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.     

Effect of thermal treatment on interfacial properties of beta-lactoglobulin

The changes in the secondary conformation and surface hydrophobicity of beta-lactoglobulin subjected to different thermal treatments were characterized at pH values of 7, 5.5 and 4 using circular dichroism (CD) and hydrophobic dye binding. Heating resulted in a decrease in alpha-helix content with a corresponding increase in random coil at all pH values, this change being more pronounced for small heating times. Heating also resulted in an increase in surface hydrophobicity as a result of partial denaturation, this increase being more pronounced at pH 4. Thermal treatment resulted in a shift of the spread monolayer isotherm at air-water interface to smaller area per molecule due to increased flexibility and more loop formation. Thermal treatment led to an increase in interfacial shear elasticity and viscosity of adsorbed beta-lactoglobulin layer at pH 5.5 and 7. Interfacial shear elasticity, shear viscosity, stability of beta-lactoglobulin stabilized emulsion and average coalescence time of a single droplet at a planar oil-water interface with adsorbed protein layer exhibited a maximum for protein subjected to 15 min heat treatment at pH 7. At pH 5.5, the interfacial shear rheological properties and average single drop coalescence time were maximum for 15 min heat treatment whereas emulsion stability was maximum for 5 min heat treatment. At pH 7, thermal treatment was found to enhance foam stability. Analysis of thin film drainage indicated that interfacial shear rheological properties do not influence thin film drainage.     

Structure–property relationships of latex films: a special emphasis on viscoelastic behavior and water vapor permeability

The purpose of this work is to investigate the structure and related properties of polymer films obtained upon latex dehydration and coalescence of the particles. Coalesced latex films can be considered as cellular structures, in which the cell cores consist of the hydrophobic particle cores, while the array of interfacial membranes mainly contains hydrophilic species. The linear viscoelastic behavior of the films and their water vapor permeability properties are investigated using dynamic micromechanical analysis and vapor sorption, respectively. It is shown that both core and membrane have a strong effect on the film properties. The structure and viscoelastic behavior of polymer films obtained from sterically stabilized latexes are also studied and compared with that observed for films obtained from electrostatically stabilized ones.     

An Insoluble Surfactant Model for a Vertical Draining Free Film

A mathematical model is constructed to study the evolution of a vertically oriented thin liquid film draining under gravity when there is an insoluble surfactant with finite surface viscosity on its free surface. Lubrication theory for this free film results in three coupled nonlinear partial differential equations describing the free surface shape, the surface velocity, and the surfactant transport at leading order. We will show that in the limit of large surface viscosity, the evolution of the free surface is that obtained for the tangentially immobile case. For mobile films with small surface viscosity, transition from a mobile to an essentially immobile film is observed for large Marangoni effects. It is verified that increasing surface viscosity and the Marangoni effect retard drainage, thereby enhancing film stability. The theoretical results are compared with experiment; the purpose of both is to act as a model problem to evaluate the effectiveness of surfactants for potential use in foam-fabrication processes. Copyright 2000 Academic Press.     

Stability of mechanical properties of molecular layer–deposited alucone

We report on the effect of aging on the mechanical properties of molecular layer–deposited (MLD) thin films. We studied the mechanical failure of the films during uniaxial tensile testing and observed a sixfold difference in the crack-onset strain (COS) and related flexibility within the first two days after the samples were exposed to ambient air. The MLD films made using trimethylaluminum and ethylene glycol are notorious for exhibiting structural changes after the fabrication; we show that these changes are detrimental for mechanical robustness of the films. This information aids to plan the handling or the protection of these films to achieve better performance with these materials. The interfacial shear strains and COSs of the shortly air-exposed 300-nm-thick films were observed to be roughly 0.3% and 1.8%, respectively. These values are the highest reported so far for hybrid organic–inorganic MLD thin films and would extrapolate to about 14% COS for 5-nm-thick film, indicating potential applications as interfacial adhesion layer for films on polymer substrates and as a protective coating in battery applications.     

Dewetting of thin liquid films near soft elastomeric layers

Thin liquid film instabilities driven by van der Waals forces and in the proximity of soft elastomeric layers are considered in this work through two model problems: (i) a liquid film resting on an elastomeric layer and (ii) a liquid film bounded from one side by a rigid substrate and from the other side by an elastomeric layer. The elastomeric layers are modeled as linear viscoelastic solids, van der Waals forces are assumed to act only in the liquid, and lubrication theory and linear stability analysis are applied. For a liquid film resting on an elastomeric layer, substrate deformability has a destabilizing effect, as evidenced by an increase in the maximum growth rate and range of unstable wavenumbers. The destabilization worsens for thicker solid layers and is due to a lowering of the effective liquid-air interfacial tension. For an elastomeric layer resting on a liquid film, layer deformability has a stabilizing effect for thin layers but a destabilizing effect for thicker layers, with the former due to an enhancement and the latter due to a reduction of the effective solid-air interfacial tension. The results presented here suggest the possibility of exploiting the dewetting of thin liquid films to create topographically patterned surfaces on soft polymeric solids.     

Effect of limited hydrolysis on the interfacial rheology and foaming properties of beta-lactoglobulin A

Hydrolysis of beta-lactoglobulin (beta-Lg), genetic variant A, using a serine protease specific for glutamic and aspartic acid residues from Bacillus licheniformis (BLP), resulted in improved foam overrun and foam stability. Limited hydrolysis (19-26% hydrolysed beta-Lg) led to a more rapid increase in the viscoelastic properties of air/water interfacial films and a concomitant increase in foam overrun compared with intact beta-Lg, presumably due to increased exposure of hydrophobic areas. The increased exposure did not, however, cause formation of an interfacial layer with increased viscoelastic properties. More extended hydrolysis (86% hydrolysed beta-Lg) resulted in a higher initial overrun than the unhydrolysed sample and the best foam stability. The interfacial elasticity and viscosity, though, was the lowest observed. Thus, high maximum values of these interfacial properties are not necessary prerequisites for formation of a voluminous and stable foam.     

Cyclic nonlinear behavior of a glassy polymer using a contact method

The effects of repeated large strain shear cycles on the dynamics of a glassy acrylate polymer are investigated using an original contact method. It is based on the measurement of the shear properties of thin (about 50 μm) polymer films geometrically confined within contacts between elastic substrates. Under small amplitude (300 nm–10 μm) oscillating lateral displacements, friction at the contact interface can be neglected and the measurement of the contact lateral response thus provides information about the rheology of the sheared polymer film. Using this approach, the complex shear modulus of the polymer film can be measured both in the linear (viscoelastic) and in the nonlinear regimes. The investigations are focused on the changes in mechanical properties induced in a large strain regime where the polymer glass is cyclically sheared up to the yield point. During the application of large strain cycles, the mechanical response of the polymer glass slowly evolves toward a quasi stabilized state which is described from the measurement of an apparent–strain dependent–complex shear modulus. When the applied strain is increased by a tenfold factor, this apparent shear modulus decreases by about one decade. These underlying changes are investigated from a consideration of the time dependent linear viscoelastic properties after the mechanical stimulus. Both mechanical rejuvenation and recovery (ageing) effects are evidenced. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Influences of chain heterogeneity on instability of polymeric thin films: dewetting of polystyrenes, polychloromethylstyrenes and its copolymers

This study compares the stability of various polymeric thin films supported on SiO(x)/Si substrate. Dewetting behaviors of polystyrenes (PS), polychloromethylstyrenes, and random poly(styrene-co-chloromethylstyrene)s are investigated by utilizing atomic force microscopy. A systematic addition of the chloromethylstyrene (ClMS) unit into PS chain causes the increase of segment polarity, affecting interfacial and interchain interactions in thin films. It is found that stability of the polymeric films depends on two major parameters, ratio of the ClMS unit and film thickness. For approximately 5 nm thick film, the addition of only 5 mol% ClMS unit causes a drastic increase of its stability, attributed to the enhanced interfacial interactions between ClMS group and SiO(x) layer. Further increasing the ClMS mole ratio to 20, 45, and 100% is accompanied by a systematic increase of the film stability. Thicker films (thicknesses approximately 22 and approximately 45 nm) of the copolymer with 5 mol% ClMS unit exhibit rather different behavior. They are found to be less stable compared to the PS films. However, the films of copolymers with ClMS unit of 20, 45, and 100% are still much more stable than the PS films. These dewetting behaviors of the copolymers are correlated to the interfacial interactions, interchain interactions and segmental segregation in thin films.     

Structure and mechanical properties of a polyglycerol ester at the air-water surface

We studied the structure and mechanical properties of surface films resulting from the adsorption of a dispersed L beta phase at the air-water interface. This L beta phase corresponds to multilamellar vesicles and is formed by a commercial polyglycerol fatty acid ester (PGE) in aqueous solution at temperatures below the main chain-melting temperature (Tm=58 degrees C). We measured the adsorption kinetics using the pendant drop technique and mechanical properties of PGE films using oscillatory surface shear and dilatational rheometric methods. Though the adsorption kinetics are very slow, we show that the L beta phase of PGE is surface-active and forms viscoelastic films at the air-water surface after sufficiently long adsorption times. The rheological response functions to shear and dilatational deformation are reminiscent of those of temporary networks, indicating an intermolecular connectivity at the surface. This temporary network is probably created by hydrophobic interactions of alkyl chains. We obtained more detailed information about the properties of this network by comparing the rheological signature of an adsorbed PGE film (unknown structure) with a solvent-spread monolayer (known structure). We characterized the structural features of spread PGE films by recording the Langmuir isotherm and Brewster angle micrographs (BAM).We show that the rheological responses of the adsorbed film and the solvent-spread monolayer are very close to each other, indicating a structural similarity. From this study, we conclude that a dispersed L beta phase of PGE is able to adsorb at the air-water surface at T相似文献   

Time-scale- and temperature-dependent mechanical properties of viscoelastic poly(3,4-ethylenedioxythiophene) films

The viscoelastic properties of thin films of poly(3,4-ethylenedioxythiophene) (PEDOT) have been studied using the method of acoustic impedance. The films were deposited on the Au electrodes of 10 MHz AT-cut quartz thickness shear mode resonators and exposed to acetonitrile solutions of 0.1 M TEABF4 and LiClO4. For p-doped films, admittance spectra as a function of potential (E), temperature (T), and time scale (frequency, via harmonics, in the range 10-110 MHz) were acquired. Shear modulus components extracted from these responses surprisingly showed virtually no variation with E (and thus film solvation) or with T, but the variation with frequency was dramatic. This qualitative behavior and the numerical values of the shear moduli contrast strongly with recently reported data for the related poly(3-hexylthiophene) system, which shares the same conducting spine but differs substantially in the substitution pattern. Accordingly, the models and interpretation for PEDOT are quite different: film dynamics are determined by free-volume effects, and side-chain motion is not a significant factor. Qualitatively similar potential and time-scale effects were seen for n-doped PEDOT, but the scope of the measurements was limited by film stability.     

Effect of Interfacial Adsorption on the Stability of Thin Polymer Films in a Solvent-induced Process

The stability of ultrathin polymer films plays a crucial role in their technological applications. Here, we systematically investigated the influence of interfacial adsorption in physical aging and the stability of thin polymer films in the solvent-induced process. We further identify the stability mechanism from the theory of thin film stability. Our results show that the aging temperature and film thickness can strongly influence the stability of thin PS films in acetone vapor. Physical aging can greatly improve the stability of thin polymer films when the aging temperature T_(aging1)T_g. A thinner PS film more quickly reaches a stable state via physical aging. At short aging time, the formation of the adsorbed layer can reduce the polar interaction; however, it slightly influences the stability of thin polymer films in the solvent-induced process. At later aging stage,the conformational rearrangement of the polymer chains induced by the interfacial effect at the aging temperature T_(aging1) plays an important role in stabilizing the thin polymer films. However, at T_(aging2)T_g, the process of physical aging slightly influences the stability of the thin polymer films.The formation of the adsorbed layer at T_(aging2) can reduce the short-range polar interaction of the thin film system and cannot suppress the instability of thin polymer films in the solvent-induced process. These results provide further insight into the stable mechanism of thin polymer films in the solvent-induced process.     

掺硼p型非晶硅薄膜的制备及光学性能的表征

以高氢稀释的硅烷(SiH₄ )为反应气体,硼烷(B₂H₆)为掺杂气体,利用RF-PECVD方法,在玻璃衬底上制备出掺硼的氢化非晶硅(a-Si:H)薄膜,研究了硼掺杂量对氢化非晶硅(a-Si:H)薄膜的光学性能的影响.利用NKD-7000 W光学薄膜分析系统测试薄膜的透射谱和反射谱,并利用该系统的软件拟合得出薄膜的折射率、消光系数、吸收系数等光学性能参数,利用Tauc法计算掺硼的非晶硅薄膜的光学带隙.实验结果表明,随着硼掺杂量的增加,掺杂非晶硅薄膜样品在同一波长处的折射率先增大后减小,而且每一样品均随着入射光波长的增加而减小,在波长500 nm处的折射率均达到4.3以上;薄膜的消光系数和吸收系数随着硼掺杂量的增大而增大,在500 nm处的吸收系数可高达1.5×10⁵cm^-1.在实验的硼掺杂范围内,光学带隙从1.81 eV变化到1.71 eV.     

Stability of draining plane-parallel films containing surfactants

The stability of partially mobile draining thin liquid films with respect to axisymmetric fluctuations was studied. The material properties of the interfaces (Gibbs elasticity, surface and bulk diffusions) were taken into account. When studying the long wave stability of films, the coupling between the drainage and perturbation flows was considered and the lubrication approximation was applied. Two types of wave modes were examined: radially-bounded and unbounded waves. The difference between the thickness of loss of stability, h(st), the transitional thickness, h(tr), at which the critical wave causing rupture becomes unstable, and the critical thickness, h(cr), when the film ruptures, is demonstrated. Both the linear and the non-linear theories give h(st) > h(tr) > h(cr). The numerical results show that the interfacial mobility does not significantly influence the thickness of the draining film rupture. The interfacial tension and the disjoining pressure are the major factors controlling the critical thickness. The available experimental data for critical thicknesses of foam and emulsion films show excellent agreement with the theoretical predictions. The important role of the electromagnetic retardation term in the van der Waals interaction is demonstrated. Other published theories of the film stability are discussed.     

Instability and dewetting of ultrathin solid viscoelastic films on homogeneous and heterogeneous substrates

Instability and dewetting engendered by the van der Waals force in soft thin (<100 nm) linear viscoelastic solid (e.g., elastomeric gel) films on uniform and patterned surfaces are explored. Linear stability analysis shows that, although the elasticity of the film controls the onset of instability and the corresponding critical wavelength, the dominant length-scale remains invariant with the elastic modulus of the film. The unstable modes are found to be long-wave, for which a nonlinear long-wave analysis and simulations are performed to uncover the dynamics and morphology of dewetting. The stored elastic energy slows down the temporal growth of instability significantly. The simulations also show that a thermodynamically stable film with zero-frequency elasticity can be made unstable in the presence of physico-chemical defects on the substrate and can follow an entirely different pathway with far fewer holes as compared to the viscous films. Further, the elastic restoring force can retard the growth of a depression adjacent to the hole-rim and thus suppress the formation of satellite holes bordering the primary holes. These findings are in contrast to the dewetting of viscoelastic liquid films where nonzero frequency elasticity accelerates the film rupture and promotes the secondary instabilities. Thus, the zero-frequency elasticity can play a major role in imposing a better-defined long-range order to the dewetted structures by arresting the secondary instabilities.     

Effect of Surfactants on the Film Drainage

Drainage of a partially mobile thin liquid film between two deformed and nondeformed gas bubbles with different radii is studied. The lubrication approximation is used to obtain the influence of soluble and insoluble surfactants on the velocity of film thinning in the case of quasi-steady state approach. The material properties of the interfaces (surface viscosity, Gibbs elasticity, surface diffusivity, and/or bulk diffusivity) are taken into account. In the case of deformed bubbles the influence of the meniscus is illustrated assuming simple approximated shape for the local film thickness. Simple analytical solutions for large and small values of the interfacial viscosity, and for deformed and nondeformed bubbles, are derived. The correctness of the boundary conditions used in the literature is discussed. The numerical analysis of the governing equation shows the region of transition from partially mobile to immobile interfaces. Quantitative explanation of the following effects is proposed: (i) increase of the mobility due to increasing bulk and surface diffusivities; (ii) role of the surface viscosity, comparable to that of the Gibbs elasticity; and (iii) significant influence of the meniscus on the film drainage due to the increased hydrodynamic resistance. Copyright 1999 Academic Press.     

双层铜金属薄膜纳米压痕机械性能的分子动力学模拟

多层金属薄膜的机械性质在纳米组件的设计上是非常重要的.目前,纳米尺度材料的机械性质测量的最主要方法为纳米压痕检测技术.本文应用分子动力学理论对双层铜金属薄膜界面的结构形态与特性进行分析探讨.选用FCC结构单晶铜的(100)面,(110)面和双层铜金属薄膜作为探讨界面性质的材料,进而探讨了单晶铜及双层铜金属薄膜的纳米压痕变形性质.     

Rheological studies of freely suspended soap films

 We have developed an original viscometer that allows the determination of the viscoelastic properties of freely suspended soap films. We have found that soap films have a very high shear viscosity and a small shear modulus that might be associated with a glassy (gel-like) behavior. The incorporation of polymer chains inside the soap films does not change very significantly these viscoelastic properties that are governed by the dense packing of the surfactant in the interfacial films; nevertheless, the role of the polymer can be qualitatively described by scaling laws. Received: 12 July 1999/Accepted in revised form: 7 September 1999     

Effect of Lipid Phase State and Foam Film Type on the Properties of DMPG Stabilized Foams

The drainage and stability of DMPG (l-α-phosphatidyl-dl-glycerol dimyristoyl) foams were studied by a microconductivity method under conditions where three different foam film types could be formed—thin foam films (TFF), common black foam films (CBF), and Newton black foam films (NBF). Foaming properties were investigated at 20 and 28°C where DMPG is in the gel and liquid-crystalline states. Higher conductivity signals were observed at the higher temperature where DMPG was in the liquid-crystalline state, which is indicative of wetter or more stable foams under these conditions. This effect was observed independent of foam film type. However, for a given phase state, the type of foam films formed significantly influenced the stability and rate of drainage of the foam. Indeed, the water content of the foams, obtained under conditions for formation of different foam films, is ranked in the order TFF > CBF > NBF. When the temperature was increased to 28°C (i.e., in the liquid-crystalline state), CBF and NBF showed a slight decrease in film thickness and an increase in film lifetime and surface molecular diffusion coefficient in the adsorbed layer. It is likely that the fluidity of the interfacial layer is an important factor contributing to DMPG foam stabilization.     

Mechanical characterization of nanoclay-filled PDMS thin films

Polydimethylsiloxane (PDMS) reinforced by nanoclay platelets exhibits excellent mechanical properties for microfluidic systems. We tested PDMS-clay nanocomposite thin films under flat-ended cylindrical indentation and measured the elastic modulus and shear strength. A simple formulation based on a shear-lag model, fed by numerical simulations, was introduced to estimate the interfacial shear strength of thin films. Increase in the nanoclay content improved the elasticity of PDMS-clay thin films but reduced their interfacial shear strength. Shear thinning behavior of nanoclay platelets probably reduced the strength of PDMS nanocomposites. The proposed approach can be used for characterization of any polymeric thin films.