Temperature-Insensitive Nonpolar Suspensions of Polyoxyethylene Alkyl Ether-Grafted Silica Nanoparticles.

Nonpolar suspensions of organically modified particles exhibit a strong temperature sensitivity owing to the high-temperature-induced desorption/decomposition and the low-temperature-induced disorder/order conformational transition of the modifiers. This strong temperature sensitivity limits their applications, such as lubricants and oil-based drilling fluids, which require the suspensions to operate over a wide temperature range (e.g., 0-200 °C). We hypothesize that the introduction of a flexible ethylene oxide (EO) chain into the modifiers can disrupt the low-temperature-induced ordered conformation to improve the stability of the nonpolar suspensions. In this article, nonpolar suspensions with temperature insensitivity in the range of 5-160 °C were obtained via the covalent modification of silica NPs and the introduction of EO chains into the modifier molecules. Here, octadecyl-grafted silica NPs (C18-SiO2) and polyoxyethylene alkyl ether-grafted silica NPs (AEOn-SiO2) were synthesized and subsequently dispersed in mineral oil. The rheological properties of each suspension at different temperatures were evaluated, and the thermal stability of AEOn-SiO2 in mineral oil was investigated along with the conformational changes of the grafted chains. In the temperature range of 5-160 °C, the apparent viscosity and gel strength of the C18-SiO2 suspension changed dramatically, whereas the AEOn-SiO2 suspensions exhibited constant rheological properties over this temperature range. This temperature insensitivity of AEOn-SiO2 suspensions is attributed to the excellent thermal stability of AEOn-SiO2 in mineral oil and the disordered conformation of the EO chains upon cooling. This study provides a novel approach to preparing temperature-insensitive nonpolar suspensions, which have potential applications in the petroleum and lubricant industries.

Nanoemulsions Stable against Ostwald Ripening.

Ostwald ripening, the dominant mechanism of droplet size growth for an O/W nanoemulsion at high surfactant concentrations, depends on micelles in the water phase and high aqueous solubility of oil, especially for spontaneously formed nanoemulsions. In our study, O/W nanoemulsions were formed spontaneously by mixing a water phase with an oil phase containing fatty alcohol polyoxypropylene polyoxyethylene ether (APE). By monitoring periodically the droplet size of the nanoemulsions via dynamic light scattering, we demonstrated that the formed O/W nanoemulsions are stable against Ostwald ripening, i.e., droplet growth. In contrast, the nanoemulsion droplets grew with the addition of micelles, demonstrating the pivotal role of the presence of micelles in the water phase in the occurrence of Ostwald ripening. The influence of the initial phase of APE, the oil or water phase in which APE is present, on the micelle formation is discussed by the partition coefficient and interfacial adsorption of APE between the oil and water phase using a surface and interfacial tensiometer. In addition, the spontaneously formed O/W nanoemulsion, which is stable against Ostwald ripening, can be used as a nanocarrier for the delivery of water-insoluble pesticides. These results provide a novel approach for the preparation of stable nanoemulsions and contribute to elucidating the mechanism of instability of nanoemulsions.

Nanoscale Transport during Liquid Film Thinning Inhibits Bubble Coalescing Behavior in Electrolyte Solutions.

The long-standing puzzle of why two colliding bubbles in an electrolyte solution do not coalesce immediately upon contact is resolved. The water film between the bubbles needs to be drained out first before its rupture, i.e., coalescence. Experiments reveal clearly that the film thinning exhibits a rather sudden slowdown (around 30-50 nm), which is orders of magnitude smaller than similar experiments involving surfactants. A critical step in explaining this phenomenon is to realize that the solute concentration is different in bulk and at the surface. During thinning, this will generate an electrolyte concentration difference in film solution along the interacting region, which in turn causes a Marangoni stress to resist film thinning. We develop a film drainage model that explains the experimentally observed phenomena well. The underlying physical mechanism, that confused the scientific community for decades, is now finally revealed.

A Hierarchical Si/C Nanocomposite of Stable Conductive Network Formed Through Thermal Phase Separation of Asphaltenes for High-Performance Li-Ion Batteries.

Silicon is one of the most promising anode materials for lithium-ion batteries. However, the huge volume change of silicon during lithiation/delithiation triggers continuous growth of solid-electrolyte interphase, loss of conductive contacts and structural collapse of the electrode, which causes a rapid deterioration of battery capacities. Inspired by the polyaromatic molecular nature and phase separation of asphaltenes in bitumen during thermal cracking, a hierarchical Si/C nanocomposite of robust carbon coatings and a firmly connected carbon framework on the silicon surface is synthesized by controlling the concentration of asphaltenes as carbon source and hence desired phase separation during the subsequent carbonization. The electrode made using this special Si/C nanocomposite exhibits a high reversible capacity of 1149 mAh g-1 after 600 cycles with a capacity retention of 98.5% and the operation ability at a high mass loading over 10 mg cm-2 or an area capacity of 23.8 mAh cm-2 , which represents one of the highest area capacities reported in open literature but with much more stable and prolonged operations. This simple and efficient strategy is easy to scale up for commercial production to meet the rapid growth of the electric vehicle industry.

Bitumen-Derived Onion-Like Soft Carbon as High-Performance Potassium-Ion Battery Anode.

Potassium-ion batteries (PIBs) have been regarded as a competitive alternative for lithium-ion batteries, owing to the natural abundance, low cost, and similar rocking-chair working mechanism of potassium element. However, it is challenging to simultaneously prepare suitable potassium ion anode materials of low voltage plateau, high capacity, and long cycle life. In this work, onion-like soft carbon (OLSC) of high heteroatom content is prepared by using solvent-sensitive self-assembly properties of asphaltene molecules. The OLSC electrode exhibits a low voltage plateau because of a high degree of graphitization. Meanwhile, it possesses excellent cycling stability and rate capability due to the high stability of the onion-like structure and fast transport of potassium ions, the latter of which is caused by heteroatom-induced expanded interlayers as found by first-principle calculations. Compared with existing carbon materials, the OLSC synthesized in this study exhibits a high reversible capacity of 466 mAh g-1 at 20 mA g-1 , a reversible capacity of 222 mAh g-1 and capacity retention of 95% after 1600 cycles at 1 A g-1 . This work connects the nanostructure of carbon materials and electrochemical performance and provides new insights in improving carbon-based anodes for PIBs.

N, S-Coordinated Co Single Atomic Catalyst Boosting Adsorption and Conversion of Lithium Polysulfides for Lithium-Sulfur Batteries.

Boosting reversible solid-liquid phase transformation from lithium polysulfides to Li2 S and suppressing the shuttling of lithium polysulfides from the cathode to the lithium anode are critical challenges in lithium-sulfur batteries. Here, sulfiphilic single atomic cobalt implanted in lithiophilic heteroatoms-dopped carbon (SACo@HC) matrix with a CoN3 S structure for high-performance lithium-sulfur batteries is reported. Density functional theory calculation and in situ experiments demonstrate that the optimal CoN3 S structure in SACo@HC can effectively improve the adsorption and redox conversion efficiency of lithium polysulfides. Consequently, the S-SACo@HC composite with sulfur loading of 80 wt% delivers a high capacity of 1425.1 mAh g-1 at 0.05 C and outstanding rate performance with 745.9 mAh g-1 at 4 C. Furthermore, a capacity of 680.8 mAh g-1 at 0.5 C with a low electrolyte/sulfur ratio (6 µL mg-1 ) can be achieved even after 300 cycles. With the harsh conditions of lean electrolyte (E/S = 4 µL mg-1 ) and high sulfur loading (5.4 mg cm-2 ), a superior area capacity of 5.8 mAh cm-2 can be obtained. This work contributes to building a profound understanding of the adsorption and interface engineering of lithium polysulfides and provides ideas to tackle the long-standing polysulfide shuttle problem of lithium-sulfur batteries.

A novel highly specific colorimetric fluorescent probe for the detection of nitrite in aqueous solution.

Developing an effective method for the detection of nitrite (NO2 - ) ions in the natural environment especially in environmental waters and soils is very necessary, since they will cause serious damage to human health once excess NO2 - ions enters the human body. Therefore, a new colorimetric fluorescent probe NB-NO2 - for determining NO2 - ions was designed, which possesses good water-solubility and satisfactory selectivity over other common ions for NO2 - ions. The addition of NO2 - ions changed the color of solution from blue to colorless seen by the naked-eye. Furthermore, through test and calculation, the detection limit of the probe NB-NO2 - is 129 nM. Based on the earlier excellent characteristics, the probe NB-NO2 - was successfully used for monitoring NO2 - ions in environmental waters and soils.

Water Film Drainage between a Very Viscous Oil Drop and a Mica Surface.

We investigate thin film drainage between a viscous oil drop and a mica surface, clearly illustrating the competing effects of Laplace pressure and viscous normal stress (τ_{v}) in the drop. τ_{v} dominates the initial stage of drainage, leading to dimple formation (h_{d}) at a smaller critical thickness with an increase in the drop viscosity (the dimple is the inversion of curvature of the drop in the film region). Surface forces and interfacial tension control the last stage of film drainage. A scaling analysis shows that h_{d} is a function of the drop size R and the capillary numbers of the film (Ca_{f}) and drop (Ca_{d}), which we estimate by h_{d}=0.5Rsqrt[Ca_{f}/(1+2Ca_{d})]. This equation clearly indicates that the drop viscosity needs to be considered when Ca_{d}>0.1. These results have implications for industrial systems where very viscous liquids are involved, for example, in 3D printing and heavy oil extraction process.

Inward Flow of Intervening Liquid Films Driven by the Marangoni Effect during Bubble-Solid Collisions in Ethyl Alcohol-NaCl Aqueous Solutions.

The drainage dynamics of confined thin liquid films between an air bubble and a freshly cleaved mica surface were investigated in ethyl alcohol aqueous solutions. Focus was given to the holding stage, in which an unexpected increase in the thickness of a few hundred nanometers at the center of the film was captured by interferometry in ethyl alcohol-500 mM NaCl aqueous solutions. Such an increase in film thickness occurred when the ethyl alcohol concentration exceeded the critical value at a bubble approach velocity of 100 µm/s. For a given ethyl alcohol concentration, the increase in thickness at the center of the film did not happen when the bubble approach velocity was decreased to 10 µm/s. Compared to the cases in ethyl alcohol-500 mM NaCl solutions, no increase in thickness at the center of the film was observed in ethyl alcohol-water solutions under the same ethyl alcohol concentration and bubble approach velocity. The phenomenon of the increasing thickness at the center of the film was attributed to the net inward flow in the film, resulting from competition between the inward Marangoni flow and the outward drainage flow that was hindered by the narrow channel at the barrier rim of the film under a high electrolyte concentration. The inward Marangoni flow was achieved by a concentration gradient of ethyl alcohol between the film and the bulk solution resulting from the mobile air-liquid interface in the initial approaching period.

The effect of chitosan molecular weight on CO2-triggered switching between emulsification and demulsification.

The role of molecular weight as a key physical property of macromolecules in determining the CO2-triggered switching characteristics of responsive emulsions prepared using CO2-switchable macromolecules has not been studied and is the focus of the current study. In this work, CO2-switchable chitosan of four different molecular weights is used to investigate the effect of molecular weight on CO2-triggered switching of CO2-responsive emulsions. The molecular weight of chitosan is shown to have an opposite effect on emulsification and demulsification by the CO2 trigger. Before bubbling of CO2, chitosan of higher molecular weight forms a more stable three-dimensional network structure in the continuous phase of oil-in-water (O/W) emulsions, which leads to the formation of a more stable emulsion. After bubbling of CO2, the chitosan of higher molecular weight makes the continuous phase more viscous, which leads to an incomplete demulsification as compared with the chitosan of lower molecular weight. Experimental evidence from the measurement of conductivity, interfacial tension and rheological properties is provided to support the proposed mechanism. This work is of great significance in guiding the selection of desirable CO2-switchable polymers for switchable emulsions of desired switching characteristics.

Simulation and optimization of hydraulic performance of small baffled subsurface flow constructed wetland.

The water body inside the constructed wetland is affected by various factors, and the flow state is relatively complicated. There will always be a certain degree of low velocity area and rapid outflow phenomenon, which makes part of the space in the wetland unable to be effectively used. Based on Computational Fluid Dynamics (CFD) technology, this paper uses Fluent's porous media model and discrete phase model to establish a hydrodynamic model of up and down baffled subsurface flow constructed wetland system. The internal flow field of the wetland is simulated, and the hydraulic performance of different baffle settings and substrate laying methods in the wetland is systematically evaluated. The results show that when the number of baffles is the same, the hydraulic efficiency is higher when the first baffle is located on the lower part of the substrate. Compared with the position of the baffle, the increase in the number of baffles does not significantly improve the hydraulic efficiency of the constructed wetland. The substrate layer thickness ratio has a significant effect on the two parameters of the variance of the hydraulic residence time distribution (σ2) and the flow divergence (σ02). By increasing the thickness of the middle substrate, the low flow rate phenomenon caused by the small porosity substrate area of the upper layer and the rapid outflow phenomenon of the lower substrate can be improved to a certain extent, the utilization efficiency of the middle substrate layer is improved, and the hydraulic performance is increased. The research results are of great significance for improving the utilization of wetland space and ensuring its efficient decontamination and purification function.

Interaction Between the Cyclopentane Hydrate Particle and Water Droplet in Hydrocarbon Oil.

The presence of immiscible water drops in bulk hydrocarbon is likely to bridge hydrate particles to cause hydrate agglomeration, leading to potential pipeline blockage. This can become a major challenge for flow assurance in offshore petroleum transportation. To avoid hydrate aggregation, the attachment between hydrate and water drops should be avoided. In this study, we used our home-designed integrated thin film drainage apparatus to investigate the interactions between a hydrate particle and a water drop inside model oil (i.e., mixture of cyclopentane and toluene with a volumetric ratio of 1:1). Our experiments showed that asphaltenes, a natural component in crude oil, were an effective inhibitor for the attachment between water drops and hydrate particles. Without asphaltenes in the system, the water drop adhered to the hydrate particle immediately after the two surfaces contacted. By adding 0.03 g/L asphaltenes into the oil phase, the attachment was delayed by 0.7 s when the applied preload force was set to around 0.05 mN. By increasing the asphaltenes addition to 0.05 g/L, the attachment between the hydrate and water drop was prevented even when the contact time lasted up to 25 s. This phenomenon could be explained by the adsorption of an asphaltenes layer along the interface between the aqueous drop and hydrocarbon. Measurements of the dynamic interfacial tension and crumping ratio confirmed the presence of the adsorption layer. The addition of 0.6 mol/L NaCl or 0.3 mol/L CaCl2 in the aqueous drop could further enhance the strength of the adsorption layer. Results of this research provide understanding of the benefits of asphaltenes and salt in preventing hydrate agglomeration.

Coalescence of Bubbles with Mobile Interfaces in Water.

The fluid flow inside a thin liquid film can be dramatically modified by the hydrodynamic boundary condition at the interfaces. Aqueous systems can be easily contaminated by trace amounts of impurities, rendering the air-liquid interface immobile, thereby significantly resisting the fluid flow. Using high speed interferometry, rapid thinning of the liquid film, on the order of the collision speed, was observed between two fast approaching air bubbles in water, indicating negligible resistance and a fully mobile boundary condition at the air-water interface. By adding trace amounts of surfactants that changed the interfacial tension by 10^{-4} N/m, a transition from mobile to immobile was observed. This provides a fundamental explanation why the bubble coalescence time can vary by over 3 orders of magnitude.

Spontaneous Displacement of High Viscosity Micrometer Size Oil Droplets from a Curved Solid in Aqueous Solutions.

Spontaneous displacement of high viscosity (∼103 Pa·s) micrometer size oil droplets from a curved solid in aqueous solutions was investigated. For high viscosity oils, the dynamic droplet shape was found to deviate significantly from a spherical cap shape due to the considerable viscous force in the oil phase. The displacement dynamics of high viscosity droplets were analyzed using molecular kinetic and hydrodynamic models. The molecular kinetic model was found to describe the dynamic displacement well for the droplets of small departure from the spherical cap shape, while the hydrodynamic model is more applicable to the droplets of higher three-phase contact line displacement velocities and hence larger deviation of the droplets from the spherical cap shape.

Temperature and CO2 Dual-Responsive Pickering Emulsions Using Jeffamine M2005-Modified Cellulose Nanocrystals.

Cellulose nanocrystals (CNCs) with excellent biodegradability are promising biomaterials for use as responsive Pickering emulsifiers. However, the high hydrophilicity of CNCs limits their emulsification ability. Some existing studies have utilized complicated covalent modification procedures to increase the hydrophobicity of CNCs. To simplify the modification process, we prepared hydrophobically modified CNCs (CNCs-M2005) via simple and controllable electrostatic interactions with thermosensitive M2005. The obtained CNCs-M2005 exhibited temperature and CO2 dual-responsive properties. Subsequently, stable oil/water Pickering emulsions were prepared using the partially hydrophobic CNCs-M2005 at 20 °C. However, demulsification occurred when the temperature increased to 60 °C. This temperature-induced demulsification resulted from the dehydration of polyethylene oxide and polypropylene oxide, causing the aggregation of the CNCs-M2005, as shown by dynamic light scattering and transmission electron microscopy experiments. In addition, demulsification was also achieved after bubbling CO2, which was attributed to the dissociation of the partially hydrophobic CNCs-M2005. The temperature and CO2 dual-responsive biosafe Pickering emulsions open up opportunity for the design of intelligent food, cosmetic, and drug delivery systems.

Probing Anisotropic Surface Properties of Illite by Atomic Force Microscopy.

For the purpose of understanding the colloidal behaviors of illite in mineral processing, probing the surface charging property of illite is of great significance. This research explored the edge and basal surfaces of illite using an atomic force microscope (AFM). The interaction forces between Si/Si3N4 probes and illite edge/basal surfaces were measured, respectively, at different pH values in 10 mM KCl solutions. Theoretical Derjaguin-Landau-Verwey-Overbeek forces were matched up with the measured forces to derive the surface potentials of the two surfaces. On the illite basal surface, an attractive force occurred at pH 3.0, while repulsive forces dominated from pH 5.0 to 10.0. On the illite edge surface, a slight attractive force was also obtained at pH 3.0. However, the interaction changed into repulsion at pH 5.0, and this repulsive force increased gradually from pH 6.0 to 10.0. Illite basal and edge surfaces were both negatively charged, but the basal surface exhibited more negative charges than the edge surface from pH 3.0 to 10.0. Increasing solution pH from 3.0 to 10.0, there was no detection of the point of zero charge (PZC) of the illite basal surface; however, the PZC of the illite edge surface should have occurred at a pH slightly lower than 3.0. This is the first time that surface potentials of illite edge and basal surfaces were attained separately by direct force measurements. These findings provide insights into the colloidal behaviors of illite in mineral processing and oil sands extraction.

Stimuli-Responsive Hybrid Polymer for Enhanced Solid-Liquid Separation of Industrial Effluents.

In the current study, a novel stimuli-responsive hybrid polymer with aluminum hydroxide colloids incorporated into a cationic copolymer of N-isopropylacrylamide and N-[3-(dimethylamino)propyl]methacrylamide was synthesized to enhance the settling and filtration performance of fine clay suspensions. The conformation of the synthesized hybrid copolymer was shown to respond to changes in both temperature and pH. Compared with a cationic copolymer of similar structure without aluminum hydroxide colloids, settling and filtration rates were significantly enhanced using the hybrid copolymer, which is attributed to the synergy between the inorganic aluminum hydroxide cores and organic copolymer. While the ideal treatment protocol for the hybrid polymer involved the addition of the polymer at room temperature, followed by heating to 45 °C for enhanced settling and dewatering, the synergistic effect between colloidal cores and polymer also allowed the hybrid polymer to perform well when added at temperatures above the LCST, demonstrating the robustness of the hybrid polymer to the process environment. The ideal treatment protocol resulted in an optimal adsorption of polymer on clays before inducing a coil-globule transition to form large and dense flocs, resulting in a more porous filter cake.

Mechanism of Goethite Precipitation on Magnetite and Maghemite Nanoparticles Studied by Surface Complexation/Precipitation Modeling.

Precipitation of goethite on magnetic nanoparticles (MNPs) has been proposed as an effective means to separate goethite from calcium sulfate in the iron removal process of zinc hydrometallurgy, which allows reuse of the hazardous residues. This study focuses on investigating the underlying mechanisms of goethite precipitation on magnetite and maghemite MNPs, providing insights on Fe(III)aq adsorption and nucleation of goethite on MNPs. A predictive surface complexation/precipitation model of the system was developed based on the results from two different types of experiments: the potentiometric titration of MNPs to calculate proton binding constants ( Ka) of discrete MNP surface functional groups and the corresponding site concentrations; and adsorption of Fe(III)aq onto MNP surfaces to determine metal binding constants ( Kf). The composition of the surface complexes on MNPs was determined by time-of-flight secondary ion mass spectrometry. The results indicated the formation of polynuclear surface complexes. The content of polynuclear surface complexes was found to be significantly higher on maghemite MNPs than on magnetite MNPs. This trend is consistent with our experimental results of a greater goethite precipitation on maghemite than on magnetite. Overall, the formation of Fe(III) polynuclear surface complexes correlates directly to the nucleation and precipitation of goethite on the surfaces of both types of MNPs.

Contributions of van der Waals Interactions and Hydrophobic Attraction to Molecular Adhesions on a Hydrophobic MoS2 Surface in Water.

Pushing the boundaries of the investigation of hydrophobic attraction (HA) to the molecular scale readily ensures the collection of experimental results free of secondary effects, thereby facilitating the unraveling of the underlying mechanism by providing clean experimental results that truly reflect the hydrophobic attraction. Regardless of the feasibility of this approach, investigations using this promising method are stagnant due to the difficulties in determining the individual contributions of HA and van der Waals (vdW) interactions at the molecular scale. Here, a novel approach was proposed for the first time to determine the individual contributions of vdW interactions and HA by studying the single-molecule adhesion forces of a neutral oligo ethylene glycol methacrylate copolymer on a MoS2 crystal exposed to different water chemistry. The anisotropic surface properties of MoS2 enabled the partitioning of vdW interactions and hydrophobic attraction in total single-molecule adhesion forces and also enabled determining the contribution of electrostatic interaction (ESI). When the presence of ESI is excluded, the study of single-molecule adhesion forces using single-molecule force spectroscopy (SMFS) revealed that the contribution of vdW interactions to total molecular interactions was smaller than 9 pN. The strong single-molecule adhesion forces of oligo ethylene glycol copolymer on the hydrophobic basal surface of MoS2 demonstrated that HA plays a dominant role with contribution up to 89% to the total single-molecule adhesion force. By utilizing the derived theoretical model, we quantified the individual contribution of each fundamental interaction under a variety of conditions. This study proposed a facile approach to quantitatively clarify the roles of vdW interactions and HA at the molecular scale, which may help assist future experimental and theoretical investigations of hydrophobic (solvophobic) effects and vdW interactions in aqueous solutions.

Molecular Dynamics Study of Hydrophilic Sphalerite (110) Surface as Modified by Normal and Branched Butylthiols.

Molecular dynamics simulation was used to study the wettability of the hydrophilic sphalerite (110) surface chemically modified by butylthiols made up of normal and branched alkyl tails, referred to as n-butylthiol and i-butylthiol hereafter, at different adsorption site coverages. Butylthiol molecules were grafted onto the adsorption sites of the surface in two different distributions-ordered and random. The results showed that for a given butylthiol at a given site coverage, random surface distribution yielded a slightly larger contact angle. This observation was attributed to the fact that average distances between the first and second nearest neighbors of butylthiol molecules are shorter in the case of random surface distribution, resulting in smaller patches of bare surface exposed to water molecules compared to those of the ordered surface distribution. Regardless of the tail structure, the random surface distribution exhibited hydrophobic character (i.e., contact angle ≥ 90°) at a relatively low site coverage of about 25%. The test area method and the Kirkwood and Buff approach were adopted to estimate surface energies (γSV) of the bare sphalerite (110) surface and the collector monolayer, respectively. Using the obtained γSV values of these two pure states, the apparent surface energy as a function of surface coverage was determined based on Cassie's law. This allowed us to estimate the corresponding values of solid-liquid apparent interfacial tension (γSL). Both γSV and γSL exhibit a linear inverse dependence on surface coverage with a crossover point at 25% site coverage (about 50% surface coverage), above which γSV falls below γSL, leading to contact angles greater than 90°. The results also revealed that contact angles of the two butylthiols are comparable at site coverages below ∼85%, but above that, they are significantly lower for the branched thiols compared to their normal counterparts. Considering the Lennard-Jones interaction energies between the water cluster and the butylthiols, stronger attractive interactions were present in the case of i-butylthiol due to the presence of two methyl groups in its alkyl chain. This difference was the most intense at site coverages above ∼85%.