are ignited and burn in the hot exhaust of a premixed CH4/O2/N2 flat flame with remaining 20vol% O2, provided by a laminar flow reactor with well-defined thermal and flow boundary conditions. During particle combustion, key parameters of oxidation progress are determined optically in a time-resolved manner, such as the time-resolved particle surface temperature and the reaction time relative to the instant of the particle peak temperature. Furthermore, individually burning particles are rapidly quenched at different combustion stages and then extracted from the exhaust gas using an isokinetic extraction probe. The bulk composition of the quenched particles with respect to α-Fe and its three oxides FeO, Fe3O4, and Fe2O3 is determined using Wide-angle X-ray Scattering and 57Fe Mössbauer Spectroscopy. Combining the information obtained from in-situ and ex-situ measurements, it is shown that iron particles oxidize rapidly to FeO during the initial stage of combustion, followed by a much slower oxidation to Fe3O4 as the particles cool down. The peak particle temperatures are measured during the fast initial oxidation. Finally, particles sampled from representative positions of the oxidation process are analyzed by Energy-Dispersive X-ray Spectroscopy and Focused Ion Beam Scanning Electron Microscopy, revealing different particle morphology and internal structures. For the first time, the clear presence of an oxide shell and iron-core structure in quenched particles suggests that liquid iron and liquid iron oxide are layered during liquid phase combustion, if the particle remains within the miscible gap.

Cross-sectional surface analysis of magnetic domains, microstructures, and magnetic properties of the low-temperature phase MnBi prepared by low-temperature vacuum sintering

In this work, the low-temperature phase MnBi prepared by a low-temperature vacuum sintering process at 325 °C was studied. We found a significant increase in the energy product from 2.63 MGOe in the 12-h sintered sample to 3.64 MGOe in the 48-h sintered sample. This improvement is attributed to the solid-liquid diffusion process. Cross-sectional scanning electron microscopy (SEM) reveals that MnBi forms at the external surface of Mn particles and along interior surfaces, notably within cracks. Transmission electron microscopy further demonstrates that the Mn ratio increases and Bi decreases with distance from the crack. The selected area diffraction showed variations in the Mn ratio with distance from cracks and identified both Bi and MnBi phases in the MnBi layer. Magnetic force microscopy (MFM) analysis exhibited large phase shifts indicating repulsive or attractive forces in single ferromagnetic domains. This provides valuable insight into magnetic domains in the MnBi regions near Mn cracks. The MnBi formation model, developed for the vicinity of single cracks with uniform MnBi content, partly explains the magnetic interactions and phase shifts observed near these cracks. These findings provide significant insights into the MnBi microstructural and magnetic properties, potentially useful in tailoring and engineering magnetic structures.

Leveraging anchoring ligands for efficient one-pot solvothermal synthesis of PDMS functionalized iron oxide polymer nanocomposites (PNC’s)

Producing substantial quantities of high purity, narrow size distribution, magnetic polymer nanocomposites (PNC’s) has been a challenge for the nanoparticle synthesis community. In this study, we introduce a novel one-pot solvothermal synthesis technique to produce a type of PNC known as a ferrofluid. By employing a polymer (polydimethylsiloxane (PDMS)) modified with anchoring ligands as the surfactant, we eliminate the need for a post-synthesis ligand exchange, resulting in high yield and purity of the final product. This approach offers greater flexibility in polymer selection and simplifies the synthetic process. Electron microscopy, magnetic characterization, infrared spectroscopy, and thermal analysis were employed to investigate particle size, crystallinity, magnetic behavior, and surface environment. Our findings suggest that this new synthetic technique could significantly advance the development of magnetic nanoparticle-based theranostics.

Development of inhaled moxifloxacin-metformin formulation as an alternative for pulmonary tuberculosis treatment

Resistant M. tuberculosis strains threaten pulmonary tuberculosis (P-TB) control since they limit drug options. Drug repositioning and new development strategies are urgently required to overcome resistance. Studies have already shown the beneficial role of the oral antidiabetic metformin as an anti-tuberculosis adjuvant drug. This work aimed to develop an inhalatory dry powder co-formulation of metformin and moxifloxacin to figure out a future option for P-TB treatment. Pre-formulation evaluations indicated the physicochemical compatibility of constituents, demonstrating powder crystallinity and acceptable drug content. Eight moxifloxacin-metformin dry powder formulations were produced by spray drying, and solid-state characterizations showed partial amorphization, ascribed to moxifloxacin. Four formulations containing L-leucine exhibited micromeritic and in vitro deposition profiles indicating pulmonary delivery suitability, like spherical and corrugated particle surface, geometric diameters < 5 μm, high emitted doses (>85 %), and mass median aerodynamic diameters between 1–5 μm. The use of a second spray dryer model further optimized the aerodynamic properties and yield of the best formulation, demonstrating the influence of the equipment used on the product obtained. Moreover, the final formulation showed high in vitro cell tolerability and characteristics in permeability studies indicative of good drug retention in the lungs.

Creating High Yield Stress Particle-Laden Oil/Water Interfaces Using Charge Bidispersity.

Interfacial engineering has been increasingly used to stabilize Pickering emulsions in commercial products and biomedical applications. Pickering emulsion stabilization is aided by interfacial viscoelasticity; however, typically the primary means of stabilization are steric hindrances between high surface concentration shells of particles around the drops. In this work, the concept of creating large interfacial viscoelastic yield stresses with low particle surface concentrations (<50%) using bidisperse charged particle systems is tested to evaluate their potential efficacy in emulsion stabilization. To explore this hypothesis, interfacial rheology and visualization experiments are conducted at o/w interfaces using positively charged amidine, negatively charged carboxylate, and negatively charged sulfate-coated latex spheres and compared to a model based on interparticle forces. Bidisperse particle systems have been observed to create more networked structures than monodisperse systems. For surface concentrations of <50%, bidisperse interfaces created measurable viscoelastic moduli ∼1 order of magnitude larger than monodisperse interfaces. Furthermore, these interfaces have measurable yield stresses on the order of 10-4 Pa·m when monodisperse systems have none. Bidispersity impacts surface viscoelasticity primarily by increasing the overall magnitude of attraction between particles at the interface and not due to changes in the microstructure. The developed model predicts the relative surface fraction that creates the largest moduli and shows good agreement with the experimental data. The results demonstrate the ability to create large viscoelastic moduli for small surface fractions of particles, which may enable stabilization using fewer particles in future applications.

Non-steady flow decomposition behaviors of heat and mass transfer on intrinsic kinetics for methane hydrate particles transported in pipelines

The differential equations governing the decomposition rate and activation energy, convective mass transfer, methane diffusion and fugacity, as well as heat conduction and enthalpy change were derived by integrating thermal convection, heat conduction, mass transfer and intrinsic kinetics. Mathematical models for decomposition kinetics and thermodynamics in a non-steady field were solved using a radial logarithmic grid for node division and discretization of the equations. The study elucidated the heat and mass transfer processes as well as decomposition kinetics in pipelines by analyzing the impacts of particle size, temperature, pressure, flow rate and activation energy on decomposition rate. The results indicated that compared with the isothermal decomposition of the intrinsic kinetic model and static experimental decomposition, the complex non-steady multiphase flow model offers a more accurately simulation of hydrate decomposition as well as associated heat and mass transfer processes. Hydrate decomposition is characterized as a non-isothermal dynamic ablation process with heat transfer rate and intrinsic kinetics dominating during the preliminary stage and the stable stage, respectively. An increasing in the slurry temperature, temperature fluctuation and flow rate accelerated the heat transfer rate capacity, enhanced convective heat transfer capacity and facilitated hydrate decomposition, with the mass transfer rate exhibiting lesser influence. The particle surface area and slurry temperature exhibited the most significant influence on hydrate decomposition, which was followed by flow rate. Upon increasing particle size from 1 mm to 5 mm and the temperature from 293 K to 313 K, the decomposition rate increased by 20.7 times and 13.5 times, respectively. Furthermore, enhancing temperature and flow rate while decreasing particle size and pressure decreased both the decomposition time and the duration required for the decomposition rate to reach its peak. Additionally, the decomposition rate and its constant vary with the activation energy.

Enhancing the Self-Propelled Motion of Hydrogen Peroxide Fueled Active Particles with Formic Acid and Other Oxygen Scavengers.

We report enhanced active particle motion in hydrogen peroxide-fueled self-diffusiophoretic active particle systems of up to 400% via addition of low concentrations of oxygen scavenging agents such as formic acid (as well as other organic acids, hydrazine, and citric acid), whereas active motion was inhibited at higher concentrations. Control experiments showed that enhanced motion was decoupled from catalytic hydrogen peroxide decomposition rate and insensitive to particle surface chemistry. Experimental results point to bulk oxygen scavenging as the cause for the enhanced active motion, representing a realization of recently predicted promotional effects of product sinks on self-diffusiophoretic motion. Diminished active motion at high oxygen scavenger concentrations was attributed to catalytic site blocking by adsorbed solute.

Grain Size Distribution, Organic Carbon and Geochemical Markers in the Surface Layer of Bottom Sediments in the Northeastern Part of the Kara Sea

The upper layer of bottom sediments in the northeastern part of the Kara Sea is studied. It is shown that the composition of sediments is dominated by silt, the proportion of sand increases towards the shore. The content of organic carbon (average value — 1.1% wt.) is close to the average content in sediments of the Kara Sea, increasing at deep-sea stations. The revealed linear relationship between the content of organic carbon and the surface area of sediment shows that sorption on the particles surface is the predominant accumulation form of organic matter (OM) in sediments. The average n-alkanes concentration in the analysed samples is 1.1 μg/g of sediment, the distribution spectrum is dominated by terrigenous origin odd high-molecular homologues.

Photoluminescence decay of mobile carriers influenced by imperfect quenching at particle surfaces with subdiffusive spread.

We recently presented a quantitative model to explain the particle-size dependence of photoluminescence (PL) quantum yields and revealed that exciton quenching is not diffusion controlled, but limited by surface reactions. However, the exciton decay kinetics has not been analyzed yet using our theoretical model. Here, we study kinetic aspects of the model and show that it should be extended to take into account subdiffusion rather than normal diffusion to maintain consistency with the observed complex decay kinetics; we also show that the PL decay kinetics is nonexponential even when the PL quenching is limited by surface reactions under subdiffusion. Our theoretical analysis of the PL quantum yield and the PL decay kinetics provides a comprehensive picture of mobile charge carriers, immobile polarons, and self-trapped excitons.

Beyond plastic pollution: Unveiling chemical release from plastic debris in river water and seawater using non-target screening

Oceans and rivers are predominant sinks, reservoirs, and carriers of plastic debris that are proposed to be long term sources of a variety of contaminants in the environments. This research unveiled kinetics of chemical releases from plastic debris in freshwater and marine environment via artificial river water (ARW) and seawater (ASW) in combination of nontarget screening. Chemical leaching from PVC cord particles in the ARW and ASW basically followed the first order kinetics, reaching pseudo-equilibrium in 30d and 14d, respectively, associated with both particle surface – water partitioning and inner-particle diffusion of chemicals. Dissolved organic carbon, finer size, and weathering of plastic particles might enhance whereas metal ions potentially hinder chemical releases from plastic debris in waters, respectively. Salinity and pH showed moderate effects on chemical leaching. In addition, chemicals’ physiochemical properties might also affect their leaching behavior. Hundreds to thousands of chemicals would be released from plastic debris in days once entering waters, among which > 80% were unknown with rare or no information about eco-toxicity and environmental fate, posing unpredicted risks to the environment. Furthermore, new chemicals may keep being released with increasing weathering and extending retention time of plastics in waters, leading to increases in both numbers and complexities of released chemicals. Chemical leaching from plastics showed product-dependence and certain differences in freshwater and seawater. Large numbers of unknown chemicals potentially released from plastic debris in rivers, lakes, and oceans and subsequent environmental risks warrant in-depth research.

Investigation on the Adhesion Force between Tetrabutylammonium Bromide Hydrate Particles Using Atomic Force Microscopy.

This work investigates the adhesion force between tetrabutylammonium bromide (TBAB) hydrate particles dispersed in decane at different temperatures and TBAB concentrations using an atomic force microscopy. The thickness of the quasi-liquid layer (QLL) on the surface of the hydrate particles is calculated based on an adhesion force model. The results of force measurements indicate that the adhesion force between the hydrate particles increases with increasing temperature when TBAB concentration is 30 wt %. The increment of adhesion force between particles could be due to the increase in the QLL thickness on the particle surfaces. Furthermore, the force results also reveal that the adhesion force between hydrate particles(ice) at 253 K decreases when TBAB concentration increases from 0 to 30 wt %. The calculation indicates that QLL on the surface of formed hydrate particles becomes thinner at higher TBAB concentrations, which could be due to the conversion rate of water to hydrate within particles. The thickness of QLL is directly influenced by the temperature and TBAB concentration, which contributes to the adhesion force between hydrate particles.

An investigation on pyrite floatability using stable micro-nanobubble-assisted flotation

This study critically examines the impact of micro-nanobubble (MNB)-assisted flotation on pyrite recovery in bulk ore, and clarifies the intricate relationship between pyrite and its associated ore. The physicochemical properties of MNBs and the interaction mechanisms between xanthate collector and pure pyrite mineral were evaluated using advanced analytical techniques, including Dynamic Light Scattering (DLS), Field-Emission Scanning Electron Microscopy coupled with Energy-Dispersive X-ray Spectroscopy (FESEM-EDX), and Ultraviolet-Visible Spectroscopy (UV-Vis), in the absence and the presence of MNBs. MNBs were created through hydrodynamic cavitation, and their characteristics revealed a size increase from 600 nm to 3 µm over 25 days. Notably, the zeta potential measurements indicated an increase from -2.5 to 0 mV at a constant pH of 8, correlating with the geometric mean size of MNBs coarsening from 600 nm to 2-3 µm. The FESEM and EDS analyses disclosed that ultrasonic treatment effectively dispersed ultrafine surface coatings on pyrite particles, increasing iron and sulfur purity by 8% and 6%, respectively, and significantly reducing surface oxygen by 53%. Micro-flotation and batch rougher kinetic flotation experiments were conducted with and without MNBs, leading to a 7% and 8% improvement in recovery for pyrite mono-minerals (-105+53 µm) and its ore (d&lt;sub&gt;80&lt;/sub&gt;=150 µm), respectively. The sorption behavior of sodium isopropyl xanthate (SIPX) collector on the particle surface was also investigated at various concentrations (ca. 10-160 µM) in the presence and absence of stable MNBs and demonstrated that the presence of MNBs resulted in a 1.6-fold increase in collector absorption on the pyrite surface, confirming the findings obtained from micro-flotation. Moreover, adsorption behavior is up to 1.3 times compared to the scenario without MNBs. The adsorption process was controlled by a pseudo-second-order model, indicating a chemical sorption mechanism.

Anomalous Diffusion and Non-Markovian Reaction of Particles near an Adsorbing Colloidal Particle

We investigate the diffusion phenomenon of particles in the vicinity of a spherical colloidal particle where particles may be adsorbed/desorbed and react on the surface of the colloidal particle. The mathematical model comprises a generalized diffusion equation to govern bulk dynamics and kinetic equations which can describe non-Debye relaxations and is used for the colloid’s surface. For the reaction processes, we also consider the presence of convolution kernels, which offer the flexibility of describing a single process or process with intermediate reactions before forming the final species. Our analysis focuses on analytical and numerical calculations to obtain the particles’ behavior on the colloidal particle’s surface and to determine how it affects the diffusion of particles around it. The solutions obtained show various behaviors that can be connected to anomalous diffusion phenomena and may be used to describe the ever-richer science of colloidal particles better.

Single-Particle Crushing Test of Coated Calcareous Sand Based on MICP

Calcareous sand is a crucial construction material for island and reef development and reinforcing it using Microbially Induced Calcite Precipitation (MICP) technology is a promising new method. This study employed 3D scanning technology to assess changes in the particle size and morphology of MICP-treated, coated calcareous sand particles. Single-particle crushing tests were conducted to analyze their crushing strength, crushing energy, crushing modes, and fragment fractal dimensions. The results indicated that MICP treatment significantly increased particle size, surface area, and volume, while reducing flatness. At a cementation solution concentration of 1 mol/L, both crushing strength and crushing energy were optimized. The coated particles exhibited three crushing modes: explosive crushing, mixed crushing, and splitting crushing. Thicker coatings led to a tendency for particles to break into larger fragments through the mixed and splitting crushing modes. Fractal analysis revealed that coating thickness directly affects the local crushing characteristics of the particles.

Internal and surface temperature profiles of spherical biosolids particles during convective drying

The convective drying of spherical biosolids particles from two wastewater treatment plants (Type 1: anaerobic/anoxic treatment with belt filter press dewatering; Type 2: aerobic/anoxic treatment with centrifuge dewatering) was studied under 10 conditions across 44 trials. A wide spectrum of conditions including three drying temperatures (88, 109, and 138 ° C ), two gas velocities (1.6 and 2 m s − 1 ), and particle sizes of 2 cm and 4 cm were investigated. Measured variables included particle mass, center/internal temperature, surface temperature, shrinkage, and qualitative observations of morphological changes. Most samples showed two drying periods, a constant rate period followed by a falling rate period. Additionally, it was found that drying rates and morphological changes depended significantly on particle size and drying intensity (i.e., drying gas temperature and gas velocity) with higher intensities resulting in larger, more porous particles. Internal temperature profiles displayed a consistent pattern, an initial heating phase where internal temperatures quickly rose to approximately the wet bulb temperature of the drying gas, a quasi-constant temperature phase at that temperature, and a final sharp increase/spike to reach equilibrium with the drying gas temperature. Moreover, IR images showed that sub-surface temperatures (between the core and surface) were significantly lower than surface temperatures. Surface temperatures showed a more linear increase throughout drying until equilibrium with the drying gas temperature. The consistent temperature difference between the center and surface, as well as the internal temperature profile, suggests the existence of a drying front, moving radially inward as the particle dries. This research contributes to a better understanding of biosolids drying dynamics, offering insights to improve thermal treatment strategies thereby contributing to the broader field of waste management.

Zwitterion assisted in-situ grain boundary coating on Li-rich cathode boosting electrochemical performance in Li-ion batteries

High-capacity and high-voltage Li-rich cathode materials are promising candidates for next-generation LIB cathodes due to their high energy density characteristics. However, they face challenges such as electrolyte side reactions at high voltages and slow kinetic properties. To overcome these challenges, this study proposed a one-pot Li2WO4 (LWO) grain boundary coating method. Additionally, a novel synthesis process utilizing zwitterions was introduced to uniformly position heavy tungsten on the surface of a cathode material. Through grain boundary coating, the cathode material was modified not only at the secondary particle level, but also between primary particles by filling grain boundaries with the coating compound. The synthesized LWO grain boundary coated Li-rich cathode exhibited significantly superior rate capability and cycle stability compared to the pristine material. Furthermore, it demonstrated a more stable cycling behavior after high-temperature storage than pristine counterpart. This study presents a primary particle surface modification technique through grain boundary coating and a one-pot synthesis process leveraging zwitterions as a new driving force, providing a new perspective for enhancing the performance of Li-rich cathode materials.

Surface Catalytic Repair for the Efficient Regeneration of Spent Layered Oxide Cathodes.

Direct recycling is considered to be the next-generation recycling technology for spent lithium-ion batteries due to its potential economic benefits and environmental friendliness. For the spent layered oxide cathode materials, an irreversible phase transition to a rock-salt structure near the particle surface impedes the reintercalation of lithium ions, thereby hindering the lithium compensation process from fully restoring composition defects and repairing failed structures. We introduced a transition-metal hydroxide precursor, utilizing its surface catalytic activity produced during annealing to convert the rock-salt structure into a layered structure that provides fast migration pathways for lithium ions. The material repair and synthesis processes share the same heating program, enabling the spent cathode and added precursor to undergo a topological transformation to form the targeted layered oxide. This regenerated material exhibits a performance superior to that of commercial cathodes and maintains 88.4% of its initial capacity after 1000 cycles in a 1.3 Ah pouch cell. Techno-economic analysis highlights the environmental and economic advantages of surface catalytic repair over pyrometallurgical and hydrometallurgical methods, indicating its potential for practical application.