Off-campus UMass Amherst users: To download campus access dissertations, please use the following link to log into our proxy server with your UMass Amherst user name and password.

Non-UMass Amherst users: Please talk to your librarian about requesting this dissertation through interlibrary loan.

Dissertations that have an embargo placed on them will not be available to anyone until the embargo expires.

Author ORCID Identifier

https://orcid.org/0000-0002-0993-1544

Document Type

Campus-Only Access for One (1) Year

Degree Name

Doctor of Philosophy (PhD)

Degree Program

Polymer Science and Engineering

Year Degree Awarded

2019

Month Degree Awarded

September

First Advisor

Thomas Russell

Second Advisor

Narayanan Menon

Third Advisor

Gregory Grason

Fourth Advisor

David Hoagland

Subject Categories

Polymer and Organic Materials

Abstract

In this dissertation, we aim to understand the mechanical properties of thin films and classes of wrinkle patterns of polymer films using capillary wrinkling. We discuss four independent research subjects.

In the first project, we measure the thickness (t) dependence of Young’s modulus (E) of polymer thin films. Thin films were measured from bulk thicknesses down to thickness less than the radius of gyration (6 nm). E does not show any systematic change with t, although an increase in modulus was found for the thinnest poly(styrene) (PS) film.

The second topic is stretching (Y) and bending (B) moduli of PS/poly(methyl methacrylate) (PMMA) and PS/gold (Au) bilayer films inferred from wrinkle patterns. The Y, B, and wrinkle patterns for PS/PMMA and PMMA/PS bilayers were not affected by the difference in surface energies nor the ratio of the thicknesses. However, the normalized length of wrinkles (L/a) from PS/Au and Au/PS showed no significant variation against Y while Au/PS increased in the number of wrinkles when B ≤ ~ 10-12 N·m.

We also investigated the concentration and thickness dependence of the composite modulus (Ec) of PS-gold nanoparticles (GNPs) nanocomposites. Different wt% of 124 kg/mol Mw PS capped 12 nm diameter GNPs were mixed with a 97 kg/mol Mw PS matrix (30 nm ≤ tPS-GNPs ≤ 148 nm). An increase in the L/a value was found for tPS-GNPs ~ 148 nm with 13 wt% loading. The normalized number of wrinkles (N/a0.5) in a 30 nm thick film with 5 wt% GNPs loading was found to increase by 2.7 times over that of PS homopolymer, but showed a decrease when the GNPs loadings were increased. As tPS-GNPs ≥ 102 nm, N/a0.5 became ~ (Et3)-1/4, similar to PS homopolymer. Furthermore, Ec was observed to be double that of PS homopolymer when tPS-GNPs ≥102 nm with 13 wt% GNPs loading.

Finally, we observed classes of wrinkle patterns from different PS film thicknesses: Single mode in regime (i) t ≥ 600 nm, period-doubling in regime (ii) 50 nm ≤ t ≤ 600 nm, and Double mode in regime (iii) t ≤ ~ 50 nm.

DOI

https://doi.org/10.7275/jevc-yj26

Creative Commons License

Creative Commons Attribution-Noncommercial 4.0 License
This work is licensed under a Creative Commons Attribution-Noncommercial 4.0 License

Available for download on Tuesday, September 01, 2020

Share

COinS