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<title>Polymer Science and Engineering Department Dissertations Collection</title>
<copyright>Copyright (c) 2013 University of Massachusetts - Amherst All rights reserved.</copyright>
<link>http://scholarworks.umass.edu/pse_diss</link>
<description>Recent documents in Polymer Science and Engineering Department Dissertations Collection</description>
<language>en-us</language>
<lastBuildDate>Tue, 26 Mar 2013 09:40:20 PDT</lastBuildDate>
<ttl>3600</ttl>


	



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<title>Characterization of Self-Assembled Functional Polymeric Nanostructures:  I. Magnetic Nanostructures from Metallopolymers  II. Zwitterionic Polymer Vesicles in Ionic Liquid</title>
<link>http://scholarworks.umass.edu/open_access_dissertations/694</link>
<guid isPermaLink="true">http://scholarworks.umass.edu/open_access_dissertations/694</guid>
<pubDate>Wed, 20 Mar 2013 12:31:10 PDT</pubDate>
<description>
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	<p>Two diverse projects illustrate the application of various materials characterization techniques to investigate the structure and properties of nanostructured functional materials formed in both bulk as well as in solutions. In the first project, ordered magnetic nanostructures were formed within polymer matrix by novel metallopolymers. The novel metal-functionalized block copolymers (BCPs) enabled the confinement of cobalt metal ions within nanostructured BCP domains, which upon simple heat treatment resulted in room temperature ferromagnetic (RTFM) materials. On the contrary, cobalt functionalized homopolymer having similar chemical structure and higher loading of metal-ion are unstructured and exhibited superparamagnetic (SPM) behavior at room temperature. Based on a series of detailed investigations, using various materials characterization techniques, it was hypothesized that the SPM cobalt particles within BCP microdomains exhibited a collective behavior due to increased dipolar interactions between them under the nanoconfinement of cylindrical domains in BCP, resulting in RTFM behavior. On contrary, the same SPM cobalt particles formed within homopolymer, without any confinement exhibited SPM behavior either due to lack of interactions or random interactions between them.</p>
<p>To further support this hypothesis, a series of BCPs were prepared in which the BCP morphology was varied between the cylindrical, lamellar, and inverted cylindrical phases and their magnetic properties were compared. All these BCPs, which are nanostructured, exhibited RTFM behavior, further supporting the proposed hypothesis. Different dimensionality or degree of nanoconfinement in BCP morphologies affected the magnetization reversal processes in these BCPs, yielding different macroscopic magnetic properties. Most strongly constrained cylindrical morphology has shown best magnetic properties (highest coercivity) among other BCP morphologies. Inverted cylindrical morphology, in which a 3-D matrix is confined between the non-magnetic cylinders, had second highest and lamellar morphology with least confinement among BCPs, exhibited lowest coercivity.</p>
<p>The proposed hypothesis was further tested by systematically varying the dipolar interactions between the SPM cobalt nanoparticles by reducing the density of cobalt within the cylindrical domains and varying the dimensions of the cylindrical domains (i.e. diameter). A series of novel ferrocene-cobalt containing block copolymers were developed and cobalt density within the cylindrical domains of BCP was varied by changing the chemical composition of the metal functionalized block. Further, the diameter of the cylindrical domains was varied by varying the molecular weight of the cobalt-containing BCPs. These studies allowed us to understand the fundamental correlations between the self-assembled nanostructures and their macroscopic magnetic properties.</p>
<p>In the second part of the thesis, a novel amphiphilic block copolymer (ABC), composed of a hydrophilic zwitterionic block and a hydrophobic PS block, was synthesized by ROMP. The formation of zwitterionic vesicles in an ionic liquid, as well as in PBS buffer, was confirmed by TEM and DLS characterization. The dispersion of vesicles within ionic liquid enabled the usage of conventional, room temperature TEM to visualize them in their solution state. This technique of materials characterization could be extended for the visualization of other hydrophilic soft matter.</p>

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<author>Maddikeri, Raghavendra Raj</author>

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<title>Impact Resistant Glassy Polymers: Pre-Stress And Mode Ii Fracture</title>
<link>http://scholarworks.umass.edu/open_access_dissertations/681</link>
<guid isPermaLink="true">http://scholarworks.umass.edu/open_access_dissertations/681</guid>
<pubDate>Tue, 19 Mar 2013 11:30:34 PDT</pubDate>
<description>
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	<p>Model glassy polymers, polymethyl methacrylate (PMMA) and polycarbonate (PC) are used to experimentally probe several aspects of polymer fracture. In Chapter 1, the method of pre-stress is employed as a means of improving the fracture properites of brittle PMMA. Samples are tested under equi-biaxial compression, simple shear and a combination of biaxial compression and shear. Equi-biaxial compression is shown to increase the threshold stress level for projectile penetration whereas shear pre-stress has a large effect on the overall energy absorbed during an impact. There is also an apparent interaction observed between compression and shear to dramatically increase the threshold stress. Pre-stressed laminates of PMMA and PC show an increase in damage area because of the unique formation of a secondary cone.</p>
<p>In Chapter 2, the effect of stress state on stress relaxation in PMMA and PC is investigated. Direct comparisons are made between uniaxial and biaxial loading conditions. The experimental methods used highlight the effect of hydrostatic stress on the relaxation process. The data shows an increase in relaxation time and increase in the breadth of the relaxation spectrum with increases in hydrostatic stress. This suggests that the stress state can have a significant effect on the useful lifetime of pre-stressed articles.<strong></strong></p>
<p>In Chapter 3, Mode I and II fracture studies are performed from quasi-static to low velocity impact rates on PMMA and PC. Mode II testing utilizes an angled double-edge notched specimen loaded in compression. The shear banding response of PMMA is shown to be highly sensitive to rate, with diffuse shear bands forming at low rates and sharp distinct shear bands forming at high rates. As the rate increases, shear deformation becomes more localized to the point where Mode II fracture occurs. PC is much less rate dependent and stable shear band propagation is observed over the range of rates studied with lesser amounts of localization. A new theory is formulated relating orientation in a shear band to intrinsic material properties obtained from true-stress true-strain tests. In a qualitative sense the theory predicts the high rate sensitivity of PMMA. A kinematic limit for orientation within a shear band is also derived based on entanglement network parameters. Mode II fracture in PMMA is shown to occur at this kinematic limit. For the case of PC, the maximum impact rates were not high enough to reach the kinematic limit.<strong></strong></p>
<p>In Chapter 4, the deformation response, as observed in a shear band is interpreted through the characterization of the "intrinsic material properties" obtained from true stress - true strain 8compression tests. The relatively high rate sensitivity of PMMA deformed at room temperature is related to the proximity of the beta transition to the test temperature. This is also shown in corollary experiments on PC where deformation near the beta transition is accompanied by an increase in rate sensitivity. Physical aging results in a more narrow alpha transition and is shown to increase strain localization and decrease rate sensitivity at low strain rates.<strong></strong></p>

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<author>Archer, Jared Steven</author>

<source></source>

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