Determination of Interfacial Mixing in Tapered Block Polymer Thin Films: Experimental and Theoretical Investigations

Tapered block polymers are an emerging class of macromolecules with unique and diverse self-assembly behavior and properties. Herein, we directly examine the manipulation of self-assembled interfaces in poly­(isoprene-<i>b</i>-styrene) (I-S)-based block polymers (BPs) by synthesizing non-tapered (I-S), normal tapered (I-IS-S), and inverse tapered (I-SI-S) BPs with controlled monomer segment distributions. We provide the first direct measurements of interfacial mixing for these tapered polymers through X-ray reflectivity (XRR). The density profiles from XRR are compared to results from fluids density functional theory (fDFT) with good agreement. We find that our normal tapered BPs (30 vol % tapering) have similar interfacial mixing to diblock polymers, while our inverse tapered BPs (30 vol % tapering) have much wider interfaces. Additionally, differential scanning calorimetry (DSC) studies elucidate the influence of tapering on the glass transition temperature (<i>T</i>_g) and change of heat capacity (Δ<i>C</i>_<i>P</i>) for each BP phase, and quantitative analysis from Δ<i>C</i>_<i>P</i> also indicates enhanced mixing in the inverse tapered I-SI-S BPs. Finally, we investigate the free surface morphologies of these tapered polymers in thin film geometries. The inverse tapered BP form larger island/hole structures likely due to decreased surface elasticity from mixing as a result of the modified interblock interfacial characteristics. These results demonstrate that BPs with similar molecular weights and compositions can exhibit different thermodynamic properties and free surface morphologies in thin film geometries, as influenced by monomer sequence