Connie B. Roth

Communication: Experimentally determined profile of local glass transition temperature across a glassy-rubbery polymer interface with a Tg difference of 80 K

Studying the local glass transition temperature T(g) across a boundary, we investigate the characteristic length scales of cooperative dynamics. High molecular weight polymers have a large separation in time scales between cooperative segmental motion (α-relaxation) and chain diffusion allowing us to measure the local T(g)(z) profile across a glassy-rubbery interface of polystyrene/poly(n-butyl methacrylate) using fluorescence. We find this profile in cooperative dynamics does not correlate with the 7-nm wide symmetric composition profile of the interface, but instead is very broad, spanning 350-400 nm from one bulk T(g) value to another, and highly asymmetric, extending further into the glassy side.

Local glass transition temperature Tg(z) of polystyrene next to different polymers: Hard vs. soft confinement

The depth to which the local glass transition temperature Tg and alpha-relaxations are perturbed near a boundary is believed to be related to the characteristic length scales associated with cooperative dynamics in dynamically heterogeneous glasses. Following our recent work [R. R. Baglay and C. R. Roth, J. Chem. Phys. 143, 111101 (2015)] that measured a very broad 350-400 nm local Tg(z) profile across a glassy-rubbery interface of polystyrene (PS)/poly(n-butyl methacrylate) (PnBMA), we compare here how the Tg(z) profile in PS varies when changing the neighboring polymer from a lower Tg material to a higher Tg material. Here we report local Tg(z) profiles for PS when in contact with polysulfone (PSF), poly(methyl methacrylate) (PMMA), and poly(isobutyl methacrylate) (PiBMA). We find that the distance from the interface before bulk Tg of PS (Tgbulk=101 °C) is recovered depends on whether PS forms the high-Tg glassy component experiencing so-called soft confinement, z ≈ 225-250 nm for PS next to PiBMA (Tgbulk=62 °C) and PnBMA (Tgbulk=21 °C), or PS forms the low-Tg rubbery component experiencing hard confinement, z ≈ 100-125 nm for PS next to PSF (Tgbulk=186 °C) and PMMA (Tgbulk=120 °C). The depth to which these Tg(z) perturbations persist and the magnitude of the local Tg perturbation at the interface are independent of the difference in Tgbulk between the two polymers, the interaction parameter, and the chemical structure. We demonstrate that these broad, extended Tg(z) length scales appear to be universal across these different systems but show that the strong dynamical coupling across the dissimilar polymer-polymer interface only occurs when this interface has been annealed to equilibrium. We consider why dissimilar polymer-polymer interfaces exhibit continuous local dynamics across the interface in contrast to polymer-free surface, polymer-substrate, or polymer-liquid interfaces that show discontinuous local dynamics.

Differential pressure experiment to probe hole growth in freely standing polymer films

We have developed a sensitive experiment which allows the measurement of the growth of holes in thin freely standing polystyrene (PS) films at elevated temperatures. In the experiment, a constant small pressure difference is applied and maintained across the freely standing film, and the formation and growth of holes is detected as a flow of air through the film. From measurements of freely standing PS films for which the glass transition temperature Tg is equal to the bulk value Tgbulk, as well as for films that are sufficiently thin that Tg is 30 °C less than Tgbulk, we find that substantial chain mobility occurs only at temperatures that are comparable to Tgbulk. The results can be interpreted as a shear thinning effect, which is consistent with previous optical microscopy measurements of hole growth in freely standing PS films.

Instabilities in Thin Polymer Films: From Pattern Formation to Rupture

SUMMARY: Thermal fluctuations of the surfaces of thin polymer films can be amplified by the long-range van der Waals or dispersion force which acts across the film. When freely-standing polymer films are heated, this instability leads to the formation of holes. We have measured the formation and growth of holes in very thin, freely-standing polystyrene (PS) films to learn about the mobility of the confined polymer molecules. We have also symmetrically capped freely-standing PS films with thin, solid layers to probe the effects of mechanical confinement. Aggressive annealing of the trilayer films produces a novel in-plane morphology which can be understood in terms of the balance between the decrease in free energy associated with the dispersion interaction and the increase in free energy associated with the bending of the capping layers. The general nature of the morphology, and its reversibility, is demonstrated.

Novel Effects of Confinement and Interfaces on the Glass Transition Temperature and Physical Aging in Polymer Films and Nanocomposites

Recently, it has become evident that the magnitude of the glass transition (Tg)‐confinement effect depends strongly on the polymer repeat unit and that the magnitude of the physical aging rate can be dramatically reduced relative to neat polymer when attractive polymer‐nanofiller interactions are present in well‐dispersed nanocomposites. However, in neither case has a quantitative, fundamental understanding been developed. By studying polymers with different chain backbone stiffness, e.g., polystyrene (PS) vs. polycarbonate (PC) vs. polysulfone (PSF) and that lack attractive interactions with the substrate interface, we show that the Tg‐confinement effect is the weakest in the polymer with the least stiff backbone (PS) and strongest in the polymer with the most stiff backbone (PSF). These results are consisten with the notion that, other things being equal, a larger requirement by the polymer for the cooperativity of the segmental mobility that is associated with the glass transition will result in a grea...

Changes in the temperature-dependent specific volume of supported polystyrene films with film thickness

Recent studies have measured or predicted thickness-dependent shifts in density or specific volume of polymer films as a possible means of understanding changes in the glass transition temperature Tg(h) with decreasing film thickness with some experimental works claiming unrealistically large (25%-30%) increases in film density with decreasing thickness. Here we use ellipsometry to measure the temperature-dependent index of refraction of polystyrene (PS) films supported on silicon and investigate the validity of the commonly used Lorentz-Lorenz equation for inferring changes in density or specific volume from very thin films. We find that the density (specific volume) of these supported PS films does not vary by more than ±0.4% of the bulk value for film thicknesses above 30 nm, and that the small variations we do observe are uncorrelated with any free volume explanation for the Tg(h) decrease exhibited by these films. We conclude that the derivation of the Lorentz-Lorenz equation becomes invalid for very thin films as the film thickness approaches ∼20 nm, and that reports of large density changes greater than ±1% of bulk for films thinner than this likely suffer from breakdown in the validity of this equation or in the difficulties associated with accurately measuring the index of refraction of such thin films. For larger film thicknesses, we do observed small variations in the effective specific volume of the films of 0.4 ± 0.2%, outside of our experimental error. These shifts occur simultaneously in both the liquid and glassy regimes uniformly together starting at film thicknesses less than ∼120 nm but appear to be uncorrelated with Tg(h) decreases; possible causes for these variations are discussed.

Electric fields enhance miscibility of polystyrene/poly(vinyl methyl ether) blends

How the presence of electric fields alters the miscibility of mixtures has been studied since the 1960s with conflicting reports on both the magnitude and direction of the shift in the phase separation temperature Ts. Theoretical understanding of the phenomenon has been hampered by the lack of experimental data with unambiguously large shifts in Ts outside of experimental error. Here, we address these concerns by presenting data showing that uniform electric fields strongly enhance the miscibility of polystyrene (PS)/poly(vinyl methyl ether) (PVME) blends. Reliable shifts in Ts of up to 13.5 ± 1.4 K were measured for electric fields strengths of E = 1.7 × 10(7) V/m in a 50/50 PS/PVME mixture. By using a sensitive fluorescence method to measure Ts, the PS/PVME blend can be quenched back into the one phase region of the phase diagram when the domains are still small allowing the blend to be remixed such that Ts can be measured repeatedly on the same sample. In this manner, highly reproducible Ts values at non-zero and zero electric field can be ascertained on the same sample. Our results agree with the vast majority of existing experimental data on various mixtures finding that electric fields enhance miscibility, but are opposite to the one previous study on PS/PVME blends by Reich and Gordon [J. Polym. Sci.: Polym. Phys. Ed. 17, 371 (1979)] reporting that electric fields induce phase separation, a study which has been considered anomalous in the field.

Aging near rough and smooth boundaries in colloidal glasses

We use a confocal microscope to study the aging of a bidisperse colloidal glass near rough and smooth boundaries. Near smooth boundaries, the particles form layers, and particle motion is dramatically slower near the boundary as compared to the bulk. Near rough boundaries, the layers nearly vanish, and particle motion is nearly identical to that of the bulk. The gradient in dynamics near the boundaries is demonstrated to be a function of the gradient in structure for both types of boundaries. Our observations show that wall-induced layer structures strongly influence aging.