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.

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.

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.

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.

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.

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.

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.

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.

Influence of ionic strength on the surface charge and interaction of layered silicate particles.

The surface charge densities and surface potentials of selected phyllosilicate surfaces were calculated from AFM surface force measurements and reported as a function of ionic strength at pH 5.6. The results show that the silica faces of clay minerals follow the constant surface charge model because of isomorphous substitution in the silica tetrahedral layer. A decreasing surface charge density sequence was observed as follows: muscovite silica face>kaolinite silica face>talc silica face, which is expected to be due to the extent of isomorphous substitution. In contrast, at pH 5.6, the alumina face and the edge surface of kaolinite follow the constant surface potential model with increasing ionic strength, and the surface charge density increased with increasing ionic strength. The cluster size of suspended kaolinite particles at pH 5.6 was found to increase with increasing ionic strength due to an increase in the surface charge density for the alumina face and the edge surface. However, the cluster size decreased at 100mM KCl as a result of an unexpected decrease in the surface charge of the alumina face. When the ionic strength continued to increase above 100mM KCl, the van der Waals attraction dominated and larger clusters of micron size were stabilized.

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.

The primacy of physicochemical characterization of nanomaterials for reliable toxicity assessment: a review of the zebrafish nanotoxicology model.

Engineered nanomaterials (ENMs) have become increasingly prevalent in the past two decades in academic, medical, commercial, and industrial settings. The unique properties imbued with nanoparticles, as the physiochemical properties change from the bulk material to the surface atoms, present unique and often challenging characteristics that larger macromolecules do not possess. While nanoparticle characteristics are indeed exciting for unique chemistries, surface properties, and diverse applications, reports of toxicity and environmental impacts have tempered this enthusiasm and given cause for an exponential increase for concomitant nanotoxicology assessment. Currently, nanotoxicology is a steadily growing with new literature and studies being published more frequently than ever before; however, the literature reveals clear, inconsistent trends in nanotoxicological assessment. At the heart of this issue are several key problems including the lack of validated testing protocols and models, further compounded by inadequate physicochemical characterization of the nanomaterials in question and the seminal feedback loop of chemistry to biology back to chemistry. Zebrafish (Danio rerio) are emerging as a strong nanotoxicity model of choice for ease of use, optical transparency, cost, and high degree of genomic homology to humans. This review attempts to amass all contemporary nanotoxicology studies done with the zebrafish and present as much relevant information on physicochemical characteristics as possible. While this report is primarily a physicochemical summary of nanotoxicity studies, we wish to strongly emphasize that for the proper evolution of nanotoxicology, there must be a strong marriage between the physical and biological sciences. More often than not, nanotoxicology studies are reported by groups dominated by one discipline or the other. Regardless of the starting point, nanotoxicology must be seen as an iterative process between chemistry and biology. It is our sincere hope that the future will introduce a paradigm shift in the approach to nanotoxicology with multidisciplinary groups for data analysis to produce predictive and correlative models for the end goal of rapid preclinical development of new therapeutics into the clinic or insertion into environmental protection.

Surface charge and wetting characteristics of layered silicate minerals.

The surface characteristics, including surface charge and wettability, of layered silicates are reviewed based on experimental results and molecular dynamics simulation (MDS) results. The surface charge features of important layered silicates including mica, talc, and kaolinite are described from atomic force microscopy (AFM) measurements, electrophoresis measurements, and/or results from potentiometric titration. In addition, the wetting characteristics of the silica tetrahedral surface which is common to all layered silicates are examined with different experimental techniques and results are discussed. The wettability of trilayer silicates and bilayer silicates is discussed, particularly the wettability of the silica tetrahedral face and alumina octahedral face of kaolinite based on MDS results as well as recent AFM results.

Indirect electrochemical Cr(III) oxidation in KOH solutions at an Au electrode: the role of oxygen reduction reaction.

The indirect electro-oxidation of Cr(III) by in situ generated superoxide at a gold electrode has been investigated in KOH solutions using cyclic voltammetry and UV-vis spectroscopy. It is observed that the indirect Cr(III) oxidation behavior is substantially affected by the media pH and there is a pH-modulated oxygen reduction reaction (ORR) process to generate reactive oxygen species which promotes Cr(III) oxidation. The ORR in KOH solutions is attributed to a quasi-reversible diffusion-controlled reaction. In dilute KOH solution (0.2 M), 4e reduction occurs and no reactive oxygen species are generated for the indirect Cr(III) oxidation. Moreover, Cr(III) oxidation is inhibited due to competition for the electrode active sites. As the alkaline concentration increases (3.0 M), the protonation of superoxide is greatly suppressed, and thus, 1e ORR to generate superoxide is observed. This change in mechanism facilitates the indirect Cr(III) oxidation through the superoxide as a mediator to oxidize Cr(III) to Cr(IV), which is the rate-determining step of Cr(III) oxidation to Cr(VI).

Particle interactions in kaolinite suspensions and corresponding aggregate structures.

The surface charge densities of the silica face surface and the alumina face surface of kaolinite particles, recently determined from surface force measurements using atomic force microscopy, show a distinct dependence on the pH of the system. The silica face was found to be negatively charged at pH>4, whereas the alumina face surface was found to be positively charged at pH<6, and negatively charged at pH>8. The surface charge densities of the silica face and the alumina face were utilized in this study to determine the interaction energies between different surfaces of kaolinite particles. Results indicate that the silica face-alumina face interaction is dominant for kaolinite particle aggregation at low pH. This face-face association increases the stacking of kaolinite layers, and thereby promotes the edge-face (edge-silica face and edge-alumina face) and face-face (silica face-alumina face) associations with increasing pH, and hence the maximum shear-yield stress at pH 5-5.5. With further increase in pH, the face-face and edge-face association decreases due to increasing surface charge density on the silica face and the edge surfaces, and decreasing surface charge density on the alumina face. At high pH, all kaolinite surfaces become negatively charged, kaolinite particles are dispersed, and the suspension is stabilized. The face-face association at low pH has been confirmed from cryo-SEM images of kaolinite aggregates taken from suspension which show that the particles are mostly organized in a face-face and edge-face manner. At higher pH conditions, the cryo-SEM images of the kaolinite aggregates reveal a lower degree of consolidation and the edge-edge association is evident.

Understanding the role of ion interactions in soluble salt flotation with alkylammonium and alkylsulfate collectors.

There is anecdotal evidence for the significant effects of salt ions on the flotation separation of minerals using process water of high salt content. Examples include flotation of soluble salt minerals such as potash, trona and borax in brine solutions using alkylammonium and alkylsulfate collectors such as dodecylamine hydrochloride and sodium dodecylsulfate. Although some of the effects are expected, some do not seem to be encompassed by classical theories of colloid science. Several experimental and modeling techniques for determining solution viscosity, surface tension, bubble-particle attachment time, contact angle, and molecular dynamics simulation have been used to provide further information on air-solution and solid-solution interfacial phenomena, especially with respect to the interfacial water structure due to the presence of dissolved ions. In addition atomic force microscopy, and sum frequency generation vibrational spectroscopy have been used to provide further information on surface states. These studies indicate that the ion specificity effect is the most significant factor influencing flotation in brine solutions.

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.

Crystal lattice imaging of the silica and alumina faces of kaolinite using atomic force microscopy.

The crystal lattice images of the two faces of kaolinite (the silica face and the alumina face) have been obtained using contact-mode atomic force microscopy (AFM) under ambient conditions. Lattice resolution images reveal the hexagonal surface lattice of these two faces of kaolinite. Analysis of the silica face of kaolinite showed that the hexagonal surface lattice ring of oxygen atoms had a periodicity of 0.50±0.04nm between neighboring oxygen atoms, which is in good agreement with the surface lattice structure of the mica basal plane. The center of the hexagonal ring of oxygen atoms is vacant. Analysis of the alumina face of kaolinite showed that the hexagonal surface lattice ring of hydroxyls surround a hydroxyl in the center of the ring. The atomic spacing between neighboring hydroxyls was determined as 0.36±0.04nm. Ordering of the kaolinite particles for examination of the silica and alumina surfaces was accomplished using different substrates, a procedure previously established. Crystal lattice imaging supports previous results and independently confirms that the two faces of kaolinite have been properly identified.

Surface force measurements at the basal planes of ordered kaolinite particles.

An experimental procedure is presented to order kaolinite particles on substrates for interrogation of the two basal plane surfaces by atomic force microscopy. Surface force measurements were performed between a silicon nitride tip and each of the two faces (silica tetrahedral face and alumina octahedral face) of kaolinite in 1 mM KCl solution at pH 4, 5, 6, 8 and 10, using atomic force microscopy. The colloidal force measurements reveal that the silica tetrahedral face of kaolinite is negatively charged at pH>4, whereas the alumina octahedral face of kaolinite is positively charged at pH<6, and negatively charged at pH>8. Such measurements have not been reported previously and the results suggest that the iso-electric point of the silica tetrahedral face is at pH<4, and that the iso-electric point of the alumina octahedral face lies between pH 6 and 8. These results contradict the generally accepted view that basal plane surfaces of kaolinite carry a permanent negative charge due to minor substitution of Al(3+) for Si(4+) in the silica tetrahedral layer, and suggest some surface charge dependency of the two faces with respect to solution pH. With this new information it may be possible to further explain the electrokinetic behavior of kaolinite particles, and their interactions in aqueous suspensions.

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.

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.