Molecular confinement of solid and gaseous phases of self-standing bulk nanoporous polymers inducing enhanced and unexpected physical properties

- Molecular confinement of polymer chains on self-standing nanoporous PMMA is evidenced.
- Scale-reduction related phenomena appear on both polymer and gaseous phases.
- Influence on the macroscopic physical properties of the confinement is demonstrated.

In this work it is provided the first evidence of the polymer chains confinement within self-standing pore walls of nanoporous materials based on poly (methyl methacrylate) (PMMA). This was made possible by producing a series of porous samples with a wide range of pore sizes between 90 nm and 3 μm using processes combining CO2 sorption, selective block copolymer swelling or homogeneous physical foaming. Mobility restrictions of the PMMA chains in the porous samples with pore size below 200 nm was consistently demonstrated with several experimental techniques, including differential scanning calorimetry, Raman spectroscopy, and broadband dielectric spectroscopy.In addition, several scale-reduction phenomena related to the constitutive elements of the porous materials, both in the polymeric and gaseous phases, and to the porous architecture are identified. The significance of these phenomena on macroscopic electrical conductivity and permittivity of the nanoporous materials is demonstrated, and the presented observations support previous explanations of improved mechanical properties and thermal insulation of this type of nano-materials.

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