A novel nano-bubble inflation method for determining the viscoelastic properties of ultrathin polymer films.

We describe a novel experimental technique for measuring the absolute creep compliance of ultrathin polymer films. The method is based on the classical bubble inflation technique for measuring the biaxial creep compliance of films, reduced in size to measure films with thicknesses down to at least 11.3 nm. The method uses the imaging capabilities of the atomic force microscope (AFM) to determine the time evolution of the geometry of nano-bubbles and thus avoids the problems with data interpretation that can arise due to "contact mechanics" issues when the AFM is used as a direct mechanical testing device.

Novel nanobubble inflation method for determining the viscoelastic properties of ultrathin polymer films.

We describe a novel experimental technique for measuring the viscoelastic properties of ultrathin polymer films. The method is based on the classic bubble inflation technique for measuring the biaxial creep compliance of films, reduced in size to measure films with thicknesses down to at least 13 nm. The method uses the imaging capabilities of the atomic force microscope to determine the time evolution of the geometry of nanobubbles. Using these data, along with the applied pressure, the absolute creep compliance of the films can be determined.

Dramatic stiffening of ultrathin polymer films in the rubbery regime.

Recently, we (P.A. O'Connell, G.B. McKenna, Science 307, 1760 (2005)) introduced a novel nano-bubble inflation method to measure the absolute creep compliance of nanometer thick polymer films. In that work it was shown that even at film thicknesses as small as 27.5nm the glass temperature was unchanged for poly(vinyl acetate) (PVAc). Perhaps more importantly, and the subject of the present work, was the observation that these ultrathin films show a dramatic stiffening in the rubbery plateau regime, i.e., the compliance was reduced by over two orders of magnitude compared to the bulk material. In the present work we substantiate the previous results in a study of the thickness dependence of the rubbery compliance of PVAc and polystyrene (PS) films for thicknesses from 13nm to 276nm. We show the substantial stiffening of the plateau region for both materials. Furthermore, the rubbery compliance (inverse of stiffness) scales with approximately the second power ( 1.8+/-0.2) in the film thickness for both materials.

Rheological measurements of the thermoviscoelastic response of ultrathin polymer films.

Measurement of the thermoviscoelastic behavior of glass-forming liquids in the nanometer size range offers the possibility of increased understanding of the fundamental nature of the glass-transition phenomenon itself. We present results from use of a previously unknown method for characterizing the rheological response of nanometer-thick polymer films. The method relies on the imaging capabilities of the atomic force microscope and the reduction in size of the classical bubble inflation method of measuring the biaxial creep response of ultrathin polymer films. Creep compliance as a function of time and temperature was measured in the linear viscoelastic regime for films of poly(vinyl acetate) at a thickness of 27.5 nanometers. Although little evidence for a change in the glass temperature is found, the material exhibits previously unobserved stiffening in the rubbery response regime.

Foot deformities in children with cerebral palsy.

Clinical observation suggests that deformities of the foot and ankle are common in children with cerebral palsy. Two hundred children with cerebral palsy attending the Central Remedial Clinic were examined and photographed. The children had no previous surgical intervention and were between 1.5 and 19 years of age. Deformities were assessed and related to the type of cerebral palsy and mobility status.

Refractive index determination using an orthogonalized dispersion equation.

An orthogonal form of a general three-term dispersion equation is presented which is useful for determination of the refractive index of transparent optical materials from measured spectral data. The orthogonal basis functions are dependent on the spectral range of the data and whether the spacing of the data is uniform with respect to wavelength or wavenumber. The application of the technique to the reduction of ellipsometric measurements of a single layer thin film of zirconia on a fused silica substrate is presented. The measured data were fit to a Conrady dispersion equation and to the corresponding orthogonal basis set. The convergence to the solution was an order of magnitude faster for the orthogonal form of the dispersion equation.