Balance Of Electrostatic Forces Research Articles

Development of a high precision electrostatic force balance for measuring quantity of dispensed fluid as a new calibration standard for the becquerel

The 2019 redefinition of the kilogram not only changes the way mass is defined but also broadens the horizon for a direct realization of other standards. The true becquerel project at the national institute of standards and technology is creating a new paradigm for realization and dissemination of radionuclide activity. Standard reference materials for radioactivity are supplied as aqueous solutions of specific radionuclides which are characterized by massic activity in the units becquerel per gram of solution, Bq/g. The new method requires measuring the mass of a few milligrams of dispensed radionuclide liquid solution. An electrostatic force balance is used, due to its suitability for a milligram mass range. The goal is to measure the mass of dispensed fluid of 1 mg–5 mg with a relative uncertainty of less than 0.05%. A description of the balance operation is presented. Results of preliminary measurements with a reference mass indicate relative standard deviations less than 0.5% for tens of tests and differ 0.54% or less from an independent measurement of the reference mass.

Effects of charge and size on the coadsorption of counterionic colloids in Gibbs monolayers

This study uses a coarse-grained Monte Carlo algorithm to model and simulate the coadsorption of a binary mixture of counterionic colloids in Gibbs monolayers. These monolayers form at a idealized air-water interface, with one non-soluble species confined at the interface and the second one partially soluble in the aqueous phase. The investigation focuses on the effect of colloidal size and charge on the thermodynamics and microstructure of the monolayer. We find that the composition of the monolayer evolves non-trivially with surface coverage, depending on the balance of steric and electrostatic forces. When the electrostatic interactions are weak, the soluble species is expelled from the monolayer upon compression, yielding a phase behaviour particularly sensitive to the relative size of the soluble and non-soluble colloids. By contrast, strong electrostatic interactions favour the stabilization of the soluble particles in the monolayer and the formation of quasi-equimolar fluids, with only a weak dependence on particle size. The combination of these phenomena results in the formation of a number of two-dimensional mesoscopic arrangements in the monolayer, ranging from diluted gas-phase behaviour to domains of aggregates and percolates, and to incipient crystalline structures.

Local Environments Created by the Ligand Coating of Nanoparticles and Their Implications for Sensing and Surface Reactions.

ConspectusThe ligand shells of colloidal nanoparticles (NPs) can serve different purposes. In general, they provide colloidal stability by introducing steric repulsion between NPs. In the context of biological applications, the ligand shell plays a critical role in targeting, enabling NPs to achieve specific biodistributions. However, there is also another important feature of the ligand shell of NPs, namely, the creation of a local environment differing from the bulk of the solvent in which the NPs are dispersed. It is known that charged ligand shells can attract or repel ions and change the effective charge of a NP through Debye-Hückel screening. Positively charged ions, such as H+ (or H3O+) are attracted to negatively charged surfaces, whereas negatively charged ions, such as Cl- are repelled. The distribution of the ions around charged NP surfaces is a radial function of distance from the center of the NP, which is governed by a balance of electrostatic forces and entropy of ions and ligands. As a result, the ion concentration at the NP surface is different from its bulk equilibrium concentration, i.e., the charged ligand shell around the NPs has formed a distinct local environment. This not only applies to charged ligand shells but also follows a more general principle of induced condensation and depletion. Polar/apolar ligand shells, for example, result in a locally increased concentration of polar/apolar molecules. Similar effects can be seen for biocatalysts like enzymes immobilized in nanoporous host structures, which provide a special environment due to their surface chemistry and geometrical nanoconfinement. The formation of a local environment close to the ligand shell of NPs has profound implications for NP sensing applications. As a result, analyte concentrations close to the ligand shell, which are the ones that are measured, may be very different from the analyte concentrations in bulk. Based on previous work describing this effect, it will be discussed herein how such local environments, created by the choice of used ligands, may allow for tailoring the NPs' sensing properties. In general, the ligand shell around NPs can be attractive/repulsive for molecules with distinct properties and thus forms an environment that can modulate the specific response. Such local environments can also be optimized to modulate chemical reactions close to the NP surface (for example, by size filtering within pores) or to attract specific low abundance proteins. The importance hereby is that this is based on interaction with low selectivity between the ligands and the target molecules.

Методический подход к изучению седиментационной устойчивости тонкодисперсных отходов переработки минерального сырья по спутниковым данным загрязнения природных водоемов

The paper presents the results of the study of sedimentation stability of suspended finely-dispersed mineral particles based on satellite observations of their aggregation and sedimentation. The authors studied satellite data on self-purification of subarctic lakes polluted by apatite-nepheline, iron, and copper-nickel ore processing wastes. The multispectral images of lakes taken by Sentinel-2 spacecraft have allowed determining the average size of suspended finely-dispersed mineral processing wastes and the density of particle size distribution. To account for aggregation, the authors have designed a computer model of the dynamics of suspended particles and have set parameters of the forces of electrostatic and dispersion interactions of mineral particles from the Kola deposits. It is shown that the balance of repulsive electrostatic and dispersion attractive forces appears in the generation of aggregates of finely-dispersed mineral particles with characteristic fractal dimension, using Nepheline, Hematite, Quartz, and Pyrite as examples. The authors have developed an algorithm for matching the computer simulation results of the dynamics of suspended particles with the results of satellite images processing of lakes. The developed methodological approach makes it possible to determine the sedimentation stability of lakes’ pollution by finedispersed mineral processing wastes without surface observations. The research results allow calculating the sedimentation velocity of mineral particles and their aggregates of a given size. The good correspondence between the calculated parameters of particles aggregation and sedimentation and satellite observations data can be used to monitor the pollution of water bodies when adapting mineral processing technologies to modern production ecologization requirements, as well as to assess the waterenvironmental potential of the territory for rational management of natural resources.

Assembly of planar chiral superlattices from achiral building blocks

The spontaneous assembly of chiral structures from building blocks that lack chirality is fundamentally important for colloidal chemistry and has implications for the formation of advanced optical materials. Here, we find that purified achiral gold tetrahedron-shaped nanoparticles assemble into two-dimensional superlattices that exhibit planar chirality under a balance of repulsive electrostatic and attractive van der Waals and depletion forces. A model accounting for these interactions shows that the growth of planar structures is kinetically preferred over similar three-dimensional products, explaining their selective formation. Exploration and mapping of different packing symmetries demonstrates that the hexagonal chiral phase forms exclusively because of geometric constraints imposed by the presence of constituent tetrahedra with sharp tips. A formation mechanism is proposed in which the chiral phase nucleates from within a related 2D achiral phase by clockwise or counterclockwise rotation of tetrahedra about their central axis. These results lay the scientific foundation for the high-throughput assembly of planar chiral metamaterials.

Zwitterions Layer at but Do Not Screen Electrified Interfaces.

The role of ionic electrostatics in colloidal processes is well-understood in natural and applied contexts; however, the electrostatic contribution of zwitterions, known to be present in copious amounts in extremophiles, has not been extensively explored. In response, we studied the effects of glycine as a surrogate zwitterion, ion, and osmolyte on the electrostatic forces between negatively charged mica–mica and silica–silica interfaces. Our results reveal that while zwitterions layer at electrified interfaces and contribute to solutions’ osmolality, they do not affect at all the surface potentials, the electrostatic surface forces (magnitude and range), and solutions’ ionic conductivity across 0.3–30 mM glycine concentration. We infer that the zwitterionic structure imposes an inseparability among positive and negative charges and that this inseparability prevents the buildup of a counter-charge at interfaces. These elemental experimental results pinpoint how zwitterions enable extremophiles to cope with the osmotic stress without affecting finely tuned electrostatic force balance.

Osmotic pressure and swelling behavior of ionic microcapsules

Ionic microcapsules are hollow shells of hydrogel, typically 10-1000nm in radius, composed of cross-linked polymer networks that become charged and swollen in a good solvent. The ability of microcapsules to swell/deswell in response to changes in external stimuli (e.g., temperature, pH, and ionic strength) suits them to applications, such as drug delivery, biosensing, and catalysis. The equilibrium swelling behavior of ionic microcapsules is determined by a balance of electrostatic and elastic forces. The electrostatic component of the osmotic pressure of a microcapsule-the difference in the pressure between the inside and outside of the particle-plays a vital role in determining the swelling behavior. Within the spherical cell model, we derive exact expressions for the radial pressure profile and for the electrostatic and gel components of the osmotic pressure of a microcapsule, which we compute via Poisson-Boltzmann theory and molecular dynamics simulation. For the gel component, we use the Flory-Rehner theory of polymer networks. By combining the electrostatic and gel components of the osmotic pressure, we compute the equilibrium size of ionic microcapsules as a function of particle concentration, shell thickness, and valence. We predict concentration-driven deswelling at relatively low concentrations at which steric interactions between particles are weak and demonstrate that this response can be attributed to crowding-induced redistribution of counterions. Our approach may help to guide the designand applications of smart stimuli-responsive colloidal particles.

PH influence on the mechanisms of interaction between chitosan and ovalbumin: a multi-spectroscopic approach

The forces behind supramolecular structures (SS) formation need to be deeply understood, to allow identifying conditions under which their production can be optimized. In this study, a multi-spectroscopic approach was used to study SS formation upon ovalbumin (OVA) and chitosan (CHS) interaction in HCl solution, at pH 4.0 (both biomacromolecules positively charged) or 6.0 (biomacromolecules oppositely charged). UV-Vis and fluorescence spectroscopies showed that the biomacromolecules interacted and formed complexes without suggesting major modifications in the protein’s structure. The increase in CHS concentration progressively augmented the UV-vis absorption of OVA-CHS structures at 278 nm, whereas reduced the fluorescence emission of OVA, at both pH values, without promoting obvious shift of the maximum fluorescence wavelength, with an estimated center of spectral mass of <λ> = 341.41 ± 0.31 nm (at pH 4.0) and <λ> = 342.30 ± 0.40nm (at pH 6.0). Additionally, a conjoint analysis of CD and FT-IR spectroscopies revealed that the presence of CHS promoted alterations on the secondary structure of OVA. Indeed, CHS may have affected the hydrogen bonding network that stabilized the structure in the native protein, increasing the stability of α-helix and random coil structures, which was reflected in the loss of β-sheet. Results suggested that the OVA-CHS interaction, at pH 6.0, are driven mainly by electrostatic forces (attractive) and H-bonds. At pH 4.0, these macromolecules are more likely to interact through a balance of electrostatic forces (repulsive), hydrophobic interactions and H-bonds.

Dim and bright void regimes in capacitively-coupled RF complex plasmas

We demonstrate experimentally that the void in capacitively-coupled RF complex plasmas can exist in two qualitatively different regimes. The ‘bright’ void is characterized by bright plasma emission associated with the void, whereas the ‘dim’ void possesses no detectable emission feature. The transition from the dim to the bright regime occurs with an increase of the discharge power and has a discontinuous character. The discontinuity is manifested by a kink in the void size power dependencies. We reproduce the bright void (mechanically stabilized due to the balance of ion drag and electrostatic forces) by a simplified time-averaged 1D fluid model. To reproduce the dim void, we artificially include the radial ion diffusion into the continuity equation for ions, which allows to mechanically stabilize the void boundary due to very weak electrostatic forces. The electric field at the void boundary occurs to be so small that it, in accordance with the experimental observation, causes no void-related emission feature.

Toward a New Primary Standardization of Radionuclide Massic Activity Using Microcalorimetry and Quantitative Milligram-Scale Samples.

We present a new paradigm for the primary standardization of radionuclide activity per mass of solution (Bq/g). Two key enabling capabilities are 4π decay-energy spectrometry using chip-scale sub-Kelvin microcalorimeters and direct realization of mass by gravimetric inkjet dispensing using an electrostatic force balance. In contrast to traditional traceability, which typically relies on chemical separation of single-radionuclide samples, 4π integral counting, and additional spectrometry methods to verify purity, the system described here has both 4π counting efficiency and spectroscopic resolution sufficient to identify multiple radionuclides in the same sample at once. This enables primary standardization of activity concentrations of mixed-radionuclide samples. A major benefit of this capability, beyond metrology, is in assay of environmental and forensics samples, for which the quantification of multiplenuclide samples can be achieved where presently inhibited by interferences. This can be achieved without the need for chemical separations or efficiency tracers, thereby vastly reducing time, radioactive waste, and resulting measurement uncertainty.

Segmentation of dust particles and spatial distribution of ion density in dusty plasmas

In dusty plasmas, dust particles are levitated in balance of electrostatic, ion drag and gravitational forces. These forces depend on the size of the dust particles and discharge conditions. The dust particles can be segmented on the basis of their sizes, i.e., the dust particles are levitated at different positions depending on their sizes. In this work, the dust particles with two different sizes were observed in a plasma and they were divided into segments by changing radio frequency voltage put into the plasma. Meanwhile a numerical model analyzed the forces acting on the dust particles based on ion densities measured in the plasma. The dust particles were horizontally segmented in the plasma depending on their sizes. The lager ones were distributed outside of the smaller ones. This behaviors was explained by balance of the forces on the dust particles derived in the numerical model with the ambipolar diffusion taken into account.

Modeling deswelling, thermodynamics, structure, and dynamics in ionic microgel suspensions.

Ionic microgel particles in a good solvent swell to an equilibrium size determined by a balance of electrostatic and elastic forces. When crowded, ionic microgels deswell owing to a redistribution of microions inside and outside the particles. The concentration-dependent deswelling affects the interactions between the microgels and, consequently, the suspension properties. We present a comprehensive theoretical study of crowding effects on thermodynamic, structural, and dynamic properties of weakly cross-linked ionic microgels in a good solvent. The microgels are modeled as microion- and solvent-permeable colloidal spheres with fixed charge uniformly distributed over the polymer gel backbone, whose elastic and solvent-interaction free energies are described using the Flory-Rehner theory. Two mean-field methods for calculating the crowding-dependent microgel radius are investigated and combined with calculations of the net microgel charge characterizing the electrostatic part of an effective microgel pair potential, with charge renormalization accounted for. Using this effective pair potential, thermodynamic and static suspension properties are calculated, including the osmotic pressure and microgel pair distribution function. The latter is used in our calculations of dynamic suspension properties, where we account for hydrodynamic interactions. Results for diffusion and rheological properties are presented over ranges of microgel concentration and charge. We show that deswelling mildly enhances self- diffusion and collective diffusion and the osmotic pressure, lowers the suspension viscosity, and significantly shifts the suspension crystallization point to higher concentrations. This paper presents a bottom-up approach to efficiently computing suspension properties of crowded ionic microgels using single-particle characteristics.

Study of the polyribosyl-ribitol-phosphate precipitation mechanism by salts and organic solvents

Precipitation has been widely applied to purification and fractionation of biological macromolecules. Several physical-chemical factors contribute to the destabilization of those solutions, such as the nature of solvent employed, presence of salts, temperature, and concentration of the macromolecule. In the case of charged biopolymers, electrostatic forces are the major contributors to their stability in solution. However, the role of each variable and the exact mechanism of precipitation are not completely understood yet. The aim of this work was to study the precipitation of polyribosyl-ribitol-phosphate (PRP, a linear homogeneous anionic biopolymer) in presence of salts and non-solvents, in order to contribute to the elucidation of its precipitation mechanism. The solvents tested (acetone, ethanol, and isopropanol) presented distinct dielectric constants. The salts used (NH4Cl, NaCl, KCl, MgCl2, and CaCl2) differ by their cations. For each salt concentration, the solvent fraction that induces precipitation was identified and the dielectric constant of the bulk solution was calculated. Precipitation always occurred at well-defined combinations of solvents and salts. At low concentration of monovalent salts, there was a linear correlation between the logarithm of the salt concentration and the inverse of the medium dielectric constant at a defined precipitation point. This is a strong indication that the stability of the solution depends almost exclusively on the balance of electrostatic forces. This behavior is compatible with the DLVO modeling of colloidal systems. When divalent salts were used, low concentrations of the counterion were sufficient to induce precipitation, due to a phenomenon called ionic condensation. Apparently, PRP precipitates when around 90% of its charges are neutralized, value that is similar to charge neutralization for DNA precipitation.

Mobilization of Attached Clustered Colloids in Porous Media

AbstractThe models for colloidal mobilization in porous media are often based on Derjaguin‐Landau‐Verwey‐Overbeek interaction energy profiles. Despite abundant evidence on mobilization of particle clusters, the models to date have been limited to single colloid‐surface Derjaguin‐Landau‐Verwey‐Overbeek calculations. We show through visualization tests, qualitative and quantitative modeling, and data evaluation, that the widely accepted single colloid‐single surface isolation does not always adequately describe colloid behavior. The experiments were performed with kaolinite and latex particles mobilized from sand grains and glass beads in a transparent visualization cell. The particles were mobilized under increasing velocity and pH and decreasing salinity. The detachment conditions were determined by a torque balance of electrostatic, drag, lifting, and gravity forces, combined with a theory of a contact area between a single soft particle and a plane surface. The tests show that the calculations based on the mechanical equilibrium of a single particle on a plane surface significantly underestimate the critical detachment velocity. A better prediction is obtained using a cluster approximation. High‐resolution images taken during mobilization tests show 2‐12 particle clusters on media surface and in its proximity. The mechanical‐equilibrium calculations show that the attaching torque for clusters with assumed size and cylindrical shape is significantly higher than that for single particles. The critical detachment velocity of clusters, derived from the mechanical‐equilibrium force and torque balances, is higher than for single particles and provides a better fit to the experimental data. Our study suggests that a cluster approximation can accurately predict the mobilization of colloids in porous media.

Measurement of Submilligram Masses Using Electrostatic Force

The redefinition of the kilogram within the International system of units provides a direct link between mass and Planck’s constant. With this in place, it becomes possible to realize the kilogram using electrical metrology. We describe a method that scales this mass measurement approach to the submilligram level using an electrostatic force balance (EFB). Through traceable determination of capacitance, voltage, and position within the balance, the mass values of submilligram artifacts are determined. An uncertainty analysis is carried out on these measurements. Results show a substantial reduction in uncertainty relative to those currently available through conventional approaches based on kilogram subdivision for true mass. Since the EFB measurements are carried out in a vacuum, conversion to conventional mass requires an air buoyancy correction at the location of use. Despite additional uncertainty added by buoyancy correction, the use of the EFB method decreases uncertainty in submilligram mass measurement by an order of magnitude.

Comparison of electrostatic and photon pressure force references at the nanonewton level

This work describes a metrological comparison between nanonewton force references derived from an electrostatic force balance (EFB) and photon pressure from laser optical power in the 1 Watt range. An EFB is used to measure photon pressure force in the 10 nanonewton range from the reflection of a laser from a low (approximately 10−5) loss III–V semiconductor distributed Bragg reflector (DBR) mirror while the power of the reflected beam was simultaneously monitored with a traceable thermopile detector. This work demonstrates a method to link mass, force and laser power within the international system of units (SI) with explicit treatment of absorption, diffuse reflection, and a detailed uncertainty analysis. Additionally, it demonstrates a viable method to scale this force continuously using a pulsed laser technique while maintaining the constant thermal load necessary for precision measurement of nanonewton forces with a mechanical balance.

Ionic Liquids – Further Progress on the Fundamental Issues

Ionic liquids continue to challenge conventional descriptions of liquids and their behaviour. Indeed, the ever-increasing variety of ionic liquid compounds has generated a need for multiple descriptions of the different molecular families, including protic, aprotic, solvate, and metal coordination complex families of ionic liquids, that exhibit very different behaviours. Within families, the balance of long-range electrostatic and short-range dispersion forces plays out in nanoscale heterogeneity that also impacts markedly on properties. In this perspective, we highlight some of the issues in the field that continue to deserve further investigation and development at both the experimental and fundamental levels. We also propose a set of nomenclature abbreviations in an attempt to systematise the plethora of confusing abbreviations that appear in the field. The distinction between ionic liquids, ionic liquid–solvent mixtures, and deep eutectic solvents is also discussed.

Cationic polyacrylamide induced nanoparticles assembly in a cellulose nanofiber network

Polyacrylamides of different molecular weight, charges and dosages allow to control the retention and distribution of nanoparticles (NPs) in composites, and optimise composite properties and functionality. Our aim is to evaluate the effect of high molecular weight (13 MDa) cationic polyacrylamide (CPAM) charge and dosage on SiO2 (74 nm) NP’s assembly in cellulose nanofibers composites.Engineered cellulose/SiO2 composites were investigated by SEM, SAXS and DLS. SEM images show the local area retention of NPs into the cellulose matrix. SAXS provides an average NPs distribution and inter-NPs distance over complete volume of composite. DLS gives the hydrodynamic radius of CPAM adsorbed onto SiO2 NPs in a suspension.SAXS analysis reveals a structure conformation made of spherical SiO2 NPs core of diameter 74 nm surrounded by a CPAM polyelectrolyte shell 2.5 nm thick. Surprisingly, CPAM induced assembly of SiO2 NPs with constant inter-nanoparticle distance, which is irrelevant of polymer charge density. However, NPs retention in the cellulose fibre network increases with CPAM dosage. The assembly mechanism is governed by the balance of electrostatic and steric forces following CPAM coverage onto NPs and the inter-nanoparticle CPAM bridging conformation. This maintains the constant inter-nanoparticle distance and the assembly of NPs in the cellulose network.

Droplet coalescence as a potential marker for physicochemical fate of nanoemulsions during in-vitro small intestine digestion

Intestinal droplet coalescence is central to the lipid digestibility of oil-in-water nanoemulsions. In the present study, a methodology has been proposed to investigate the rheological transformations of nanoemulsions in response to the simulated conditions of small intestinal mechanical forces. The relationship between rheological changes and droplet coalescence phenomenon was probed. Elastic moduli of nanoemulsions attained a maximum at a specific point of digestion time, which was found to be characteristic of the emulsifier used. The onset of droplet coalescence showed evident dependence on the elastic modulus. The above correlation was quantified with an improved empirical model for droplet coalescence frequency. However, droplet coalescence was beyond the scope of rheology and depended on changes in the zeta potential of droplets, which eventually determined the release of free fatty acids. The critical time point was mapped at which the balance of rheological and electrostatic forces on droplet coalescence was altered as the lipolysis proceeds during the simulated small intestinal digestion of nanoemulsions.

Obtaining Thickness-Limited Electrospray Deposition for 3D Coating.

Electrospray processing utilizes the balance of electrostatic forces and surface tension within a charged spray to produce charged microdroplets with a narrow dispersion in size. In electrospray deposition, each droplet carries a small quantity of suspended material to a target substrate. Past electrospray deposition results fall into two major categories: (1) continuous spray of films onto conducting substrates and (2) spray of isolated droplets onto insulating substrates. A crossover regime, or a self-limited spray, has only been limitedly observed in the spray of insulating materials onto conductive substrates. In such sprays, a limiting thickness emerges, where the accumulation of charge repels further spray. In this study, we examined the parametric spray of several glassy polymers to both categorize past electrospray deposition results and uncover the critical parameters for thickness-limited sprays. The key parameters for determining the limiting thickness were (1) field strength and (2) spray temperature, related to (i) the necessary repulsive field and (ii) the ability for the deposited materials to swell in the carrier solvent vapor and redistribute charge. These control mechanisms can be applied to the uniform or controllably-varied microscale coating of complex three-dimensional objects.