Thermocapillary flow in double-layer fluid structures: an effective single-layer model

Thermocapillary flows are of considerable technological importance in materials processing applications such as crystal growth from the melt, particularly under microgravity conditions where the influence of buoyancy-driven convection is minimized. In this study, thermally driven convection within a differentially heated rectangular cavity containing two immiscible liquid layers is considered in the absence of gravity. The introduction of a more viscous encapsulant layer leads to a significant reduction in the intensity of the thermocapillary flow within the encapsulated layer. Interface deformations are small when the contact line of the interface is pinned on the solid boundaries. The higher viscosity of the encapsulant layer gives rise to a larger pressure gradient in that layer, thereby resulting in interface deformations that are qualitatively different from those observed at the free surface in the absence of the encapsulant layer. The flow pattern in the encapsulated layer and the resulting interface deformations are strongly dependent on both the thickness and the viscosity of the encapsulant layer. It is shown that the flow within the encapsulated layer may be closely approximated by simply considering the single-layer problem with a modified stress condition at the interface. The modified tangential stress balance for the effective single-layer model is derived based on asymptotic results for small-aspect-ratio double-layer systems and the insight gained from double-layer computations for finite-aspect-ratio systems. It is shown that the single-layer model accurately predicts the flow in the double-layer system even for large aspect-ratios.     

Structure of the B4 liquid crystal phase near a glass surface

The B4 liquid crystal phase of bent-core molecules, a smectic phase of helical nanofilaments, is one of the most complex hierarchical self-assemblies in soft materials. We describe the layer topology of the B4 phase of mesogens in the P-n-OPIMB homologous series near the liquid crystal/glass interface. Freeze-fracture transmission electron microscopy reveals that the twisted layer structure of the bulk is suppressed, the layers instead forming a structure with periodic layer undulations, with the topography depending on the distance from the glass. The surface layer structure is modeled as parabolic focal conic arrays generated by equidistant parabolas whose foci are defect lines along the glass surface. Nucleation and growth of toric focal conics near the glass substrate is also observed. Although the growth of twisted nanofilaments, the usual manifestation of structural chirality in the B4 phase, is suppressed near the surface, the smectic layers are intrinsically chiral, and the helical filaments that form on top of them grow with specific handedness.     

Development of morphology and properties of injection‐molded bars of HDPE/PA6 blends along flow direction

The structure and mechanical properties of injection‐molded bars of high‐density polyethylene (HDPE)/PA6 blends were studied in this article. The experimental results showed that the morphologies of injection‐molded bars change gradually along the flow direction, which is tightly related to the melt viscosity and processing conditions. The higher melt viscosity, lower mold temperature, and shorter packing time, restricting the macromolecular relaxation, enhance the difference in morphologies and properties at near and far parts of a mold. An injection‐molded bar (namely H2C5), consisting of 75 wt % of HDPE, 20 wt % of PA6, and 5 wt % of compatibilizer (HDPE‐g‐MAH), showed a greater difference in mechanical properties at near and far parts because of its higher melt viscosity. A clear interface between the skin and core layers of near part in it leads to a much higher impact strength than that of far part. And tensile tests show that its tensile strength of near part is higher than that of far part due to the higher orientation degrees of HDPE matrix and PA6 dispersed phase in near part. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 184–195, 2007     

Thermocapillary Flow and Aggregation of Bubbles on a Solid Wall

Theory suggests that thermocapillary flow about neighboring bubbles in liquids on hot walls pulls the bubbles together. A temperature gradient perpendicular to the wall establishes a surface tension gradient at the bubble-liquid interface, which in turn sustains a shear stress gradient that pumps adjacent fluid away from the wall. Neighboring bubbles are mutually entrained in this flow and also respond thermophoretically to lateral temperature gradients in the temperature near field. The theory predicts that the aggregation velocity scales with the temperature gradient, the radius of the bubbles, the derivative of the surface tension with respect to temperature, and the reciprocal of the liquid's viscosity. Bubble aggregation experiments under controlled conditions were performed to test the theory. Scaling the experimental bubble trajectories according to the theory substantially collapses all of the data onto a master curve when the interbubble separation is greater than 3 radii, which suggests that the theory is correct. Calculated velocities agree with the experimental results when hindrance of bubble motion due to the wall is included. Values for the parameter that describes the hindrance effect are obtained from fitting the data to the theory, from independent measurements, and from direct hydrodynamic calculation. The results of the three determinations agree within 15% of the possible range of the value of the parameter. Copyright 2000 Academic Press.     

Bending elasticity of charged surfactant layers: the effect of layer thickness

The bending properties of charged one-component surfactant films of finite thickness have been theoretically investigated. It is demonstrated that finite thickness effects are of crucial importance for layers formed by an ionic surfactant with a flexible hydrophobic tail, whereas the influence on layers formed by a surfactant with a rigid tail is less pronounced. As a matter of fact, in the former case, the spontaneous curvature and mean and Gaussian bending constants all become significantly modified as compared to an infinitely thin surface and assume identical values as if the surfactant layer were bent at constant layer thickness. As a result, the spontaneous curvature is found to decrease, whereas the magnitudes of the mean and Gaussian bending constants both increase with increasing layer thickness as well as with increasing hydrophobic-hydrophilic interfacial tension. All of these trends are consistent with experimental observations. In addition, it is demonstrated that separating the hydrophilic-hydrophobic interface and the surface of charge a certain distance from each other tends to increase the spontaneous curvature and the mean bending constant, whereas the Gaussian bending constant becomes increasingly negative. It is also found that the work of bending a bilayer into a geometrically closed vesicle is substantially raised to large positive values for surfactants with flexible aliphatic chains, whereas the corresponding quantity is negative for surfactants with rigid tails, indicating that stable bilayer structures may only be formed by the former surfactant. Furthermore, each of the bending elasticity constants for monolayers formed by a double-chain ionic surfactant are found to assume lower values as compared with layers formed by the corresponding single-chain surfactant.     

Reflective interferometric fourier transform spectroscopy: a self-compensating label-free immunosensor using double-layers of porous SiO2

An interferometric biosensor comprised of two layers of porous Si, stacked one on top of the other, is described. A fast Fourier transform (FFT) of the reflectivity spectrum reveals three peaks that correspond to the optical thickness of the top layer, the bottom layer, and both layers together. Binding of immunoglobulin G to a protein A capture probe adsorbed to the surface of the top layer induces changes in reflectivity at the top layer/solution interface. The FFT method allows discrimination of target analyte binding from matrix effects due to nonspecific changes in the analyte solution. The sensor response is shown to be insensitive to the addition of 4000-fold excess sucrose or 80-fold excess bovine serum albumin interferents.     

Electrophoresis of a colloidal sphere in a spherical cavity with arbitrary zeta potential distributions

An analytical study is presented for the quasi-steady electrophoretic motion of a dielectric sphere situated at the center of a spherical cavity when the surface potentials are arbitrarily nonuniform. The applied electric field is constant, and the electric double layers adjacent to the solid surfaces are assumed to be much thinner than the particle radius and the gap width between the surfaces. The presence of the cavity wall causes three basic effects on the particle velocity: (1) the local electric field on the particle surface is enhanced or reduced by the wall; (2) the wall increases the viscous retardation of the moving particle; and (3) a circulating electroosmotic flow of the suspending fluid exists because of the interaction between the electric field and the charged wall. The Laplace and Stokes equations are solved analytically for the electric potential and velocity fields, respectively, in the fluid phase, and explicit formulas for the electrophoretic and angular velocities of the particle are obtained. To apply these formulas, one has to calculate only the monopole, dipole, and quadrupole moments of the zeta-potential distributions at the particle and cavity surfaces. It is found that the contribution from the electroosmotic flow developing from the interaction of the imposed electric field with the thin double layer adjacent to the cavity wall and the contribution from the wall-corrected electrophoretic driving force to the particle velocities can be superimposed as a result of the linearity of the problem.     

Mobility of water near charged interfaces

The location of the hydrodynamic shear surface is discussed for micelles of Na dodecyl sulfate and for clay particles (platelets of montmorillonite and of vermiculite). Micelles are characterized by a combination of experiments: light scattering, micellar self-diffusion, intrinsic viscosity, electrophoresis and electric conductance. The concerted interpretation of these experiments shows that the shear surface of micelles coincides within 0.1 nm with the surface enveloping the heads of the micellized ions. Claims of structured water in clays and an abnormally high viscosity of clay-held water have been based on the low self-diffusion of water in swollen clays, and on the temperature dependence of the hydraulic resistance of clay plugs (anomalous activation energy). It is shown that the self-diffusion of water between the platelets requires corrections for a wall effect and for the hydration of the exchangeable, slow moving cations. After application of such corrections, the viscosity of water in clay is found to be about the same as of bulk water, with the shear surface located at 0.1 ± 0.1 nm from the clay/water interface. The small anomaly in the activation energy of water in clay plugs is reasonably explained by a slight change with temperature of the pore size distribution in the plugs. Approximate calculations of the dielectric constant of water in electric double layers suggest some restriction in the orientation of water molecules in the first layer next to highly charged interfaces such as vermiculite/water. The various results all indicate that changes in the water mobility induced by a charged interface are small and do not reach beyond the first layer of water molecules.     

Oxidation studies of Indian reduced activation ferritic martensitic steel

The paper reports the oxidation behaviour of Indian variety of reduced activation ferritic martensitic steel (RAFMS) proposed to be used as a first wall material in test blanket module in ITER and future fusion reactors. Oxidation of first wall can occur in case of a catastrophic leak in the vacuum vessel of fusion reactor. The oxidation of Indian RAFMS was done at 450–650 °C. Long-term oxidation for 25, 50 and 100 h was studied at 550 °C. A mass gain/unit area vs time was plotted and oxidation kinetics determined. The cross section SEM of the oxidised RAFMS was done. The SEM micrographs showed two distinct layers of oxides that have formed with total thickness of around 10 µm. Glancing-angle XRD showed that the top layer is essentially a mixture of magnetite and haematite. A strong enrichment of Cr is visible in a narrow band below the top layer near the scale/alloy interface. It was found that formation of this Cr-rich spinel mid-layer ensures the short-term and long-term oxidation resistance of IN-RAFMS in case of any accidental leak in fusion reactor conditions.     

Effect of gamma irradiation on gas-ionic liquid and water-ionic liquid interfacial stability

The effect of γ-radiation on gas-ionic liquid (IL) and water-IL interfacial stability was investigated. Three phosphonium-based ILs, which vary considerably in their viscosity, conductivity and miscibility with water, were examined. The gas phase above the IL samples (headspace gas) was analyzed using gas chromatography with a mass spectrometer detector while the changes in the IL and aqueous phases were followed by conductivity measurements and Raman spectroscopy. For the gas-IL systems, the headspace samples showed trace amounts of the radiolytic decomposition products of the ILs that were small and volatile enough to become airborne. The type of cover gas, air or Ar, had no effect on the gas speciation. Negligible changes in the conductivity and the Raman spectra of the IL phase due to irradiation indicate that γ-irradiation induces negligible chemical changes in the IL phase when it is in contact with a gas phase. For the water-IL systems, the initially immiscible layers slowly developed an interfacial emulsion layer, even in the absence of radiation. This layer started at the water-IL interface and then grew downwards, eventually converting the entire IL phase to an emulsion. Gamma-irradiation accelerated the conversion of the IL phase to an emulsion. The development of the emulsion layer was accompanied by changes in the conductivity and the Raman spectra of both the IL and water phases. Based on these results, a mechanism involving the formation of micelles at, or near, the water-IL interface has been proposed to explain the development of an emulsion layer. We also suggest that radiolytic decomposition of ILs produces surfactants that can accumulate at the interface and, even at low concentrations, accelerate the emulsification process.     

Localisation d'un front de solidification en interaction avec un bain fondu instationnaire

The interaction between unsteady thermal convection and a solid/melt front is studied numerically. This concerns crystal growth applications using the vertical Bridgman technique. The physical domain contains a liquid phase, a solid phase and a small intermediate phase modelled as a porous medium. An enthalpy-porosity homogeneous formulation is proposed with a finite volume approximation. The interface localisation method gives the significant changes of the interface over time due to oscillatory melt in inverted configuration. It is qualified with respect to the results obtained with a front tracking method for various values of the Rayleigh number.     

Molecular Dynamics Simulation: Influence of External Electric Field on Bubble Interface in Air Flotation Process

Molecular dynamics(MD) simulation was performed to investigate the influence of external electric field on the vapour-liquid interface of the bubble during the process of toluene separation by air flotation. The physicochemical properties of vapour-liquid interface, surface tension, probability of a hydrogen bonding near the vapour-liquid interface and the viscosity of liquid phase caused by external electric field were analyzed. The results show that the angle between the water molecule dipole moment and the normal z axis in the vapour phase changes smaller when the external electric field is applied. The surface tension and the probability of hydrogen bonding near the vapour-liquid interface increase with the increase of electric field strength. And the viscosity also increases under an external electric field. The results confirm that the external electric field has a positive effect on the performance of bubbles in air flotation, which may provide useful guidance for the combination of electric field and air flotation technology.     

Effect of sucrose on the properties of caffeine adsorption layers at the air/solution interface

Sweet and bitter tastes are known to be mediated by G-protein-coupled receptors. The relationship between the chemical structure of gustable molecules and their molecular organization in saliva (aqueous solution) near the surface of the tongue provides a useful tool for elucidating the mechanism of chemoreception. The interactions between stimulus and membrane receptors occur in an anisotropic system. They might be influenced by the molecular packing of gustable molecules within an aqueous solvent (saliva) close to the receptor protein. To investigate the molecular organization of a sweet molecule (sucrose), a bitter molecule (caffeine), and their mixture in an aqueous phase near a "wall", a hydrophobic phase, we modeled this using an air/liquid interface as an anisotropic system. The experimental (tensiometry and ellipsometry) data unambiguously show that caffeine molecules form an adsorption layer, whereas sucrose induces a desorption layer at the air/water interface. The adsorption of caffeine molecules at the air/water interface gradually increases with the volume concentration and is delayed when sucrose is added to the solution. Spectroscopic ellipsometry data show that caffeine in the adsorption layer has optical properties practically identical to those of the molecule in solution. The results are interpreted in terms of molecular association of caffeine with itself at the interface with and without sucrose in the subphase, using the theory of ideal gases.     

链段刚性对非溶剂致相分离成膜过程影响的耗散粒子动力学模拟

通过分子动力学(MD)模拟映射方法构建了符合聚醚砜(PES)刚性结构的耗散粒子动力学(DPD)简谐力场, 并研究了PES链段刚性对PES/N-甲基-2-吡咯烷酮(NMP)/水体系非溶剂致相分离(NIPS)过程的影响. 结果表明, 由于非溶剂和溶剂在两相界面上发生的质量交换, 导致在相界面处PES链段发生堆积, 形成了薄而致密的聚合物表层, 在PES溶液内部, 由于非溶剂的侵入导致体系发生了旋节相分离, 从而在整体上得到了明显的非对称结构; 同时, PES链段刚性的提升能够明显加快体系的相分离速度, 导致相界面处的PES薄层形成得更加快速, 薄层更加致密、 孔径更小, 而对内部的疏松结构影响较小; 此外, 结合不同力场下聚合物浓度对相分离过程的影响可以发现, 不同PES浓度下, 链段刚性的提升对相分离过程的特征和演变趋势没有造成根本性的影响, 与经典的弹簧力场的模拟结果在整体趋势上有相似性. 研究结果表明, 简谐力场能提升PES链段的刚性, 从而能更真实地模拟实际体系的非溶剂相分离法成膜过程.     

Emulsification and stabilization mechanisms of o/w emulsions in the presence of chitosan

We study emulsification of paraffin oil in aqueous solutions of chitosan without adding any other surfactant. By monitoring the surface tension of the water-paraffin interface, we show that chitosan itself has only a weak surface activity. Nevertheless, chitosan dissolved in the aqueous phase allows the dispersion of oil by increasing the matrix viscosity and provides stabilization of the oil-water interface by forming a dense polyelectrolitic brush on the water side of this interface. We characterize emulsions with varying oil content, and concentrations of chitosan, and follow their long-term stability. Finally, we show that by precipitating the chitosan the rigid elastic network is formed in the aqueous phase, making a very stable suspension.     

Computational insights into the molecular mechanisms for chromium passivation of stainless-steel surfaces

First principles DFT calculations are used to gain insights into the molecular mechanism of Cr passivation of FeCr alloy surfaces. The systems studied represent early stages of oxidation of FeCr alloys when the oxide layers extend just a few atomic layers into the bulk. A Monte-Carlo atom-swapping algorithm was developed to efficiently explore possible atomic positions and identify the most promising structures that yield overall energy lowering. Analysis of the resulting low energy structures show that the surface oxide layer is rich in chromium while there is a reduction in chromium in the metallic phase near the alloy-oxide interface. Furthermore, there is an increased concentration of Fe near the oxide-air surface. Analysis of the molecular structure of the oxide layers found that oxidized Cr was predominantly in the Cr₂O₃ phase, while oxidized Fe was present as both FeO and Fe₂O₃. We propose that the oxidative variability of Fe facilitates O diffusion in the iron-rich phases because of the range of geometries available for accommodating the O atom. In contrast, O diffusion is less facile in Cr, which has little variability in oxidation state.     

Effects of polymer adsorption on the effective viscosity in microchannel flows: phenomenological slip layer model from molecular simulations

Molecular simulations (Dissipative Particle Dynamics - DPD) were used to quantify the effect of polymer adsorption on the effective shear viscosity of a semi-dilute polymer solution in microchannel Poseuille flow. It is well known that polymer depletion layers develop adjacent to solid walls due to hydrodynamic forces, causing an apparent wall slip and reduced effective viscosity (increased total flow rate). We found that depletion layers also developed in the presence of hydrodynamically rough adsorbed layers on the wall. Polymer-polymer (steric) repulsion between flowing and adsorbed polymer expanded the depletion layer compared to no-adsorption cases, and the effective viscosity was reduced further. Desorption occurred for higher shear rates, reducing the repulsion effect and shrinking the depletion layers. A phenomenological algebraic model for the depletion layer thickness, including a shear modified adsorption isotherm, was developed based on the simulation data. The depletion layer model can be used together with the effective viscosity model we developed earlier.     

Buried interfacial layer of highly oriented molecules in copper phthalocyanine thin films on polycrystalline gold

The growth of copper phthalocyanine thin films evaporated on polycrystalline gold is examined in detail using near edge x-ray absorption fine structure spectroscopy and surface sensitive x-ray photoemission spectroscopy. The combination of both methods allows distinguishing between the uppermost layers and buried interface layers in films up to approximately 3 nm thickness. An interfacial layer of approximately 3 ML of molecules with an orientation parallel to the substrate surface was found, whereas the subsequent molecules are perpendicular to the metal surface. It was shown that even if the preferred molecular orientation in thin films is perpendicular, the buried interfacial layer can be oriented differently.     

A molecular model for cohesive slip at polymer melt/solid interfaces

A molecular model is proposed which predicts wall slip by disentanglement of polymer chains adsorbed on a wall from those in the polymer bulk. The dynamics of the near-wall boundary layer is found to be governed by a nonlinear equation of motion, which accounts for such mechanisms on surface chains as convection, retraction, constraint release, and thermal fluctuations. This equation is valid over a wide range of grafting regimes, including those in which interactions between neighboring adsorbed molecules become essential. It is not closed since the dynamics of adsorbed chains is shown to be coupled to that of polymer chains in the bulk via constraint release. The constitutive equations for the layer and bulk, together with continuity of stress and velocity, are found to form a closed system of equations which governs the dynamics of the whole "bulk+boundary layer" ensemble. Its solution provides a stick-slip law in terms of the molecular parameters and extruder geometry. The model is quantitative and contains only those parameters that can be measured directly, or extracted from independent rheological measurements. The model predictions show a good agreement with available experimental data.     

Interactions between two bubbles on a hot or cold wall

A temperature gradient normal to a planar wall produces two-dimensional motion and aggregation or separation of bubbles on the hot or cold wall, respectively. The origin of the motion is fluid convection driven by the thermal Marangoni stress on the surface of the bubbles. Previous theories for the dynamics of two or more bubbles have been based on an analysis of flow about a single bubble and the resulting convection that entrains its neighbors. Here we extend the theory by solving the quasi-steady equations for the temperature and velocity fields for two bubbles. The result is a quantitative model for the relative velocity between two bubbles as a function of both the distance between them and the gap between each bubble and the surface. Interactions between the bubbles strongly increase the approach velocity, which is counter-intuitive because the hydrodynamic resistance increases as the bubbles approach each other. An asymptotic analysis indicates the thermocapillary force bringing them together or pushing them apart is singular in the separation when the bubbles are close to each other. The two-bubble theory agrees reasonably well with the experimentally measured velocities of pairs of bubbles on hot or cold surfaces, though it slightly overestimates the velocities.