(441g) Molecular Weight Dependence of the Intrinsic Size Effect on Tg in AAO Template-Supported Polymer Nanorods: A DSC Study

Wei, T., Northwestern University
Torkelson, J. M., Northwestern University
Askar, S., Northwestern University
Tan, A., Northwestern University
Many studies have established a major effect of nanoscale confinement on the glass transition temperature (Tg) of polystyrene (PS), most commonly in thin films with one or two free surfaces. Here, we characterize smaller yet significant intrinsic size effects (in the absence of free surfaces or significant attractive polymer-substrate interactions) on the Tg and fragility of linear PS (see J. Chem. Phys. 2017, 146, 203323). Melt infiltration of various molecular weights (MWs) of PS into anodic aluminum oxide (AAO) templates is used to create nanorods supported on AAO with rod diameter (d) ranging from 24 to 210 nm. The Tg (both as Tg,onset and fictive temperature) and fragility values are characterized by differential scanning calorimetry. No intrinsic size effect is observed for 30 kg/mol PS in template-supported nanorods with d = 24 nm. However, effects on Tg are present for PS nanorods with Mn and Mw ≥ ~ 175 kg/mol, with effects increasing in magnitude with increasing MW. For example, in 24-nm-diameter template-supported nanorods, Tg,rod – Tg,bulk = -2.0 to -2.5 °C for PS with Mn = 175 kg/mol and Mw = 182 kg/mol, and Tg,rod – Tg,bulk = ~ -8 °C for PS with Mn = 929 kg/mol and Mw = 1420 kg/mol. In general, reductions in Tg occur when d ≤ ~ 2Rg, where Rg is the bulk polymer radius of gyration. Thus, intrinsic size effects are significant when rod diameter is smaller than the diameter (2Rg) associated with the spherical volume pervaded by coils in bulk. We hypothesize that the Tg reduction occurs when chain segment packing frustration is sufficiently perturbed by confinement in the nanorods. This explanation is supported by observed reductions in fragility with increasing extent of confinement. We also explain why these small intrinsic size effects do not contradict reports that the Tg-confinement effect in supported PS films with one free surface exhibits little or no MW dependence. This point can be understood by comparing template-supported nanorod and thin film Tg reductions at a similar characteristic length scale, t*. For PS nanorods with dm = 63 nm or t* = 15.8 nm, as measured by DSC there is no reduction in Tg relative to bulk response when Mn and Mw ≤ ~500 kg/mol, and Tg,rod – Tg,bulk = ~ -2 °C for PS with Mn = 929 kg/mol and Mw = 1420 kg/mol. As determined by ellipsometry, supported PS films with thickness of 16 nm (t* = 16 nm) exhibit Tg,film – Tg,bulk = ~ -19 °C (Europhys. Letter.1994, 27,59). Thus, at MWs of PS most commonly used in studies of Tg-confinement effects in the presence of a free surface, intrinsic size effects contribute nothing within error to the measured effect; at extremely high PS MW, the contribution of intrinsic size effects is only a very small percentage of the reported Treduction.

The characterization of intrinsic size effect on Tg is being extended to a crosslinked, supported PS nanorod system. Linear precursor polystyrene-co-vinylbenzoycyclobutene (VBCB) nanorods with Mn = 30 kg/mol exhibit no intrinsic size effect on Tg, where d > 2Reven in template with 24-nm pore diameter. Upon crosslinking the VBCB units, the network structure exhibit effectively infinite MW. The comparison of Tg-confinement effects in linear and crosslinked PS nanorods is being studied and will be discussed.