Attachment, Coalescence, and Spreading of Carbon Dioxide Nanobubbles at Pyrite Surfaces.

Recently, it was reported that using CO2 as a flotation gas increases the flotation of auriferous pyrite from high carbonate gold ores of the Carlin Trend. In this regard, the influence of CO2 on bubble attachment at fresh pyrite surfaces was measured in the absence of collector using an induction timer, and it was found that nitrogen bubble attachment time was significantly reduced from 30 ms to less than 10 ms in CO2 saturated solutions. Details of CO2 bubble attachment at a fresh pyrite surface have been examined by atomic force microscopy (AFM) measurements and molecular dynamics (MD) simulations, and the results used to describe the subsequent attachment of a N2 bubble. As found from MD simulations, unlike the attached N2 bubble, which is stable and has a contact angle of about 90°, the CO2 bubble attaches, and spreads, wetting the fresh pyrite surface and forming a multilayer of CO2 molecules, corresponding to a contact angle of almost 180°. These MDS results are complemented by in situ AFM images, which show that, after attachment, CO2 nano-/microbubbles spread to form pancake bubbles at the fresh pyrite surface. In summary, it seems that CO2 bubbles have a propensity to spread, and whether CO2 exists as layers of CO2 molecules (gas pancakes) or as nano-/microbubbles, their presence at the fresh pyrite surface subsequently facilitates film rupture and attachment of millimeter N2 bubbles and, in this way, improves the flotation of pyrite.

Interaction forces for symmetric hydrophilic and hydrophobic systems in aqueous isopropanol solutions.

Interaction force measurements were performed for a silica-silica hydrophilic system and for a silanated silica-silanated silica hydrophobic system using the atomic force microscopy colloidal probe technique. The influence of the solution composition on interaction forces was investigated. The hydrophilic silica-silica interactions were found to be described as a typical Derjaguin-Landau-Verwey-Overbeek (DLVO) system in solutions of various compositions, whereas silanated silica-silanated silica interactions were dominated by a long-range hydrophobic force. An increase in the isopropyl alcohol content of the solution diminishes both the repulsive forces in the case of the hydrophilic system and the attractive interactions in the case of the hydrophobic system.

Aggregation of fullerol C60(OH)24 nanoparticles as revealed using flow field-flow fractionation and atomic force microscopy.

The effects of solution pH and 1:1 electrolyte concentration on the aggregation behavior of fullerol C(60)(OH)(24) nanoparticles were investigated using flow field-flow fractionation (FlFFF). Particle separations were confirmed by examining FFF fractions using atomic force microscopy (AFM). Results showed that fullerol C(60)(OH)(24) nanoparticles remain stable at low salt concentration (0.001 M NaCl) and basic pH (pH 10). Changing the pH did not affect the size significantly, but increasing the salt concentration promoted some aggregation. Fullerol C(60)(OH)(24) nanoparticles did not form large clusters and reached a maximum size of at most several nanometers. Particle interaction analysis using the colloid interaction theory as described by the energetics of electrostatic repulsion and van der Waals attraction explained the differences in the colloidal stability of the fullerol C(60)(OH)(24) nanoparticles under different solution conditions.

Advanced Nanoclay-Based Nanocomposite Solid Polymer Electrolyte for Lithium Iron Phosphate Batteries.

High-performance solid polymer electrolytes (SPEs) have long been desired for the next generation of lithium batteries. One of the most promising ways to improve the morphological and electrochemical properties of SPEs is the addition of fillers with specific nanostructures. However, the production of such fillers is generally expensive and requires complicated preparation procedures. Halloysite nanotubes (HNTs), with their tubular structure, resemble carbon nanotubes in terms of geometric features and can be obtained at a relatively low cost. Previously, we reported that the HNT poly(ethylene oxide) composite SPE possesses excellent electrochemical and mechanical properties and outstanding cycling performance for all-solid-state lithium sulfur batteries. However, the HNT/SPE was not effective for lithium iron phosphate (LFP) batteries. The compatibility between the electrodes and the electrolyte sharply decreased, and no decent cycling performance was achieved. Therefore, a modification was studied which involves a minor addition of LFP during the preparation procedure. With this modification, good ionic conductivity (9.23 × 10-5 S cm-1 at 25 °C) is achieved, and compatibility between the electrodes and the electrolyte is enhanced. At the same time, an electrochemical stability window of 5.14 V and lithium-ion transference number of 0.46 are found. All-solid-state LFP batteries possessing excellent cycling performance are further demonstrated.

Interfacial Water Features at Air-Water Interfaces as Influenced by Charged Surfactants.

The features of interfacial water at air-water interfaces of anionic sodium dodecyl sulfate (SDS) and cationic dodecyl amine hydrochloride (DDA) solutions were examined by combining sum frequency generation (SFG) vibrational spectroscopy measurements and molecular dynamics simulations (MDS). The SFG spectra revealed that interfacial water molecules for SDS solutions were highly ordered compared with those for DDA solutions. To elucidate this observation, in addition to agreement with the literature in regards to the interfacial electric field at the interfaces, we investigated the features of interfacial water molecules with respect to their network and their interaction with surfactant head groups. Our simulation analysis results revealed a higher number density, more strongly connected hydrogen bonding, and more orderly oriented interfacial water molecules at the interface of the SDS solutions as compared to the DDA solutions. The goal of this research is  to identify significant features of interfacial water for our improved understanding of such interfacial phenomena.

The hydrophobic surface state of talc as influenced by aluminum substitution in the tetrahedral layer.

Talc is both an important industrial mineral product recovered by flotation, and also in other cases, a gangue mineral of concern in the flotation of certain sulfide ores, such as the PGM ores from South Africa and from the United States. The talc face surface is naturally hydrophobic with a water sessile drop contact angle of nearly 80°, which accounts for its flotation recovery in one case, and its contamination of sulfide mineral concentrates in other instances. Due to the presence of impurities in the talc structure the surface properties change. One such effect is the presence of aluminum, which can replace silicon in the silica tetrahedral layer of the talc structure. This results in a charge imbalance on the face surface because Si+4 is replaced by Al+3. Sessile drop contact angle and bubble attachment time measurements were made, and these results were compared to the results from molecular dynamics simulations (MDS). The extent of aluminum substitution in the silica tetrahedral layer was considered, and the sessile drop contact angle was found to decrease with increased aluminum content, decreasing from about 80° for no substitution (talc) to 0° for extensive substitution (phlogopite). The water film was found to be stable at the surface of highly aluminum substituted crystals due to the interaction between water molecules and the increased polarity of the surface state. This stable water film restricts the air bubble from attaching to such face surfaces. However, in the absence of aluminum substitution, no interactions between the water molecules and the face surface were observed and the air bubble readily attached to the face surface. This study provides additional understanding of how aluminum substitution in the tetrahedral layer affects the fundamental surface properties of talc, paving the way for the design of improved reagents for talc flotation as an industrial mineral product, and for talc depression in the recovery of sulfide mineral concentrates.

A novel method to detect unlabeled inorganic nanoparticles and submicron particles in tissue by sedimentation field-flow fractionation.

UNLABELLED: A novel methodology to detect unlabeled inorganic nanoparticles was experimentally demonstrated using a mixture of nano-sized (70 nm) and submicron (250 nm) silicon dioxide particles added to mammalian tissue. The size and concentration of environmentally relevant inorganic particles in a tissue sample can be determined by a procedure consisting of matrix digestion, particle recovery by centrifugation, size separation by sedimentation field-flow fractionation (SdFFF), and detection by light scattering. BACKGROUND: Laboratory nanoparticles that have been labeled by fluorescence, radioactivity, or rare elements have provided important information regarding nanoparticle uptake and translocation, but most nanomaterials that are commercially produced for industrial and consumer applications do not contain a specific label. METHODS: Both nitric acid digestion and enzyme digestion were tested with liver and lung tissue as well as with cultured cells. Tissue processing with a mixture of protease enzymes is preferred because it is applicable to a wide range of particle compositions. Samples were visualized via fluorescence microscopy and transmission electron microscopy to validate the SdFFF results. We describe in detail the tissue preparation procedures and discuss method sensitivity compared to reported levels of nanoparticles in vivo. CONCLUSION: Tissue digestion and SdFFF complement existing techniques by precisely identifying unlabeled metal oxide nanoparticles and unambiguously distinguishing nanoparticles (diameter<100 nm) from both soluble compounds and from larger particles of the same nominal elemental composition. This is an exciting capability that can facilitate epidemiological and toxicological research on natural and manufactured nanomaterials.

Distribution of multiphase fluids in porous media: comparison between lattice Boltzmann modeling and micro-x-ray tomography.

A parallel implementation of the three-dimensional Shan-and-Chen multicomponent, multiphase lattice Boltzmann method (LBM) was used to simulate the equilibrium distributions of two immiscible fluids in porous media. The simulations were successfully validated against cone-beam x-ray microtomographic data on the distribution of oil (decane), water, and air phases in a 5-mm cube of porous medium composed of packed quartz sand grains. The results confirm that LBM models allow for the straightforward incorporation of complex pore space geometry determined from x-ray microtomography measurements and that simulated wetting and nonwetting phase distributions are consistent with x-ray observations on both macroscopic and microscopic scales.

Characteristics of dextrin adsorption by elemental sulfur.

Characteristics of dextrin adsorption by elemental sulfur were investigated by the means of diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, total organic carbon (TOC) measurements, BET measurements as well as molecular dynamics simulation (MDS). Adsorption isotherms for dextrin adsorption by sulfur were compared to isotherms for dextrin adsorption by other hydrophilic and hydrophobic surfaces taken from the literature. The three-dimensional structure of dextrin was studied in detail and possible mechanisms of adsorption are discussed. Additionally, molecular dynamics simulations provided further insight into the mechanism of dextrin adsorption by elemental sulfur.

Molecular features of the air/carbonate solution interface.

The nature of the air/carbonate solution interface is considered with respect to water structure by sum-frequency vibrational spectroscopy (SFVS) and molecular dynamics simulations (MDS). Results from this study provide further understating regarding previous observations that the surface tensions of structure making sodium carbonate solutions have been shown to be significantly greater than the surface tensions of structure breaking bicarbonate solutions at equivalent concentrations. This difference in surface tension and its variation with salt concentration is related to the organization of water and ions at the air/solution interface. Spectral results from SFVS show at equivalent concentrations that, for the carbonate solution, the strong water structure signal of 3200 cm(-1) at the air/carbonate solution interface is increased by a factor of 4 when compared to the same signal for the air/bicarbonate solution interface, which spectrum is weaker than the spectrum for the air/water interface in the absence of salt. These results from SFVS are explained by the results from MDS which show that in the case of carbonate solutions the structure making carbonate ions are excluded from the interfacial water region which region is extended in depth. On the other hand, in the case of bicarbonate solutions, the bicarbonate ions are accommodated in the interfacial water region and there is no evidence of an increase in the extent of water structure. These SFVS experimental and MD simulation results provide further information to understand interfacial phenomena of soluble salts at the molecular level.

The nature of hematite depression with corn starch in the reverse flotation of iron ore.

The function of corn starch and the significance of the order of addition of corn starch and mono ether amine in the reverse flotation of iron ore has been investigated. Understanding hematite depression with starch and the corresponding hydrophilic state involves consideration of adsorption with amine as well as flocculation of fine hematite. Captive bubble contact angle and micro-flotation experiments indicated that amine has an affinity towards both hematite and quartz, and that the role of starch is to hinder the adsorption of amine at the hematite surface so that flotation is inhibited. Micro-flotation results confirmed that quartz does not have affinity towards starch at pH 10.5. In addition to competitive adsorption, flocculation of fine hematite occurs and images from high resolution X-ray computed tomography (HRXCT) and cryo-SEM reveal further detail regarding floc structure. These results provide substantial evidence that the fine hematite particles are flocculated in the presence of corn starch, and flocculation is dependent on the particle size of hematite, with greater flocculation for finer particles. Thus, starch is playing a dual role in the reverse flotation of iron ore, acting as a depressant by hindering amine adsorption at the hematite surface in order to maintain the hydrophilic surface state of hematite, and acting as a flocculant to aggregate fine hematite particles, which if not flocculated, could diminish the flotation separation efficiency by being transported to the froth phase during reverse flotation.

Ultrasound-assisted leaching of cobalt and lithium from spent lithium-ion batteries.

Recovery of cobalt and lithium from spent Li-ion batteries (LIBs) has been studied using ultrasound-assisted leaching. The primary purpose of this work is to investigate the effects of ultrasound on leaching efficiency of cobalt and lithium. The results were compared to conventional leaching. In this study sulfuric acid was used as leaching agent in the presence of hydrogen peroxide. The cathode active materials from spent battery were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) before and after leaching. Effects of leaching time, leaching temperature, H2SO4 concentration, H2O2 concentration, solid/liquid ratio, and ultrasonic power have been studied. Optimal leaching efficiency of 94.63% for cobalt, and 98.62% for lithium, respectively, was achieved by using 2 M H2SO4 with 5% (v/v) H2O2 at a solid/liquid ratio of 100 g/L, and an ultrasonic power of 360 W, and the leaching time being 30 min under 30 °C. Compared with conventional leaching, the ultrasound-assisted leaching gave a higher leaching rate and improved leaching efficiency under the same experimental conditionals. The kinetic analysis of ultrasound-assisted leaching showed that the activation energy of cobalt and lithium were 3.848 KJ/mol and 11.6348 KJ/mol, respectively, indicating that ultrasound-assisted leaching of cobalt and lithium from spent LIBs was controlled by diffusion.

Structural and dynamic properties of concentrated alkali halide solutions: a molecular dynamics simulation study.

The physicochemical properties of alkali halide solutions have long been attributed to the collective interactions between ions and water molecules in the solution, yet the structure of water in these systems and its effect on the equilibrium and dynamic properties of these systems are not clearly understood. Here, we present a systematic view of water structure in concentrated alkali halide solutions using molecular dynamics simulations. The results of the simulations show that the size of univalent ions in the solution has a significant effect on the dynamics of ions and other transport properties such as the viscosity that are correlated with the structural properties of water in aqueous ionic solution. Small cations (e.g., Li+) form electrostatically stabilized hydrophilic hydration shells that are different from the hydration shells of large ions (e.g., Cs+) which behave more like neutral hydrophobic particles, encapsulated by hydrogen-bonded hydration cages. The properties of solutions with different types of ion solvation change in different ways as the ion concentration increases. Examples of this are the diffusion coefficients of the ions and the viscosities of solutions. In this paper we use molecular dynamics (MD) simulations to study the changes in the equilibrium and transport properties of LiCl, RbCl, and CsI solutions at concentrations from 0.22 to 3.97 M.

Sum-frequency spectroscopy analysis of two-component langmuir monolayers and the associated interfacial water structure.

Sum-frequency spectroscopy (SFS) in the CH and OH stretching regions was employed to obtain structural information about Langmuir monolayers on the H(2)O subphase of the model lipid dioctadecyldimethylammonium bromide (DOMA) and of the neutral surfactant methyl stearate (SME) and their mixtures and about the interfacial water structure underneath the films. These results were compared with the sum-frequency spectra of the interface between Langmuir monolayers of stearic acid and stearic acid-DOMA monolayers and water to prove that the uncompensated headgroup charge of DOMA at the interface is the reason for structuring of interfacial water close to the studied monomolecular films. Sum-frequency spectra on D(2)O subphase were also studied to account for the interference between the CH and OH spectral signatures because of the coherent nature of the SFS signals. Interfacial water structure proved to be a determining factor in the behavior of the mixed lipid monolayers. A mixing induced amplification in the surface potential DeltaV observed in our previous work was explained with total increase of the dipole moment for the mixed films, bigger than the arithmetic average for DOMA and SME monolayers alone. The increase is due to the better packing of the molecules in the mixed films and to the decrease in the interfacial water dipole moment arising from a more disordered water structure underneath the mixed monolayers.

The surface state of hematite and its wetting characteristics.

Apart from being a resource for iron/steel production, the iron oxide minerals, goethite and hematite, are used in the paint, cosmetics, and other industries as pigments. Surface characteristics of these minerals have been studied extensively both in resource recovery by flotation and in the preparation of colloidal dispersions. In this current research, the wetting characteristics of goethite (FeOOH) and hematite (Fe2O3) have been analyzed by means of contact angle, bubble attachment time, and Atomic Force Microscopy (AFM) measurements as well as by Molecular Dynamics Simulation (MDS). Goethite is naturally hydroxylated and wetted by water at all pH values. In contrast, the anhydrous hematite surface (001) was found to be slightly hydrophobic at natural pH values with a contact angle of about 50°. At alkaline pH hydroxylation of the hematite surface occurs rapidly and the hematite becomes hydrophilic. The wetting characteristics of the hematite surface then vary between the hydrophobic anhydrous hematite and the completely hydrophilic hydroxylated hematite, similar to goethite. The hydrophobicity can be restored by heating of the hydroxylated hematite surface at 60°C. The hydrophobic character of the anhydrous hematite (001) surface is confirmed by MDS which also reveals that after hydrolysis the hematite (001) surface can be wetted by water, similar to the goethite (001) surface.

Some physicochemical aspects of water-soluble mineral flotation.

Some physicochemical aspects of water-soluble mineral flotation including hydration phenomena, associations and interactions between collectors, air bubbles, and water-soluble mineral particles are presented. Flotation carried out in saturated salt solutions, and a wide range of collector concentrations for effective flotation of different salts are two basic aspects of water-soluble mineral flotation. Hydration of salt ions, mineral particle surfaces, collector molecules or ions, and collector aggregates play an important role in water-soluble mineral flotation. The adsorption of collectors onto bubble surfaces is suggested to be the precondition for the association of mineral particles with bubbles. The association of collectors with water-soluble minerals is a complicated process, which may include the adsorption of collector molecules or ions onto such surfaces, and/or the attachment of collector precipitates or crystals onto the mineral surfaces. The interactions between the collectors and the minerals include electrostatic and hydrophobic interactions, hydrogen bonding, and specific interactions, with electrostatic and hydrophobic interactions being the common mechanisms. For the association of ionic collectors with minerals with an opposite charge, electrostatic and hydrophobic interactions could have a synergistic effect, with the hydrophobic interactions between the hydrophobic groups of the previously associated collectors and the hydrophobic groups of oncoming collectors being an important attractive force. Association between solid particles and air bubbles is the key to froth flotation, which is affected by hydrophobicity of the mineral particle surfaces, surface charges of mineral particles and bubbles, mineral particle size and shape, temperature, bubble size, etc. The use of a collector together with a frother and the use of mixed surfactants as collectors are suggested to improve flotation.

Hydrophobic attraction as revealed by AFM force measurements and molecular dynamics simulation.

Spherical calcium dioleate particles ( approximately 10 mum in diameter) were used as AFM (atomic force microscope) probes to measure interaction forces of the collector colloid with calcite and fluorite surfaces. The attractive AFM force between the calcium dioleate sphere and the fluorite surface is strong and has a longer range than the DLVO (Derjaguin-Landau-Verwey-Overbeek) prediction. The AFM force between the calcium dioleate sphere and the mineral surfaces does not agree with the DLVO prediction. Consideration of non-DLVO forces, including the attractive hydrophobic force and the repulsive hydration force, was necessary to explain the experimental results. The non-DLVO interactions considered were justified by the different interfacial water structures at calcite- and fluorite-water interfaces as revealed by the numerical computation experiments with molecular dynamics simulation.

Adsorption density of spherical cetyltrimethylammonium bromide (CTAB) micelles at a silica/silicon surface.

In situ Fourier transform infrared internal reflection spectroscopy (FT-IR/IRS) was used to calculate the adsorption density values for spherical cetyltrimethylammonium bromide (CTAB) micelles at the silica/silicon (SiO2/Si) surface based on a previously developed adsorption density equation. Recent advances in atomic force microscopy (AFM) imaging methodology have led to the ability to image surface micelles, which was not possible previously. These AFM images have been used to independently calculate adsorption density values through offline fast Fourier transform (FFT) analysis. The adsorption density values measured from in situ FT-IR/IRS spectra and from AFM images showed good agreement and provide further validation of the FT-IR/IRS adsorption density equation in the low concentration range.

The dynamic nature of contact angles as measured by atomic force microscopy.

Atomic force microscopy appears to be a useful tool for determining the contact angle for small particles. It is shown in this paper that the contact angle of a spherical polyethylene particle changes with the speed of the AFM piezoelectric translator. Such dynamic behavior of the contact angle and other uncertainties such as the position of the three-phase contact on the particle surface during bubble-particle interaction make it difficult to decide whether or not the AFM single-particle contact angle can be used to describe the hydrophobic state of the particle surface.

Surface force measurements at kaolinite edge surfaces using atomic force microscopy.

Fundamental results obtained from research on the properties of the edge surfaces of kaolinite particles (~500 nm) are reported. Of particular significance was the development of the experimental protocol. Well-ordered kaolinite edge surfaces were prepared as an epoxy resin sandwich structure having layered kaolinite particles in the center of the epoxy resin sandwich. Images of the sectioned kaolinite edge surfaces were examined by atomic force microscopy (AFM), and the average thickness of kaolinite particles in this study was determined to be 38.3 nm±11.7 nm. Furthermore, the surface charge of the kaolinite edge surfaces was evaluated with a super sharp Si tip. The point of zero charge (PZC) of the kaolinite edge surface was determined to be below pH 4, in contrast to the traditional view that the edge surfaces of kaolinite particles may carry a positive charge at pH 4. This lower PZC of the kaolinite edge surface was attributed to the lack of isomorphous substitution in the silica tetrahedral layer when compared to the PZC for the muscovite edge surface. Our results are consistent with the particle aggregation and flotation behavior of kaolinite, and should provide the basis for improved flotation strategies leading to the efficient recovery and utilization of mineral and energy resources.