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

Luo, Ming; Brown, Jonathan R.; Remy, Roddel A.; Scott, Douglas M.; Mackay, Michael E.; Hall, Lisa M.; Epps, Thomas H.

doi:10.1021/acs.macromol.6b00946

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

Journal Article · Wed Jul 13 00:00:00 EDT 2016 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.6b00946· OSTI ID:1468592

Luo, Ming ^[1]; Brown, Jonathan R. ^[2]; Remy, Roddel A. ^[3]; Scott, Douglas M. ^[4]; Mackay, Michael E. ^[5]; Hall, Lisa M. ^[2]; Epps, Thomas H. ^[5]

Univ. of Delaware, Newark, DE (United States). Dept. of Chemical and Biomolecular Engineering; The Ohio State University
The Ohio State Univ., Columbus, OH (United States). William G. Lowrie Dept. of Chemical and Biomolecular Engineering
Univ. of Delaware, Newark, DE (United States). Dept. of Materials Science and Engineering
Univ. of Delaware, Newark, DE (United States). Dept. of Chemical and Biomolecular Engineering
Univ. of Delaware, Newark, DE (United States). Dept. of Chemical and Biomolecular Engineering and Dept. of Materials Science and Engineering

Tapered block polymers are an emerging class of macromolecules with unique and diverse self-assembly behavior and properties. Here, we directly examine the manipulation of self-assembled interfaces in poly(isoprene-b-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 (T_g) and change of heat capacity (ΔC_P) for each BP phase, and quantitative analysis from ΔC_P 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.

View Accepted Manuscript (DOE)

Research Organization:: The Ohio State Univ., Columbus, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); DuPont Young Professor Award; National Inst. of Standards and Technology (NIST); National Inst. of Health (NIH)

Grant/Contract Number:: SC0014458; SC0014209

OSTI ID:: 1468592

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 14 Vol. 49; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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