Effects of temperature,pH, and ionic strength on the adsorption of nanoparticles at liquid–liquid interfaces

The effects of temperature, pH and sodium chloride (NaCl) concentration on the equilibrium and dynamic interfacial tension (IFT) of 4.4-nm gold nanoparticles capped with n-dodecanethiol at hydrocarbon–water interfaces was studied. The pendant drop technique was used to study the adsorption properties of these nanoparticles at the hexane–water and nonane–water interfaces. The physical size of the gold nanoparticles was determined by TEM image analysis. The interfacial properties of mixtures of these nanoparticles, having different sizes and capping agents, were then studied. The addition of NaCl was found to cause a decrease of the equilibrium and dynamic IFT greater than that which accompanies the adsorption of nanoparticles at the interface in the absence of NaCl. Although IFT values for acidic and neutral conditions were found to be similar, a noticeable decrease in the IFT was found for more basic conditions. Increasing the temperature of the system was found to cause an increase in both dynamic and equilibrium IFT values. These findings have implications for the self-assembly of functionalized gold nanoparticles at liquid–liquid interfaces.     

The effects of size,shape, and surface composition on the diffusive behaviors of nanoparticles at/across water–oil interfaces via molecular dynamics simulations

We have employed molecular dynamics simulations to systematically investigate the effects of nanoparticles’ structural and chemical properties on their diffusive behaviors at/across the water–benzene interface. Four different nanoparticles were studied: modified hydrocarbon nanoparticles with a mean diameter of 1.2 nm (1.2HCPs), modified hydrocarbon nanoparticles with a mean diameter of 0.6 nm (0.6HCPs), single-walled carbon nanotubes (SWCNTs), and buckyballs. We found that the diffusion coefficients of 0.6 and 1.2HCP were larger than the corresponding values predicted using the Stokes–Einstein (SE) equation and attributed this deviation to the small particle size and the anisotropy of the interface system. In addition, the observed directional diffusive behaviors for various particles were well-correlated with the derivative of the potential of mean force (PMF), which might indicate an effective driving force for the particles along the direction perpendicular to the interface. We also found that nanoparticles with isotropic shape and uniform surface, e.g., buckyballs, tend to have smaller diffusion coefficients than those of nanoparticles with comparable dimensions but anisotropic shapes and non-uniform surface composition, e.g., SWCNT and 0.6HCP. One possible hypothesis for this behavior is that the “perfect” isotropic shape and uniform surface of buckyballs result in a better-defined “solvation shell” (i.e., a shell of solution molecules), which leads to a larger “effective radius” of the particle, and thus, a reduced diffusion coefficient.     

Hydrodynamics and mass-transfer characteristics analysis of vapor–liquid flow of dual-flow tray

In the present study, the behavior and details of vapor–liquid contact on the dual-flow trays (DFTs) were investigated using a 3D CFD model within the two-phase Eulerian framework. The simulation provided good agreement with experimental results, which verified the reliability of the model. Firstly, the operation range was divided into four regimes having different characteristics of flow phenomena, and most attention was paid to the hydrodynamic behavior of froth regime and fluctuating regime due to its importance in operation and structure improvement. Then, the liquid flow characteristics of these two regimes were revealedwith the analysis of velocity profiles and liquid phase distribution contour. Meanwhile, some in-depth picturing of local events of hydrodynamics and mass-transfer performance was also presented through the discussion of cyclohexane liquid volume fraction distribution and vapor-phase mole fraction distribution. The froth regime was proved to have higher and homogeneous point efficiency at bulk zone around the plate center area than the fluctuating regime. Thus, the improvement of DFT should be focused on the restriction of “free-flow” to prolong the froth regime and delay the formation of vortex flow with circulation cells. Finally, an orthogonal wave tray (OWT) was designed and compared with DFT for evaluation of the effect of proposed modifications on the enhancement of tray hydraulics, mass-transfer efficiency and stability.     

Current investigations in theoretical studies of nanostructure–liquid interfaces

Wettability of surfaces is a significant factor affecting properties like water dispersion, spreading, evaporation, dissociation and etc. Surface wettability and wetting behavior of a surface are a subject of broad interest, there is then a great interest to understand better liquid–solid interfaces and water contact angle, in addition to the potential applications in micro- and nano fluidics. This subject is interesting as the growing attractions on the wetting and dynamical properties of water on 2D materials. Also, two clearly defined rigid water layers on solid surfaces are a well-known phenomenon and have been described on several surfaces. Detailed molecular dynamic simulation studies on the origin of this phenomenon are also of general interest. In this current review, recent attempts concerning to the wettability of graphene, graphene oxide and also some metal surfaces obtained by theoretical are presented. Their result contents, therefore, is of interest in order to understand the behavior of water nano-droplets when physisorbed on different substrates. The information is relevant for experimental teams working in this subject, with application in areas as catalysis, friction, surface chemistry, adsorption, etc.     

Finite size melting of spherical solid–liquid aluminium interfaces

We have investigated the melting of nano-sized cone shaped aluminium needles coated with amorphous carbon using transmission electron microscopy. The interface between solid and liquid aluminium was found to have spherical topology. For needles with fixed apex angle, the depressed melting temperature of this spherical interface, with radius R, was found to scale linearly with the inverse radius 1/R. However, by varying the apex angle of the needles we show that the proportionality constant between the depressed melting temperature and the inverse radius changes significantly. This led us to the conclusion that the depressed melting temperature is not controlled solely by the inverse radius 1/R. Instead, we found a direct relation between the depressed melting temperature and the ratio between the solid–liquid interface area and the molten volume.     

Linear stability analysis of electrohydrodynamic instabilities at fluid interfaces in the “small feature” limit

The endeavour to effectively harness interfacial electrohydrodynamic instabilities, to create small patterns, involves reducing the wavelength of the instability. This can be accomplished by decreasing the separation between the electrodes which may not always be possible. One may therefore have to reduce the surface tension or increase the applied voltage at a fixed electrode spacing. This can result in the wavelength of the pattern becoming of the same order as the electrode separation. Pease and Russel (J. Chem. Phys. 118, 3790 (2003)) were the first to argue that the commonly used Thin-Film Approximation (TFA) that involves an asymptotic expansion in the small parameter δ = (ε ₀ φ ₀²/(γh ₀))^1/2 (where ε ₀ is the permittivity of vacuum, φ ₀ is the root mean square value of the applied potential, γ is the surface tension and h ₀ is the thickness of the thin film) need not always be valid and γ may not be small in experiments. Higher-order corrections to the TFA might therefore be necessary. We extend the Direct Current (DC) field analysis of Pease and Russel to an Alternating Current (AC) field. AC field has been suggested as an effective way of controlling the wavelength of electrohydrodynamic instabilities at fluid-fluid interfaces. Infact, the perfect and leaky dielectric limits can be realised in the same fluid at very high and very low electric field frequencies, respectively. Recently, Roberts and Kumar (J. Fluid Mech. 631, 255 (2009)) carried out an analysis using TFA to investigate AC-field-induced instabilities at air-polymer interfaces. We propose a Generalized Model (GM), without the lubrication approximation, and carry out detailed comparison with the TFA. We consider the top fluid to be air, a perfect dielectric, and the bottom fluid to be a perfect or a leaky dielectric. The analysis is carried out for both DC and AC fields, and the deviation from TFA is expressed in terms of the parameter B = γh ₀/(ε ₀ φ ₀²) = δ ^{− 2}. We discuss variation of the wavelength of the fastest growing mode with frequency of the applied field for any arbitrary value of B, unlike the analysis of Roberts and Kumar which is restricted to B ≫ 1(δ ≪ 1) . We also revisit the analysis of Pease and Russel for instabilities under DC field and present the results in terms of the single parameter, B.     

Rayleigh–Taylor instability at spherical interfaces of incompressible fluids

Rayleigh–Taylor instability(RTI) of three incompressible fluids with two interfaces in spherical geometry is derived analytically. The growth rate on the two interfaces and the perturbation feedthrough coefficients between two spherical interfaces are derived. For low-mode perturbation, the feedthrough effect from outer interface to inner interface is much more severe than the corresponding planar case, while the feedback from inner interface to the outer interface is smaller than that in planar geometry. The low-mode perturbations lead to the pronounced RTI growth on the inner interface of a spherical shell that are larger than the cylindrical and planar results. It is the low-mode perturbation that results in the difference between the RTI growth in spherical and cylindrical geometry. When the mode number of the perturbation is large enough, the results in cylindrical geometry are recovered.     

Brittle and ductile fracture of semiconductor nanowires – molecular dynamics simulations

Fracture of silicon and germanium nanowires in tension at room temperature is studied by molecular dynamics simulations using several interatomic potential models. While some potentials predict brittle fracture initiated by crack nucleation from the surface, most potentials predict ductile fracture initiated by dislocation nucleation and slip. A simple parameter based on the ratio between the ideal tensile strength and the ideal shear strength is found to correlate very well with the observed brittle versus ductile behaviours for all the potentials used in this study. This parameter is then computed by ab initio methods, which predict brittle fracture at room temperature. A brittle-to-ductile transition (BDT) is observed in MD simulations at higher temperature. The BDT mechanism in semiconductor nanowires is different from that in the bulk, due to the lack of a pre-existing macrocrack that is always assumed in bulk BDT models.     

Modelling of nonlinear crack–wave interactions for damage detection based on ultrasound—A review

The past decades have been marked by a significant increase in research interest in nonlinearities in micro-cracked and cracked solids. As a result, a number of different nonlinear acoustic methods have been developed for damage detection. A general consensus is that – under favourable conditions – nonlinear effects exhibited by cracks are stronger than crack-induced linear phenomena. However, there is still limited understanding of physical mechanisms related to various nonlinearities. This problem remains essential for implementation of nonlinear acoustics for damage-detection applications. This paper reviews modelling approaches used for nonlinear crack–wave interactions. Various models of classical and nonclassical crack-induced elastic, thermo-elastic and dissipative nonlinearities have been discussed.     

Two-photon absorption and two-photon induced absorption of liquid toluene at 347.15 nm

Pump pulse transmission and time-delayed probe pulse transmission measurements through liquid toluene were performed with linear and circular polarized second harmonic pulses of a mode-locked ruby laser system. Two-photon absorption and two-photon induced absorption are observed. The induced absorption anisotropy is investigated. A theory of two-photon absorption in isotropic media is presented. The two-photon absorption cross-section components, the effective excited-state absorption cross-section, the absorption anisotropy relaxation time and the excited singlet-state relaxation time are determined.     

Processes of DNA condensation induced by multivalent cations： Approximate annealing experiments and molecular dynamics simulations

The condensation of DNA induced by spermine is studied by atomic force microscopy （AFM） and molecular dynamics （MD） simulation in this paper. In our experiments, an equivalent amount of multivalent cations is added to the DNA solutions in different numbers of steps, and we find that the process of DNA condensation strongly depends on the speed of adding cations. That is, the slower the spermine cations are added, the slower the DNA aggregates. The MD and steered molecular dynamics （SMD） simulation results agree well with the experimental results, and the simulation data also show that the more steps of adding multivalent cations there are, the more compact the condensed DNA structure will be. This investigation can help us to control DNA condensation and understand the complicated structures of DNA--cation complexes.     

Inelastic phonon interactions at solid–graphite interfaces

The presented model predicts thermal boundary conductance at interfaces where one material comprising the junction is characterized by high elastic anisotropy. In contrast to previous approaches, the current methodology accounts for contributions from inelastic scattering through consideration of multiple-phonon interactions. Inelastic contributions become significant as the temperature, as well as the degree of acoustic mismatch between the materials, increases. Inclusion of the inelastic interactions is necessary for a variety of interfacial systems including the metal–graphite boundary examined here. Improvement is shown over existing approaches that address only elastic scattering as both three- and four-phonon interactions significantly augment the transport.     

Calculation of the surface tension of pure tin from atomistic simulations of liquid–vapour systems

Monte Carlo simulations of heterogeneous systems of tin at liquid–vapour equilibrium have been performed at several temperatures from 600 to 1500 K, using a modified embedded atom model potential. Surface tension of the corresponding planar interfaces has been evaluated using the test area method. Calculation results are in good agreement with experiments presenting a maximum deviation of 10% from experiments. In addition, the Monte Carlo simulations provide a temperature coefficient (the derivative of the surface tension in regard with temperature) in reasonable agreement with the experimental coefficient.     

Multiplexer–Demultiplexer based on nematic liquid crystal photonic crystal fiber coupler

A novel design of Multiplexer–Demultiplexer (MUX–DEMUX) based on index guiding soft glass nematic liquid crystal (NLC) based photonic crystal fiber coupler is proposed and analyzed. The simulation results are obtained using the full vectorial finite difference method as well as the full vectorial finite difference beam propagation method. The numerical results reveal that the proposed MUX–DEMUX of length 3.265 mm can provide low crosstalk better than −20dB with great bandwidths of 40 and 24 nm around the wavelengths of 1.3 and 1.55 μm, respectively. In addition, the reported MUX–DEMUX has a tolerance of ±3% in its length which makes the design more robust to the perturbation introduced during the fabrication process.     

Sum frequency generation (SFG) – surface vibrational spectroscopy studies of buried interfaces: catalytic reaction intermediates on transition metal crystal surfaces at high reactant pressures; polymer surface structures at the solid–gas and solid–liquid interfaces

SFG spectra of polyethylene and polypropylene show monolayer sensitivity and reveal temperature-dependent changes of surface structure. For polymer blends, the hydrophobic component segregates to the solid–air interface, and the hydrophilic component segregates at the solid–water interface. Changes in SFG spectra of polymer blends as a function of bulk concentration correlate with changes of contact angle. SFG is an excellent probe of surface-structure and surface-composition changes as the polymer interface is altered. Received: 20 September 1998     

Electrically induced deformations of water–air and water–oil interfaces in relation with electrocoalescence

In connection with the phenomenon of electrocoalescence of water droplets in oil, the electrically induced deformations of some water–oil interfaces are studied. Such problems involve the strong coupling of hydrodynamics and electrostatics as well as the accurate tracking/capturing of the evolving interfaces. The paper presents a Finite–Element Arbitrary Lagrangian–Eulerian (FE–ALE) approach in deforming meshes to investigate the time-dependent deformation of the interface between highly conductive water and an insulating immiscible fluid. The developed numerical scheme is first tested and then used to solve two 2D axisymmetric EHD problems. Computed results are compared with predictions from asymptotic developments and with experimental measurements.     

Performance comparison of Fabry–Perot and Mach–Zehnder interferometers for molecular Doppler lidar based on fringe-imaging technique

Fringe-imaging Fabry–Perot interferometer (FIFPI) and fringe-imaging Mach–Zehnder interferometer (FIMZI) used as frequency discriminator for incoherent molecular Doppler lidar were analyzed, respectively. For a pure molecular backscattered signal, performances (wind measurement sensitivity and signal-to-noise ratio) of both FIFPI and FIMZI systems were simulated based on the U.S. standard atmospheric model. Comparisons of two systems were made under the same emitting and receiving parameters with certain wind speed dynamic range. Simulated results show that, though relatively lower sensitivity to Doppler shift, the single-channel FIMZI system provides a factor of 1.3 times smaller error in the horizontal wind velocity than that of FIFPI at a range of 20 km. We expect that the FIMZI frequency discriminator would provide an effective technique to improve the measurement accuracy for incoherent molecular Doppler lidar.     

Force-field dependence on the interfacial structure of oil–water interfaces

We investigate the performance of different force-fields for alkanes, united (TraPPE) and all atom (OPLS-AA) models, and water (SPC/E and TIP4P-2005), in the prediction of the interfacial structure of alkane (n-octane, and n-dodecane)–water interfaces. We report an extensive comparison of the interfacial thermodynamic properties as well as the interfacial structure (translational and orientational). We use the recently introduced intrinsic sampling method, which removes the averaging effect of the interfacial capillary waves and provides a clear view of the interface structure. The alkane interfacial structure is sensitive to the environment, i.e. alkane–vapour or alkane–water interfaces, showing a stronger structure when it is in contact with the water phase. We find that this structure is fairly independent of the level of detail, full or united atom, employed to describe the alkane phase. The water surface properties show a small dependence on the water model. The dipole moment of the SPC/E model shows asymmetric fluctuations, with a tendency to point both towards the alkane and water phases. On the other hand the dipole moment of the TIP4P-2005 model shows a tendency to point towards the water phase only. Analysis of the intrinsic electrostatic field indicates that the surface water potential is confined to an interfacial region of about 8 Å. Overall we find that the intrinsic structure of alkane–water interfaces is a robust interfacial property, which is independent of the details of the force-field employed. Hence, it should provide a good reference to interpret experimental data.     

Gas—liquid interfaces of room temperature ionic liquids

The structure of the gas-liquid surface of dimethylimidazolium chloride has been studied using atomistic simulation. We find that there is a region of enhanced density immediately below the interface in which the cations are oriented with their planes perpendicular to the surface and their dipoles in the surface plane. There is negligible segregation of cations and anions. The temperature dependence of the surface tension is predicted to be anomalously low or be reversed in sign. The vapour-liquid interfaces between mixtures of water and dimethylimidazolium chloride show similar regions of enhanced density and preferential orientation of the cations. Water molecules also show preferential orientation in the interface region and are preferentially adsorbed on the vapour side of the interface. The surface tension decreases with increase in the mole fraction of water.