Stability of thin polymer films on a corrugated substrate

We study the wetting behaviour of thin polystyrene (PS) films on regularly corrugated silicon substrates. Below a critical film thickness the PS films are unstable and dewet the substrates. The dewetting process leads to the formation of nanoscopic PS channels filling the grooves of the corrugated substrates. Films thicker than the critical thickness appear stable and follow the underlying corrugation pattern. The critical thickness is found to scale with the radius of gyration of the unperturbed polymer chains. Received 6 April 2000 and Received in final form 24 August 2000     

Chain radius dependence on concentration in a 2D living polymer system

A living polymer system is used to study the effect of concentration on a broad, polydisperse two-dimensional polymer system. It is found that the mean squared end-to-end radius of a chain of L monomers does not decrease by following a simple power law of the concentration but by a function of the form . An origin for such a behaviour is proposed. Received: 21 November 1997 / Received in final form: 21 April 1998 / Accepted: 24 April 1998     

Linear polymer with hydrogen bonds as a nonequilibrium system

A two-temperature nonequilibrium model of a linear polymer with possible formation of hydrogen bonds between monomers is proposed. A molecule is considered to be in an adiabatic stationary state far from equilibrium. The dependence of the mean-square distance between the chain ends on the number of monomers is calculated with the simplest approach of Flory in case T > Θ.     

Structural relaxation of spin-cast glassy polymer thin films as a possible factor in dewetting

Reiter [1] has recently reported a situation in which the dewetting of quasi-solid films is linked to plastic deformation - rather than viscous flow - resulting from capillary forces. Herein we propose that, in thin films of some glassy polymers - especially poly(methyl methacrylate) (PMMA) - prepared by spin-casting from solvent, structural relaxation might impart sufficient stress to cause plastic deformation. We find that PMMA films decrease in thickness by several percent, which is sufficient to create significant stress in those cases in which the film is attached to a rigid substrate. The floating technique, which can take tens of minutes, might allow most of the structural relaxation to occur prior to dewetting experiments.Received: 1 August 2003PACS: 65.40.De Thermal expansion; thermomechanical effects - 82.60.Lf Thermodynamics of solutions - 61.41. + e Polymers, elastomers, and plasticsM. Sferrazza: Current address: Département de Physique, Université Libre de Bruxelles, Boulevard du Triomphe, CP223, 1050 Bruxelles, Belgium     

Polysulfone as polymer matrix for a novel polymer-dispersed liquid crystals system

We report the preparation and thermotropic characterization of a novel polymer-dispersed liquid crystal (PDLC) system based on the polysulfone (PSU) UDEL-1700 as a polymer matrix and on 4-[4-(n-butyloxy)phenylene-imino-methylidene]benzonitrile as a liquid crystal. PDLC films have been prepared using the thermal-induced phase separation (TIPS) technique, with different compositions in the two components. A detailed optical polarized microscopy and differential scanning calorimetry study has been carried out to evaluate a correlation between the composite composition and the PDLC formation. We found that PSU could be a good matrix for the formation of PDLC systems.     

Stability of polyacetylene films

The oxidative and radiation stability of polyacetylene films have been determined. The radiation stability of the material is found to be quite good but the intrinsic thermal oxidative stability is poor and presents a serious obstacle to widespread terrestrial or space use.     

Surface dynamics of polymer films

The dynamics of supported polymer films were studied by probing the surface height fluctuations as a function of lateral length scale using x-ray photon correlation spectroscopy. Measurements were performed on polystyrene (PS) films of thicknesses varying from 84 to 333 nm at temperatures above the PS glass transition temperature. Within a range of wave vectors spanning 10(-3) to 10(-2) nm(-1), good agreement is found between the measured surface dynamics and the theory of overdamped thermal capillary waves on thin films. Quantitatively, the data can be accounted for using the viscosity of bulk PS.     

Dewetting as an investigative tool for studying properties of thin polymer films

Employing mass conservation, time-resolved dewetting experiments of thin polymer films allow to determine in real time the dynamic contact angle and the slippage length. Moreover, based on a systematic variation of interfacial properties of a polymer brush, dewetting makes it possible to calculate the force it needs to extract a single polymer chain from its own melt. In the visco-elastic regime close to the glass transition, the temperature and molecular weight dependence of the relaxation time of residual stresses resulting from film preparation by spin-coating can be obtained from the evolution of the shape of the dewetting rim. The presented examples demonstrate that dewetting represents a powerful approach for a sensitive characterization of rheological, frictional and interfacial properties of thin polymer films.     

Dewetting of glassy polymer films

Dynamics and morphology of hole growth in a film of power hardening viscoplastic solid [ yield stress approximately (strain-rate)(n)] is investigated. At short times the growth is exponential and depends on the initial hole size. At long times, for n>1 / 3, the growth is again exponential but with a different exponent. However, for n<1 / 3 the hole growth slows and the hole radius approaches an asymptotic value at long times. The rim shape is highly asymmetric, the height of which has a power law dependence on the hole radius (exponent close to unity for 0.25相似文献   

Ultrasound-assisted exfoliation of a layered 2D coordination polymer with HER electrocatalytic activity

Large blue rectangular crystals of the 2D layered coordination polymer 1 have been obtained. The interest for this complex is two-fold. First, complex 1 is made of 2D layers packing along the (0–11) direction favored by the presence of lattice and coordinated water molecules. And second, nanostructures that could be derived by delamination are potentially suitable for catalytic purposes. Therefore it represents an excellent example to study the role of interlayer solvent molecules on the ultrasound-assisted delamination of functionally-active 2D metal-organic frameworks in water, a field of growing interest. With this aim, ultrasound-assisted delamination of the crystals was optimized with time, leading to stable nanosheet colloidal water suspensions with very homogeneous dimensions. Alternative bottom-up synthesis of related nanocrystals under ultrasound sonication yielded similar shaped crystals with much higher size dispersions. Finally, experimental results evidence that the nanostructures have higher catalytic activities in comparison to their bulk counterparts, due to larger metallic center exposition. These outcomes confirm that the combination of liquid phase exfoliation and a suitable synthetic design of 2D coordination polymers represents a very fruitful approach for the synthesis of functional nanosheets with an enhancement of catalytic active sites, and in general, with boosted functional properties.     

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.     

Spin-magnetoplasma waves in a 2D electron system

Oscillations of a 2D electron plasma in a transverse magnetic field have been theoretically studied taking into account spin-orbit interaction. Four branches of spin-plasmon oscillations associated with different selection rules for spin and orbital quantum numbers have been shown to appear at a small plasmon momentum in a semiclassical limit (the Fermi energy is much higher than the Landau quantum). In the quantum case (the filling factor ν is about unity), the number of branches changes from three to six depending on ν value.     

One-electron states of a 2D spatially limited system

The spectrum of a particle in a 2D potential as a polar-angle-dependent well is investigated. One-electron states of 2D systems are considered within the framework of the simplest quantum-mechanical models. Such states can be realized by dusting the atoms of various substances which are posited on a substrate.     

Colloidal dipolar interactions in 2D smectic-C films

We use a two-dimensional (2D) elastic free energy to calculate the effective interaction between two circular disks immersed in smectic-C films. For strong homeotropic anchoring, the distortion of the director field caused by the disks generates topological defects that induce an effective interaction between the disks. We use finite elements, with adaptive meshing, to minimize the 2D elastic free energy. The method is shown to be accurate and efficient for inhomogeneities on the length scales set by the disks and the defects, that differ by up to 3 orders of magnitude. We compute the effective interaction between two disk-defect pairs in a simple (linear) configuration. For large disk separations, D, the elastic free energy scales as ∼D ^-2, confirming the dipolar character of the long-range effective interaction. For small D the energy exhibits a pronounced minimum. The lowest energy corresponds to a symmetrical configuration of the disk-defect pairs, with the inner defect at the mid-point between the disks. The disks are separated by a distance that is twice the distance of the outer defect from the nearest disk. The latter is identical to the equilibrium distance of a defect nucleated by an isolated disk. Received 26 October 2001 and Received in final form 14 December 2001     

Aging of thin polymer films cast from a near-theta solvent

We have examined the aging behavior of spin-cast thin polymer films as a function of their processing history. Films prepared from solutions close to the Θ?temperature were aged for varying times at room temperature, followed by a dewetting experiment above the glass transition temperature of the polymer. The characteristic aging time varied strongly with the quality of the solvent, which is attributed to distorted chain conformations in the as-cast films. This is an indication for the nonequilibrium nature of thin polymer films, possibly causing some of their unexplained properties.