Stress generation by solvent absorption and wrinkling of a cross-linked coating atop a viscous or elastic base

An in-plane constrained cross-linked gel layer absorbs an equilibrium amount of solvent and experiences in-plane compressive stress. A stability analysis of such an elastic gel layer that is attached to either a viscous or an elastic bottom layer atop a rigid substrate is considered. The effects of the top and bottom layer moduli (E(t) and E(b)), the bottom-to-top layer thickness ratio (H/h), and the polymer solvent interaction parameter (chi) on the critical condition of wrinkling, wrinkle wavelength, and amplitude are examined. When the bottom layer is viscous, the compressed top layer is always unstable, and wrinkling is rate-controlled. The viscous flow of the bottom layer governs the rate and determines the fastest growing wavelength. As E(t) rises, the bending stiffness of the elastic layer does as well, and so the fastest growing wavelength (lambda(m)) rises and the equilibrium amplitude (A(e)) falls. As H/h rises, the constraint of the rigid substrate diminishes, and so lambda(m) and A(e) rise. As chi falls or as the solvent has higher affinity for the polymeric gel, lambda(m) falls and A(e) rises because better solvents create higher compressive strain that promote low-wavelength, high-amplitude wrinkles. When the bottom layer is elastic, a critical compressive stress exists. If the generated compressive stress by solvent absorption is greater than the critical stress, the top layer wrinkles. It was found that wrinkling is most likely at intermediate E(t), low E(b), high H/h, and low chi. Further, lower chi, higher H/h, and lower E(b) were found to promote higher equilibrium amplitude and higher wavelength wrinkles.     

Self-organized anisotropic wrinkling of molecularly aligned liquid crystalline polymer

Anisotropic wrinkling which utilizes the anisotropic nature of liquid crystalline polymer (LCP) is demonstrated as a means of physical self-assembly to produce periodic microstructures. Through the plasma treatment on the molecularly aligned LCP film surface, one-dimensionally ordered wrinkle pattern was spontaneously formed on glass substrates without employing external thin-film deposition or prestrain control of the system. Experimental results indicate that the directionality of the wrinkle pattern can be tailored by the structural ordering of LCP molecules in the bilayer system of a hard skin layer on a soft substrate. Studies on process variables, such as the plasma treatment time and the film thickness, were conducted to figure out the effect on the wrinkling morphology. Due to its spatial periodicity over a large area and undemanding requirement of the process, this approach can be a candidate for the microfabrication in various applications.     

Foams and surface rheological properties of β-casein, gliadin and glycinin

Interfacial rheological properties and their suitability for foam production and stability of two vegetable proteins were studied and compared to β-casein. Proteins used ranged from flexible to rigid/globular in the order of β-casein, gliadin and soy glycinin. Experiments were performed at pH 6.7. Network forming properties were characterised by the surface dilational modulus (determined with the ring trough) and the critical falling film length (L_still) at which a stagnant protein film will break. Gliadin had the highest dilational modulus, followed by glycinin and β-casein, whereas glycinin formed the strongest film against fracture in the overflowing cylinder. The rate of decrease in the surface tension was studied at the air–water (Wilhelmy plate method) and the oil–water interface (bursting membrane) and the dynamic surface tension during compression and expansion in the caterpillar. Gliadin had the lowest equilibrium interfacial tensions and β-casein the lowest dynamic surface tension during expansion. Hardly any foam could be formed at a concentration of 0.1 g/l by shaking. At a concentration of 1.4 g/l most foam was formed by β-casein, followed by gliadin and glycinin. It seems that in the first place the rate of adsorption is important for foam formation. For the vegetable proteins, adsorption was slow. This resulted in lower foamability, especially for glycinin.     

Dynamic instability of a sol-gel-derived thin film

We present a study on the dynamic instability of a sol-gel-derived (SG) thin film on a nonwettable substrate. Because of the structural instability accompanied by syneresis stress in a film deposited on the substrate, there exists a regular distribution of dewetting patterns required to relieve the in-plane stress, such as holes in the earlier stages, and droplets accompanying a regular polygonal distribution in the later stages of the dynamic instability. The characteristic length scales in each stage scaled linearly with the film thickness during the duration of dewetting. For the formation of holes during the earlier stages of rupture of the film, the dewetting velocity was analyzed with a viscous sintering theory of a SG thin film. In the earlier stages of the dynamic instability, the dewetting velocity decreases with increasing dewetting time and increases with increasing the initial film thickness, which indicates that the SG thin film behaves partially like a slipping polymer thin film. In the final times of the film rupture, the radius of the hole has a linear relationship with the film thickness, and the growth rate of the hole (dewetting velocity) is nearly constant, regardless of the film thickness. These dewetting behaviors indicate that the SG thin film in the final times of the rupture is somewhat similar to nonslipping film. From these observations, we found that the dewetting behavior of a SG thin film has ambivalent dewetting characteristics of slipping and nonslipping films and that a SG thin film is not a purely viscous film.     

Surface Wrinkling Induced by Photofluidization of Low Molecular Azo Glasses

Photoinduced surface wrinkling is demonstrated for a low molecular azo compound confined between a substrate and a thin inorganic elastic layer. The wrinkling process is investigated by time‐resolved light scattering as well as by two‐dimensional autocorrelation analysis of microscopic images. It is shown that the temporal evolution of the wrinkling pattern is directly controlled by the amount of photons absorbed by the sample and that there is no significant dependence of the equilibrium wavelength on irradiation intensity. Finally, the comparison of thermal and photoinduced wrinkling revealed that photoinduced wrinkles are characterized by a narrower mode distribution and less coarsening.     

The effect of a magnetic tape coating process on the structure and properties of a semi-crystalline polymer

A combination of structure identifying and bulk property experiments were combined with a two-phase analytical methodology to elucidate the influence of a magnetic tape coating process on the substrate polymer film. Employing a typical tape manufacturing process that utilizes coating, drying, and calendering stages, polyethylenete-rephthalate polymer film samples with and without the magnetic coating were prepared.Experiments and modeling studies performed on these samples demonstrate that the drying and calendering processes may increase the crystallinity and noncrystalline orientation of the substrate film. In addition, dynamic mechanical experiments identified a viscoelastic transition at 50 °C for the PET substrate film sample which is near the glass transition of the magnetic coating utilized. Overall, the results of this investigation provide a basis for evaluating structure property interrelations of polymer-based magnetic tapes.     

Solubilization and phase equilibria of water-in-oil microemulsions : II. Effects of alcohols, oils, and salinity on single-chain surfactant systems

The solubilization and phase equilibria of w/o microemulsions have been shown to be dependent on two phenomenological parameters, namely the spontaneous curvature and elasticity of the interfacial film, when interfacial tension is very low. The spontaneous curvature of an interface is basically determined by the geometric packing of surfactant and cosurfactant molecules at the interface, whereas the interfacial elasticity is related to the energy required to bend the interface. The droplet size and solubilization of microemulsions is mainly determined by the radius of spontaneous curvature, and is further influenced by interfacial elasticity and interdroplet interactions. A w/o microemulsion with a highly curved and relatively rigid interfacial film can exist in equilibrium with excess water at the solubilization limit due to the interfacial bending stress. Increasing the natural radius and fluidity of the interface can increase the droplet size and hence the solubilization in the microemulsion. On the other hand, a w/o microemulsion with a highly fluid interfacial film can exist in equilibrium with an excess oil phase containing a low density of microemulsion droplets due to attractive interdroplet interaction. Increasing the interfacial rigidity and decreasing the natural radius in this case can increase water solubilization in the microemulsion by retarding the phase separation process. Thus, a maximum water solubilization in a w/o microemulsion can be obtained by minimizing both the interfacial bending stress of rigid interfaces and the attractive interdroplet interaction of fluid interfaces at an optimal interfacial curvature and elasticity. The study of phase equilibria of microemulsions can serve as a simple method to evaluate the property of the interface and provide phenomenological guidance for the formulation of microemulsions with maximum solubilization capacity.     

基于表面起皱法的梯度图案的可控制备

报道了基于非刻蚀法的表面起皱机制来实现高分子薄膜表面的周期性梯度图案的简单可控制备.即对于处于机械拉伸状态的聚二甲基硅氧烷(PDMS)弹性基底,在其底部垫入"积木",而后对其进行紫外-臭氧(UVO)和氧等离子体(OP)的联合表面处理."积木"的加入引起了表面处理后表面硅氧层(SiOx)梯度厚度的形成,进而当释放拉伸应变后,诱导产生了梯度皱纹图案.结果表明:当UVO与OP联用处理时,不仅实现了较小拉伸应变下梯度皱纹形貌的制备,而且扩大了UVO单独使用时梯度皱纹周期的变化范围.通过OP与UVO的处理顺序和处理时间等因素的简单调节,进一步实现了不同梯度皱纹微结构的精细构筑.     

Residual stress and optical properties of fully rod-like poly(p-phenylene pyromellitimide) in thin films: Effects of soft-bake and thermal imidization history

A soluble poly(amic acid) precursor solution of fully rod-like poly(p-phenylene pyromellitimide) (PMDA-PDA) was spin cast on silicon substrates, followed by soft bake at 80–185°C and subsequent thermal imidization at various conditions over 185–400°C in nitrogen atmosphere to be converted to the polyimide in films. Residual stress generated at the interface was measured in situ during imidization. In addition, the imidized films were characterized in the aspect of polymer chain orientation and ordering by prism coupling and X-ray diffraction. The soft-baked precursor film revealed a residual stress of 16–28 MPa at room temperature, depending on the soft bake condition: higher temperature and longer time in the soft bake gave higher residual stress. The stress variation in the soft-baked precursor film was not significantly reflected in the final stress in the resultant polyimide film. However, the residual stress in the polyimide film varied sensitively with variations in imidization process parameters, such as imidization temperature, imidization steps, heating rate, and film thickness. The polyimide film exhibited a wide range of residual stress, −7 MPa to 8 MPa at room temperature, depending on the imidization condition. Both rapid imidization and low-temperature imidization generated high stress in the tension mode in the polyimide film, whereas slow imidization as well as high temperature imidization gave high stress in the compression mode. Thus, a moderate imidization condition, a single- or two-step imidization at 300°C for 2 h with a heating rate of < 10 K/min was proposed to give a relatively low stress in the polyimide film of < 10 μm thickness. However, once a precursor film was thermally imidized at a chosen process condition, the residual stress–temperature profile was insensitive to variations in the cooling process. All the films imidized were optically anisotropic, regardless of the imidization history, indicating that rod-like PMDA-PDA polyimide chains were preferentially aligned in the film plane. However, its degree of in-plane chain orientation varied on the imidization history. It is directly correlated to the residual stress in the film, which is an in-plane characteristic. For films with residual stress in the tension mode, higher stress films exhibited lower out-of-plane birefringence, that is, lower in-plane chain orienta-tion. In contrast, in the compression mode, higher stress films showed higher in-plane chain orientation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1261–1273, 1998     

Instabilities and pattern miniaturization in confined and free elastic-viscous bilayers

We present an analysis of the instabilities engendered by van der Waals forces in bilayer systems composed of a soft elastic film (<10 microm) and a thin (<100 nm) viscous liquid film. We consider two configurations of such systems: (a) Confined bilayers, where the bilayer is sandwiched between two rigid substrates, and (b) free bilayers, where the viscous film is sandwiched between a rigid substrate and the elastic film. Linear stability analysis shows that the time and length scales of the instabilities can be tuned over a very wide range by changing the film thickness and the material properties such as shear modulus, surface tension, and viscosity. In particular, very short wavelengths comparable to the film thickness can be obtained in bilayers, which is in contrast to the instability wavelengths in single viscous and elastic films. It is also shown that the instabilities at the interfaces of the free bilayers are initiated via an in-phase "bending" mode rather than out-of-phase "squeezing" mode. The amplitudes of deformations at both the elastic-air and elastic-viscous interfaces become more similar as the elastic film thickness decreases and its modulus increases. These findings may have potential applications in the self-organized patterning of soft materials.     

Mechanical behavior and wrinkling patterns of phase-separated binary polymer blend film

The wrinkling of phase-separated binary polymer blend film was studied through combining the Monte Carlo (MC) simulation for morphologies with the lattice spring model (LSM) for mechanical properties. The information of morphology and structure obtained by use of MC simulation is input to the LSM composed of a three-dimensional network of springs, which allows us to determine the wrinkling and the mechanical properties of polymer blend film, such as strain, stress, and Young’s modulus. The simulated results show that the wrinkling of phase-separated binary polymer blend film is related not only to the structure of morphology, but also to the disparity in elastic moduli between polymers of blend. Our simulation results provide fundamental insight into the relationship between morphology, wrinkling, and mechanical properties for phase-separated polymer blend films and can yield guidelines for formulating blends with the desired mechanical behavior. The wrinkling results also reveal that the stretching of the phase-separated film can form the micro-template, which has a wide application prospect.     

Magnetic field‐assisted liquid crystal alignment on a solid substrate: drift of easy orientation axis,anchoring energy and angular distribution of adsorbed liquid crystal molecules

The anchoring properties of a film of anisotropically adsorbed liquid crystal (LC) molecules on a rigid substrate have been studied. The LC film was prepared by cooling it from the isotropic phase in the presence of a magnetic field parallel to the surface of the substrate. Relationship between the anchoring energy, easy axis direction and angular distribution of the adsorbed molecules, and changes in their angular distribution due to adsorption–desorption, were studied. The dependence of the anchoring energy on the duration and the temperature at which the LC film is annealed allowed an estimation of the activation energy of desorption of LC molecules on ITO surface, ΔE≈0.55 eV. The results suggest that hydrogen bonds are responsible for the adsorption of LC molecules on the substrate.     

Magnetic field-assisted liquid crystal alignment on a solid substrate: drift of easy orientation axis, anchoring energy and angular distribution of adsorbed liquid crystal molecules

The anchoring properties of a film of anisotropically adsorbed liquid crystal (LC) molecules on a rigid substrate have been studied. The LC film was prepared by cooling it from the isotropic phase in the presence of a magnetic field parallel to the surface of the substrate. Relationship between the anchoring energy, easy axis direction and angular distribution of the adsorbed molecules, and changes in their angular distribution due to adsorption-desorption, were studied. The dependence of the anchoring energy on the duration and the temperature at which the LC film is annealed allowed an estimation of the activation energy of desorption of LC molecules on ITO surface, ΔE≈0.55 eV. The results suggest that hydrogen bonds are responsible for the adsorption of LC molecules on the substrate.     

Role of capillary stresses in film formation

Stresses generated during film formation were deduced from the deflection of a copper cantilever coated with a drying latex. Experiments with particles of varying radii and glass transition temperatures (Tg) focused on conditions for which capillary stresses normal to the film deform the particles to close the voids. Soft particles (low Tg) formed continuous films, but hard ones (high Tg) produced fascinating arrays of cracks. For both soft and rigid particles, the lateral stresses were tensile and scaled on the surface tension divided by the particle radius. Clearly, tensile stresses in the plane of the film responsible for cracking arise from the same capillary pressure that drives compression in the normal direction. Solving the model (Routh & Russel 1996, 1999) for lateral flow of the fluid dispersion prior to close packing and deformation of the solid beyond close packing yields volume fraction, film thickness, and stress profiles for comparison with observations for both film-forming and film-cracking cases.     

Total internal reflectance fluorescence (TIRF) measurements of tracer diffusion through swollen supported polymer films

This work introduces a new method for tracer diffusion studies which emphasizes interfacial effects. Total internal reflectance fluorescence (TIRF) was employed to monitor rhodamine dye tracer diffusion normal to the interface in PDMS films whose swelling in THF was constrained by adhesion to a rigid support. In these constrained films, the tracer diffusivities were equal to or lower than those in freely swollen samples, with the difference most pronounced in samples of relatively low crosslink density. This indicated that swelling was reduced by adhesion to the substrate. In the supported films, tracer diffusion deviated from Fickian kinetics, suggesting that the region of the film near the substrate contained relatively less solvent at equilibrium than did the bulk film. © 1996 John Wiley & Sons, Inc.     

Contact instability of thin elastic films on patterned substrates

The free surface of a soft elastic film becomes unstable and forms an isotropic labyrinth pattern when a rigid flat plate is brought into adhesive contact with the film. These patterns have a characteristic wavelength, lambda approximately 3H, where H is the film thickness. We show that these random structures can be ordered, modulated, and aligned by depositing the elastic film (cross-linked polydimethylsiloxane) on a patterned substrate and by bringing the free surface of the film in increasing adhesive contact with a flat stamp. Interestingly, the influence of the substrate "bleeds" through the film to its free surface. It becomes possible to generate complex two-dimensional ordered structures such as an array of femtoliter beakers even by using a simple one-dimensional stripe patterned substrate when the instability wavelength, lambda approximately 3H, nearly matches the substrate pattern periodicity. The free surface morphology is modulated in situ by merely varying the stamp-surface separation distance. The free surface structures originating from the elastic contact instability can also be made permanent by the UV-ozone induced oxidation and stiffening.     

Measuring the work of adhesion between a soft confined film and a flexible plate

We present a theoretical and experimental study of a method for the determination of the adhesion strength between a thin elastomeric film bonded to a rigid substrate and a flexible plate in a geometry common in the peel test. In particular, we characterize the work of adhesion in terms of the length of an equilibrium crack, generated by a spacer of known thickness wedged between the flexible plate and adhesive film, and the elastic and geometric properties of the film and the plate. We treat both the limit of perfect bonding and that of perfect slippage at the interface of the adhesive film and the flexible plate. A series of experiments allow us to verify the theory quantitatively and thus validate our method, which ought to be of value in many technological situations.     

Langmuir–Blodgett films of stearic acid deposited on substrates at different orientations relative to compression direction: alignment layer for nematic liquid crystal

The Langmuir monolayer at an air–water interface shows remarkably different surface pressure (π)–area (A) isotherm, when measured with the surface normal of a Wilhelmy plate parallel or perpendicular to the direction of compression of the monolayer. Such difference arises due to difference in stress exerted by the monolayer on the plate in different direction. In this article, we report the effect of changing the direction of substrate normal with respect to the compression of the monolayer during Langmuir–Blodgett (LB) film deposition on the morphology of the films. The morphology of the LB film of stearic acid is studied using an atomic force microscope. The morphology of the LB films is found to be different due to difference in the stress in different directions. The role of such surface morphology on the alignment of a nematic liquid crystal (LC) in LC cells is studied. The granular texture of LB films of stearic acid supports the homogeneous alignment of the LC whereas the uniform texture supports the homeotropic alignment of the LC.     

Adhesive transfer of thin viscoelastic films

Micellar suspensions of acrylic diblock copolymers are excellent model materials for studying the adhesive transfer of viscoelastic solids. The micellar structure is maintained in films with a variety of thicknesses, giving films with a well-defined structure and viscoelastic character. Thin films were cast onto elastomeric silicone substrates from micellar suspensions in butanol, and the adhesive interactions between these coated elastomeric substrates and a rigid indenter were quantified. By controlling the adhesive properties of the film/indenter and film/substrate interfaces we were able to obtain very clean transfer of the film from the substrate to the portion of the glass indenter with which the film was in contact. Adhesive failure at the film/substrate interface occurs when the film/indenter interface is able to support an applied energy release rate that is sufficient to result in cavity nucleation at the film/substrate interface. Cavity formation is rapidly followed by delamination of the entire region under the indenter. The final stage in the transfer process involves the failure of the film that bridges the indenter and the elastomeric substrate. This film is remarkably robust and is extended to three times its original width prior to failure. Failure of this film occurs at the periphery of the indenter, giving a transferred film that conforms to the original contact area between the indenter and the coated substrate.     

Quantifying the elasticity and viscosity of geometrically confined polymer films via thermal wrinkling

We apply thermal wrinkling, which is a surface instability that occurs during thermal annealing of polymer films geometrically confined by a rigid substrate and a flexible superstrate, to study the elasticity and viscosity of chemically crosslinked polymer systems. Specifically, we study the thermal wrinkling of aluminum‐capped polyhydroxystyrene films with different extent of chemical crosslinking and find that that the rate of change of the wrinkling wavelength with annealing time and temperature has unique relationships with the elasticity and viscosity of the polymer network. With the aid of analytical expressions that relate the time‐ and temperature‐dependent evolution of the wrinkle wavelength to the elasticity and viscosity, we are able to quantify the elastic modulus and shear viscosity of geometrically confined polymer thin films as a function of the degree of crosslinking. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012