Colloidal Forces Research Articles

Roles of catalytic ozonation by bimetallic Fe/Ce loading sludge-derived biochar in amelioration of sludge dewaterability: Performance and implementation mechanisms

In this study, an environmentally friendly alternative was developed using catalytic ozonation by sludge-derived biochar loaded with bimetallic Fe/Ce (O3/SBC-FeCe) for enhanced sludge dewatering. The results indicated that the lowest capillary suction time (CST) of 20.9 s and water content of dewatered sludge cake (Wc) of 64.09% were achieved under the dosage of 40 mg O3/g dry solids (DS) and 0.4 g SBC-FeCe/g DS which were considered as the optimum condition. In view of excellent electron exchanging capacity of SBC-FeCe with rich Lewis acid sites and conversions of valence sates of Fe and Ce, more O3 were decomposed into reactive oxygen species under the catalytic action of SBC-FeCe, which strengthened oxidizing capacity. Enhanced oxidation rendered sludge cells inactivation and compact network structure rupture releasing intracellular water and organic substances. Subsequently, hydrophilic organic matters were attacked and eliminated lessening sludge viscosity and colloidal forces and intensifying hydrophobicity and flowability. In addition, changes of sludge morphology suggested that sludge roughness was alleviated, structural strength and compressibility were raised and porous and retiform structure was constructed providing channels for water outflow by adding skeleton builder of SBC-FeCe. Overall, the synergistic interaction of strengthened oxidation and skeleton construction improved sludge dewaterability.

Dissipation Mechanisms and Superlubricity in Solid Lubrication by Wet-Transferred Solution-Processed Graphene Flakes: Implications for Micro Electromechanical Devices.

Solution-processed few-layer graphene flakes, dispensed to rotating and sliding contacts via liquid dispersions, are gaining increasing attention as friction modifiers to achieve low friction and wear at technologically relevant interfaces. Vanishing friction states, i.e., superlubricity, have been documented for nearly-ideal nanoscale contacts lubricated by individual graphene flakes. However, there is no clear understanding if superlubricity might persist for larger and morphologically disordered contacts, as those typically obtained by incorporating wet-transferred solution-processed flakes into realistic microscale contact junctions. In this study, we address the friction performance of solution-processed graphene flakes by means of colloidal probe atomic force microscopy. We use a state-of-the-art additive-free aqueous dispersion to coat micrometric silica beads, which are then sled under ambient conditions against prototypical material substrates, namely, graphite and the transition metal dichalcogenides (TMDs) MoS2 and WS2. High resolution microscopy proves that the random assembly of the wet-transferred flakes over the silica probes results into an inhomogeneous coating, formed by graphene patches that control contact mechanics through tens-of-nanometers tall protrusions. Atomic-scale friction force spectroscopy reveals that dissipation proceeds via stick-slip instabilities. Load-controlled transitions from dissipative stick-slip to superlubric continuous sliding may occur for the graphene-graphite homojunctions, whereas single- and multiple-slips dissipative dynamics characterizes the graphene-TMD heterojunctions. Systematic numerical simulations demonstrate that the thermally activated single-asperity Prandtl-Tomlinson model comprehensively describes friction experiments involving different graphene-coated colloidal probes, material substrates, and sliding regimes. Our work establishes experimental procedures and key concepts that enable mesoscale superlubricity by wet-transferred liquid-processed graphene flakes. Together with the rise of scalable material printing techniques, our findings support the use of such nanomaterials to approach superlubricity in micro electromechanical systems.

From successive deposition to clogging of poly(styrene) particles in the cross-flow through a T-shaped microchannel

Predicting and mitigating pore clogging are complex and challenging problems in fluid transport and filtration systems. This paper investigates the mechanism of particle deposition and pore clogging in a T-shaped microchannel under cross-flow conditions, using polystyrene particles dispersed in the glycerol solution. In this study, the flow rate and glycerol concentration are systematically controlled to analyze the effect of hydrodynamic stress on the clogging mechanism. Through flow visualization and image processing, the study identifies the step-by-step process of particle deposition and accumulation including the phenomena like “edge deposition”, “growth of deposition”, “rolling”, and “agglomerate breakup”. This study suggests that there is a critical stress that inhibits particle deposition and prevents pore clogging, and this stress is determined by the balance between the hydrodynamic force and the colloidal interaction force. The study also quantifies the clogging with the “blockage ratio” and “deposition ratio”, and shows that the stress correlates with the number of particles required for clogging. The methodology and findings of this study can aid in designing flow operating conditions to control particle deposition and clogging in various filtration systems and can serve as a critical first step toward understanding the behavior of particles in complex fluids with viscoelastic properties.

Molecular mechanisms of the metal oxide sol-gel process and their application in approaches to thermodynamically challenging complex oxide materials

This review presents a brief overview of recent insights into general reaction pathways in sol-gel synthesis of metal oxides. Metal-based sol-gel precursors display kinetically unhindered reactivity, combining high reaction speed with reversibility on a molecular level. The process producing metal oxide sols can thus be described as nucleation of an oxide phase with growth option efficiently precluded by extremely low solubility. The emerging nuclei are essentially Polyoxometalate (POM) species, with sizes in the colloid range starting from about 2 nm. They are stabilized in solution by colloid forces (charge interactions, hydrogen bonding, van der Waals forces), defined by the nature and arrangement of species on their surface, which permits them to be denoted as Micelles Templated by Self-Assembly of Ligands (MTSALs). The sol-gel transition occurs on aggregation of particles resulting in percolation. Exploiting this mechanism, it is possible to produce materials with controlled porosity, biocompatibility, and even to access thermodynamically challenging phases that cannot be produced by conventional synthetic techniques.Graphical Metal oxide Sol-Gel can be described as nucleation of an oxide phase resulting from one-step coordination equilibrium in solution, followed by aggregation without growth.

Effects of liquid surface tension on gas capillaries and capillary forces at superamphiphobic surfaces

The formation of a bridging gas capillary between superhydrophobic surfaces in water gives rise to strongly attractive interactions ranging up to several micrometers on separation. However, most liquids used in materials research are oil-based or contain surfactants. Superamphiphobic surfaces repel both water and low-surface-tension liquids. To control the interactions between a superamphiphobic surface and a particle, it needs to be resolved whether and how gas capillaries form in non-polar and low-surface-tension liquids. Such insight will aid advanced functional materials development. Here, we combine laser scanning confocal imaging and colloidal probe atomic force microscopy to elucidate the interaction between a superamphiphobic surface and a hydrophobic microparticle in three liquids with different surface tensions: water (73 mN m−1), ethylene glycol (48 mN m−1) and hexadecane (27 mN m−1). We show that bridging gas capillaries are formed in all three liquids. Force-distance curves between the superamphiphobic surface and the particle reveal strong attractive interactions, where the range and magnitude decrease with liquid surface tension. Comparison of free energy calculations based on the capillary menisci shapes and the force measurements suggest that under our dynamic measurements the gas pressure in the capillary is slightly below ambient.

Connecting Colloidal Forces to the Equilibrium Thickness of Particulate Deposits on a Substrate in Contact with a Suspension Using Classical Density Functional Theory

We study contributions of colloidal forces, i.e., hydrophobic, van der Waals, and electrical double layer interactions, to the thickness of a colloidal deposit in equilibrium with an aqueous suspension by using classical density functional theory, which we expand to obtain a Ginzburg-Landau type energy functional. We regard colloidal particles as clusters of molecular segments-a reminiscent of polymer statistical physics and of the classic Hamaker treatment of van der Waals interactions between particles. This approach appropriately accounts for the integral interaction energy between colloidal particles, which may take magnitudes of many times the characteristic molecular thermal energy kBT (Boltzmann constant times temperature). The analysis highlights the well-known insight that entropy is mostly governed by the solvent molecules and gives physical values to the statistical coefficients in a Ginzburg-Landau type energy functional.

Self-Assembled Tetratic Crystals by Orthogonal Colloidal Force.

Bonding simple building blocks to create crystalline materials with design has been sophisticated in the molecular world, but this is still very challenging for anisotropic nanoparticles or colloids, because the particle arrangements, including position and orientation, cannot be manipulated as expected. Here biconcave polystyrene (PS) discs to present a shape self-recognition route are used, which can control both the position and orientation of particles during self-assembly by directional colloidal forces. An unusual but very challenging two-dimensional(2D) open superstructure-tetratic crystal (TC)-is achieved. The optical properties of the 2D TCs are studied by the finite difference time domain method, showing that the PS/Ag binary TC can be used to modulate the polarization state of the incident light, for example, converting the linearly polarized light into left-handed or right-handed circularly polarized light. This work paves an important way for self-assembling many unprecedented crystalline materials.

Precise quantification of nanoparticle surface free energy via colloidal probe atomic force microscopy

Interfacial interactions of nanoparticles (NPs) in colloids are greatly influenced by the NP surface free energy (SFE). Due to the intrinsic physical and chemical heterogeneity of the NP surface, measuring SFE is nontrivial. The use of direct force measurement methods, such as colloidal probe atomic force microscopy (CP-AFM), have been proven to be effective for the determination of SFE on relatively smooth surfaces, but fail to provide reliable measurements for rough surfaces generated by NPs. Here, we developed a reliable approach to determine the SFE of NPs by adopting Persson’s contact theory to include the effect of surface roughness on the measurements in CP-AFM experiments. We obtain the SFE for a range of materials varying in surface roughness and surface chemistry. The reliability of the proposed method is verified by the SFE determination of polystyrene. Subsequently, the SFE of bare and functionalized silica, graphene oxide, and reduced graphene oxide were quantified and validity of the results was demonstrated. The presented method unlocks the potential of CP-AFM as a robust and reliable method of the SFE determination of nanoparticles with a heterogeneous surface, which is challenging to obtain with conventionally implemented experimental techniques.

Clarifying and quantifying the driving force for the evolution of static yield stress of cement pastes

The static yield stress evolution of cement paste is mainly driven by the colloidal force and cement hydration, while their respective roles and contributions are not yet clear. In this paper, three stages are distinguished in the first 3 h evolution of static yield stress of cement pastes (with or without steel slag powder), including the initial stage (up to 30 min), the induction stage (30–60 min) and the acceleration stage (after 60 min). It was found that colloidal force mainly contributes to the large static yield stress before the acceleration stage. The role of hydration was found to have determined the evolution trend of the static yield stress since the induction stage, which was identified by quantifying the interaction force between the C-S-H instead of solely considering C-S-H volume fraction. Based on quantitative results, how the physico-chemical parameters control the static yield stress evolution at each stage is identified comprehensively. This study provides a deep and quantitative understanding of structural build-up process of cement paste.

Colloidal Perspective on Targeted Drug Delivery to the Central Nervous System.

This article describes a new approach in targeted drug delivery to the central nervous system (CNS) in a significant departure from the predominant systematic drug administration attempting to penetrate the blood-brain barrier (BBB). Nanoparticles chemically conjugated to neural tract tracer proteins are capable of path-specific axonal retrograde transport, transneuronal transport, and anatomical tract flow to bypass the BBB. To celebrate the work by Dr. Bettye Washington Greene on the physical chemistry of colloidal particles, this article focuses on the physiochemical characteristics of the nanoparticles, various colloidal forces that impact the colloidal stability of nanoparticles in biological media, and surface chemistry strategies to avoid nanoparticle aggregation-induced poor therapeutic outcomes. The biological environment for the anatomical retrograde transport of neural tract tracers is examined to directly link factors impacting the colloidal stability of the new class of CNS-targeting nanoconjugates such as nanoconjugate size, shape, surface charge, surface chemistry, ionic strength, pH, and protein adsorption on the nanoparticle. We conclude with opportunities and challenges for future research.

Effect of branching in zwitterionic polymer brushes grafted from PES UF membrane surfaces via AGET-ATR(c)P

This research explored the relationship between the antifouling behavior of porous ultrafiltration (UF) membranes and linear or branched brushes adorning their surfaces. Polyethersulfone UF membranes were functionalized via one-pot lithiation/acylation to enable surface-initiated activators generated by electron transfer for atom transfer radical (co)polymerization of sulfobetaine methacrylate (SBMA) and N,N′-methylenebisacrylamide (MBAm). Changing the SBMA/MBAm ratio and polymerization time grafted brushes at different branching and thicknesses. Surface analyses verified differences in brush architecture and that the degree of grafting increased with grafting time – it was higher for linear brushes than branched ones. Colloidal probe lateral force atomic force microscopy (LFM) showed ideal hydration–lubrication propensity of the lower branching degree poly(SBMA-co-MBAm) over pristine, linear poly(SBMA), and higher branching poly(SBMA-co-MBAm)-grafted membranes. Sharp-tip LFM predicted a critical size of <15 nm for penetrating the branched brush layers. Fouling experiments with bovine serum albumin (∼10 nm) and dextran (∼18 nm) revealed that linear and branched modifications had significantly less fouling than the pristine membrane. An optimal degree of branching can limit foulant adsorption, but fouling could be enhanced if the polymers' hydration capacity was diminished relative to a less dense network. Fouling experiments with soluble microbial products further demonstrated the branched membrane's high antifouling activity.

Nanoscale friction of biomimetic hair surfaces.

We investigate the nanoscale friction between biomimetic hair surfaces using chemical colloidal probe atomic force microscopy experiments and nonequilibrium molecular dynamics simulations. In the experiments, friction is measured between water-lubricated silica surfaces functionalised with monolayers formed from either octadecyl or sulfonate groups, which are representative of the surfaces of virgin and ultimately bleached hair, respectively. In the simulations, friction is monitored between coarse-grained model hair surfaces with different levels of chemical damage, where a specified amount of grafted octadecyl groups are randomly replaced with sulfonate groups. The sliding velocity dependence of friction in the simulations can be described using an extended stress-augmented thermally activation model. As the damage level increases in the simulations, the friction coefficient generally increases, but its sliding velocity-dependence decreases. At low sliding velocities, which are closer to those encountered experimentally and physiologically, we observe a monotonic increase of the friction coefficient with damage ratio, which is consistent with our new experiments using biomimetic surfaces and previous ones using real hair. This observation demonstrates that modified surface chemistry, rather than roughness changes or subsurface damage, control the increase in nanoscale friction of bleached or chemically damaged hair. We expect the methods and biomimetic surfaces proposed here to be useful to screen the tribological performance of hair care formulations both experimentally and computationally.

Self-Healable, Injectable, and Conductive Supramolecular Eutectogel for the Encapsulation and Sustained Release of the Anticancer Drug Curcumin

The intriguing properties such as high environmental compatibility of supramolecular gels made solely through reversible noncovalent interactions are of recent interest. To offer proof of concept for the new-age sustainable materials, herein we have designed the self-healable, injectable, and ionic conductive supramolecular eutectogel in natural deep eutectic solvent (NADES). The studied eutectogels were prepared by dissolving the pharmaceutically active cetylpyridinium chloride (C16PyCl) and cetylpyridinium bromide (C16PyBr) in the NADES. The NADES was formed by interacting choline chloride (ChCl) with mono-, di-, and trimeric acids, i.e., formic acid (FA), oxalic acid (OA), and citric acid (CA) through hydrogen bonding. The gelation kinetics of the eutectogel was assessed using turbidity measurement as a function of time, whereas the morphology and mechanical properties were assessed using scanning electron microscopy (SEM) and rheology. To further verify the shape and size of the aggregate within the eutectogel, small angle neutron scattering (SANS) was performed. The eutectogel offers excellent self-healing, injectable, and ionic conductive properties as well as excellent antimicrobial properties, and offers high encapsulation efficiency for curcumin. The sustained release characteristics and release kinetics of curcumin was also investigated. Gel phases, in particular, show high colloidal forces, which, along with their environmentally benign nature, make them a great candidate not only for biomedical applications but also for the industries that require high performance with minimal environmental impact.

Can We Structure Biomaterials to Spray Well Whilst Maintaining Functionality?

Structured fluid biomaterials, including gels, creams, emulsions and particle suspensions, are used extensively across many industries, including great interest within the medical field as controlled release vehicles to improve the therapeutic benefit of delivered drugs and cells. Colloidal forces within these materials create multiscale cohesive interactions, giving rise to intricate microstructures and physical properties, exemplified by increasingly complex mathematical descriptions. Yield stresses and viscoelasticity, typically arising through the material microstructure, vastly improve site-specific retention, and protect valuable therapeutics during application. One powerful application route is spraying, a convenient delivery method capable of applying a thin layer of material over geometrically uneven surfaces and hard-to-reach anatomical locations. The process of spraying is inherently disruptive, breaking a bulk fluid in successive steps into smaller elements, applying multiple forces over several length scales. Historically, spray research has focused on simple, inviscid solutions and dispersions, far from the complex microstructures and highly viscoelastic properties of concentrated colloidal biomaterials. The cohesive forces in colloidal biomaterials appear to conflict with the disruptive forces that occur during spraying. This review explores the physical bass and mathematical models of both the multifarious material properties engineered into structured fluid biomaterials and the disruptive forces imparted during the spray process, in order to elucidate the challenges and identify opportunities for rational design of sprayable, structured fluid biomaterials.

Viscosity transition from dilute to concentrated cementitious suspensions: the effect of colloidal interactions and flocs percolation

The current paper deals with the effect of powder type and chemical admixtures on the rheological properties of mineral suspensions. The plastic viscosity of calcite, cement, and fly ash suspensions with or without superplasticizers (SP) and hydration retarders was characterized in a wide range of solid volume fractions. The results show that the plastic viscosity of suspensions increases with the decrease in particle size, and strongly decreases with the presence of superplasticizers. Besides, for reactive suspensions, hydration retarders decrease the plastic viscosity of the suspension, while competitive adsorption occurs when adding retarders to suspensions containing SP, leading to an increase in the plastic viscosity. Based on the experimental results, a relative plastic viscosity, i.e., the ratio between the total plastic viscosity and the theoretical viscosity contributed by the hard-sphere, is proposed to assess the effect of the contribution of colloidal forces. Moreover, the solid volume fraction of flocs in colloidal suspensions before percolation is identified by comparing the measured plastic viscosity with the Krieger-Dougherty model. Finally, a theoretical approach to determine the percolation packing fraction of minerals powders is further proposed.

Mechanism and design of fluid catalytic cracking ash-blended cementitious composites for high performance printing

As a common waste in the oil refinery industry, fluid catalytic cracking (FCC) ash is used to partially replace cement for high-performance high-speed 3D concrete printing (3DCP). Effects of FCC ash on hydration, rheology, and compressive strength were evaluated systematically, and the optimal substitution rate was determined as 20 wt. % of cement. A cylinder with 240 mm diameter and 500 mm height was successfully printed at a high speed of 100 mm/s with the optimal mixture in 5 min 53 s only. Moreover, the optimal mixture shows good leaching performance, and it also reduces CO2 emission by 21.45 % and materials’ cost by 17.98 % compared with the control. In addition to material optimization, the contributions of FCC ash to the early hydration and static yield stress were extensively analyzed. Complementary calorimetric and mineralogical investigations show that FCC ash accelerates the initial hydrolysis of cement and hydration of C3A and C3S. On the other hand, the quantitative analyses of static yield stress reveal the contributions of FCC ash on the colloidal force, volume fractions, particle size distribution, and ultimately static yield stress evolution. The developed 3D printable cementitious material possesses multiple advantages, including high-speed printing compatibility, enhanced sustainability, and high commercial values for oil refinery and construction industries. Based on the mineralogical property of FCC ash, the study also enlightens potential research and application of zeolite in 3D concrete printing in the future.

Active microrheology of protein condensates using colloidal probe-AFM

Protein condensates resulting from liquid–liquid phase separation have long been studied as bio-adhesives and coating materials for various applications. More recently, they are also being scrutinized as models for membraneless organelles in cells. Quantifying their interfacial mechanics and rheology at micrometer scales is vital for better understanding the physics underlying membraneless organelles in cells and for developing and improving technological applications of protein condensates. This study demonstrates how colloidal probe atomic force microscopy with an oscillating tip can be used to simultaneously investigate the interfacial mechanics and dynamic rheological properties of micro-scale protein condensates, formed via carefully controlled capillary condensation. This new approach can access oscillation frequencies ranging from 1 to 104 rad/s. By analyzing the data using an equivalent mechanical model, three characteristic frequency domains for the mechanics of micro-scale protein condensates are found: an interfacial tension-dominated domain at low frequencies, a transition domain (viscous-to-elastic crossover) at intermediate frequencies, and an elasticity-dominated domain at high frequencies, covering a broad range of time scales relevant in biology and technological applications of protein condensates.

Avalanche Coalescence of Liquid Metal Particles for Uniform Flexible and Stretchable Electrodes

AbstractSelf‐sinterable gallium‐based liquid metal (LM) ink for a handy drop‐casting coating method is developed. The fabricated LM electrode is coffee‐ring‐free and bilayer‐free, which guarantees high electrical conductivity, wettability, flexibility, and stretchability. The ink consists of Galinstan, ethanol‐water mixture, hydrochloric acid, and polyvinylpyrrolidone. The binary mixture provides excellent wetting conditions and suppresses a coffee‐ring stain from Marangoni mixing. The acid removes an oxide layer on the LM interface. The colloidal interaction forces by self‐assembled polyvinylpyrrolidone induce avalanche coalescences of the particles at the end of evaporation, which produces a thin and uniform dried conductive layer. The acid and polymer provide a bilayer‐free structure and electrification without any post sintering. The drop‐casted self‐transformed LM electrode showed excellent electrical resistance of O (0.1–1 Ω) on folding and stretching conditions. It is believed that this method can serve as flexible and stretchable electrodes, on various substances for soft robots and wearable devices, without any complicated post‐process.

Review of Particle Detachment and Attachment in Porous Media

Particle detachment, migration and attachment are common processes in porous media, especially in unconsolidated formations. In this review, the processes are discussed and equations describing the processes are presented. Two particle detachment processes analyzed are the hydrodynamic forces and electric double-layer forces. The particle detachments equations were critically examined to determine if they reflect crucial factors that trigger particle detachment in porous media. Essential factors that are missing in the equation are the effect of pressure and the level of rock consolidation. Incorporating the level of rock cementation and the effect of pressure in the equations will make the models more empirical and less theoretical. For particle attachment, Van der Waals forces, adhesion, particle attachment efficiency, and straining processes and their equations are considered. The colloidal forces are all embraced in terms of capturing important elements that mobilize particles in porous media, however, the practical application of the models can pose a challenge. For particle adsorption on grain surfaces, it is recommended that the effect of pressure and temperature be studied.

Using colloidal AFM probe technique and XDLVO theory to predict the transport of nanoplastics in porous media

The plastic concentration in terrestrial systems is orders of magnitude higher than that found in marine ecosystems, which has raised global concerns about their potential risk to agricultural sustainability. Previous research on the transport of nanoplastics in soil relied heavily on the qualitative prediction of the mean-field extended Derjaguin–Landau–Verwey–Overbeek theory (XDLVO), but direct and quantitative measurements of the interfacial forces between single nanoplastics and porous media are lacking. In this study, we conducted multiscale investigations ranging from column transport experiments to single particle measurements. The maximum effluent concentration (C/C0) of amino-modified nanoplastics (PS–NH2) was 0.94, whereas that of the carboxyl-modified nanoplastics (PS–COOH) was only 0.33, indicating PS-NH2 were more mobile than PS-COOH at different ionic strengths (1–50 mM) and pH values (5–9). This phenomenon was mainly attributed to the homogeneous aggregation of PS-COOH. In addition, the transport of PS-NH2 in the quartz sand column was inhibited with the increase of ionic strength and pH, and pH was the major factor governing their mobility. The transport of PS-COOH was inhibited with increasing ionic strength and decreasing pH. Hydrophilicity/hydrophobicity-mediated interactions and particle heterogeneity strongly interfered with interfacial forces, leading to the qualitative prediction of XDLVO, contrary to experimental observations. Through the combination of XDLVO and colloidal atomic force microscopy, accurate and quantitative interfacial forces can provide compelling insight into the fate of nanoparticles in the soil environment.