<html><head></head><body style="word-wrap: break-word; -webkit-nbsp-mode: space; -webkit-line-break: after-white-space; color: rgb(0, 0, 0); font-size: 14px; font-family: Calibri, sans-serif; "><div><div><div><br></div></div></div><span id="OLK_SRC_BODY_SECTION"><div><div style="word-wrap: break-word; -webkit-nbsp-mode: space; -webkit-line-break: after-white-space; color: rgb(0, 0, 0); font-size: 14px; font-family: Calibri, sans-serif; "><span id="OLK_SRC_BODY_SECTION"><div xmlns:v="urn:schemas-microsoft-com:vml" xmlns:o="urn:schemas-microsoft-com:office:office" xmlns:w="urn:schemas-microsoft-com:office:word" xmlns:m="http://schemas.microsoft.com/office/2004/12/omml" xmlns="http://www.w3.org/TR/REC-html40"><div lang="EN-US" link="blue" vlink="purple"><div class="WordSection1"><div><div><p class="MsoNormal" align="center" style="mso-margin-top-alt:auto;mso-margin-bottom-alt:auto;text-align:center;line-height:15.75pt"><b><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: black; ">Student: Shu Wang</span></b><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: black; "><o:p></o:p></span></p><p class="MsoNormal" align="center" style="mso-margin-top-alt:auto;mso-margin-bottom-alt:auto;text-align:center;mso-line-height-alt:12.1pt"><b><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: black; ">Defense Date:</span></b><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: black; "> Tuesday, April 21 2015 <b>Time:
</b>2:00 pm<o:p></o:p></span></p><p class="MsoNormal" align="center" style="mso-margin-top-alt:auto;mso-margin-bottom-alt:auto;text-align:center;mso-line-height-alt:12.1pt"><b><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: black; ">Location Room:</span></b><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: black; "> </span><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: rgb(34, 34, 34); ">S234</span><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: black; "> (Chemical
Engineering conference room)<o:p></o:p></span></p><p class="MsoNormal" align="center" style="mso-margin-top-alt:auto;mso-margin-bottom-alt:auto;text-align:center;mso-line-height-alt:12.1pt"><b><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: black; ">Committee Chair: </span></b><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: black; ">Dr. Megan Robertson</span><a name="14cd74d06dd3ba5c_14cd7441b2954379_14cb3a"></a><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: rgb(0, 176, 240); "><o:p></o:p></span></p><h1 align="center" style="text-align:center"><span style="font-size: 10.5pt; font-family: Rockwell, serif; color: rgb(0, 176, 240); "><hr size="2" width="100%" align="center"></span></h1><p class="MsoNormal" align="center" style="text-align:center"><b><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: black; ">Title: </span></b><b><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: rgb(34, 34, 34); "><o:p></o:p></span></b></p><p class="MsoNormal" align="center" style="mso-margin-top-alt:auto;mso-margin-bottom-alt:auto;text-align:center;line-height:15.75pt"><b><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: rgb(34, 34, 34); ">Development of Sustainable Thermoplastic Elastomers<o:p></o:p></span></b></p><p class="MsoNormal" align="center" style="mso-margin-top-alt:auto;mso-margin-bottom-alt:auto;text-align:center;line-height:15.75pt"><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: black; "><o:p> </o:p></span></p><h1 align="center" style="text-align:center"><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: rgb(34, 34, 34); ">Abstract</span><span style="font-size: 14pt; font-family: Calibri, sans-serif; color: black; "><o:p></o:p></span></h1><p class="MsoNormal" style="mso-margin-top-alt:auto;mso-margin-bottom-alt:auto;text-align:justify"><span style="font-size: 10.5pt; font-family: Calibri, sans-serif; color: black; ">Sustainable poly(styrene-<i>b</i>-(lauryl-<i>co</i>-stearyl acrylate)-<i>b</i>-styrene) (SAS) triblock copolymers containing a rubbery midblock derived from fatty acids were designed
with targeted properties appropriate for thermoplastic elastomer applications, using reversible addition fragmentation chain transfer (RAFT) polymerization. SAS exhibited elastomeric behavior at room temperature and were processable upon heating above the
order-disorder transition (ODT) temperature.<a name="14cd74d06dd3ba5c_14cd7441b2954379__GoBac"></a> The alkyl side-chain length of the polyacrylates (as well as the related midblock composition of the triblock copolymers) was utilized as a convenient parameter
for tuning the physical properties of SAS, including the melting temperature and zero-shear viscosity of the midblock polyacrylate, melt viscosity of the triblock copolymer above the ODT, and tensile properties including tensile strength and strain at break.
<o:p></o:p></span></p><p class="MsoNormal" style="mso-margin-top-alt:auto;mso-margin-bottom-alt:auto;text-align:justify"><span style="font-size: 10.5pt; font-family: Calibri, sans-serif; color: black; ">The thermodynamic interactions between the components of the SAS triblock copolymers, long-chain poly(<i>n</i>-alkyl acrylates) and polystyrene, were explored through determination
of the Flory-Huggins interaction parameter, </span><span style="font-size:10.0pt">$B&V(B, thr</span><span style="font-size: 10.5pt; font-family: Calibri, sans-serif; color: black; ">ough cloud point measurements on binary polymer blends and measurement of the ODT
of SAS. It was shown that $B&V(B was independent of the length of the alkyl side-chain of the polyacrylates, in the limit of large alkyl side-chains (i.e. more than 10 carbon atoms), in stark contrast to theoretical predictions using group contribution methods
and solubility parameter theory.</span><o:p></o:p></p><p class="MsoNormal" style="mso-margin-top-alt:auto;mso-margin-bottom-alt:auto;text-align:justify"><span style="font-size: 10.5pt; font-family: Calibri, sans-serif; color: black; ">The morphology of SAS was probed by transmission electron microscopy, showing the presence of spherical polystyrene domains in the polyacrylate matrix, as well as small angle
X-ray scattering, indicating the presence of randomly oriented grains upon compression molding. Large amplitude oscillatory shear was employed at a temperature below ODT to align the randomly oriented grains. The predominant orientation was determined to be
hexagonally close-packed spherical domains with the {0001} planes parallel to the shear plane, with a small population of face-centered cubic spherical domains with the {1-10} planes parallel to the shear plane.<o:p></o:p></span></p><p class="MsoNormal" style="mso-margin-top-alt:auto;mso-margin-bottom-alt:auto;text-align:justify"><span style="font-size: 10.5pt; font-family: Calibri, sans-serif; color: black; ">Fully sustainable triblock copolymers with midblocks derived from fatty acids and endblocks derived from salicylic acid (found in fruits and vegetables) were also successfully
synthesized with RAFT polymerization. The properties of the resulting poly(acetylsalicylic ethyl methacrylate-<i>b</i>-lauryl methacrylate-<i>b</i>-acetylsalicylic ethyl methacrylate) (ALA) triblock copolymers were examined for their utility as thermoplastic
elastomers. Poly(acetylsalicylic ethyl methacrylate) was found to be a suitable replacement for polystyrene as the end-blocks of the triblock copolymer, with a glass transition temperature above room temperature. The morphology and mechanical properties of
ALA were comparable to that observed in the partially sustainable SAS triblock copolymers.</span><span style="font-size: 10.5pt; font-family: Calibri, sans-serif; color: rgb(0, 176, 240); "><o:p></o:p></span></p></div></div></div></div></div></span><style><!--
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