Molecular confinement accelerates deformation of entangled polymers during squeeze flow.

The squeezing of polymers in narrow gaps is important for the dynamics of nanostructure fabrication by nanoimprint embossing and the operation of polymer boundary lubricants. We measured stress versus strain behavior while squeezing entangled polystyrene films to large strains. In confined conditions where films were prepared to a thickness less than the size of the bulk macromolecule, resistance to deformation was markedly reduced for both solid-glass forging and liquid-melt molding. For melt flow, we further observed a complete inversion of conventional polymer viscosity scaling with molecular weight. Our results show that squeeze flow is accelerated at small scales by an unexpected influence of film thickness in polymer materials.

Variable temperature thin film indentation with a flat punch.

We present modifications to conventional nanoindentation that realize variable temperature, flat punch indentation of ultrathin films. The technique provides generation of large strain, thin film extrusion of precise geometries that idealize the essential flows of nanoimprint lithography, and approximate constant area squeeze flow rheometry performed on thin, macroscopic soft matter samples. Punch radii as small as 185 nm have been realized in ten-to-one confinement ratio testing of 36 nm thick polymer films controllably squeezed in the melt state to a gap width of a few nanometers. Self-consistent, compressive stress versus strain measurements of a wide variety of mechanical testing conditions are provided by using a single die-sample system with temperatures ranging from 20 to 125 degrees C and loading rates spanning two decades. Low roughness, well aligned flat punch dies with large contact areas provide precise detection of soft surfaces with standard nanoindenter stiffness sensitivity. Independent heating and thermometry with heaters and thermocouples attached to the die and sample allow introduction of a novel directional heat flux measurement method to ensure isothermal contact conditions. This is a crucial requirement for interpreting the mechanical response in temperature sensitive soft matter systems. Instrumented imprint is a new nanomechanics material testing platform that enables measurements of polymer and soft matter properties during large strains in confined, thin film geometries and extends materials testing capabilities of nanoindentation into low modulus, low strength glassy, and viscoelastic materials.

Measuring glassy and viscoelastic polymer flow in molecular-scale gaps using a flat punch mechanical probe.

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.