Title page for ETD etd-09022011-155812


Type of Document Dissertation
Author Liu, Yang
Author's Email Address yl2z@vt.edu
URN etd-09022011-155812
Title Synthesis and Characterization of Polyhedral Oligomeric Silsesquioxane (POSS) Based Amphiphiles
Degree PhD
Department Chemistry
Advisory Committee
Advisor Name Title
Esker, Alan R. Committee Chair
Gandour, Richard D. Committee Member
Marand, Hervé L. Committee Member
Morris, John R. Committee Member
Keywords
  • Π–A isotherms
  • air/water (A/W) interface
  • Brewster angle microscopy (BAM)
  • POSS
  • Langmuir films
Date of Defense 2011-08-23
Availability unrestricted
Abstract
Polyhedral oligomeric silsesquioxanes (POSS) have attracted substantial academic interest for many years as hybrid materials and nanofillers for controlling thermal and mechanical properties, and providing thermal and chemical resistance while retaining ease of processing. A natural extension of these studies has been POSS-based amphiphiles and thin film coatings. Studies at the air/water (A/W) interface have shown that trisilanol-POSS derivatives are amphiphilic and form uniform Langmuir films, whereas closed-cage POSS derivatives are hydrophobic and aggregate.

In previous work, a triester (POSS-triester) and a triacid (POSS-triacid) were synthesized from PSS-(3-hydroxypropyl)-heptaisobutyl (POSS-OH) and Weisocyanate and fully characterized by surface pressure – area per molecule (Π-A) isotherm and Brewster angle microscopy (BAM) studies at the A/W interface. The results indicated that POSS-triester is surface active forming a liquid expanded (LE) monolayer, whereas POSS-triacid forms a liquid condensed (LC) monolayer that is only weakly affected by pH. A face-on conformation was proposed and examined to understand the packing of POSS-based amphiphilic molecules at the A/W interface. The face-on/vertex-on comparison is rarely discussed for Langmuir monolayers at the A/W interface.

In this thesis, three other POSS-based esters were synthesized from POSS-OH and aminopropylisobutyl-POSS (POSS-NH2) using Weisocyanate and a similar isocyanate containing two tert-butyl protected carboxylic acids. The synthesized materials are characterized by Π-A isotherm and BAM. For POSS-OH based diester (PAlDE) and POSS-NH2 based diester (PAmDE), LE/LC phase transitions were observed in Π-A isotherms over part of the experimentally accessible temperature range and were attributed to a change from a vertex-on to face-on conformation. Apparent BAM images confirmed LC islands coexisted with the LE phase. The experimentally observed dynamic estimates of the critical temperatures (Tc) were estimated from a two-dimensional Clausius-Clapeyron analysis and were consistent with the temperature dependence of the Π-A isotherms. These LE/LC phase transitions are the first observed for POSS amphiphiles.

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