Aqueous electrolyte surfaces in strong electric fields: molecular insight into nanoscale jets and bridges

Exposing aqueous surfaces to a strong electric field gives rise to interesting phenomena, such as formation of a floating water bridge or an eruption of a jet in electrospinning. In an effort to account for the phenomena at the molecular level, we performed molecular dynamics simulations using several protocols on both pure water and aqueous solutions of sodium chloride subjected to an electrostatic field. All simulations consistently point to the same mechanisms which govern the rearrangement of the originally planar surface. The results show that the phenomena are primarily governed by an orientational reordering of the water molecules driven by the applied field. It is demonstrated that, for pure water, a sufficiently strong field yields a columnar structure parallel to the field with an anisotropic arrangement of the water molecules with their dipole moments aligned along the applied field not only in the surface layer but over the entire cross section of the column. Nonetheless, the number of hydrogen bonds per molecule does not seem to be affected by the field regardless of its strength and molecule’s orientation. In the electrolyte solutions, the ionic charge is able to overcome the effect of the external field tending to arrange the water molecules radially in the first coordination shell of an ion. The ion–water interaction interferes thus with the water–electric field interaction, and the competition between these two forces (i.e., strength of the field versus concentration) provides the key mechanism determining the stability of the observed structures.     

Numerical assessment of ultrasound supported coalescence of water droplets in crude oil

In this study, a numerical assessment of the coalescence of binary water droplets in water-in-oil emulsion was conducted. The investigation addressed the effect of various parameters on the acoustic pressure and coalescence time of water droplets in oil phase. These include transducer material, initial droplet diameter (0.05–0.2 in), interfacial tension (0.012–0.082 N/m), dynamic viscosity (10.6–530 mPas), temperature (20–100 °C), US (ultra sound) frequency (26.04–43.53 kHz) and transducer power (2.5–40 W). The materials assessed are lead zirconate titanate (PZT), lithium niobate (LiNbO₃), zinc oxide (ZnO), aluminum nitride (AlN), polyvinylidene fluoride (PVDF), and barium titanate (BaTiO₃). The numerical simulation of the binary droplet coalescence showed good agreement with experimental data in the literature. The US implementation at a fixed frequency produced enhanced coalescence (t = 5.9–8.5 ms) as compared to gravitational settling (t = 9.8 ms). At different ultrasound (US) frequencies and transducer materials, variation in the acoustic pressure distribution was observed. Possible attenuation of the US waves, and the subsequent inhibitive coalescence effect under various US frequencies and viscosities, were discussed. Moreover, the results showed that the coalescence time reduced across the range of interfacial tensions which was considered. This reduction can be attributed to the fact that lower interfacial tension produces emulsions which are relatively more stable. Hence, at lower interface tension between the water and crude oil, there was more resistance to the coalescence of the water droplets due to their improved emulsion stability. The increment of the Weber number at higher droplet sizes leads to a delay in the recovery of the droplet to spherical forms after their starting deformation. These findings provide significant insights that could aid further developments in demulsification of crude oil emulsions under varying US and emulsion properties.     

Forming concentric double-emulsion droplets using electric fields

Double-emulsion droplets may be assembled into highly concentric shells using a uniform AC electric field to induce dipole/dipole interactions. The resulting force centers the inner droplet with respect to the outer shell if the outer droplet has a higher dielectric constant than the ambient, suspending liquid. The dielectric constant of the inner droplet does not influence this condition. Applying an electric field >10⁴ V_rms/m achieves centering of approximately 3–6 mm diameter droplets suspended in ～10 centipoise liquids within ～60 s. If the outer shell is electrically conductive, the effect depends strongly on frequency. In the case of the monomer-containing liquids requisite to forming foam shells for laser target fabrication, the electrical field frequency must be ～10 MHz or higher. Because of very stringent requirements imposed on the concentricity and sphericity of laser targets, electric field induced droplet distortion must be minimized. Consequently, the liquid constituents must be matched in density to ～0.1%.     

Deformation and breakup of aqueous drops in viscous oil under a uniform AC electric field

Electric coalescence in alternating current (AC) electric fields is an important electrical dehydration technology. The deformation and breakup of water drops are crucial to the application of this process. In this study, these procedures were examined experimentally in an AC electric field using a high-speed camera. The deformation and breakup of drops depend on the intensity and frequency of this field. Deformation is aggravated by the increase in frequency under a constant electric field strength. Furthermore, the electric strength of breakup weakens as the frequency increases. Thus, understanding the deformation process can help advance electrocoalescencer design.     

Field-induced self-assembly: does size matter?

ABSTRACT

Simulated external electric fields are applied to polarisable species containing either a monodisperse of bidisperse distribution of polarisabilities. The magnitude of the external field and the polarisabilities are systematically varied. The application of an external field (of sufficient magnitude) is found to induce chain formation (as expected). The monodisperse systems are found to ‘self-assemble’ with larger induced dipole moments effectively clustering in chains as a result of significant dipole-induced dipole effects. The distribution of the chain lengths is characterised as a function of the applied field and the atom polarisability. For the bidisperse systems, the external field induces chain formation and a partial segregation, in which the more polarisable species preferentially form chains. The chain lengths are again determined as a function of field strength and the atom polarisabilities. Scaling behaviour is analysed.     

Electromagnetic radiation from linearly and nonlinearly oscillating charge drops

It has been shown that analytic calculations of the intensity of electromagnetic radiation from an oscillating charged drop in the approximation linear in the oscillation amplitude (small parameter is on the order of 0.1) give only the quadrupole component of the total radiation. The dipole component can only be obtained in calculations using higher-order approximations. Nevertheless, the intensity of the dipole radiation turns out to be substantially higher (by 14–15 orders of magnitude). This is because the decomposition of radiation from a system of charges into multipole components (differing even in the rates of decrease in the potential with the distance) is carried out using the expansion in a substantially smaller parameter, viz., the ratio of the size of the emitting system (in our case, a drop of radius ~10 μm) to the distance to the point of observation in the wave zone of the emission of radiation (emitted wavelength) of 100–1000 m. As a result, this second small parameter is on the order of 10^–7 to 10^–8. On the other hand, in accordance with the field theory, the ratio of intensities of quadrupole and dipole radiations is proportional to the squared ratio of the hydrodynamic velocity of the oscillating surface of a charged drop to the velocity of propagation of an electromagnetic signal in vacuum (velocity of light), which yields a ratio of 10^–14 to 10^–15.     

Electro‐optic switching with liquid crystal graphene

Graphene oxide (GO) particles in aqueous dispersions can form liquid crystal (LC) phases at extremely low concentrations due to the extremely high aspect ratio of the flakes and noticeably, they possess an extremely large Kerr coefficient attractive for low power consumption electro‐optic devices. Reduced graphene does not easily form LC phases in water due to its hydrophobic nature but here we show that stable dispersions of reduced graphene oxide can be realized with surfactants and that they exhibit birefringence upon shearing as well as under application of electric fields. The performance of the system is largely superior to GO LC possessing longer time stability and drastically improved electro‐optic properties with an induced birefringence twice as large at the same field strength thanks to the almost recovery of graphene properties upon reduction. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Effect of low frequency ultrasound on the surface properties of natural aluminosilicates

Structural and surface properties of different natural aluminosilicates (layered, chain and framework structural types) exposed of 20 kHz ultrasound irradiation (0–120 min) in aqueous and 35 wt%. aqueous H₂O₂ dispersions were studied by X-ray diffraction (XRD), dynamic light scattering (DLS), nitrogen adsorption–desorption, thermal analysis, and Fourier transform infrared spectroscopy (FTIR) techniques. It was confirmed that sonication caused slight changes in the structure of investigated minerals whereas their textural properties were significantly affected. The aqueous dispersions of montmorillonite (Mt), clinoptilolite (Zlt), glauconite (Glt) and palygorskite (Pal) were represented by several particles size fractions according to DLS-study. Ultrasound irradiation produced a decrease of the average particle diameter by 4–6 times in water and by 1.3–5 times in H₂O₂ dispersions except for Pal, which underwent strong agglomeration. A significant increase of total pore volume and pore diameter was observed for Glt sonicated in H₂O₂ dispersions whereas for Pal mainly micropore volume sharply increased in both aqueous and H₂O₂ dispersions.     

Field-modulated low-energy electronic and optical properties of armchair silicene nanoribbons

The tight-binding model including spin–orbit coupling is used to study electronic and optical properties of armchair silicene nanoribbons (ASiNRs) in electric fields. Perpendicular electric field monotonically increases band-gap, the DOS, and absorption frequency and strength. It does not change spin-degeneracy, edge-states, and optical selection rule. However, parallel electric field strongly modulates energy dispersions resulting in oscillatory band-gaps, shift in edge-states, and destruction of spin-degeneracy. It induces more transition channels and constructs new selection rules that exhibits richer optical spectra. Modulations of electronic and optical properties of ASiNRs have strong dependence on the direction of electric field and nanoribbon's geometry.     

Effect of electric field on the enhanced heat transfer characteristic of an evaporator with multilayered sintered copper mesh

In this paper, it was investigated experimentally that the effect of different kinds of working fluid on the thermal performance of evaporator with capillary wick consisted by multilayered sintered copper mesh under different electric field strengths at the operating pressure of 1.01 × 10⁵ Pa R141b and R123 were used as the working fluids. The electric field strength in this study was in the range of 0kV/m–1600 kV/m, respectively. The experimental results showed that the applied electric field strength has significant effect on heat transfer characteristic. The heat transfer enhancement effects increased with the increase of the electric field. Under the applied electric field strength, the maximum heat transfer enhancement factors could reach as high as 1.5 and 1.32 for the two kinds of working fluids in the experiment.     

Electron band structure detection by high-order optical harmonic generation in solids

As the threshold field strength for the breakdown in air significantly exceeds the maximum measured thundercloud strength 3 kV/cm/atm, the problem of lightning initiation remains unclear. According to the popular idea, lightning can be initiated from streamer discharges developed in the enhanced electric field in a vicinity of hydrometeors. To test the idea, we carry out numerical simulations of positive streamer development around charged water drops at air pressure typical at thundercloud altitudes and at different background fields, drop sizes and charges. With real drop sizes and charges, the electric field required for the streamer formation is stronger than the measured fields; therefore, second mechanism is required to amplify the local field.     

Techno-economic comparative assessment of the ultrasound,electrostatic and microwave supported coalescence of binary water droplets in crude oil

In this study, comparative assessment of the technical performance, energy usage and economic impact of ultrasound, electrostatics and microwave on the coalescence of binary water droplets in crude oil was conducted. The effect of different oil properties such as crude oil viscosity (10.6–106 mPa s) and interfacial tension (IFT) (20–250 mN/m) on the coalescence time and energy consumption was examined. In addition, operation conditions such as inlet emulsion flow velocity (10–100 mm/s), electric field type, ultrasound frequency and applied voltage amplitude (0–30 kV) were evaluated. The numerical models showed good agreement with experimental findings in the literature. Moreover, the process time of the dewatering process increased with rising inlet flow velocities. The elevation of the coalescence time with velocity can be attributed to the increasing effect of flow disturbance, and the reduction of the emulsion residence time. As regards the IFT, the coalescence time reduced as the IFT was increased. This can be associated with the improved stability of emulsions formed at lowered IFT. As the maximum droplet size is directly proportional to the IFT, lowering the IFT reduces the peak diameter of the droplets that are present in the emulsion. Moreover, the coalescence time followed the order: ultrasound < microwave < electrostatics approaches under varying IFT. The coalescence energy increased from ∼15 J, ∼90 J and ∼25 mJ to ∼61 J, ∼235 J and ∼26 mJ for microwave, electrostatics and ultrasound techniques, respectively, as the viscosity was raised from 10.6 to 106 mPa s. Ultrasound coalescence showed significant energy and economic savings in comparison to microwave and electro-coalescence. Hence, ultrasound coalescence would be a potential method for standalone or integrated demulsification over the two other techniques. However, there are indications that beyond a viscosity of 300 mPa s, the effect of ultrasound becomes weak with significant hindrance to droplet movement and accumulation. This analysis provides fundamental insights on the comparative behavior of the three emulsion separation techniques.     

Effects of plasticizer and nanofiller on the dielectric dispersion and relaxation behaviour of polymer blend based solid polymer electrolytes

Solid polymer electrolytes consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend (50:50 wt/wt%) with lithium triflate (LiCF₃SO₃) as a dopant ionic salt at stoichiometric ratio [EO + (CO)]:Li⁺ = 9:1, poly(ethylene glycol) (PEG) as plasticizer (10 wt%) and montmorillonite (MMT) clay as nanofiller (3 wt%) have been prepared by solution cast followed by melt–pressing method. The X–ray diffraction study infers that the (PEO–PMMA)–LiCF₃SO₃ electrolyte is predominantly amorphous, but (PEO–PMMA)–LiCF₃SO₃–10 wt% PEG electrolyte has some PEO crystalline cluster, whereas (PEO–PMMA)–LiCF₃SO₃–10 wt% PEG–3 wt% MMT electrolyte is an amorphous with intercalated and exfoliated MMT structures. The complex dielectric function, ac electrical conductivity, electric modulus and impedance spectra of these electrolytes have been investigated over the frequency range 20 Hz to 1 MHz. These spectra have been analysed in terms of the contribution of electrode polarization phenomenon in the low frequency region and the dynamics of cations coordinated polymer chain segments in the high frequency region, and also their variation on the addition of PEG and MMT in the electrolytes. The temperature dependent dc ionic conductivity, dielectric relaxation time and dielectric strength of the plasticized nanocomposite electrolyte obey the Arrhenius behaviour. The mechanism of ions transportation and the dependence of ionic conductivity on the segmental motion of polymer chain, dielectric strength, and amorphicity of these electrolytes have been explored. The room temperature ionic conductivity values of the electrolytes are found ∼10⁻⁵ S cm⁻¹, confirming their use in preparation of all-solid-state ion conducting devices.     

Coalescence behaviour of two large water-drops in viscous oil under a DC electric field

Electrically driven coalescence is one of the important methods to separate water from crude oils. In this paper, the coalescence behaviour of two water drops was studied experimentally using a high-speed imaging. The results show that the electric force induces the drops migrating towards each other before their contact. However the electric force drags the drops to separate after contact. There is a critical electric field strength above which the two drops would be separated again after they have been coalesced together. The understanding of the electric coalescence could be helpful to advance the design of the electrocoalescencers.     

Insulator-based dielectrophoresis in viscous media—Simulation of particle and droplet velocity

The velocity of micro-particles in a nonuniform electric field was examined as a function of electrical potential and particle size to illustrate the possible application of dielectrophoresis (DEP) as a new separation technique in viscous media. A new comprehensive model is presented that combines the effects of DEP and electrohydrodynamic forces on particle motion. The current model simulation takes into account the possible significant influence of electrohydrodynamic effects depending on the particle size, electrode distance, and voltage applied during DEP particle separation. The heat generated as a consequence of high electric field strength leads to density gradients in the liquid, thus inducing buoyancy forces that cause fluid convective motion.Experimental velocity measurements using two materials having extreme properties, i.e. polyethylene (PE) particles (diameter range 100–2000 μm) and water droplets (diameter range 25–275 μm), both suspended in a viscous medium (silicone oil), correspond with the proposed theoretical predictions. The comprehensive model presented was applied to insulator-based DEP in a direct current (dc) electric field, but it is expected to allow predictions of various similar systems.     

Electric field dependence of phase equilibria of binary Stockmayer fluid mixtures

A perturbation theory based study of the effect of an external electric field on the phase equilibrium properties of binary Stockmayer fluids is presented. The dipole–dipole interaction and the applied field are treated as independent perturbations to a Lennard–Jones mixture, and the reference fluid is treated by the van der Waals one-fluid approximation. A third-order free energy expression in the electric field strength is established, and the dielectric constant is calculated for a needle-shaped sample parallel to the field direction. We present and discuss vapour–liquid and liquid–liquid equilibrium curves at a given temperature for some dipolar mixtures exposed to an electric field, including chlorodifluoromethane +?difluoromethane and acetonitrile +?methanol. A sufficiently high electric field may result in massive shifts of vapour pressures and critical or azeotropic points, and can considerably alter the properties of coexisting phases. The vapour pressure decreases with increasing field strength.     

Modeling of cellular pearl chain formation using a double photoconductive layer biochip

A typical double photoconductive layer biochip focusing biological cells and forming specific pearl chains has been studied theoretically in this paper. It was composed of two photoconductive layers coated on the bottom and top of ITO-based glass. A light pattern was used to create face-to-face virtual electrodes and the resulting oscillatory spatial electric field was employed to induce the motion of polarizable neutral particles. In order to estimate the behaviors of the suspended particles, a numerical model including dielectrophoretic forces, dipole–dipole forces and other forces, was implemented by means of the Monte Carlo method. The results indicated that steady-state chains could be formed in a uniform electric field owing to the dipole moment effect. In a non-uniform electric field created by the use of a light pattern, the positive DEP force created a more focused pattern of chains. The work concerning the numerical simulation indicated that this chip could form fixed-length particle chains in perpendicular alignment to satisfy the structured assembly of tissues in the histological engineering application.     

二氢化钚分子激发态结构的外场效应

采用密度泛函(DFT)方法B3LYP/Gen，在Pu为SDD基组、H为6-311++G^**基组水平上优化得到了分子轴方向不同电偶极场(-0.005—0.005a.u.)作用下，二氢化钚的基态电子状态、几何结构、电偶极矩和分子总能量.在优化构型下用同样的基组采用含时密度泛函(TDDFT)方法(TD-B3LYP)研究了同样外电场条件下对二氢化钚的激发能和振子强度的影响.计算结果表明，分子几何构型与电场大小和方向呈现较强的依赖，电场强度增加基态偶极矩随电场强度线性增加，H-Pu-H的角度线性减小，分子总能量线性减小；激发能随电场强度增加而减小，且对电场方向的依赖呈现近似对称性，满足Grozema关系.电场对振子强度的影响比较复杂，但仍满足跃迁选择定则. 关键词： 二氢化钚 激发态 电偶极场 TD-DFT     

Paraelectric alignment of NH 2 - centres in alkali halide crystals

The low temperature paraelectric alignment of substitutional NH ₂ ^- dipole centres in alkali halide crystals is studied measuring the electric field induced variation of the UV absorption and the electro-birefringence (Kerr-effect). We obtain the magnitude of the electric dipole moment and of the anisotropy of the oscillator strength. The reorientation of the dipoles between their equilibrium orientations is investigated by measuring the time dependence of the electro-birefringence after rapid changes of the applied electric field. The results indicate the predominance of one-phonon assisted tunneling processes.     

Vortices in dipolar Bose–Einstein condensates in synthetic magnetic field

We study the formation of vortices in a dipolar Bose–Einstein condensate in a synthetic magnetic field by numerically solving the Gross–Pitaevskii equation. The formation process depends on the dipole strength, the rotating frequency, the potential geometry, and the orientation of the dipoles. We make an extensive comparison with vortices created by a rotating trap, especially focusing on the issues of the critical rotating frequency and the vortex number as a function of the rotating frequency. We observe that a higher rotating frequency is needed to generate a large number of vortices and the anisotropic interaction manifests itself as a perceptible difference in the vortex formation. Furthermore, a large dipole strength or aspect ratio also can increase the number of vortices effectively. In particular, we discuss the validity of the Feynman rule.