Dewetting of thin polymer films at temperatures close to the glass transition

We present detailed studies on dewetting of thin polystyrene (PS) films which were deposited onto silicon wafers coated with a polydimethylsiloxane (PDMS) monolayer. Experiments were performed at temperatures close to the glass transition temperature of PS. Several significant deviations from the dewetting behaviour of Newtonian liquids were observed. The length of the PS molecules, and thus the viscosity, turned out to be of minor importance in determining the dewetting velocity, in particular for the later regimes. In stark contrast, the geometry of the drying spot had a striking influence on the dewetting velocity. Initially, dewetting from straight contact lines proceeded faster than the opening of circular holes. At later stages, the process slowed down significantly in both cases. Under the conditions at which our experiments were performed, PS cannot flow like a simple liquid. Thus, the observed dewetting has to be the consequence of plastic deformation induced by capillary forces. Our results indicate that under such conditions the energy dissipation process is strongly affected by geometry, which is not the case for viscous liquids.Received: 1 January 2003, Published online: 14 October 2003PACS: 68.60.-p Physical properties of thin films, nonelectronic - 61.41. + e Polymers, elastomers, and plastics - 68.55.-a Thin film structure and morphology - 83.50.-v Deformation and flow     

Pattern formation in drying drops

Ring formation in an evaporating sessile drop is a hydrodynamic process in which solids dispersed in the drop are advected to the contact line. After all the liquid evaporates, a ring-shaped deposit is left on the substrate that contains almost all the solute. Here I show that the drop itself can generate one of the essential conditions for ring formation to occur: contact line pinning. Furthermore, I show that when self-induced pinning is the only source of pinning an array of patterns-that include cellular and lamellar structures, sawtooth patterns, and Sierpinski gaskets-arises from the competition between dewetting and contact line pinning.     

Cascade of shocks in inertial liquid-liquid dewetting

We study the inertial dewetting of water films (A) (thickness e) deposited on highly hydrophobic liquid substrates (B). On these ideal surfaces, thin films can be made which dewet at large velocities obeying under those conditions the Culick law for the bursting of soap films. The rim collecting the water film can become coupled to the surface waves characterized by a surface tension gamma(B) upstream of the rim (coated substrate) and gamma = gamma(B) downstream, where the water film has dried. Upon decreasing the thickness, we observe a sequence of two hydraulic shocks during the dewetting inducing gravity waves behind the rim, and capillary waves ahead.     

Open questions and promising new fields in dewetting

This contribution summarizes the present understanding of dewetting focusing on three points that are either controversial or open. The first issue concerns the initial formation of holes, i.e. the film rupture. The second point concerns the unstable growth of holes, i.e. the transversal instability of the receding contact line. Finally, recent extensions towards dewetting on heterogeneous substrates are examined. In passing the long time evolution in dewetting and the coupling of dewetting with other effects are discussed.Received: 1 August 2003PACS: 68.15. + e Liquid thin films - 68.55.-a Thin film structure and morphology - 47.20.Ma Interfacial instability     

Viscoelastic dynamics of polymer thin films and surfaces

The strain relaxation behavior in a viscoelastic material, such as a polymer melt, may be strongly affected by the proximity of a free surface or mobile interface. In this paper, the viscoelastic surface modes of the material are discussed with respect to their possible influence on the freezing temperature and dewetting morphology of thin polymer films. In particular, the mode spectrum is connected with mode coupling theory assuming memory effects in the melt. Based on the idea that the polymer freezes due to these memory effects, surface melting is predicted. As a consequence, the substantial shift of the glass transition temperature of thin polymer films with respect to the bulk is naturally explanied. The experimental findings of several independent groups can be accounted for quantitatively, with the elastic modulus at the glass transition temperature as the only fitting parameter. Finally, a simple model is put forward which accounts for the occurrence of certain generic dewetting morphologies in thin liquid polymer films. It demonstrates that by taking into account the viscoelastic properties of the film, a morphological phase diagram may be derived which describes the observed structures of dewetting fronts. It is demonstrated that dewetting morphologies may also serve to determine nanoscale rheological properties of liquids.Received: 1 January 2003, Published online: 14 October 2003PACS: 47.50. + d Non-Newtonian fluid flows - 68.47.Mn Polymer surfaces - 68.60.Dv Thermal stability; thermal effects     

Persistent droplet motion in liquid-liquid dewetting

When a nonvolatile liquid film dewets from a partly compatible liquid substrate, the advancing dewetting front leaves behind droplets formed through a Rayleigh instability mechanism at its rim. We have found that these droplets continue to move in the direction of the dewetting front for extended periods (of order one day) with an initial droplet velocity varying linearly with the droplet size, and a displacement varying logarithmically with time. We attribute this persistent motion to a transient surface tension gradient on the substrate liquid surface trailing the dewetting front.     

金属纳米薄膜在石墨基底表面的动力学演化

采用分子动力学方法研究了金属Au和Pt纳米薄膜在石墨(烯)基底表面的动力学演化过程,探讨了金属薄膜和石墨(烯)基底间的相互作用对金属纳米薄膜在固态基底表面的去湿以及脱附的动力学演化的影响.研究结果表明,在高温下,相同层数的Au和Pt纳米薄膜在单层石墨基底表面上存在不同的去湿现象,主要表现为厚度较小的Pt纳米薄膜在去湿过程中有纳米空洞形成,而同样厚度的Au薄膜在去湿过程中没有形成空洞.Au和Pt两种金属薄膜在高温下都去湿形成纳米液滴,这些液滴最终都以一定的速度脱离基底.在模拟的薄膜厚度范围内(0.2—2.3 nm),Au和Pt纳米液滴脱离基底的速度随厚度增加表现出不同的变化规律.Pt纳米液滴的脱离速度随薄膜初始厚度的增加先增加后减少,而Au脱离速度随厚度的增加先减少,达到一个临界厚度后脱离速度突然迅速增加.利用薄膜与基底间相互作用的不同导致去湿过程中的黏滞耗散不同,定性分析了这种变化规律的原因.此外,进一步研究还发现金属液滴的脱离时间与薄膜厚度和模拟温度的依赖关系,发现脱离时间随薄膜厚度的增加而增加,随模拟温度的升高而减小.这些研究结果可以为金属镀膜、浮选、表面清洁、器件表面去湿等工业生产过程提供理论指导.     

Stabilization of discotic liquid organic thin films by ITO surface treatment

Discotic liquid crystals (LCs) are promising materials in the field of electronic components and, in particular, to make efficient photovoltaic cells due to their good charge transport properties. These materials generally exhibit a mesophase in which the disk-shaped molecules can self-assemble into columns, which favorize charge displacement, and may align themselves uniformly on surfaces to form well-oriented thin films. In order to orientate such a columnar thin film on an indium tin oxide (ITO) substrate, the film is heated up to the temperature range of the isotropic liquid phase and subsequently cooled down again. This treatment may lead not only to the desired alignment, but also to dewetting, which leads to an appreciable inhomogeneity in film thickness and to short circuits during the realization of photovoltaic cells. In this article, we describe how this dewetting and the film morphology can be influenced by ITO surface treatments. The chemical modifications of the surface by these treatments were studied by X-ray photoelectron spectroscopy (XPS). Such ITO treatments are shown to be efficient to prevent thin film dewetting when combined with rapid cooling through the isotropic-to-LC phase transition.     

Dewetting of thin polymer films

We study the dewetting of thin polymer films deposited on slippery substrate. Recent experiments on these systems have revealed many unexpected features. We develop here a model that takes into account the rheological properties of polymer melts, focussing on two dewetting geometries (the receding of a straight edge, and the opening of a hole). We show that the friction law associated with the slippage between the film and the substrate has a direct influence on the dewetting dynamic. In addition, we demonstrate that residual stresses, which can be stored in the films due to their viscoelasticity, are a source of destabilization for polymer films, and accelerate the dewetting process.     

Regular surface patterns on Rayleigh-Taylor unstable evaporating films heated from below

We study a thin liquid film with a free surface on the underside of a cooled horizontal substrate. We show that if the fluid is initially in equilibrium with its own vapor in the gas phase below, regular surface patterns in the form of long-wave hexagons having a well-defined lateral length scale are observed. This is in sharp contrast to the case without evaporation where rupture or coarsening to larger and larger patterns is seen in the long time limit. In this way, evaporation could be used for regular structuring of the film surface. Finally, we estimate the finite wave length for the simplified case of an extended Cahn-Hilliard equation.     

Self-organization in a chromium thin film under laser irradiation

Self-organization of chromium on glass was observed during laser ablation of the metal film with partially overlapping laser pulses. The beam of a nanosecond pulse laser tightly focused to a line was applied to the back-side ablation of the chromium thin film on a glass substrate. While the line ablated with a single laser pulse had sharp edges on both sides with ridges of the melted metal, the use of partially overlapping pulses formed a complicated structure made of the metal remaining from the ridges. Regular structures of ripples were developed in a certain range of laser fluence and pulse overlap. The ripple period could be controlled from 2.5 to 4 μm by variation of the processing parameters. Various experimental techniques were applied to test the structures, and different models of the ripple formation in the thin metal film were considered. The initial quasi-periodical formation started because of dewetting of thin liquid metal films on the glass substrate after its melting. Similar to the evaporation of liquid films, the small perturbation in the ridge thickness was able to induce instability in evaporation of the thin melted metal film. Freezing of the nonequilibrium state between laser pulses was one of the stabilizing factors in self-organization of the metal.     

A mesoscopic model for (de)wetting

We present a mesoscopic model for simulating the dynamics of a non-volatile liquid on a solid substrate. The wetting properties of the solid can be tuned from complete wetting to total non-wetting. This model opens the way to study the dynamics of drops and liquid thin films at mesoscopic length scales of the order of the nanometer. As particular applications, we analyze the kinetics of spreading of a liquid drop wetting a solid substrate and the dewetting of a liquid film on a hydrophobic substrate. In all these cases, very good agreement is found between simulations and theoretical predictions.     

Role of the external pressure on the dewetting of soft interfaces

We consider dewetting at soft interfaces, e.g., a rubber ball squeezed in a fluid against a flat hard substrate. We show that the applied squeezing pressure, which was not taken into account in earlier studies of the dewetting transition, may have a big effect on the squeeze-out dynamics.Received: 10 August 2003, Published online: 3 September 2003PACS: 68.15. + e Liquid thin films - 81.40.Pq Friction, lubrication, and wear     

Reduced viscosity in thin polymer films

The dewetting of thin polystyrene films (20-500 nm) on a liquid substrate is studied at time scales that are long compared to the reptation time. It is shown that the kinetics correspond to those of purely viscous flow and that the viscosity measured by this technique is, for the thickest films, consistent with bulk measurements. Films on the order of the coil size are then studied. The effective viscosity of these films displays a large decrease when the film thickness h is below several radius of gyration, R(g). This viscosity reduction is found to depend only on the ratio h/R(g).     

Direct visualisation of homogeneous and heterogeneous crystallisation in an ensemble of confined domains of poly(ethylene oxide)

We present a study of homogeneous and heterogeneous nucleation in polymer crystallisation. In bulk samples the crystallization is typically dominated by nucleation from defects (heterogeneous nucleation), and consequently studies must rely on sample preparation to minimize this effect. We present a study of nucleation within discrete droplets of poly(ethylene oxide) that are formed by the dewetting of a thin film on an unfavourable substrate. The samples provide an ensemble of impurity-free droplets, with length scales that can easily be measured. We show that the data for heterogeneous and homogeneous nucleation is qualitatively different, and that the data mirrors the fundamental differences in the underlying mechanisms for the two nucleation processes. The experiments presented here provide a simple method that can be used to study heterogeneous and homogeneous nucleation in great detail.Received: 1 January 2003, Published online: 30 October 2003PACS: 61.41. + e Polymers, elastomers, and plastics - 68.55.-a Thin film structure and morphology - 81.10.-h Methods of crystal growth; physics of crystal growth     

Templating of thin films induced by dewetting on patterned surfaces

The instability, dynamics, and morphological transitions of patterns in thin liquid films on chemically heterogeneous striped surfaces are investigated based on 3D nonlinear simulations. The film breakup is suppressed on some potentially destabilizing nonwettable sites when their spacing is below a characteristic length scale of the instability, lambda(h). The thin film pattern replicates the substrate surface energy pattern closely only when (i) the periodicity of substrate pattern lies between lambda(h) and 2lambda(h), and (ii) the stripe width is within a range bounded by a lower critical length, below which no heterogeneous rupture occurs, and an upper transition length above which complex morphological features unlike the substrate pattern are formed.     

Viscoelastic thin polymer films under transient residual stresses: two-stage dewetting on soft substrates

A nonmonotonic, two-stage dewetting behavior was observed for spin coated thin viscoelastic polymer films on soft elastic substrates. At times shorter than the relaxation time of the polymer (ttau_{rep}), dewetting accelerated, accompanied by an unstable rim. However, holes nucleated at t相似文献   

含活性剂液膜去润湿演化的稳定性特征

针对含非溶性活性剂的液膜在固体基底上的去润湿过程,基于润滑理论建立了基态和扰动态下液膜厚度和表面活性剂浓度的演化模型,应用非模态理论分析了演化过程的稳定性特征,探讨了分子间力对液膜去润湿过程的影响. 研究表明,微扰动波的引入（k=1）有利于液膜去润湿过程的稳定进行,扰动能量逐渐衰减,然而,该效果随着扰动波数的增加而显著改变,k ≥ 2时,液膜演化的稳定性反而恶化,扰动能量被逐步放大,演化呈现出非稳定特征. 增大初始液膜厚度可以有效改善液膜流动的稳定性. 范德华力放大了液膜表面的微扰动,使得液膜演化的稳定性下降;相反,Born斥力和静电斥力具有增强去润湿稳定性的作用. 关键词： 活性剂 去润湿 分离压 稳定性     

Instability of thin liquid films by density variations: a new mechanism that mimics spinodal dewetting

Based on the linear stability analysis and nonlinear simulations, conditions are established under which instability and dewetting of a thin liquid film can be engendered solely by the density variations (for example, due to confinement, layering, defects, and restructuring) related to changes in the local film thickness. An increase in the density with the increasing film thickness can stabilize a thermodynamically unstable film, and, equally interesting, a decrease in the density with increasing film thickness can render a thermodynamically stable film unstable. Morphological characteristics of this novel density variation induced instability closely resemble the well-known spinodal dewetting.     

Fingering instabilities in dewetting nanofluids

The growth of fingering patterns in dewetting nanofluids (colloidal solutions of thiol-passivated gold nanoparticles) has been followed in real time using contrast-enhanced video microscopy. The fingering instability on which we focus here arises from evaporatively driven nucleation and growth in a nanoscopically thin precursor solvent film behind the macroscopic contact line. We find that well-developed isotropic fingering structures only form for a narrow range of experimental parameters. Numerical simulations, based on a modification of the Monte Carlo approach introduced by Rabani et al. [Nature (London) 426, 271 (2003)10.1038/nature02087], reproduce the patterns we observe experimentally.