Two Relaxation Mechanisms for Rejuvenation of Stable Polystyrene Glass.

We report on the rejuvenation of thin films of polystyrene (PS) as they are heated from stable glassy states, prepared either through vapor deposition or physical aging. For films with thicknesses ≳ 200 nm and ≲ 50 nm, the rejuvenation of vapor-deposited stable PS glass films is quantitatively described with zero free parameters by simulations using parameters previously obtained from isothermal rejuvenation measurements in the same material. For films with thickness ∼ 140 nm, the behavior of the vapor-deposited films becomes more complicated and exhibits significant deviations from model predictions.

Film Thickness Dependent Stability and Glass Transition Temperature of Polymer Films Produced by Physical Vapor Deposition.

We report measurements of the onset temperature of rejuvenation, T_{onset}, and the fictive temperature, T_{f}, for ultrathin stable polystyrene with thicknesses from 10 to 50 nm prepared by physical vapor deposition. We also measure the T_{g} of these glasses on the first cooling after rejuvenation as well as the density anomaly of the as-deposited material. Both the T_{g} in rejuvenated films and the T_{onset} in stable films decrease with decreasing film thickness.

Surface and bulk relaxation of vapor-deposited polystyrene glasses.

We have studied the liquid-like response of the surface of vapor-deposited glassy films of polystyrene to the introduction of gold nanoparticles on the surface. The build-up of polymer material was measured as a function of time and temperature for both as-deposited films, as well as films that have been rejuvenated to become normal glasses cooled from the equilibrium liquid. The temporal evolution of the surface profile is well described by the characteristic power law of capillary-driven surface flows.

On the bridge hypothesis in the glass transition of freestanding polymer films.

Freestanding thin polymer films with high molecular weights exhibit an anomalous decrease in the glass-transition temperature with film thickness. Specifically, in such materials, the measured glass-transition temperature evolves in an affine way with the film thickness, with a slope that weakly depends on the molecular weight. De Gennes proposed a sliding mechanism as the hypothetical dominant relaxation process in these systems, where stress kinks could propagate in a reptation-like fashion through so-called bridges, i.

Nanoscale surface roughness induced by poor solvents on polymer film surfaces.

We describe a new nanoscale morphology that is produced when polymer surfaces are exposed to a poor solvent. We have measured the morphology on polystyrene surfaces after exposure to pentane, heptane, or dodecane as well as poly(methyl methacrylate) exposed to propanol or methanol. The length scale of the morphology was determined by analyzing images obtained by atomic force microscopy.

A β-NMR study of the depth, temperature, and molecular-weight dependence of secondary dynamics in polystyrene: Entropy-enthalpy compensation and dynamic gradients near the free surface.

We investigated the depth, temperature, and molecular-weight (MW) dependence of the γ-relaxation in polystyrene glasses using implanted Li and β-detected nuclear magnetic resonance. Measurements were performed on thin films with MW ranging from 1.1 to 641 kg/mol.

Anisotropy and anharmonicity in polystyrene stable glass.

We have used ellipsometry to characterize the anisotropy in stable polymer glasses prepared by physical vapor deposition. These measurements reveal birefringence values (as measured by the magnitude of in-plane vs out-of-plane refractive index) less than 0.002 in vapor-deposited polystyrenes with N from 6 to 12 and with fictive temperatures between 10 K and 35 K below the T values.

Crystallization and melting of highly monodisperse poly(ethylene-oxide).

We present a quantitative study of the crystallization and melting behaviours of highly monodisperse PEO oligomers, and compare to previous studies. Through evaporative purification, we were able to isolate low molecular weight PEO oligomers that are much more monodisperse than the as-purchased material (as measured by mass spectrometry). Crystal structure, crystal growth rate and melting temperatures were characterized.

Ultrastable monodisperse polymer glass formed by physical vapour deposition.

Stable glasses prepared by vapour deposition are an analogue of glassy materials aged for geological timescales. The ability to prepare such materials allows the study of near-ideal glassy systems. We report the preparation and characterization of stable glasses of polymers prepared by physical vapour deposition.

Cooperative strings and glassy dynamics in various confined geometries.

Previously, we developed a minimal model based on random cooperative strings for the relaxation of supercooled liquids in the bulk and near free interfaces, and we recovered some key experimental observations. In this article, after recalling the main ingredients of the cooperative string model, we study the effective glass transition and surface mobility of various experimentally relevant confined geometries: freestanding films, supported films, spherical particles, and cylindrical particles, with free interfaces and/or passive substrates. Finally, by canceling and restarting any cooperative-chain realization reaching the boundary with a smaller number of steps than the bulk cooperativity, we account for a purely attractive substrate, and explore the impact of the latter in the previous geometries.

Crystallization of low molecular weight atactic polystyrene.

We observe and characterize the crystallization of atactic polystyrenes (PS) of nearly oligomeric M using atomic force microscopy. We find that the low M polystyrene exhibits observable crystals on the surface. The crystals appear to be a few nm thick and nm to microns wide.

Direct measurements of the temperature, depth and processing dependence of phenyl ring dynamics in polystyrene thin films by β-detected NMR.

There is indirect evidence that the dynamics of a polymer near a free surface are enhanced compared with the bulk but there are few studies of how dynamics varies with depth. β-Detected nuclear spin relaxation of implanted 8Li+ has been used to directly probe the temperature and depth dependence of the γ-relaxation mode, which is due to phenyl rings undergoing restricted rotation, in thin films of atactic deuterated polystyrene (PS-d8) and determine how the depth dependence of dynamics is affected by sample processing, such as annealing, floating on water and the inclusion of a surfactant, and by the presence of a buried interface. The activation energy for the γ-relaxation process is lower near the free surface.

Correction: Cooperative strings in glassy nanoparticles.

Correction for 'Cooperative strings in glassy nanoparticles' by Maxence Arutkin et al., Soft Matter, 2017, 13, 141-146.

A Review of Techniques to Measure Protein Sorption to Soft Contact Lenses.

Purpose: To compare and critically evaluate a variety of techniques to measure the quantity and biological activity of protein sorption to contact lenses over short time periods.

Methods: A literature review was undertaken investigating the major techniques to measure protein sorption to soft contact lens materials, with specific reference to measuring protein directly on lenses using in situ, ex situ, protein structural, and biological activity techniques.

Results: The use of in situ techniques to measure protein quantity provides excellent sensitivity, but many are not directly applicable to contact lenses.

Controlling Marangoni-induced instabilities in spin-cast polymer films: How to prepare uniform films.

In both research and industrial settings spincoating is extensively used to prepare highly uniform thin polymer films. However, under certain conditions, spincoating results in films with non-uniform surface morphologies. Although the spincoating process has been extensively studied, the origin of these morphologies is not fully understood and the formation of non-uniform spin-cast films remains a practical problem.

Cooperative strings in glassy nanoparticles.

Motivated by recent experimental results on glassy polymer nanoparticles, we develop a minimal theoretical framework for the glass transition in spherical confinement. This is accomplished using our cooperative-string model for supercooled dynamics, that was successful at recovering the bulk phenomenology and describing the thin-film anomalies. In particular, we obtain predictions for the mobile-layer thickness as a function of temperature, and for the effective glass-transition temperature as a function of the radius of the spherical nanoparticle - including the existence of a critical particle radius below which vitrification never occurs.

Cooperative strings and glassy interfaces.

We introduce a minimal theory of glass formation based on the ideas of molecular crowding and resultant string-like cooperative rearrangement, and address the effects of free interfaces. In the bulk case, we obtain a scaling expression for the number of particles taking part in cooperative strings, and we recover the Adam-Gibbs description of glassy dynamics. Then, by including thermal dilatation, the Vogel-Fulcher-Tammann relation is derived.

Analysis of Using I(125) Radiolabeling for Quantifying Protein on Contact Lenses.

Purpose: To investigate the accuracy of I(125) radiolabeling to quantitatively determine the deposition of protein onto various commercially available contact lens (CL) materials.

Methods: Commercially available silicone hydrogel and conventional hydrogel CL materials were examined for times ranging from 10 s to 1 week. Adsorption of free I(125) was measured directly for the CL.

Competitive Effects from an Artificial Tear Solution to Protein Adsorption.

Purpose: To compare the adsorption of lysozyme, lactoferrin, and albumin to various contact lens materials, between single-protein solutions and a multicomponent artificial tear solution (ATS). Additionally, extra steps were taken to distinguish loosely and tightly bound protein, the latter of which may be fully or partially denatured.

Methods: Using a previously described ATS, we measured the time-dependent adsorption of lys, lac, and alb onto one conventional hydrogel and four silicone hydrogel contact lens materials between the first minute and up to 1 week of protein interaction with the material surface.

Enhanced high-frequency molecular dynamics in the near-surface region of polystyrene thin films observed with β-NMR.

β-detected nuclear spin relaxation of (8)Li(+) has been used to probe the depth dependence of molecular dynamics in high- and low-molecular-weight deuterated polystyrene. The average nuclear spin-lattice relaxation rate, 1/T(avg)(1), is a measure of the spectral density of the polymer motion at the Larmor frequency (41 MHz at 6.55 T).

Kinetics of Competitive Adsorption between Lysozyme and Lactoferrin on Silicone Hydrogel Contact Lenses and the Effect on Lysozyme Activity.

Purpose: To determine the effect of competitive adsorption between lysozyme and lactoferrin on silicone hydrogel contact lenses and the effect on lysozyme activity.

Methods: Three commercially available silicone hydrogel contact lens materials (senofilcon A, lotrafilcon B and balafilcon A) were examined, for time points ranging from 10 s to 2 h. Total protein deposition was determined by I(125) radiolabeling of lysozyme and lactoferrin, while the activity of lysozyme was determined by a micrococcal activity assay.

Influence of particle size on the binding activity of proteins adsorbed onto gold nanoparticles.

We used optical extinction spectroscopy to study the structure of proteins adsorbed onto gold nanoparticles of sizes 5-60 nm and their resulting biological binding activity. For these studies, proteins differing in size and shape, with well-characterized and specific interactions-rabbit immunoglobulin G (IgG), goat anti-rabbit IgG (anti-IgG), Staphylococcal protein A, streptavidin, and biotin-were used as model systems. Protein interaction with gold nanoparticles was probed by optical extinction measurements of localized surface plasmon resonance (LSPR) of the gold nanoparticles.

Imaging protein deposits on contact lens materials.

Purpose: The majority of studies investigating protein deposition on contact lens materials require that the deposit of interest be removed, potentially resulting in erroneous results if some proteins are not removed adequately. The purpose of this study was to investigate the use of in situ imaging methods to examine protein deposition on conventional poly(2-hydroxyethyl methacrylate) (polyHEMA)-based and silicone hydrogel contact lens materials.

Methods: Six silicone hydrogel and five polyHEMA-based hydrogel contact lens materials were examined by Atomic Force Microscopy (AFM) and/or Scanning Electron Microscopy (SEM) techniques, after being deposited with proteins in an in vitro model.

Probing slow dynamics in supported thin polymer films.

We have used variable cooling rate ellipsometric measurements to probe the slow dynamics in thin supported polystyrene films. For the slowest cooling rates (approximately 1 K/min) the measured Tg values are reduced below the bulk value with the measured Tg of 341 K for a 6 nm film. As the cooling rate is increased the Tg reductions become smaller until at cooling rates >90 K/min there is only slight evidence for a film-thickness-dependent Tg value.