Rupture of thin stagnant films on a solid surface due to random thermal and mechanical perturbations

A generalized formalism for the rupture of a nondraining thin film on a solid support due to imposed random thermal and mechanical perturbations, modeled as a Gaussian white noise, is presented. The evolution of amplitude of perturbation is described by a stochastic differential equation. The average film rupture time is the average time for the amplitude of perturbation to equal to the film thickness and is calculated by employing a first passage time analysis for different amplitudes of imposed perturbations, wavenumbers, film thickness, van der Waals and electrostatic interactions and surface tensions. The results indicate the existence of an optimum wavenumber at which the rupture time is minimum. A critical film thickness is identified based on the sign of the disjoining pressure gradient, below which the film is unstable in that the rupture time is very small. The calculated values of rupture time as well as the optimum wavenumber in the present analysis agree well with the results of linear stability analysis for immobile as well as completely mobile gas-liquid film interfaces. For stable films, the rupture time is found to increase dramatically with film thickness near the critical film thickness. As expected, the average rupture time was found to be higher for smaller amplitudes of imposed perturbations, larger surface potentials, larger surface tensions and smaller Hamaker constants.     

Pseudopartial wetting and precursor film growth in immiscible metal systems

We explore the equilibrium wetting behavior and precursor film growth in pure and alloy metallic systems. The systems exhibit equilibrium "pseudopartial" wetting, that is, a thin film in equilibrium with a nonzero contact angle in both liquid and solid states. The film spreading kinetics clearly indicates a diffusive transport mechanism. The alloying has only a small impact on the equilibrium wetting properties but strongly affects the transport during the growth of the precursor film.     

Recent advances in studies of bubble-solid interactions and wetting film stability

Research in the area of bubble-solid interactions is reviewed and highlighted, with a focus on studies of wetting film drainage using theoretical approaches and experimental (interferometric) approaches, and also studies probing the stability of wetting films, where the stability has been affected by physical and chemical modification/factors. Significant advances have been made in recent years in the area of interferometry and force measurement of bubble-surface encounters, with multiple light wavelengths used to improve accuracy and certainty with regard to thickness of wetting films, as well as high speed interferometry. These advances have been accompanied with improvements to models to describe nonequilibrium aspects of opposing interfaces. Experimental studies of the influence of air bubbles and surface roughness have highlighted the importance of dissolved gas and surface condition in determining whether wetting films are stable. Finally, many new studies on the influence of polymer layers on wetting film stability and rupture have been published, and these are described in relation to the increase in our understanding of the role of adsorbed polymers in altering surface chemistry and physics of the underlying substrate.     

Self-assembly to monolayer graphene film with high electrical conductivity

Monolayer chemically converted graphene (CCG) nanosheets can be homogeneously self-assembled onto silicon wafer modified by 3-aminopropyl triethoxysilane (APTES) to form very thin graphene film. The CCG film was characterized by FT-IR, XRD, SEM, TEM and AFM. Results show that CCG sheets formed monolayer film after assembled onto silicon wafer and there is a very tight chemical bond between sheets and wafer. Furthermore, the electrical measurements revealed that the monolayer graphene film has an excellent electrical conductivity.     

Thermal, mechanical and electrical properties on the styrene-grafted and subsequently sulfonated FEP film induced by electron beam

This paper examined the mechanical and electrical properties of poly(tetrafluoroethylene-co-hexafluoropropylene: FEP) film modified by electron beam (EB). The simultaneous irradiation method with EB was adopted for the grafting of styrene and subsequent sulfonation onto FEP film. The thermal and mechanical characteristics of the irradiated FEP film, and also those of the grafted and sulfonated FEP films, were investigated by TGA, FT-IR spectrometer, and Instron. The simultaneous irradiation with EB facilitated the homogeneous grafting, as well as a high degree of grafting with a maximum value of around 60%, thereby allowing accurate control of the degree of grafting at doses ranging from 10 to 100 kGy.The grafting or sulfonation decreased the thermal stability of FEP, whereas it considerably increased its mechanical properties. The high radiation resistance of virgin FEP up to a dose of 100 kGy enabled the sulfonation of FEP film to considerably reinforce its polymeric structures except of 10 kGy, thereby increasing its tensile strength at 30 kGy by two-fold compared to that of the virgin FEP film. The ion conductivity (IC) and ion-exchange capacity (IEC) values of the FEP membrane (125 μm thick), which were dependant on the degree of grafting, were 0.25 S cm⁻¹ and 2.4 mmol/g, respectively, at 59.2% of the degree of grafting and were superior to those of the commercialized Nafion membrane (IC, 0.12 S cm⁻¹; IEC, 0.9-1.0 mmol/g).     

A gravity driven micro flow injection wetting film extraction system on a polycarbonate chip

A micro flow injection wetting film liquid-liquid extraction system has been developed for trace analyte concentration and on-chip detection. A hydrophobic channel fabricated on a polycarbonate chip was used to support the wetting film, and hydrostatic pressure generated by the difference in liquid levels was employed to drive the fluids. Sequential injection of segments of aqueous sample solution and organic solvent was conducted by switching the sample- or solvent-containing vials to an on-chip sampling probe, and detection was performed by a co-focused, laser induced fluorescence detector. Using butyl rhodamine B as a model analyte and butanol as the solvent for both film-coating and elution, various experimental conditions such as hydrostatic pressure, coating time, channel length, sampling volume, and sample acidity were investigated. Under optimized conditions, a 24-fold enrichment factor was obtained with the consumption of about 3 μL sample solution, and a detection limit (3σ) of 6.0 × 10⁻⁹ M butyl rhodamine B was achieved at the sampling rate of 19 h⁻¹. Eleven consecutive runs of a 1.0 × 10⁻⁵ M butyl rhodamine B solution produced a relative standard deviation of 1.5% for the detected fluorescence signals.     

Freezing transition of wetting film of tetradecane on tetradecyltrimethylammonium bromide solutions

We have performed ellipsometry and surface tensiometry at tetradecyltrimethylammonium bromide (TTAB) aqueous solution surface coexisting with tetradecane lens as a function of the molality of TTAB and the temperature under atmospheric pressure. From the theoretical analysis of the coefficient of ellipticity, it was clarified that the liquid monolayer comprising the surfactant and alkane is formed at higher surfactant concentrations by the wetting transition of tetradecane lens on the aqueous solution, and the solid monolayer is formed by lowering temperature (freezing transition). The results of the surface tension measurement support the occurrence of wetting transition and the freezing transition. A phase diagram of the wetting film was constructed by ellipsometry and surface tensiometry, of which the mixed solid monolayer had never been reported before. From the thermodynamic analysis of the phase diagram, it is also demonstrated that the TTAB surface density decreases accompanied with the freezing transition, which agrees with surface densities of TTAB calculated from surface tension vs. concentration curves.     

Effect of geometry on steady wetting kinetics and critical velocity of film entrainment

The velocity dependence of receding dynamic contact, angles θ_r/ U for siliconized cylinders of different, radii withdrawn from a glycerol-water mixture [19] show an independence on geometry and substantial influence of the material properties of the solid surface. These data are compared with the results of Ngan and Dussan [16a,b] for advancing angles θ_α / U (silicon oil displacing air), which suggest a considerable effect of geometry. A similar asymmetry of the effects of geometry and material properties on the critical velocities of liquid and air film entrainment follows from the Juxtaposition of our previous results for u_cr^R[19,20] with literature data on U_cr^A onto different solid substrates.The experimental data are interpreted on the basis of the equations of Cox-Voinov [21,22], describing the data of Ngan and Dussan quantitatively. The data for the receding meniscus can be represented quantitatively only by a combined Blake-Haynes-Voinov equation taking into account the dissipation in the three-phase contact zone and in the bulk liquid.     

Transient behaviors of interacting electrical double layers

 The unsteady-state potential and space charge distributions between two identical, planar parallel charged surfaces immersed in an a:b electrolyte solution are examined theoretically. The effects of the ratio of the diffusivities of counterions and coions, D _con/D _co, the mean diffusivity (D _con D _co)^1/2, and the separation distance between two surfaces, H, on the transient distributions of electrical potential and space charges are investigated. The result of numerical simulation reveals that the extent of a system to reach its new equilibrium state depends largely on the magni-tude of a scaled time ν(=Dtκ²). For a fixed H, the greater the value of ν, the closer a system to its new equilibrium state. For constant H and ν, the smaller the ratio (D _con/D _co), the greater the deviation of a system from its new equilibrium state. In addition, the effect of D _con on this deviation is greater than that of D _co. Received: 3 September 1997 Accepted: 16 October 1997     

Dynamics of spreading and wetting: A statistical mechanical point of view

Recent experiments have revealed the possible layering of the advancing interface during the spreading of a drop at a molecular level. This paper is devoted to a presentation of related statistical models on a lattice (solid-on-solid and Ising models) and to a comparison with phenomenology and experimental results. It is shown, in particular, that Ising models lead to a precursor film which grows diffusively.     

Direct measurement of the viscous force between two spherical particles trapped in a thin wetting film

Here we present the first direct measurement of the viscous drag force between two spherical particles of millimeter size trapped in a thin wetting film. Each particle is constrained by the liquid/air interface and the solid substrate. The viscous force is counterbalanced by another known force, the attractive capillary immersion force between identical particles protruding from the film surface. The results of the measurements provide evidence for an increased hydrodynamic force due to a non-Stokesian resistance to the particle motion. Our findings can be applied to the self-assembly of colloidal particles in a two-dimensional array for coating and to the friction between small species and a solid. Received: 19 March 1999 Accepted in revised form: 11 May 1999     

Effect of interfacial mobility on rupture of thin stagnant films on a solid surface due to random mechanical perturbations

Previous analysis of Narsimhan [G. Narsimhan, J. Colloid Interface Sci. 287 (2005) 624-633] for the evaluation of rupture of a nondraining thin film on a solid support due to imposed random mechanical perturbations modeled as a Gaussian white noise has been extended for partially mobile gas-liquid interfaces. The average rupture time of film is evaluated by first passage time analysis (as the mean time for the amplitude of perturbation to become equal to film thickness). The interfacial mobility is accounted for through surface viscosity as well as Marangoni effect. The mean rupture time for partially mobile gas-liquid interface, as characterized by two dimensionless groups, dimensionless surface viscosity and Marangoni number, lies between the two extreme limits for fully mobile and immobile films. The critical wavenumber for minimum rupture time is shown to be insensitive to interfacial mobility. However, the critical dimensionless surface viscosity and critical Marangoni number at which the behavior of thin film deviates from that of fully mobile film and the behavior approaches that of fully immobile film are smaller for higher Hamaker constants, smaller film thickness and smaller surface potentials.     

类金刚石碳薄膜对碳膜导电性能的影响

以聚酰亚胺薄膜为原料,经炭化形成碳膜;进而在碳膜表面制备了类金刚石碳(DLC)薄膜,研究了制备条件对碳膜导电性能的影响.采用扫描电镜分析了薄膜的表面形貌和微观结构;采用X射线衍射仪分析了薄膜的晶体结构.结果表明,DLC薄膜的电阻率随着沉积时间的延长先减小后增加;当沉积时间达到3 h时,相应DLC薄膜的电阻率达到最小值5.66×10-5Ω.m.     

Enhanced optical and nonlinear optical responses in a polyelectrolyte templated Langmuir-Blodgett film

Optical and nonlinear optical properties like fluorescence and second harmonic generation (SHG) of molecular materials can be strongly influenced by the mode of assembly of the molecules. The Langmuir-Blodgett (LB) technique is an elegant route to the controlled assembly of molecules in ultrathin films, and complexation of ionic amphiphiles in the Langmuir film by polyions introduced in the aqueous subphase provides a simple and efficient access to further control, stabilization, and optimization. The monolayer LB film of the hemicyanine-based amphiphile, N-n-octadecyl-4-[2-(4-(N,N-ethyloctadecylamino)phenyl)ethenyl]pyridinium possessing a "tail-head-tail" structure, shows fluorescence as well as SHG response. The concomitant enhancement of both of these linear and nonlinear optical attributes is achieved through templating with the polyanion of carboxymethylcellulose. Brewster angle and atomic force microscopy reveal the influence of polyelectrolyte templating on the morphology of the Langmuir and LB films. Polarized absorption and fluorescence spectroscopy provide insight into the impact of complexation with the polyelectrolyte on the orientation and deaggregation of the hemicyanine headgroup leading to fluorescence and SHG enhancement in the LB film.     

Experimental investigation of evaporation and condensation in the contact line region of a thin liquid film experiencing small thermal perturbations

Image-analyzing interferometry technique is successfully used to study microscale transport processes related to a curved microfilm on a solid substrate. Digital image processing is used to analyze the images of interference fringes, leading to the evaluation of liquid (heptane) film thickness and curvature profiles at different inclinations on a high refractive index glass surface. The curvature profiles obtained at different inclinations clearly demonstrate that there is a maximum in curvature near the junction of the adsorbed film (of uniform thickness) and the curved film, and then it becomes constant in the thicker portions of the film. The adsorbed film thickness is measured for horizontal as well as inclined positions. Experimentally obtained values of the dispersion constants are compared to those predicted from the Dzyaloshinskii-Lifshitz-Pitaevskii (DLP) theory, and reasonable agreements were obtained. A parameter alpha is defined and experimentally evaluated to quantify the closeness of the system to equilibrium. The nonequilibrium behavior of this parameter alpha is also observed with certain heat input at a particular inclination. A small thermal perturbation is used to force the liquid meniscus to undergo a cycle of alternating condensation and evaporation. High-speed video-microscopy and subsequent image analysis are used for data analysis. The numerical solution of a model that takes into account the balance between the suction and the capillary force is compared with the data to elicit new insights into the evaporation/condensation phenomena and to estimate the interfacial temperature differences for near-equilibrium situations.     

Transient interfacial patterns and instabilities associated with liquid film adhesion and spreading

A surface force apparatus was used to study surface shape changes during the adhesion and spreading of a polymer melt on a bare mica surface. Transient fingers were observed during the initial, rapid spreading process, pointing radially out from the initial adhesive contact point. The fingers had microscopic widths and lengths but submicroscopic thicknesses. They eventually disappeared, leaving a more slowly growing circular neck with a smooth, featureless polymer-air surface. The mean radius of the spreading meniscus (neck) was found to follow a scaling relationship with time of the form (ri + ro)/2 proportional, variant tn, with n = 0.128, while the ends of the fingers grew according to ro proportional, variant tn, with n = 0.10. These rates agree with the values of n = 0.100-0.125 predicted by classical wetting theories for circular macroscopic droplets (i.e., radially symmetric, without fingers) spreading on a solid surface. The lifetime of the transient fingering patterns increases with the polymer viscosity as tau proportional, variant etan, with n = 2.1 +/- 0.2. A circular trough or depression in the film was observed just beyond where the fingers ended, which appears to be a source of the material for the advancing fingers. In addition, beyond the trough, circular ripples/waves were observed on the polymer melt film surface. Such patterns may arise quite generally whenever a perturbation occurs that changes the local forces, thereby inducing a bulge or depression in a liquid film or surface. Thus, we observe similar fingers and ripples/waves during the spreading of liquid polybutadiene on (the immiscible and more viscous) liquid poly(dimethylsiloxane), suggesting that the phenomenon may exist in various liquid adhesion and spreading situations. For low viscosity liquids such as water and low molecular weight oils, our scaling relations suggest that the transient patterns will exist for only a few microseconds; this is likely the reason for why they have not yet been observed.     

The condition of mechanical equilibrium on the surface of a nonuniform thin film

The condition of internal mechanical equilibrium of a curved surface layer is derived, and its application to practically important cases of incomplete formation of the surface layer (as is sometimes the case, for example, in thin films) is considered. The notion of a local disjoining pressure is introduced, and the equilibrium condition for a variable-thickness thin film is obtained; this condition is valid both in the absence and in the presence of external fields. The cases of a wedge-shaped film, cylindrical film, spherical film, and transition zone of a wetting film are analyzed.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 2, 2005, pp. 235–242.Original Russian Text Copyright © 2005 by Rusanov, Shchekin.     

Periodic perturbations of a polymer

The reduction of the short range translational symmetry of a polymer chain (caused by, for example, the loss of an isoconformational structure) is accommodated as a periodic perturbation in a semi-empirical tight-binding LCAO calculation. Using the results of a calculation on an unperturbed chain in a perturbational mixing procedure an energy matrix can be calculated whose order is equal to (or even less than) that of the unperturbed structure. The method is applied to the generation of various chain conformations from all-trans polyacetylene and is shown to work successfully.