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This paper investigates molecular-scale polymer mechanical deformation during large-strain squeeze flow of polystyrene (PS) films, where the squeeze flow gap is close to the polymer radius of gyration (R(g)). Stress-strain and creep relations were measured during flat punch indentation from an initial film thickness of 170 nm to a residual film thickness of 10 nm in the PS films, varying molecular weight (M(w)) and deformation stress rate by over 2 orders of magnitude while temperatures ranged from 20 to 125 degrees C. In stress-strain curves exhibiting an elastic-to-plastic yield-like knee, the response was independent of M(w), as expected from bulk theory for glassy polymers. At high temperatures and long times sufficient to extinguish the yield-knee, the mechanical response M(w) degeneracy was broken, but no molecular confinement effects were observed during thinning. Creep measurements in films of 44K M(w) were well-approximated by bulk Newtonian no-slip flow predictions. For extrusions down to a film thickness of 10 nm, the mechanical relaxation in these polymer films scaled with temperature similar to Williams-Landel-Ferry scaling in bulk polymer. Films of 9000K M(w), extruded from an initial film thickness of 2R(g) to a residual film thickness of 0.5R(g), while showing stress-strain viscoelastic response similar to that of films of 900K M(w), suggestive of shear-thinning behavior, could not be matched to a constitutive flow model. In general, loading rate and magnitude influenced subsequent creep extrusion depth of high-M(w) films, with deeper final extrusions for high loading rates than for low loading rates. The measurements suggest that, for high-resolution nanoimprint lithography, mold flash or final residual film thickness can be reduced for high strain and strain rate loading of high-M(w) thin films.
ACS Nano 2008 Mar
PMID:Measuring glassy and viscoelastic polymer flow in molecular-scale gaps using a flat punch mechanical probe. 1920 65

Understanding the mechanical properties of polymers at the nanoscale is critical in numerous emerging applications. While it has been widely shown that the glass transition temperature (T(g)) in thin polymer films generally decreases due to confinement effects in the absence of strong favorable interactions between the polymer and substrate, there is little known about the modulus of sub-100 nm polymer films and features. Thus, one might use this depressed T(g) as a surrogate to estimate how the modulus of nanoconfined polymeric materials deviates from the bulk, based on constructs such as Williams-Landel-Ferry (WLF) time-temperature superposition principles. However, such relationships have not been thoroughly examined at the nanoscale where surface and interface effects can dramatically impact the physical properties of a material. Here, we measure the elastic modulus of a series of poly(methacrylate) films with widely varying bulk T(g)'s as a function of thickness at ambient temperature, exploiting a wrinkling instability of a thin, stiff film on an thick, elastic substrate. A decrease in the modulus is found for all polymers in ultrathin films (<30 nm) with the onset of confinement effects shifting to larger film thicknesses as the quench depth (T(g,bulk) - T) decreases. We show that the decrease in modulus of ultrathin films is not correlated with the observed T(g) decrease in films of the same thickness.
ACS Nano 2009 Sep 22
PMID:Elastic modulus of amorphous polymer thin films: relationship to the glass transition temperature. 1970 80