Enhanced Triboelectric Charge Stability by Air-Stable Radicals.

This paper demonstrates that air-stable radicals enhance the stability of triboelectric charge on surfaces. While charge on surfaces is often undesirable (e.g., static discharge), improved charge retention can benefit specific applications such as air filtration. Here, it is shown that self-assembled monolayers (SAMs) containing air-stable radicals, 2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (TEMPO), hold the charge longer than those without TEMPO. Charging and retention are monitored by Kelvin Probe Force Microscopy (KPFM) as a function of time. Without the radicals on the surface, charge retention increases with the water contact angle (hydrophobicity), consistent with the understanding that surface water molecules can accelerate charge dissipation. Yet, the most prolonged charge retention is observed in surfaces treated with TEMPO, which are more hydrophilic than untreated control surfaces. The charge retention decreases with reducing radical density by etching the TEMPO-silane with tetrabutylammonium fluoride (TBAF) or scavenging the radicals with ascorbic acid. These results suggest a pathway toward increasing the lifetime of triboelectric charges, which may enhance air filtration, improve tribocharging for patterning charges on surfaces, or boost triboelectric energy harvesting.

ab initio study of Mn-based systems for oxidative degradation.

Organic contaminants can be removed from water/wastewater by oxidative degradation using oxidants such as manganese oxides and/or aqueous manganese ions. The Mn species show a wide range of activity, which is related to the oxidation state of Mn. Here, we use ab initio molecular dynamics simulations to address Mn oxidation states in these systems. We first develop a correlation between Mn partial atomic charge and the oxidation state based on results of 31 simulations on known Mn aqueous complexes. The results collapse to a master curve; the dependence of partial atomic charge on oxidation state weakens with increasing oxidation state, which concurs with a previously proposed feedback effect. This correlation is then used to address oxidation states in Mn systems used as oxidants. Simulations of MnO2 polymorphs immersed in water give average oxidation states (AOS) in excellent agreement with experimental results, in that ß-MnO2 has the highest AOS, α-MnO2 has an intermediate AOS, and δ-MnO2 has the lowest AOS. Furthermore, the oxidation state varies substantially with the atom's environment, and these structures include Mn(III) and Mn(V) species that are expected to be active. In regard to the MnO4-/HSO3-/O2 system that has been shown to be a highly effective oxidant, we propose a novel Mn complex that could give rise to the oxidative activity, where Mn(III) is stabilized by sulfite and dissolved O2 ligands. Our simulations also show that the O2 would be activated to O22- in this complex under acidic conditions, and could lead to the formation of OH radicals that serve as oxidants.

Microscale Bipolar Charge Distributions on Surfaces after Liquid Wetting and Evaporation in an Electric Field.

Studies have shown that when insulator surfaces become electrostatically charged, complex spatial distributions of charge are produced, which are made up of micrometer-scale regions of both charge polarities. The origin of these charge patterns, often called "charge mosaics", is not understood. Here, we carried out controlled Kelvin force microscopy experiments on microfabricated interdigitated electrode systems to show that the process of wetting a surface by a liquid followed by evaporation of the liquid in an electric field can lead to neighboring micrometer-scale regions of positive and negative charge, which remain stable long after the electric field is removed. We thus suggest that local electric fields, perhaps due to the existing charge on the surface, can act in concert with liquid evaporation to contribute to the creation of charge mosaics.

Relative importance of electrostatic and van der Waals forces in particle adhesion to rough conducting surfaces.

It is commonly assumed that van der Waals forces dominate adhesion in dry systems and electrostatic forces are of second order importance and can be safely neglected. This is unambiguously the case for particles interacting with flat surfaces. However, all surfaces have some degree of roughness. Here we calculate the electrostatic and van der Waals contributions to adhesion for a polarizable particle contacting a rough conducting surface. For van der Waals forces, surface roughness can diminish the force by several orders of magnitude. In contrast, for electrostatic forces, surface roughness affects the force only slightly, and in some regimes it actually increases the force. Since van der Waals forces decrease far more strongly with surface roughness than electrostatic forces, surface roughness acts to increase the relative importance of electrostatic forces to adhesion. We find that for a particle contacting a rough conducting surface, electrostatic forces can be dominant for particle sizes as small as ∼1-10 µm.

Particle adhesion to rough surfaces.

While particle adhesion to smooth surfaces is well understood, real surfaces are not perfectly smooth, and the effects of surface roughness on adhesion are not easily characterized. We develop a theory for the effects of surface roughness on the strength of particle adhesion due to van der Waals forces, in the Derjaguin-Muller-Toporov (DMT)-type adhesion regime. We first address a well-defined rough surface created by embedding spheres in a smooth substrate, which had been previously examined experimentally. We derive an analytic expression for the adhesive force of particles to this well-defined surface, with the key distinction from the previous work being the inclusion of interactions from surface asperities not in direct contact with the particle. We show that our theory is in good agreement with experimental results in the DMT regime. Within appropriate limits, we extend our theory to general rough surfaces and verify the theory by comparing to the exact numerical results. We show that the interactions from surface asperities not in direct contact with the particle are the dominant contribution to the adhesive force under some conditions, and our theory predicts the experimental and numerical adhesion forces very accurately.

Extraction of bioactive compounds from mango (Mangifera indica L. var. Carabao) seed kernel with ethanol-water binary solvent systems.

Mango seed kernel, a by-product of the processing industry, can be valorized as a potential source of bioactive compounds. Binary mixtures of ethanol and water, used in solid-liquid extraction (SLE), have drawn interest as an effective means of recovering phytochemicals from plant materials because these solvents can be used in food applications and their synergistic effect makes them a superior solvent over their pure counterparts. Total phenolic content (TPC) and HPLC chromatograms of each ethanolic extract revealed that ethanol concentration had a significant effect on phenolic compound recovery, wherein, TPC of mango kernel varied from 18.19 to 101.68 mg gallic acid equivalence (GAE) per gram of sample. Subsequently, the antioxidant activities (AOAc) of the extracts, measured by scavenging activities with the DPPH+ (1,1-diphenyl-2-picrylhydrazyl) radical and ferric reducing antioxidant power (FRAP) assay, ranged from 8.19 to 85.45 mmol/L and 3.82-55.61 mmol/L Trolox equivalence, respectively. The solvent containing 50% (w/w) ethanol-water had the highest TPC and exhibited the most potent reducing and radical scavenging activities. With the use of an HPLC-UV/Vis, gallic acid, caffeic acid, rutin and penta-O-galloyl-ß-d-glucose were identified to be present in the mango seed kernel. Results show that the mango seed kernel is a viable source of bioactive compounds which can be recovered with water-ethanol binary solvent systems.

Humidity transforms immobile surface charges into mobile charges during triboelectric charging.

Triboelectric charging - which children see when they rub balloons on their hair - has important consequences in many industries and natural phenomena. Despite its importance, the identity of the charge carriers that lead to triboelectric charging is uncertain. For polymers, previous X-ray photoelectron spectroscopy studies definitively show that bonds break during triboelectric charging. Others have argued that a pair of co-located bond breaks release a charged fragment that acts as the charge carrier for triboelectric charging. We describe an alternative process based on density functional theory results showing that charged fragments, in the presence of water, will react to form neutral fragments and H+ or OH- ions. These results show that a single bond break, which is more likely than a pair of co-located bond breaks, can then create tethered polymer fragments that in humidity will generate mobile H+ or OH- charge carriers for triboelectric charging.

Single-stranded DNA oligomer brush structure is dominated by intramolecular interactions mediated by the ion environment.

Single-stranded DNA (ssDNA) brushes, in which ssDNA oligomers are tethered to surfaces in dense monolayers, are being investigated for potential biosensing applications. The structure of the brush can affect the selectivity and the hybridization efficiency of the device. The structure is commonly thought to result from the balance of intramolecular interactions, intermolecular interactions within the monolayer, and molecule-surface interactions. Here, we test the hypothesis that ssDNA oligomer brush structure is dominated by intramolecular interactions. We use AFM to measure the height of an ssDNA brush and molecular dynamics to simulate the end-to-end distance, both as a function of ionic strength of the surrounding solution. The brush height and the molecule end-to-end distance match quantitatively, providing evidence that the brush structure is dominated by intramolecular interactions (mediated by ions). The physical basis of the intramolecular interactions is elucidated by the simulations.

The interplay of structure and dynamics at grain boundaries.

Molecular simulations are carried out to address the structure and atomic diffusion at grain boundaries. We use an inherent structure approach, which maps each configuration in a molecular dynamics trajectory to the potential energy minimum ("inherent structure") it would reach by a steepest descent quench. Dynamics are then decomposed into a combination of displacements within an inherent structure and transitions between inherent structures. The inherent structure approach reveals a simple structural picture of the grain boundary that is normally obscured by the thermal motion. We apply our methodology to polycrystalline MgO. Grain boundary atoms are identified as atoms that are undercoordinated in the inherent structure, relative to those in the perfect crystal. Our method enables the calculation of grain boundary diffusion coefficients without arbitrary assumptions about which atoms or spatial regions belong to the grain boundary, and the results are shown to be consistent with estimates from experiments. The inherent structure approach also enables the elementary steps in the diffusion process to be elucidated. We show that the process in MgO grain boundaries primarily involves vacancy hops, but that there is also significant motion of other nearby atoms during such a hop.

Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, 15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations.

Polymerization of benzoxazine resins is indicated by the disappearance of a 960-900 cm-1 band in infrared spectroscopy (IR). Historically, this band was assigned to the C-H out-of-plane bending of the benzene to which the oxazine ring is attached. This study shows that this band is a mixture of the O-C2 stretching of the oxazine ring and the phenolic ring vibrational modes. Vibrational frequencies of 3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazine (PH-a) and 3-(tert-butyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine (PH-t) are compared with isotope-exchanged and all-substituted compounds. Deuterated benzoxazine monomers, 15N-isotope exchanged benzoxazine monomers, and all-substituted benzoxazine monomers without aromatic C-H groups are synthesized and studied meticulously. The various isotopic-exchanges involved deuteration around the benzene ring of phenol, selective deuteration of each CH2 in the O-CH2-N (2) and N-CH2-Ar (4) positions on the oxazine ring, or simultaneous deuteration of both positions. The chemical structures were confirmed by 1H nuclear magnetic resonance spectroscopy (1H NMR). The IR and Raman spectra of each compound are compared. Further analysis of 15N isotope-exchanged PH-a indicates the influence of the nitrogen isotope on the band position, both experimentally and theoretically. This finding is important for polymerization studies of benzoxazines that utilize vibrational spectroscopy.

Effect of surfactant shape on solvophobicity and surface activity in alcohol-water systems.

Here we study the relationship between a surfactant's molecular shape and its tendency to partition to the interface in ethanol-water mixtures. In general, finding surfactants that are effective in alcohol-water mixtures is more challenging than finding ones that are effective in pure water. This is because the solvophobic effect that partitions surfactants from bulk solution to the interface becomes weaker as ethanol concentration increases. We use experiments and molecular dynamics to observe the effects of increasing surfactant tail length or width. The results show that increasing surfactant tail length causes the surfactant to partition to the surface better in low ethanol concentrations, but not at high ethanol concentrations. In comparison, increasing surfactant tail width causes the surfactant to partition to the surface better at higher concentrations of ethanol. We examine the liquid structure to elucidate the mechanisms that weaken the partitioning effect as ethanol concentration increases. Ethanol-water mixtures are nanoscopically heterogeneous with protic and aprotic regions in the bulk solution. We see that the surfactant tail is most likely to be solvated in the aprotic regions where it perturbs fewer hydrogen bonds.

Surface activity of octanoic acid in ethanol-water solutions from molecular simulation and experiment.

The surface activity of a typical surfactant, octanoic acid (OA), in ethanol-water solutions is investigated with a combined experimental and molecular simulation approach. The experiments show that OA reduces the surface tension of ethanol-water solutions at low ethanol concentration, but the effectiveness decreases with increasing ethanol concentration and vanishes for ethanol concentrations above 60%. Molecular dynamics simulations are used to obtain free energy landscapes for OA as a function of the distance from the surface. The free energy driving force pushing OA to the surface decreases with increasing ethanol concentration, and becomes insignificant (i.e., less than kT) for ethanol concentrations above 70%. Thus, the decrease in the effectiveness of OA in reducing the surface tension at higher ethanol concentrations can be attributed to the decrease in the free energy driving force keeping OA at the surface. We expect these results to apply generally to hydrocarbon-based surfactants.

Particle size effects in particle-particle triboelectric charging studied with an integrated fluidized bed and electrostatic separator system.

Fundamental studies of triboelectric charging of granular materials via particle-particle contact are challenging to control and interpret because of foreign material surfaces that are difficult to avoid during contacting and measurement. The measurement of particle charge itself can also induce charging, altering results. Here, we introduce a completely integrated fluidized bed and electrostatic separator system that charges particles solely by interparticle interactions and characterizes their charge on line. Particles are contacted in a free-surface fluidized bed (no reactor walls) with a well-controlled fountain-like flow to regulate particle-particle contact. The charged particles in the fountain are transferred by a pulsed jet of air to the top of a vertically-oriented electrostatic separator consisting of two electrodes at oppositely biased high voltage. The free-falling particles migrate towards the electrodes of opposite charge and are collected by an array of cups where their charge and size can be determined. We carried out experiments on a bidisperse size mixture of soda lime glass particles with systematically varying ratios of concentration. Results show that larger particles fall close to the negative electrode and smaller particles fall close to the positive electrode, consistent with theory and prior experiments that larger particles charge positively and smaller particles charge negatively. The segregation of particles by charge for one of the size components is strongest when its collisions are mostly with particles of the other size component; thus, small particles segregate most strongly to the negative sample when their concentration in the mixture is small (and analogous results occur for the large particles). Furthermore, we find additional size segregation due to granular flow, whereby the fountain becomes enriched in larger particles as the smaller particles are preferentially expelled from the fountain.

Insertion of liquid crystal molecules into hydrocarbon monolayers.

Atomistic molecular dynamics simulations were carried out to investigate the molecular mechanisms of vertical surface alignment of liquid crystals. We study the insertion of nCB (4-Cyano-4'-n-biphenyl) molecules with n = 0,…,6 into a bent-core liquid crystal monolayer that was recently found to provide good vertical alignment for liquid crystals. The results suggest a complex-free energy landscape for the liquid crystal within the layer. The preferred insertion direction of the nCB molecules (core or tail first) varies with n, which can be explained by entropic considerations. The role of the dipole moments was found to be negligible. As vertical alignment is the leading form of present day liquid crystal displays (LCD), these results will help guide improvement of the LCD technology, as well as lend insight into the more general problem of insertion of biological and other molecules into lipid and surfactant layers.

Atomic mobility in a polymer glass after shear and thermal cycles.

Molecular dynamics simulations and energy landscape analyses are carried out to study the atomic mobility of a polymer glass during the physical aging process that follows shear and thermal cycles. The mobility is characterized by the fraction of atoms moving more than their diameter in a given time interval. The mobility is enhanced after a shear or thermal cycle, and this enhancement decays with time. These mobility results are related to the position of the system on the energy landscape, as characterized by the average energy of the energy minima visited by the system; the mobility over longer time scales increases with the average energy of the energy minima visited, but the mobility over shorter time scales does not show a correlation with this average energy. From these results, we conclude that barriers separating metabasins composed of proximate energy minima, rather than barriers between individual energy minima, control the physical aging process. We also show that, after some finite time, the mobility following shear and thermal cycle appears to behave similarly to the mobility without perturbations; however, the system is at different regions of the energy landscape in these two cases, which implies that mobility alone does not characterize the state of the system.

The unpredictability of electrostatic charging.

Capricious charges: the electrostatic charging that occurs when two surfaces come into contact is familiar to everyone, and has been known for millennia. Nonetheless, the scientific understanding of the phenomenon is poor, and it is not possible to reliably predict which surface will charge positively and which will charge negatively. Recent work shows why electrostatic charging may never be predictable.

Sheared polymer glass and the question of mechanical rejuvenation.

There has been much recent debate as to whether mechanical deformation reverses the aging of a material, and returns it to a structure characteristic of the system at a higher temperature. We use molecular dynamics simulation to address this problem by carrying out shear and temperature increase simulation on atactic glassy polystyrene. Our results show explicitly that the structure (as quantified by the torsion population) changes associated with shear and temperature increase are quantitatively--and in some cases qualitatively--different. This is due to the competition between rejuvenation and physical aging, and we show this by carrying out a relaxation simulation. The conclusion agrees with those from previous experiments and simulations, which were suggestive of mechanical deformation moving the system to structures distinct from those reached during thermal treatment.

Isotope fractionation by thermal diffusion in silicate melts.

Isotopes fractionate in thermal gradients, but there is little quantitative understanding of this effect in complex fluids. Here we present results of experiments and molecular dynamics simulations on silicate melts. We show that isotope fractionation arises from classical mechanical effects, and that a scaling relation based on Chapman-Enskog theory predicts the behavior seen in complex fluids without arbitrary fitting parameters. The scaling analysis reveals that network forming elements (Si and O) fractionate significantly less than network modifiers (e.g., Mg, Ca, Fe, Sr, Hf, and U).

Strain-induced reversal of charge transfer in contact electrification.

We have contact! Material strain can have a dominating effect on contact electrification. When a deflated (relaxed) balloon is rubbed against teflon, the teflon surface charges positively, but when the same balloon is inflated (strained), the teflon surface charges negatively. This result illustrates that material strain can control contact electrification and alter the driving force of some (yet unknown) charge-transfer species.