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.

Document Type

Open Access Dissertation

Degree Name

Doctor of Philosophy (PhD)

Degree Program

Polymer Science and Engineering

Year Degree Awarded

2014

First Advisor

James J. Watkins

Second Advisor

Thomas J. McCarthy

Third Advisor

Jonathan P. Rothstein

Subject Categories

Materials Chemistry | Polymer Chemistry

Abstract

This dissertation explores the use of block copolymers which can self-assemble into different morphologies as templates to fabricate nanostructured materials. The first section (Chapters 2-4) reports the formation of mesoporous silica films with spherical, cylindrical and bicontinuous pores up to 40 nm in diameter through replicating the morphologies of the solid block copolymer (BCP) templates, polystyrene-b-poly(tert-butyl acrylate) (PS-b-PtBA), via phase selective condensation of tetraethylorthosilicate in supercritical CO2. Next, directed self-assembly was used to control the orientation of cylindrical domains in PS-b-PtBA templates. Large-area aligned mesochannels in silica films with diameters tunable between 5 and 30 nm were achieved through the replication of oriented templates via scCO2 infusion. The long-range alignment of mesochannels was confirmed through GISAXS with sample stage azimuthal rotation.

In the second section (Chapters 5-6), enantiopure tartaric acid was used as an additive to dramatically improve ordering in poly(ethylene oxide-block-tert-butyl acrylate) (PEO-b-PtBA) copolymers. Transmission electron microscopy (TEM), atomic force microscopy (AFM) and X-ray scattering were used to study the phase behavior and morphologies within both bulk and thin films. With the addition of a photo acid generator, photo-induced disorder in the PEO-b-PtBA/tartaric acid composite system was achieved upon UV exposure which deprotected the PtBA block to yield poly(acrylic acid) (PAA), which is phase-miscible with PEO. Area-selective UV exposure using a photo-mask was applied with the assistance of trace amounts of base quencher to achieve high-resolution hierarchical patterns. Helical superstructures were observed by TEM in this BCP/chiral additive system with 3D handedness confirmed by TEM tomography.

In the last section (Chapter 7), ultra-high loadings of nanoparticles into target domains of block copolymer composites were achieved by blending the block copolymer hosts with small molecule additives that exhibit strong interactions with one of the polymer chain segments and with the nanoparticle ligands via hydrogen bonding. The addition of 40 wt% D-tartaric acid to poly(ethylene oxide-block-tert-butyl acrylate) (PEO-b-PtBA) enabled the loading of up to 150 wt% of 4-hydroxythiophenol functionalized Au nanoparticles relative to the mass of the target hydrophilic domain. This was equivalent to over 40% Au by mass of the resulting well ordered composite as measured by thermal gravimetric analysis.

Share

COinS