Date of Award

5-2007

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Legacy Department

Chemical Engineering

Advisor

Hirt, Douglas E

Abstract

Highly layered structures are important to micro- and nanofabrication technologies for understanding and controlling surface structures through manipulation of chemical and physical interactions. The objective of this work was to develop a new approach to create micro- and nanopatterned surfaces using multilayer polymer films of commercially available and inexpensive polymers instead of inorganic substrates. As an example, linear low density polyethylene (LLDPE) and ethylene-co-acrylic acid copolymer (EAA) were used as alternating inert and reactive polymers, respectively. Thin cross-sections of the multilayer molded sheets were prepared by ultra-microtoming.
As a precursor to the multilayer work, surface modification of EAA was conducted to carefully control the chemical functionality on the surface by a variety of methods. Dansyl cadaverine and polyethylene glycol (PEG) derivatives were grafted on the surface of EAA film and in its subsurface region through formation of amides and esters, respectively. First, EAA film was activated with PCl5 and then the acid chloride was reacted with dansyl cadaverine or a PEG derivative. Moreover, two other reaction schemes were developed to covalently graft PEG chains on EAA surfaces. The schemes involved surface grafting of linker molecules l-lysine or polypropyleneamine dendrimer (AM64), with subsequent covalent bonding of PEG chains to the linker molecules. Combining the data from ATR-FTIR, XPS, and contact angle goniometry, it was found that the PEG chains were grafted on the surface of the EAA film and larger surface coverage was achieved when the dendrimer was used as intermediate layer.
Research was then conducted on the EAA-LLDPE multilayer cross-sectioned templates. Regionally confined chemical functionality was confirmed by grafting an amine-terminated biotin to the alternating layers of EAA. Subsequently, fluorescently labeled streptavidin selectively adsorbed on the biotin-modified EAA layers. As a further development, polyelectrolyte multilayers (PEM) were adsorbed on the nanopatterned surfaces to significant increase the areal density of reactive groups. Using PAH and PAA as the polyelectrolytes, the EAA nano-stripes were successfully modified by PEM films, forming a nanopatterned template with alternating hydrophilic and hydrophobic regions. This kind of nano-striped surface could serve as a template for many applications, including biomedical, separation, and electronics.

Share

COinS
 
 

To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.