University of Groningen Tuning the crystalline phases of poly(vinylidene fluoride) for capacitive energy storage applications Meereboer, Niels Laurens

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Tuning the crystalline phases of poly(vinylidene fluoride) for capacitive energy storage

applications

Meereboer, Niels Laurens

IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below.

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Publication date: 2019

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Meereboer, N. L. (2019). Tuning the crystalline phases of poly(vinylidene fluoride) for capacitive energy storage applications. Rijksuniversiteit Groningen.

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529927-L-sub01-bw-Meereboer 529927-L-sub01-bw-Meereboer 529927-L-sub01-bw-Meereboer 529927-L-sub01-bw-Meereboer Processed on: 21-3-2019 Processed on: 21-3-2019 Processed on: 21-3-2019

Processed on: 21-3-2019 PDF page: 49PDF page: 49PDF page: 49PDF page: 49

Chapter 3

'YVMIXVERWMXMSRMR4:(co8V) FPSGOGSTSP]QIVW

ŚĂŶŐĞƐŝŶƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞŽĨŶĂŶŽĐŽŶĮŶĞĚƉŽůǇ;ǀŝŶǇůŝĚĞŶĞŇƵŽƌŝĚĞ-co-ƚƌŝŇƵŽƌŽĞƚŚǇůĞŶĞͿ W;s&-co-dƌ&Ϳ ĐŽƉŽůǇŵĞƌƐ ĐĂŶ ŚĂǀĞ Ă ƐĞǀĞƌĞ ŝŵƉĂĐƚ ŽŶ ƚŚĞ ĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌĂŶĚƚŚĞĂƉƉůŝĐĂƟŽŶƌĂŶŐĞŽĨƚŚĞƐĞŵĂƚĞƌŝĂůƐ͘dŚĞƌĞĨŽƌĞ͕ƚŚĞŽƌŝŐŝŶ ŽĨƚŚĞĐŚĂŶŐĞŝŶƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞƌĞƋƵŝƌĞƐĂƉƌŽĨŽƵŶĚƵŶĚĞƌƐƚĂŶĚŝŶŐ͘ /ŶƚŚŝƐǁŽƌŬ͕ďůŽĐŬĐŽƉŽůǇŵĞƌƐĞůĨͲĂƐƐĞŵďůǇŝŶƚŽĂƐƉŚĞƌŝĐĂůŵŽƌƉŚŽůŽŐǇƉƌŽǀĞƐƚŽďĞĂ ǀŝĂďůĞŵĞƚŚŽĚƚŽĞīĞĐƟǀĞůǇĐŽŶĮŶĞW;s&-co-dƌ&ͿŝŶƚŚƌĞĞĚŝŵĞŶƐŝŽŶƐĨŽƌƐƚƵĚǇŝŶŐƚŚĞ ĞīĞĐƚŽĨŶĂŶŽĐŽŶĮŶĞŵĞŶƚŽŶƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶ͘hƐŝŶŐĚŝīĞƌĞŶƟĂůƐĐĂŶŶŝŶŐĐĂůŽƌŝŵĞƚƌǇ ĂŶĚǁŝĚĞͲĂŶŐůĞyͲƌĂǇƐĐĂƩĞƌŝŶŐ͕ĞĂƐŝůǇĂĐĐĞƐƐŝďůĞĞǆƉĞƌŝŵĞŶƚĂůƚĞĐŚŶŝƋƵĞƐ͕ƚŚĞĐƌǇƐƚĂůůŝŶĞ ƉŚĂƐĞƚƌĂŶƐŝƟŽŶƐĂƌĞĨŽůůŽǁĞĚ͕ƐŚŽǁŝŶŐƚŚĂƚĐŽŶĮŶŝŶŐW;s&-co-dƌ&ͿŝŶĂŶŽŶƉŽůĂƌ ƉŽůǇƐƚǇƌĞŶĞ;W^ͿŽƌƉŽůǇ;tertͲďƵƚŽǆǇƐƚǇƌĞŶĞͿ;WtK^ͿŵĂƚƌŝǆƌĞƐƵůƚƐŝŶĂŶŝŶĐƌĞĂƐĞŽĨƚŚĞ ƵƌŝĞƚƌĂŶƐŝƟŽŶƵƉŽŶĐŽŽůŝŶŐĂŶĚŚĞĂƟŶŐ͘,ŽǁĞǀĞƌ͕ǁŚĞŶĂŵŽƌĞƉŽůĂƌŵĂƚƌŝǆŝƐƵƐĞĚ ƚŽŶĂŶŽĐŽŶĮŶĞW;s&-co-dƌ&Ϳ͕ƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞŝƐĚƌĂƐƟĐĂůůǇƌĞĚƵĐĞĚ ĚƵĞƚŽƐƵƌĨĂĐĞĞīĞĐƚƐ͘

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50

Introduction

&ĞƌƌŽĞůĞĐƚƌŝĐ ƉŽůǇŵĞƌƐ͕ ůŝŬĞ ƉŽůǇ;ǀŝŶǇůŝĚĞŶĞ ŇƵŽƌŝĚĞͿ ;Ws&Ϳ ĂŶĚ ŝƚƐ ĐŽƉŽůǇŵĞƌ ǁŝƚŚ ƚƌŝĨůƵŽƌŽĞƚŚǇůĞŶĞ ;W;s&-co-dƌ&ͿͿ͕ ĂƌĞ ĞƐƐĞŶƚŝĂů ĨŽƌ ƚŚĞ ĚĞǀĞůŽƉŵĞŶƚ ŽĨ ŽƌŐĂŶŝĐ ĞůĞĐƚƌŽŶŝĐƐ͕ ƐĞŶƐŽƌƐ͕ ĞŶĞƌŐǇ ƐƚŽƌĂŐĞ ĂŶĚ ŶŽŶǀŽůĂƟůĞ ŵĞŵŽƌǇ ĚĞǀŝĐĞƐ͘ϭʹϲ_{ƐƉĞĐŝĂůůǇ͕} W;s&-co-dƌ&Ϳ ŚĂƐ ĂƩƌĂĐƚĞĚ ŐƌĞĂƚ ŝŶƚĞƌĞƐƚ ĚƵĞ ƚŽ ƚŚĞ ĞĂƐĞ ŽĨ ƉƌŽĐĞƐƐŝŶŐ ŝŶƚŽ ƚŚĞ ferroelectric crystalline phase. 7,8 ,ŽǁĞǀĞƌ͕ƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐƉƌŽƉĞƌƟĞƐŽĨW;s&-co-dƌ&ͿƌĂƉŝĚůǇĚĞƚĞƌŝŽƌĂƚĞŝŶƚŚĞǀŝĐŝŶŝƚǇŽĨƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞ;T_crͿ͕ǁŚĞƌĞŝŶ Ă ƌĞǀĞƌƐŝďůĞ ĨĞƌƌŽĞůĞĐƚƌŝĐͲƚŽͲƉĂƌĂĞůĞĐƚƌŝĐ ĐƌǇƐƚĂůůŝŶĞ ƉŚĂƐĞ ƚƌĂŶƐŝƟŽŶ ŝƐ ŽďƐĞƌǀĞĚ͘ 8,9 Nevertheless, a low T_crŝƐďĞŶĞĮĐŝĂůĨŽƌŽƚŚĞƌĂƉƉůŝĐĂƟŽŶƐƐƵĐŚĂƐƐŽůŝĚͲƐƚĂƚĞĐŽŽůŝŶŐ ĚĞǀŝĐĞƐĂŶĚĐĂƉĂĐŝƟǀĞĞŶĞƌŐǇƐƚŽƌĂŐĞ͘10,11_{/ŶƐŽůŝĚͲƐƚĂƚĞĐŽŽůŝŶŐĚĞǀŝĐĞƐůĂƌŐĞĐŚĂŶŐĞƐŝŶ} ĚŝƉŽůĂƌŽƌĚĞƌŝŶŐƵŶĚĞƌĂŶĂƉƉůŝĞĚĞůĞĐƚƌŝĐĮĞůĚĐĂƵƐĞĂũƵŵƉŝŶĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚĂƌŽƵŶĚ the T_cr͘dŚŝƐůĞĂĚƐƚŽĂŶĞŶŽƌŵŽƵƐĞůĞĐƚƌŽĐĂůŽƌŝĐĞīĞĐƚǁŚĞŶĞŶƚƌŽƉŝĐĞŶĞƌŐǇŝƐĐĂƉƚƵƌĞĚ ĨƌŽŵƚŚĞƐƵƌƌŽƵŶĚŝŶŐƐ͘ĚĚŝƟŽŶĂůůǇ͕ĂũƵŵƉŝŶĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚĞŶƐƵƌĞƐĂŶŝŶĐƌĞĂƐĞĚ stored energy density inside dielectric materials. Therefore, a thorough understanding ŝŶŚŽǁƚŽƚƵŶĞƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞĨŽƌĂĚĞƐŝƌĞĚĂƉƉůŝĐĂƟŽŶŝƐƌĞƋƵŝƌĞĚ;i.e. a high T_crĨŽƌĨĞƌƌŽĞůĞĐƚƌŝĐĂƉƉůŝĐĂƟŽŶƐĂŶĚĂůŽǁT_crĨŽƌĐĂƉĂĐŝƟǀĞĞŶĞƌŐǇƐƚŽƌĂŐĞĂŶĚ ƐŽůŝĚͲƐƚĂƚĞĐŽŽůŝŶŐĚĞǀŝĐĞƐͿ͘ The T_crŽĨW;s&-co-dƌ&ͿŚĂƐďĞĞŶƐƵďũĞĐƚĞĚƚŽŵƵůƟƉůĞƐƚƵĚŝĞƐŝŶĐůƵĚŝŶŐƚŚĞĞīĞĐƚ ŽĨĐŽƉŽůǇŵĞƌĐŽŵƉŽƐŝƟŽŶĂŶĚĐƌǇƐƚĂůůŝǌĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞ͘ϳ͕ϭϮ͕ϭϯ_{dŚŝƐƉŚĂƐĞƚƌĂŶƐŝƟŽŶŝƐ} ĞĂƐŝůǇĨŽůůŽǁĞĚďǇĚŝīĞƌĞŶƟĂůƐĐĂŶŶŝŶŐĐĂůŽƌŝŵĞƚƌǇ;^Ϳ͕ǁŝĚĞͲĂŶŐůĞyͲƌĂǇƐĐĂƩĞƌŝŶŐ ;ty^ͿĚƵĞƚŽĂĐŚĂŶŐĞŝŶĐƌǇƐƚĂůůŝŶĞƉŚĂƐĞ͕ĂŶĚ&ŽƵƌŝĞƌƚƌĂŶƐĨŽƌŵŝŶĨƌĂƌĞĚƐƉĞĐƚƌŽƐĐŽƉǇ ;&d/ZͿƚŽŝĚĞŶƟĨǇƚŚĞĐŽŶĨŽƌŵĂƟŽŶĂůŝƐŽŵĞƌƐĐŽƌƌĞƐƉŽŶĚŝŶŐƚŽƚŚĞĐƌǇƐƚĂůůŝŶĞƉŚĂƐĞƐ͘ It is found that the T_cr is mainly dependent on the crystallite size and the interplanar ĚŝƐƚĂŶĐĞ ŝŶƐŝĚĞ ƚŚĞ ĐƌǇƐƚĂůƐ͘ dŚĞƌĞĨŽƌĞ͕ ĚƵĞ ƚŽ ƚŚĞ ďƵůŬŝŶĞƐƐ ŽĨ ƚŚĞ ĞǆƚƌĂ ŇƵŽƌŝŶĞ ĂƚŽŵ͕ŝŶĐƌĞĂƐŝŶŐƚŚĞdƌ&ĐŽŶƚĞŶƚŝŶƚŚĞĐŽƉŽůǇŵĞƌƐƌĞƐƵůƚƐŝŶĂƌĞĚƵĐƟŽŶŝŶƚŚĞT_cr. ϭϰ_{&ƵƌƚŚĞƌŵŽƌĞ͕ĂĚĚŝƟŽŶŽĨĂƚŚŝƌĚĐŽƉŽůǇŵĞƌ͕ůŝŬĞĐŚůŽƌŽƚƌŝŇƵŽƌŽĞƚŚǇůĞŶĞ͕ƌĞŶĚĞƌƐĂ} ;ƌĞůĂǆŽƌͿĨĞƌƌŽĞůĞĐƚƌŝĐƚĞƌƉŽůǇŵĞƌǁŝƚŚĂT_cr near room temperature due to an increase ŝŶƚŚĞƐŝǌĞŽĨƚŚĞĐƌǇƐƚĂůůĂƫĐĞ͕ǁŚŝĐŚƌĞĚƵĐĞƐƚŚĞĞŶĞƌŐǇďĂƌƌŝĞƌĨŽƌƚŚĞƚƌĂŶƐŝƟŽŶƚŽ occur.ϭϱ͕ϭϲ_{ǀĞŶƚŚŽƵŐŚƚŚŝƐĐƌǇƐƚĂůůŝŶĞƉŚĂƐĞƚƌĂŶƐŝƟŽŶŝŶďƵůŬŵĂƚĞƌŝĂůƐŝƐǁĞůůĞǆƉůŽƌĞĚ͕} ŵŝŶŝĂƚƵƌŝǌĂƟŽŶŽĨW;s&-co-dƌ&ͿͲďĂƐĞĚŵĂƚĞƌŝĂůƐĚŽǁŶƚŽƚŚĞŶĂŶŽƐĐĂůĞŵĂǇĂůƚĞƌƚŚĞ ĐƌǇƐƚĂůůŝǌĂƟŽŶŵĞĐŚĂŶŝƐŵĂŶĚĐƌǇƐƚĂůůŝŶĞƉŚĂƐĞƚƌĂŶƐŝƟŽŶƐĚƌĂƐƟĐĂůůǇ͘

ZĞĐĞŶƚůǇ͕ ĚŝīĞƌĞŶƚ ƚŽƉͲĚŽǁŶ ĂƉƉƌŽĂĐŚĞƐ ŚĂǀĞ ďĞĞŶ ƉĞƌĨŽƌŵĞĚ ƚŽ ĐŽŶĮŶĞ ƚŚĞ ĐƌǇƐƚĂůůŝǌĂƟŽŶŽĨW;s&-co-dƌ&ͿŝŶŶĂŶŽĚŽŵĂŝŶƐ͘&ŽƌĞǆĂŵƉůĞ͕<ĂƐƐĂet. al. nanoimprinted W;s&-co-dƌ&ͿŝŶƚŚĞƉĂƌĂĞůĞĐƚƌŝĐƉŚĂƐĞ;,dWͿƚŽĐƌĞĂƚĞĨƌĞĞƐƚĂŶĚŝŶŐŶĂŶŽƉŝůůĂƌƐ͘17 By measuring the ferroelectric contrast using piezoresponse force microscopy, they ŽďƐĞƌǀĞĚŶŽƐŝŐŶŝĮĐĂŶƚĐŚĂŶŐĞƐŝŶƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞƉƌŽďĂďůǇĚƵĞƚŽ ƚŚĞůĂƌŐĞĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶƐŝǌĞ͘&ƵƌƚŚĞƌŵŽƌĞ͕ƐŝŶĐĞƚŚĞĮƌƐƚĚĞƌŝǀĂƟǀĞŽĨƉĞƌŵŝƫǀŝƚǇ ŝƐ ƉƌŽƉŽƌƟŽŶĂů ƚŽ ƚŚĞ ĮƌƐƚ ĚĞƌŝǀĂƟǀĞ ŽĨ ĚĞŶƐŝƚǇ͕ ƚŚĞ ZƵƐƐĞůů ŐƌŽƵƉ ŝŶǀĞƐƟŐĂƚĞĚ ƚŚĞ

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ĐƌǇƐƚĂůůŝŶĞƉŚĂƐĞƚƌĂŶƐŝƟŽŶƐƵƐŝŶŐĚŝĞůĞĐƚƌŝĐƐƉĞĐƚƌŽƐĐŽƉǇ͘ 18,19_{The high interfacial area} ďĞƚǁĞĞŶW;s&-co-dƌ&ͿĂŶĚƚŚĞƉŽůĂƌĂůƵŵŝŶƵŵŽǆŝĚĞǁĂůůƐĚƌĂƐƟĐĂůůǇŝŶŇƵĞŶĐĞƐƚŚĞ ĐƌǇƐƚĂůůŝǌĂƟŽŶďĞŚĂǀŝŽƌ͘ƐĂĐŽŶƐĞƋƵĞŶĐĞŽĨƐƵƌĨĂĐĞĞīĞĐƚƐ͕ƚŚĞŶĂŶŽĐŽŶĮŶĞĚW;s&-co-dƌ&ͿƐŚŽǁƐĂƐŝŐŶŝĮĐĂŶƚůǇůŽǁĞƌƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞ͘ůƚŚŽƵŐŚ͕ƉƌŽǀŝĚŝŶŐƵƐĞĨƵů ŝŶƐŝŐŚƚƐŝŶƚŚĞďĞŚĂǀŝŽƌŽĨƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƵŶĚĞƌŶĂŶŽĐŽŶĮŶĞŵĞŶƚ͕ƚŚĞŵĞƚŚŽĚƐ ƵƐĞĚĨŽƌƚŚĞĚĞƚĞƌŵŝŶĂƟŽŶŽĨƚŚĞT_cr ĂƌĞůŝŵŝƚĞĚƚŽƚŚĞŝƌƐƉĞĐŝĮĐĐĂƐĞƐŽĨĐŽŶĮŶĞŵĞŶƚ͘ ĚĚŝƟŽŶĂůůǇ͕ƵƐŝŶŐƚŽƉͲĚŽǁŶĂƉƉƌŽĂĐŚĞƐŽŶůǇŐŝǀĞƐŝŶĨŽƌŵĂƟŽŶŽŶƚŚĞĞīĞĐƚŽĨŽŶĞͲŽƌ ƚǁŽͲĚŝŵĞŶƐŝŽŶĂůĐŽŶĮŶĞŵĞŶƚ͕ǁŚĞƌĞĂƐƚŚĞƐŝǌĞƌĞĚƵĐƟŽŶĞīĞĐƚŽŶƚŚĞT_crƵŶĚĞƌƚŚƌĞĞͲ ĚŝŵĞŶƐŝŽŶĂůĐŽŶĮŶĞŵĞŶƚŝƐƐƟůůƵŶĞǆƉůŽƌĞĚ͘ ŽŶǀĞƌƐĞůǇ͕ďŽƩŽŵͲƵƉĂƉƉƌŽĂĐŚĞƐ͕ƐƵĐŚĂƐďůŽĐŬĐŽƉŽůǇŵĞƌƐĞůĨͲĂƐƐĞŵďůǇ͕ĐĂŶĞŶƌŝĐŚ ŽƵƌƵŶĚĞƌƐƚĂŶĚŝŶŐŽĨƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞŝŶƚŚƌĞĞĚŝŵĞŶƐŝŽŶĂůŶĂŶŽĐŽŶĮŶĞĚ space. 20_{ǇƵƐĞŽĨĂďůŽĐŬĐŽƉŽůǇŵĞƌĂƉƉƌŽĂĐŚ͕ĐŽŶǀĞŶƟŽŶĂůĞǆƉĞƌŝŵĞŶƚĂůƚĞĐŚŶŝƋƵĞƐĨŽƌ} ƚŚĞĐŚĂƌĂĐƚĞƌŝǌĂƟŽŶŽĨďƵůŬŵĂƚĞƌŝĂůƐ͕ůŝŬĞ^ĂŶĚty^͕ĐĂŶďĞƵƐĞĚƚŽĞǆĂŵŝŶĞƚŚĞ ƉŚĂƐĞƚƌĂŶƐŝƟŽŶƐ͘ϭϯ͕Ϯϭ_{DŽƌĞŽǀĞƌ͕ďůŽĐŬƉŽůǇŵĞƌƐĂƌĞĂƌĞƐŽƵƌĐĞĨƵůƚŽŽůĨŽƌĐƌǇƐƚĂůůŝǌĂƟŽŶ} ƐƚƵĚŝĞƐŝŶĐŽŶĮŶĞĚŐĞŽŵĞƚƌŝĞƐĚƵĞƚŽƚŚĞůĂƌŐĞĚŝǀĞƌƐŝƚǇŝŶŶĂŶŽĚŽŵĂŝŶƐŝǌĞ͕ƐŚĂƉĞ͕ ŚĂƌĚŶĞƐƐŽƌƉŽůĂƌŝƚǇďǇǀĂƌǇŝŶŐƚŚĞŵŽůĞĐƵůĂƌǁĞŝŐŚƚ͕ďůŽĐŬƌĂƟŽŽƌƉŚǇƐŝĐĂůƉƌŽƉĞƌƟĞƐ (e.g.ƚŚĞŐůĂƐƐƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞŽƌƉŽůĂƌŝƚǇŽĨƚŚĞĂŵŽƌƉŚŽƵƐďůŽĐŬͿ͕ƌĞƐƉĞĐƟǀĞůǇ͘ ϮϭʹϮϰ_{ZĞĐĞŶƚůǇ͕ǁĞŚĂǀĞƐŚŽǁŶƚŚĂƚĐŽŶĮŶĞĚĐƌǇƐƚĂůůŝǌĂƟŽŶŽĨWs&ŝŶŶĂŶŽĚŽŵĂŝŶƐŝƐ}

easily accessible viaďůŽĐŬĐŽƉŽůǇŵĞƌƐĞůĨͲĂƐƐĞŵďůǇ͘ϮϱʹϮϵ_{ŽŶƐĞƋƵĞŶƚůǇ͕ǁŚĞŶĂƐƉŚĞƌŝĐĂů} ŵŽƌƉŚŽůŽŐǇŝƐŽďƚĂŝŶĞĚ͕ƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶďĞŚĂǀŝŽƌŽĨWs&ĚƌĂƐƟĐĂůůǇĐŚĂŶŐĞĚƌĞƐƵůƟŶŐ ŝŶ Ă ŚŽŵŽŐĞŶĞŽƵƐ ŶƵĐůĞĂƟŽŶ ŵĞĐŚĂŶŝƐŵ ůĞĂĚŝŶŐ ƚŽ Ă ůĂƌŐĞ ƵŶĚĞƌĐŽŽůŝŶŐ ĂŶĚ ƚŚĞ ĨŽƌŵĂƟŽŶŽĨƚŚĞƚŚĞƌŵŽĚǇŶĂŵŝĐĂůůǇĨĂǀŽƌĂďůĞĨĞƌƌŽĞůĞĐƚƌŝĐɴͲƉŚĂƐĞ͕ĚĞŵŽŶƐƚƌĂƟŶŐ Ă ƐƚƌŽŶŐ ĞīĞĐƚ ŽĨ ŶĂŶŽĐŽŶĮŶĞŵĞŶƚ ŽŶ ƚŚĞ ĐƌǇƐƚĂůůŝǌĂƟŽŶ ƵƐŝŶŐ Ă ďůŽĐŬ ĐŽƉŽůǇŵĞƌ approach.Ϯϲ /ŶƚŚŝƐĐŚĂƉƚĞƌ͕ǁĞŝŶǀĞƐƟŐĂƚĞƚŚĞŝŵƉĂĐƚŽĨŶĂŶŽĐŽŶĮŶĞŵĞŶƚŽŶƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶ ƚĞŵƉĞƌĂƚƵƌĞŝŶƐŝĚĞƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐ͕ǁŚĞƌĞŝŶW;s&-co-dƌ&ͿŝƐƚŚĞŵŝĚĚůĞďůŽĐŬ͕ ƵƐŝŶŐƐŝŵƉůĞƚĞĐŚŶŝƋƵĞƐĂƐty^ĂŶĚ^͘ĞƐŝĚĞƐƚŚĞƵƐĞŽĨĚŝīĞƌĞŶƚdƌ&ĐŽŶƚĞŶƚƐŝŶ ƚŚĞW;s&-co-dƌ&ͿĐŽƉŽůǇŵĞƌƐ͕ƚŚĞŵŽůĞĐƵůĂƌƐƚƌƵĐƚƵƌĞƐŽĨƚŚĞĂŵŽƌƉŚŽƵƐŵĂƚƌŝǆĂƌĞ ĐĂƌĞĨƵůůǇƐĞůĞĐƚĞĚƚŽŽďƚĂŝŶĂŚĂƌĚĐŽŶĮŶĞŵĞŶƚ;ŚŝŐŚT_gͿĞīĞĐƚŽŶƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶŝŶƐŝĚĞ W;s&-co-dƌ&ͿŶĂŶŽƐƉŚĞƌĞƐǁŚĞƌĞŝŶƚŚĞƉŽůĂƌŝƚǇŽĨƚŚĞƐƵƌƌŽƵŶĚŝŶŐŵĂƚƌŝǆŝƐŝŶĐƌĞĂƐĞĚ in situ͘dŚŝƐĂƉƉƌŽĂĐŚĂůůŽǁƐƵƐƚŽĞǆĐůƵƐŝǀĞůǇƐƚƵĚǇƚŚĞĞīĞĐƚŽĨƉŽůĂƌŝƚǇŽŶƚŚĞT_crŶĞǆƚƚŽ ƚŚĞŶĂŶŽĐŽŶĮŶĞŵĞŶƚĞīĞĐƚ͕ƉƌŽǀŝĚŝŶŐƵŶŝƋƵĞŝŶƐŝŐŚƚƐŝŶƚŽĂƐƉĞĐƚƐŽĨƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶ ŝŶĂĐĐĞƐƐŝďůĞƚŽƚŽƉͲĚŽǁŶŵĞƚŚŽĚƐ͘ŽŶƚƌĂƌǇƚŽĞĂƌůŝĞƌŽďƐĞƌǀĂƟŽŶƐ͕ƚŚĞĐŽŶĮŶĞŵĞŶƚ ŝŶƐŝĚĞƐƉŚĞƌŝĐĂůŶĂŶŽĚŽŵĂŝŶƐƐƵƌƌŽƵŶĚĞĚďǇĂŶŽŶƉŽůĂƌŵĂƚƌŝǆĚĞŵŽŶƐƚƌĂƚĞƐĂŶŝŶĐƌĞĂƐĞ in the T_crƵƉŽŶĐŽŽůŝŶŐ͘ĚĚŝƟŽŶĂůůǇ͕ĂŶŝŶĐƌĞĂƐŝŶŐƉŽůĂƌŝƚǇŽĨƚŚĞƐƵƌƌŽƵŶĚŝŶŐŵĂƚƌŝǆ ƐŝŐŶŝĮĐĂŶƚůǇƌĞĚƵĐĞĚƚŚĞT_crŽŶďŽƚŚĐŽŽůŝŶŐĂŶĚŚĞĂƟŶŐ͘

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52

Materials and Methods

Experimental Materials:Ϯ͕Ϯ഻ͲǌŽďŝƐ;ϮͲŵĞƚŚǇůƉƌŽƉŝŽŶŝƚƌŝůĞͿ;/E͕&ůƵŬĂ͕ϵϴнйͿǁĂƐƌĞĐƌǇƐƚĂůůŝǌĞĚƚǁŝĐĞ ĨƌŽŵŵĞƚŚĂŶŽů͘ŽƉƉĞƌ;/ͿďƌŽŵŝĚĞ;Ƶƌ͕^ŝŐŵĂͲůĚƌŝĐŚ͕ϵϴйͿǁĂƐƐƟƌƌĞĚĨŽƌϭŚŽƵƌŝŶ ŐůĂĐŝĂůĂĐĞƟĐĂĐŝĚĂŶĚƚŚĞŶĮůƚĞƌĞĚĂŶĚǁĂƐŚĞĚǁŝƚŚĂĐĞƟĐĂĐŝĚĂŶĚĞƚŚĂŶŽůďĞĨŽƌĞĚƌǇŝŶŐ ƵŶĚĞƌĂǀĂĐƵƵŵ͘ϰͲ;ŚůŽƌŽŵĞƚŚǇůͿďĞŶǌŽǇůƉĞƌŽǆŝĚĞ͕ϮͲ;ĚŽĚĞĐǇůƚŚŝŽĐĂƌďŽŶŽƚŚŝŽǇůƚŚŝŽͿͲ ϮͲŵĞƚŚǇůƉƌŽƉŝŽŶŝĐ ĂĐŝĚ ƉƌŽƉĂƌŐǇů ĞƐƚĞƌ ;Z&d ĂŐĞŶƚͿ͕ ĂŶĚ ƚŚĞ ƉŽůǇƐƚǇƌĞŶĞ ;W^Ϳ ĂŶĚ ƉŽůǇ;ϰͲtertͲďƵƚŽǆǇƐƚǇƌĞŶĞͿ;WtK^ͿŚŽŵŽƉŽůǇŵĞƌƐǁĞƌĞƉƌĞƉĂƌĞĚĂĐĐŽƌĚŝŶŐƚŽůŝƚĞƌĂƚƵƌĞ procedures.Ϯϴ͕ϯϬ_{sŝŶǇůŝĚĞŶĞŇƵŽƌŝĚĞ;s&͕^ǇŶƋƵĞƐƚ>ĂďƐ͕ϵϴйͿ͕ƚƌŝŇƵŽƌŽĞƚŚǇůĞŶĞ;dƌ&͕} ^ǇŶƋƵĞƐƚ>ĂďƐ͕ϵϴйͿϭ͕ϭ͕ϰ͕ϳ͕ϳͲƉĞŶƚĂŵĞƚŚǇůĚŝĞƚŚǇůĞŶĞƚƌŝĂŵŝŶĞ;WDd͕ĐƌŽƐKƌŐĂŶŝĐƐ͕ ϵϵнйͿ͕E͕EͲĚŝŵĞƚŚǇůĨŽƌŵĂŵŝĚĞ;D&͕ĐƌŽƐKƌŐĂŶŝĐƐ͕ĂŶŚǇĚƌŽƵƐ͕ϵϵ͘ϴйͿ͕ƚƌŝŇƵŽƌŽĂĐĞƟĐ ĂĐŝĚ;d&͕ĐƌŽƐKƌŐĂŶŝĐƐ͕ϵϵйͿǁĞƌĞƵƐĞĚĂƐƌĞĐĞŝǀĞĚ͘ůůŽƚŚĞƌƐŽůǀĞŶƚƐǁĞƌĞĂŶĂůǇƟĐĂů grade. ^ǇŶƚŚĞƐŝƐŽĨĐŚůŽƌŝŶĞͲƚĞƌŵŝŶĂƚĞĚW;s&ͲĐŽͲdƌ&Ϳ͗ƐŽůƵƟŽŶŽĨϰͲ;ĐŚůŽƌŽŵĞƚŚǇůͿďĞŶǌŽǇů ƉĞƌŽǆŝĚĞ;ϱϬϬŵŐ͕ϭ͘ϰϳŵŵŽůͿŝŶϯϬϬŵ>ŽĨĂŶŚǇĚƌŽƵƐĂĐĞƚŽŶŝƚƌŝůĞǁĂƐŝŶƚƌŽĚƵĐĞĚŝŶ ĂϲϬϬŵ>WĂƌƌ;ŵŽĚĞůϰϱϲϴͿŚŝŐŚƉƌĞƐƐƵƌĞƌĞĂĐƚŽƌĂŶĚƉƵƌŐĞĚǁŝƚŚE₂ĨŽƌϯϬŵŝŶƵƚĞƐ͘ ^ƵďƐĞƋƵĞŶƚůǇ͕Ϯ͘ϮďĂƌ;ϯ͘ϴďĂƌĨŽƌϮϴŵŽůйdƌ&ͿŽĨdƌ&ĨŽůůŽǁĞĚďǇƚŚĞĂĚĚŝƟŽŶŽĨ s&ƵŶƟůϮϬďĂƌƐ;ϭϱďĂƌĨŽƌϮϴŵŽůйdƌ&ͿǁĞƌĞŝŶƚƌŽĚƵĐĞĚŝŶƚŽƚŚĞƌĞĂĐƚŽƌĂƚƌŽŽŵ ƚĞŵƉĞƌĂƚƵƌĞ͘dŚĞƚĞŵƉĞƌĂƚƵƌĞŝŶƐŝĚĞƚŚĞƌĞĂĐƚŽƌǁĂƐŝŶĐƌĞĂƐĞĚƚŽϵϬΣĂŶĚƚŚĞƌĞĂĐƟŽŶ ŵŝǆƚƵƌĞǁĂƐƐƟƌƌĞĚĂƚϱϬϬƌƉŵĨŽƌĂĚĚŝƟŽŶĂůϯϬŵŝŶƵƚĞƐ͘dŚĞƌĞĂĐƚŽƌǁĂƐĐŽŽůĞĚĚŽǁŶ by water to room temperature and depressurized to remove unreacted monomer. The solvent was removed in vacuoĂŶĚƚŚĞƌĞŵĂŝŶŝŶŐƐŽůŝĚǁĂƐǁĂƐŚĞĚŵƵůƟƉůĞƟŵĞƐǁŝƚŚ DƚŽƌĞŵŽǀĞŝŶŝƟĂƚŽƌƌĞƐŝĚƵĞƐ͘dŚĞƉŽůǇŵĞƌƐǁĞƌĞĚƌŝĞĚin vacuo at room temperature ƚŽŽďƚĂŝŶĂůŝŐŚƚͲǇĞůůŽǁƉƌŽĚƵĐƚ͘1_{,EDZ;ϰϬϬD,ǌ͕ĂĐĞƚŽŶĞͲĚ} ϲͿ͗ɷ;ƉƉŵͿсϴ͘Ϭϵ;Ě͕ʹ ƌHͿ͕ϳ͘ϲϴ;Ě͕ʹƌHͿ͕ϰ͘ϲϴ;ŵ͕ʹKKH₂CF₂ʹͿ͕ϰ͘ϲϬ;Ɛ͕ʹWŚ,₂N_ϯͿ͕ϯ͘ϭϬͲϮ͘ϳϬ;ŵ͕ʹ&₂CH₂ʹ CF₂,₂ʹ͕ŚĞĂĚͲƚŽͲƚĂŝůͿ͕Ϯ͘ϰϬͲϮ͘ϮϬ;ŵ͕ʹ&₂CH₂ʹH₂CF₂ʹ͕ƚĂŝůͲƚŽͲƚĂŝůͿ͘ ^ǇŶƚŚĞƐŝƐŽĨĂǌŝĚĞͲƚĞƌŵŝŶĂƚĞĚW;s&ͲĐŽͲdƌ&Ϳ͗ŚůŽƌŝŶĞͲƚĞƌŵŝŶĂƚĞĚW;s&-co-dƌ&Ϳ ĂŶĚƐŽĚŝƵŵĂǌŝĚĞǁĞƌĞĚŝƐƐŽůǀĞĚŝŶD&ĂŶĚƐƟƌƌĞĚŽǀĞƌŶŝŐŚƚĂƚϲϬΣ͘dŚĞŶĞǆƚĚĂǇ͕ ƚŚĞƉŽůǇŵĞƌƐŽůƵƟŽŶǁĂƐĐŽŶĐĞŶƚƌĂƚĞĚĂŶĚƉƌĞĐŝƉŝƚĂƚĞĚŝŶDĞK,͗,₂K;ϭ͗ϭͿĨŽůůŽǁĞĚďǇ ĞǆƚĞŶƐŝǀĞǁĂƐŚŝŶŐǁŝƚŚ,₂K͘^ƵďƐĞƋƵĞŶƚĚƌǇŝŶŐin vacuoǇŝĞůĚĞĚƚŚĞĂǌŝĚĞͲƚĞƌŵŝŶĂƚĞĚ W;s&ͲcoͲdƌ&ͿĐŽƉŽůǇŵĞƌƐ͘1_{,EDZ;ϰϬϬD,ǌ͕ĂĐĞƚŽŶĞͲĚ} ϲͿ͗ɷ;ƉƉŵͿсϴ͘ϭϭ;Ě͕ʹƌHͿ͕ ϳ͘ϱϴ;Ě͕ʹƌHͿ͕ϲ͘ϭϬͲϱ͘ϭϮ;ŵ͕Ͳ,&₂ͲͿ͕ϰ͘ϳϮ;ŵ͕ʹKKH₂CF₂ʹͿ͕ϰ͘ϴϭ;Ɛ͕ʹWŚH₂ůͿ͕ϯ͘ϭϬͲ Ϯ͘ϳϬ;ŵ͕ʹ&₂CH₂ʹ&₂,₂ʹ͕ŚĞĂĚͲƚŽͲƚĂŝůͿ͕Ϯ͘ϰϬͲϮ͘ϮϬ;ŵ͕ʹ&₂CH₂ʹH₂CF₂ʹ͕ƚĂŝůͲƚŽͲƚĂŝůͿ͘

^ǇŶƚŚĞƐŝƐŽĨW^ͲďͲW;s&ͲĐŽͲdƌ&ͿͲďͲW^ĂŶĚWƚK^ͲďͲW;s&ͲĐŽͲdƌ&ͿͲďͲWƚK^ƚƌŝďůŽĐŬ copolymers͗ŐĞŶĞƌĂůƌŽƵƚĞĨŽƌƚŚĞƵͲĐĂƚĂůǇǌĞĚĂůŬǇŶĞĂǌŝĚĞĐǇĐůŽĂĚĚŝƟŽŶ;ƵͿ

ƵƐĞĚĨŽƌƚŚĞƉƌĞƉĂƌĂƟŽŶŽĨďůŽĐŬĐŽƉŽůǇŵĞƌƐŝƐĚĞƐĐƌŝďĞĚďĞůŽǁ͘dŚĞĂůŬǇŶĞͲƚĞƌŵŝŶĂƚĞĚ W;s&-co-dƌ&Ϳ;ϯϬϬŵŐ͕Ϭ͘ϬϮϱŵŵŽůͿ͕W^;WtK^ͿĂŶĚƵƌǁĞƌĞĂĚĚĞĚŝŶƚŽĂƉƌĞͲĚƌŝĞĚ

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3

^ĐŚůĞŶŬƚƵďĞŝŶĂŵŽůĂƌƌĂƟŽ΀Ws&΁͗΀W^΁͗΀Ƶƌ΁сϭ͗Ϯ͘ϲ͗ϰ͘ŌĞƌƉĞƌĨŽƌŵŝŶŐĚĞŐĂƐƐŝŶŐ ƉƌŽĐĞĚƵƌĞƐ ;ƚŚƌĞĞ ƌĞƉĞƟƟǀĞ ĐǇĐůĞƐ ŽĨ ĞǀĂĐƵĂƟŶŐ ĂŶĚ ďĂĐŬĮůůŝŶŐ ǁŝƚŚ E₂Ϳ͕ ϰ ŵ> ŽĨ ĂŶŚǇĚƌŽƵƐD&ǁĂƐĂĚĚĞĚ͕ĨŽůůŽǁĞĚďǇWDd;ϯϬђů͕Ϭ͘ϭϰŵŵŽůͿ͘dŚĞƌĞĂĐƟŽŶǁĂƐ ĂůůŽǁĞĚƚŽƐƟƌĨŽƌϯĚĂǇƐĂƚϲϬo_{ĂŶĚĂŌĞƌǁĂƌĚƐƐƚŽƉƉĞĚďǇĞǆƉŽƐŝŶŐƚŽƚŚĞĂŝƌ͘ZĞƐŝĚƵĂů} ĐŽƉƉĞƌĐĂƚĂůǇƐƚǁĂƐƌĞŵŽǀĞĚďǇƉĂƐƐŝŶŐƚŚĞƌĞĂĐƟŽŶŵŝǆƚƵƌĞƚŚƌŽƵŐŚĂƐŚŽƌƚŶĞƵƚƌĂů ĂůƵŵŝŶĂĐŽůƵŵŶǁŝƚŚd,&ĂƐĞůƵĞŶƚ͘dŚĞƐŽůǀĞŶƚƐǁĞƌĞƌĞŵŽǀĞĚin vacuoĂŶĚƚŚĞŵŝǆƚƵƌĞ ǁĂƐĚŝƐƐŽůǀĞĚŝŶd,&ĂŐĂŝŶ͘dŚĞƉŽůǇŵĞƌƐǁĞƌĞƉƌĞĐŝƉŝƚĂƚĞĚŝŶDĞK,͗,ϮK;ϭ͗ϭͿ͘ŌĞƌ ĮůƚƌĂƟŽŶƚŚĞƉƌŽĚƵĐƚǁĂƐĐŽůůĞĐƚĞĚviaĮůƚƌĂƟŽŶĂŶĚƚŚĞƵŶƌĞĂĐƚĞĚŚŽŵŽƉŽůǇŵĞƌǁĂƐ washed away with ether (nͲŚĞǆĂŶĞƐĨŽƌWtK^ͿĨŽůůŽǁĞĚďǇĐĞŶƚƌŝĨƵŐĂƟŽŶ;ϱŵŝŶ͕ϰϱϬϬ ƌƉŵͿ͘dŚĞƉŽůǇŵĞƌƐǁĞƌĞƉƌĞĐŝƉŝƚĂƚĞĚĨƌŽŵD&ŝŶDĞK,͗,₂K;Ϯ͗ϯͿŽŶĐĞŵŽƌĞƚŽŽďƚĂŝŶ a light brown powder. Finally, the block copolymers were dried in vacuo. 1_,EDZ;ϰϬϬ D,ǌ͕ĂĐĞƚŽŶĞͲĚ_ϲ͕W^ͲbͲW;s&-co-dƌ&ͿͲbͲW^Ϳ͗ɷ;ƉƉŵͿсϴ͘Ϭϱ;Ě͕ʹƌHͿ͕ϳ͘ϴϵ;Ɛ͕ʹHͲ͕ ƚƌŝĂǌŽůĞͿ͕ϳ͘ϰϱ;ͲƌHͿ͕ϳ͘ϰϬͲϲ͘ϰϬ;ͲƌH͕W^Ϳϲ͘ϭϬͲϱ͘ϭϮ;ŵ͕ͲHCF₂ͲͿ͕ϰ͘ϳϮ;ŵ͕ʹKKH₂CF₂ʹͿ͕ ϰ͘ϴϭ;Ɛ͕ʹWŚH₂ůͿ͕ϯ͘ϭϬͲϮ͘ϳϬ;ŵ͕ʹ&₂CH₂ʹ&₂,₂ʹ͕ŚĞĂĚͲƚŽͲƚĂŝůͿ͕Ϯ͘ϰϬͲϮ͘ϮϬ;ŵ͕ʹ&₂CH₂ʹ ,₂CF₂ʹ͕ƚĂŝůͲƚŽͲƚĂŝůͿ͕Ϯ͘ϭϴͲϭ͘ϰϬ;ͲH₂,;ƌͿͲ͕W^Ϳ͘1_{,EDZ;ϰϬϬD,ǌ͕ĂĐĞƚŽŶĞͲĚ}

ϲ, PtK^ͲbͲ W;s&Ͳdƌ&ͿͲbͲWtK^Ϳ͗ɷ;ƉƉŵͿсϴ͘Ϭϱ;Ě͕ʹƌHͿ͕ϳ͘ϴϵ;Ɛ͕ʹHͲ͕ƚƌŝĂǌŽůĞͿ͕ϳ͘ϰϱ;ͲƌHͿ͕ϲ͘ϵϬͲ ϲ͘ϬϬ;ͲƌH, PtK^Ϳϲ͘ϭϬͲϱ͘ϭϮ;ŵ͕ͲHCF₂ͲͿ͕ϰ͘ϳϮ;ŵ͕ʹKKH₂CF₂ʹͿ͕ϰ͘ϴϭ;Ɛ͕ʹWŚH₂ůͿ͕ ϯ͘ϭϬͲϮ͘ϳϬ;ŵ͕ʹ&₂CH₂ʹ&₂,₂ʹ͕ŚĞĂĚͲƚŽͲƚĂŝůͿ͕Ϯ͘ϰϬͲϮ͘ϮϬ;ŵ͕ʹ&₂CH₂ʹH₂CF₂ʹ͕ƚĂŝůͲƚŽͲ ƚĂŝůͿ͕Ϯ͘ϮϬͲϭ͘ϮϬ;ͲH₂,;ƌͿͲĂŶĚʹ;H_ϯͿ_ϯ, PtK^Ϳ͘ ůŽĐŬĐŽƉŽůǇŵĞƌĮůŵĨŽƌŵĂƟŽŶ͗ůůƚŚĞďůŽĐŬĐŽƉŽůǇŵĞƌƐ͕W^ͲbͲW;s&-co-dƌ&ͿͲbͲW^ and PtK^ͲbͲW;s&-co-dƌ&ͿͲbͲWtK^͕ǁĞƌĞĚŝƐƐŽůǀĞĚŝŶϰŵ>D&;ϭϬŵŐŵ>Ͳϭ_Ϳ͘dŚĞ ƐŽůƵƟŽŶǁĂƐĮůƚĞƌĞĚŽǀĞƌĂϬ͘ϰϱђŵWd&ĮůƚĞƌĂŶĚƐƵďƐĞƋƵĞŶƚůǇ ƉŽƵƌĞĚŝŶĂŐůĂƐƐ WĞƚƌŝ ĚŝƐŚ͘ dŚĞ ƐŽůǀĞŶƚ ǁĂƐ ĂůůŽǁĞĚ ƚŽ ĞǀĂƉŽƌĂƚĞ Ăƚ ϰϱ Σ ŽǀĞƌ ƚǁŽ ĚĂǇƐ͘ dŽ ŽďƚĂŝŶ ƚŚĞ ƐƉŚĞƌŝĐĂů ŶĂŶŽŵŽƌƉŚŽůŽŐǇ͕ ƚŚĞ ďůŽĐŬ ĐŽƉŽůǇŵĞƌ ĮůŵƐ ǁĞƌĞ ŚĞĂƚĞĚ ƚŽ ϭϴϬΣ Ăƚ ϭϬΣŵŝŶͲϭ_{͕ƚŚĞƌŵĂůůǇĂŶŶĞĂůĞĚĨŽƌϱŵŝŶĂƚϭϴϬΣ͕ĂŶĚƐƵďƐĞƋƵĞŶƚůǇĐŽŽůĞĚƚŽƌŽŽŵ} ƚĞŵƉĞƌĂƚƵƌĞĂƚϭϬΣŵŝŶͲϭ_{. The thermally annealed PtK^ͲbͲW;s&-co-dƌ&ͿͲbͲWtBOS} ƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌĮůŵƐǁĞƌĞin-situŚǇĚƌŽůǇǌĞĚďǇƐŽĂŬŝŶŐŝŶƚŽd&ĨŽƌϯϬŵŝŶƵƚĞƐ͘dŚĞ

ĮůŵƐǁĞƌĞĞǆƚĞŶƐŝǀĞůǇǁĂƐŚĞĚǁŝƚŚ,₂KĂŌĞƌǁĂƌĚƐĂŶĚĮŶĂůůǇĚƌŝĞĚin vacuo at room

temperature.

Characterization

EƵĐůĞĂƌDĂŐŶĞƟĐZĞƐŽŶĂŶĐĞ;1_{,EDZͿƐƉĞĐƚƌĂǁĞƌĞƌĞĐŽƌĚĞĚŽŶϰϬϬD,ǌsĂƌŝĂŶ;syZͿ}

spectrometer at room temperature.

'ĞůWĞƌŵĞĂƟŽŶŚƌŽŵĂƚŽŐƌĂƉŚǇ;'WͿŽĨW;s&-co-dƌ&ͿĐŽƉŽůǇŵĞƌƐĂŶĚƚŚĞW;s&Ͳ

coͲdƌ&ͿͲďĂƐĞĚďůŽĐŬĐŽƉŽůǇŵĞƌƐǁĞƌĞƉĞƌĨŽƌŵĞĚŝŶD&;ĐŽŶƚĂŝŶŝŶŐϬ͘ϬϭD>ŝƌͿƵƐŝŶŐ

sŝƐĐŽƚĞŬ'WŵĂǆĞƋƵŝƉƉĞĚǁŝƚŚŵŽĚĞůϯϬϮdĚĞƚĞĐƚŽƌƐĂŶĚƚǁŽĐŽůƵŵŶƐ;ŐŝůĞŶƚ dĞĐŚŶŽůŽŐŝĞƐͲWŽůĂƌ'ĞůͲ>ĂŶĚD͕ϴђŵϯϬĐŵͿĂƚĂŇŽǁƌĂƚĞŽĨϭ͘Ϭŵ>ͼŵŝŶͲϭ_{ĂŶĚϱϬΣ͘}

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54 EĂƌƌŽǁĚŝƐƉĞƌƐŝƚǇWDDƐƚĂŶĚĂƌĚƐ;WŽůǇŵĞƌ>ĂďŽƌĂƚŽƌŝĞƐͿǁĞƌĞƵƐĞĚĨŽƌĐŽŶƐƚƌƵĐƟŶŐ ĂŶƵŶŝǀĞƌƐĂůĐĂůŝďƌĂƟŽŶĐƵƌǀĞĂƉƉůŝĞĚĨŽƌĚĞƚĞƌŵŝŶŝŶŐŵŽůĞĐƵůĂƌǁĞŝŐŚƚƐŽĨW;s&-co-dƌ&ͿĂŶĚWtK^͘ƚƌŝƉůĞĚĞƚĞĐƟŽŶŵĞƚŚŽĚǁŝƚŚd,&͕ƐƚĂďŝůŝǌĞĚǁŝƚŚ,d͕ĂƐĞůƵĞŶƚĂŶĚ ĂŇŽǁƌĂƚĞŽĨϭ͘Ϭŵ>ͼŵŝŶͲϭ_{ĂƚϯϱΣǁĂƐƵƐĞĚƚŽĚĞƚĞƌŵŝŶĞƚŚĞŵŽůĞĐƵůĂƌǁĞŝŐŚƚĂŶĚƚŚĞ} ƉŽůǇĚŝƐƉĞƌƐŝƚǇŝŶĚĞǆ;W/ͿŽĨW^͘dŚĞƐĞƉĂƌĂƟŽŶǁĂƐĐĂƌƌŝĞĚŽƵƚďǇƵƟůŝǌŝŶŐƚǁŽW>ŐĞů ϱђŵD/yͲ͕ϯϬϬŵŵĐŽůƵŵŶƐ;ŐŝůĞŶƚdĞĐŚŶŽůŽŐŝĞƐͿĐĂůŝďƌĂƚĞĚǁŝƚŚŶĂƌƌŽǁDt ƉŽůǇƐƚǇƌĞŶĞƐƚĂŶĚĂƌĚƐ;ŐŝůĞŶƚdĞĐŚŶŽůŽŐŝĞƐĂŶĚWŽůǇŵĞƌ>ĂďŽƌĂƚŽƌŝĞƐͿ͘ƉƌĞĚĞƚĞƌŵŝŶĞĚ ƌĞĨƌĂĐƟǀĞŝŶĚĞǆŝŶĐƌĞŵĞŶƚ;ĚŶͬĚĐͿŽĨϬ͘ϭϴϱŵ>ͼŐͲϭ_{was used to calculate the molecular} ǁĞŝŐŚƚĐŚĂƌĂĐƚĞƌŝƐƟĐƐĨŽƌW^͘ ŝīĞƌĞŶƟĂů ^ĐĂŶŶŝŶŐ ĂůŽƌŝŵĞƚƌǇ ;^Ϳ ƚŚĞƌŵŽŐƌĂŵƐ ǁĞƌĞ ƌĞĐŽƌĚĞĚ ŽŶ Ă d /ŶƐƚƌƵŵĞŶƚƐ^YϭϬϬϬƵƐŝŶŐŚĞĂƟŶŐĂŶĚĐŽŽůŝŶŐƌĂƚĞƐŽĨϭϬΣͼŵŝŶͲϭ_. dĞŵƉĞƌĂƚƵƌĞͲƌĞƐŽůǀĞĚƐŵĂůůͲĂŶŐůĞyͲƌĂǇƐĐĂƩĞƌŝŶŐĂŶĚǁŝĚĞͲĂŶŐůĞyͲƌĂǇƐĐĂƩĞƌŝŶŐ ;^y^ĂŶĚty^ͿŵĞĂƐƵƌĞŵĞŶƚƐǁĞƌĞƉĞƌĨŽƌŵĞĚĂƚďĞĂŵůŝŶĞDϮϲĂƚƚŚĞƵƌŽƉĞĂŶ ^ǇŶĐŚƌŽƚƌŽŶ ZĂĚŝĂƟŽŶ &ĂĐŝůŝƚǇ ;^Z&Ϳ ŝŶ 'ƌĞŶŽďůĞ ǁŝƚŚ Ă ǁĂǀĞůĞŶŐƚŚ ʄ с Ϭ͘ϵϳ ͘ϯϭ͕ϯϮ ĐƋƵŝƐŝƟŽŶ ŽĨ ƐŝŵƵůƚĂŶĞŽƵƐůǇ ^y^ ĂŶĚ ty^ ƉĂƩĞƌŶƐ ǁĂƐ ƉĞƌĨŽƌŵĞĚ ŽǀĞƌ ƟŵĞ ŝŶƚĞƌǀĂůƐŽĨϯϬƐĞĐŽŶĚƐƵƐŝŶŐĂWŝůĂƚƵƐϭDĚĞƚĞĐƚŽƌ;ϵϴϭпϭϬϰϯƉŝǆĞůƐŽĨϭϳϮʅŵпϭϳϮ ʅŵƉůĂĐĞĚĂƚĂĚŝƐƚĂŶĐĞŽĨϯ͘ϱŵͿĂŶĚĂWŝůĂƚƵƐϯϬϬ<ĚĞƚĞĐƚŽƌ;ϭϰϳϮпϭϵϱƉŝǆĞůƐŽĨϭϳϮ ʅŵпϭϳϮʅŵƉůĂĐĞĚĂƚĂĚŝƐƚĂŶĐĞŽĨϬ͘ϮϴŵͿ͕ƌĞƐƉĞĐƟǀĞůǇ͘dŚĞƐĐĂƩĞƌŝŶŐǀĞĐƚŽƌƋŝƐ ĚĞĮŶĞĚĂƐƋсϰʋͬʄ;ƐŝŶɽͿǁŝƚŚϮɽďĞŝŶŐƚŚĞƐĐĂƩĞƌŝŶŐĂŶŐůĞ͘dĞŵƉĞƌĂƚƵƌĞͲƌĞƐŽůǀĞĚ ŵĞĂƐƵƌĞŵĞŶƚƐǁĞƌĞƉĞƌĨŽƌŵĞĚƵƐŝŶŐĂ>ŝŶŬĂŵ^ϲϬϬĐĞůů͘ĞĐŽŶǀŽůƵƟŽŶŽĨƚŚĞty^ ƉƌŽĮůĞƐǁĂƐĂĐŚŝĞǀĞĚƵƐŝŶŐDd>͘dŚĞĞǆƉĞƌŝŵĞŶƚĂůƉƌŽĮůĞƐǁĞƌĞĚĞĐŽŶǀŽůƵƚĞĚďǇ ƵƐŝŶŐƚŚĞƐƵŵŽĨĂůŝŶĞĂƌďĂĐŬŐƌŽƵŶĚĂŶĚƉƐĞƵĚŽͲsŽŝŐƚƉĞĂŬƐĚĞƐĐƌŝďŝŶŐƚŚĞƐĐĂƩĞƌŝŶŐ from the amorphous and the crystalline phases.

dƌĂŶƐŵŝƐƐŝŽŶ ůĞĐƚƌŽŶ DŝĐƌŽƐĐŽƉǇ ;dDͿ ǁĂƐ ƉĞƌĨŽƌŵĞĚ ŽŶ Ă WŚŝůŝƉƐ DϭϮ ƚƌĂŶƐŵŝƐƐŝŽŶ ĞůĞĐƚƌŽŶ ŵŝĐƌŽƐĐŽƉĞ ŽƉĞƌĂƟŶŐ Ăƚ ĂŶ ĂĐĐĞůĞƌĂƟŶŐ ǀŽůƚĂŐĞ ŽĨ ϭϮϬ Ŭs͘ ƐĞĐƟŽŶŽĨƚŚĞƚŚĞƌŵĂůůǇĂŶŶĞĂůĞĚ;^ͿďůŽĐŬĐŽƉŽůǇŵĞƌĮůŵǁĂƐĞŵďĞĚĚĞĚŝŶĞƉŽǆǇ ƌĞƐŝŶ ;ƉŽĮǆ͕ ůĞĐƚƌŽŶ DŝĐƌŽƐĐŽƉǇ ^ĐŝĞŶĐĞƐͿ ĂŶĚ ƐƵďƐĞƋƵĞŶƚůǇ ŵŝĐƌŽƚŽŵĞĚ ƵƐŝŶŐ Ă >ĞŝĐĂhůƚƌĂĐƵƚhdͲƵůƚƌĂŵŝĐƌŽƚŽŵĞŝŶŽƌĚĞƌƚŽƉƌĞƉĂƌĞƵůƚƌĂƚŚŝŶƐĞĐƟŽŶƐ;ĐĂ͘ϴϬŶŵͿ͘ EŽĂĚĚŝƟŽŶĂůƐƚĂŝŶŝŶŐŽĨƚŚĞƐĂŵƉůĞƐǁĂƐƌĞƋƵŝƌĞĚ͘

Results and Discussion

Triblock copolymer synthesis

dŚĞ ƐǇŶƚŚĞƟĐ ƌŽƵƚĞ ƚŽǁĂƌĚƐ W;s&-co-dƌ&ͿͲďĂƐĞĚ ƚƌŝďůŽĐŬ ĐŽƉŽůǇŵĞƌƐ ŝƐ ŽƵƚůŝŶĞĚ ŝŶ ^ĐŚĞŵĞ ϯ͘ϭ͘ dŚĞ ĐŚůŽƌŝŶĞ ĨƵŶĐƟŽŶĂůŝǌĞĚ ďĞŶǌŽǇů ƉĞƌŽǆŝĚĞ ŝŶŝƟĂƚŽƌ ǁĂƐ ƉƌĞƉĂƌĞĚ according to literature.28_{^ƵďƐĞƋƵĞŶƚůǇ͕ĨƌĞĞƌĂĚŝĐĂůĐŽƉŽůǇŵĞƌŝǌĂƟŽŶŽĨs&ĂŶĚdƌ&ǁĂƐ} ĐŽŶĚƵĐƚĞĚ͕ƌĞƐƵůƟŶŐŝŶƚĞůĞĐŚĞůŝĐĐŚůŽƌŝŶĞƚĞƌŵŝŶĂƚĞĚW;s&-co-dƌ&ͿĐŽƉŽůǇŵĞƌƐǁŝƚŚ

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3

molecular weights of 15.0 kg molͲϭ_{and dispersity indices (ÐͿĂƌŽƵŶĚϭ͘ϰ;ƚŚĞŵŽůĞĐƵůĂƌ} ĂŶĚƐƚƌƵĐƚƵƌĂůĐŚĂƌĂĐƚĞƌŝƐƟĐƐŽĨƚŚĞƉŽůǇŵĞƌƐƵƐĞĚŝŶƚŚŝƐƐƚƵĚǇĂƌĞƐƵŵŵĂƌŝǌĞĚŝŶ dĂďůĞϯ͘ϭͿ͘ŶĞŶĚͲŐƌŽƵƉƐƵďƐƟƚƵƟŽŶǁĂƐƉĞƌĨŽƌŵĞĚƚŽĨƵůůǇĐŽŶǀĞƌƚƚŚĞĐŚůŽƌŝŶĞĞŶĚ ŐƌŽƵƉƐŝŶƚŽĂǌŝĚĞĨƵŶĐƟŽŶĂůŝƟĞƐ͘hƐŝŶŐ1_{,EDZƐƉĞĐƚƌŽƐĐŽƉǇ;&ŝŐƵƌĞϯ͘ϭͿ͕ǁĞĐŽŶĮƌŵ} ƚŚĞƐƵĐĐĞƐƐĨƵůĨŽƌŵĂƟŽŶŽĨƚŚĞĐŽƉŽůǇŵĞƌW;s&-co-dƌ&ͿǁŝƚŚĂǌŝĚĞĞŶĚŐƌŽƵƉƐ͘,ĞƌĞŝŶ͕ ƚŚĞĐŚĂƌĂĐƚĞƌŝƐƟĐƐŝŐŶĂůƐĐĞŶƚĞƌĞĚĂƚϮ͘ϵϱƉƉŵĂŶĚϮ͘ϯϱƉƉŵĚĞŵŽŶƐƚƌĂƚĞƚŚĞƉƌĞƐĞŶĐĞ ŽĨŚĞĂĚͲƚŽͲƚĂŝůĂŶĚƚĂŝůͲƚŽͲƚĂŝůĂĚĚŝƟŽŶƐŽĨs&ƵŶŝƚƐ͕ƌĞƐƉĞĐƟǀĞůǇ͕ǁŚĞƌĞĂƐƚŚĞƉĞĂŬƐ ĐŽƌƌĞƐƉŽŶĚŝŶŐƚŽƚŚĞƉƌŽƚŽŶĨƌŽŵƚŚĞdƌ&ƵŶŝƚƐĂƌĞůŽĐĂƚĞĚŝŶďĞƚǁĞĞŶϱ͘ϬϬͲϱ͘ϱϬƉƉŵ͘ /ŶĂĚĚŝƟŽŶ͕ƚŚĞĐŽŵƉůĞƚĞƵƉĮĞůĚƐŚŝŌŽĨƚŚĞƐŝŶŐůĞƚĐŽƌƌĞƐƉŽŶĚŝŶŐƚŽƚŚĞŵĞƚŚǇůĞŶĞ ƉƌŽƚŽŶŶĞǆƚƚŽƚŚĞĐŚůŽƌŝŶĞĂƚŽŵĨƌŽŵϰ͘ϴϬƚŽϰ͘ϲϬƉƉŵƐŚŽǁƐƚŚĞĞǆĐŚĂŶŐĞŽĨƚŚĞĞŶĚ ŐƌŽƵƉƐ͘dŚĞĐŽŵƉůĞŵĞŶƚĂƌǇƉŽůǇƐƚǇƌĞŶĞ;W^ͿĂŶĚƉŽůǇ;tertͲďƵƚŽǆǇƐƚǇƌĞŶĞͿ;WtK^ͿďůŽĐŬƐ ǁŝƚŚĂŶĂůŬǇŶĞĨƵŶĐƟŽŶĂůŝƚǇǁĞƌĞƐǇŶƚŚĞƐŝǌĞĚƵƐŝŶŐƌĞǀĞƌƐŝďůĞĂĚĚŝƟŽŶͲĨƌĂŐŵĞŶƚĂƟŽŶ ĐŚĂŝŶƚƌĂŶƐĨĞƌ;Z&dͿƉŽůǇŵĞƌŝǌĂƟŽŶĂĐĐŽƌĚŝŶŐƚŽƉƌĞǀŝŽƵƐůŝƚĞƌĂƚƵƌĞƉƌŽĐĞĚƵƌĞƐ͘Ϯϴ͕ϯϬ

Scheme 3.1: Synthetic route towards PS-b-P(VDF-co-TrFE)-b-PS and

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56

^ƵďƐĞƋƵĞŶƚůǇ͕ƚŚĞŚŝŐŚůǇĞĸĐŝĞŶƚĂŶĚƋƵĂŶƟƚĂƟǀĞƵĐůŝĐŬƌĞĂĐƟŽŶǁĂƐƵƐĞĚ to prepare the PS-b-W;s&-co-dƌ&Ϳ-b-PS and PtBOS-b-W;s&-co-dƌ&ͿͲbͲWtBOS triblock

copolymers. The 1_{,EDZƐƉĞĐƚƌĂƐŚŽǁƚŚĂƚƚŚĞƐŝŐŶĂůĨƌŽŵƚŚĞŵĞƚŚǇůĞŶĞƉƌŽƚŽŶŶĞǆƚ}

ƚŽƚŚĞĂǌŝĚĞŝƐĨƵůůǇƐŚŝŌĞĚĚŽǁŶĮĞůĚĂŶĚ͕ĂĚĚŝƟŽŶĂůůǇ͕ƚŚĞƚƌŝĂǌŽůĞƉƌŽƚŽŶĂƉƉĞĂƌƐĂƚ ϳ͘ϵϬƉƉŵ͕ĚĞŵŽŶƐƚƌĂƟŶŐĂƐƵĐĐĞƐƐĨƵůĐůŝĐŬƌĞĂĐƟŽŶ͘dŚĞŐĞůƉĞƌŵĞĂƟŽŶĐŚƌŽŵĂƚŽŐƌĂƉŚǇ Table 3.1: 1SPIGYPEV [IMKLX GSQTSWMXMSR ERH WXVYGXYVEP GLEVEGXIVMWXMGW SJ 4:(*co-TrFE)

copolymers and the triblock copolymers used in this study.

Polymer D_ŶĂ͕Ğ ď vĂŵŽƌƉŚ ďůŽĐŬc vpvdf c WŽůĂƌ ďůŽĐŬ ^ƚƌƵĐƚƵƌĞ W;s&₈₂ͲcoͲdƌ&₁₈Ϳd _ϭϱ͘ϲ _ϭ͘ϰϲ ₀ ₁ _Ͳ _Ͳ W;s&₇₂ͲcoͲdƌ&₂₈Ϳd _ϭϰ͘ϴ _1.28 ₀ ₁ _Ͳ _Ͳ W^ͲbͲW;s&82Ͳdƌ&18ͿͲbͲW^ Ϯϳ͘ϰ f _Ͳ _Ϭ͘ϱϲ _Ϭ͘ϰϰ _No _Spheres W^ͲbͲW;s&72Ͳdƌ&28ͿͲbͲW^ Ϯϯ͘ϵ f _Ͳ _0.51 _Ϭ͘ϰϵ _No _Spheres

PtK^ͲbͲW;s&72Ͳdƌ&28ͿͲbͲWtBOS Ϯϰ͘ϲ

f _Ͳ _Ϭ͘ϱϰ _Ϭ͘ϰϲ _No _Spheres

W,^ͲbͲW;s&₇₂Ͳdƌ&₂₈ͿͲbͲWtBOSg _Ϯϯ͘ϭf _Ͳ _Ϭ͘ϰϳ _Ϭ͘ϱϯ _zĞƐ _Spheres a_{EƵŵďĞƌͲĂǀĞƌĂŐĞŵŽůĞĐƵůĂƌǁĞŝŐŚƚ;M} nͿ͘ b_{ŝƐƉĞƌƐŝƚǇ;сM} wͬDnͿ͘ c_{dŚĞǀŽůƵŵĞĨƌĂĐƟŽŶƐǁĞƌĞ} ĐĂůĐƵůĂƚĞĚ ƵƐŝŶŐ ƚŚĞ ǁĞŝŐŚƚ ĨƌĂĐƟŽŶƐ ĚĞƚĞƌŵŝŶĞĚ ďǇ1_{, EDZ ƐƉĞĐƚƌŽƐĐŽƉǇ ĂŶĚ ƚŚĞ ĚĞŶƐŝƚǇ}

ŽĨW^;ϭ͘ϬϰŐĐŵͲϯ_{Ϳ͕WtBOS (1.00 g cm}Ͳϯ_{Ϳ͕W,^;ϭ͘ϭϲŐĐŵ}Ͳϯ_{ͿĂŶĚW;s&Ͳdƌ&Ϳ;ϭ͘ϳϴŐĐŵ}Ͳϯ_Ϳ͘d_The

W;s&Ͳdƌ&ͿĐŽƉŽůǇŵĞƌƐĂƌĞĚĞƐŝŐŶĂƚĞĚĂĐĐŽƌĚŝŶŐƚŚĞŵŽůĂƌƌĂƟŽs&ĂŶĚdƌ&ĚĞƚĞƌŵŝŶĞĚďǇ

1_{,EDZƐƉĞĐƚƌŽƐĐŽƉǇ͘}e_{dŚĞŵŽůĞĐƵůĂƌǁĞŝŐŚƚĐŚĂƌĂĐƚĞƌŝƐƟĐƐŽĨW;s&-co-dƌ&ͿǁĞƌĞĐĂůĐƵůĂƚĞĚ}

ƵƐŝŶŐ'WǁŝƚŚD&;Ϭ͘ϬϭD>ŝƌͿĂƐĞůƵĞŶƚĂŶĚŵŽŶŽĚŝƐƉĞƌƐĞWDDƐƚĂŶĚĂƌĚƐ͘f_{The block}

copolymer molecular weights were calculated using the MnŽĨW;s&-co-dƌ&ͿĂŶĚǁĞŝŐŚƚĨƌĂĐƟŽŶƐ

ŽĨƚŚĞĚŝƐƟŶĐƚďůŽĐŬƐ͘g_{DŽůĞĐƵůĂƌǁĞŝŐŚƚ͕ĐŽŵƉŽƐŝƟŽŶĂŶĚŵŽƌƉŚŽůŽŐǇĂƌĞŽďƚĂŝŶĞĚĂŌĞƌin situ}

hydrolysis of PtK^ͲbͲW;s&72-co-dƌ&28ͿͲbͲWtK^ƵƐŝŶŐƚƌŝŇƵŽƌŽĂĐĞƟĐĂĐŝĚ͘

Figure 3.1: (a) Characteristic 1_{,216WTIGXVESJXLIFPSGOGSTSP]QIVWYWIHMRXLMWWXYH]WLS[MRKXLI} successful in-situ hydrolysis of PtBOS-b-P(VDF-co-TrFE)-b-PtBOS. (b) Enlarged spectrum showing the successful end group transformation after the CuAAC reaction.

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3

;'WͿĞůƵŐƌĂŵƐ;&ŝŐƵƌĞϯ͘ϮͿƐŚŽǁĂĐŚĂŶŐĞŽĨƚŚĞŶĞŐĂƟǀĞW;s&-co-dƌ&ͿƌĞĨƌĂĐƟǀĞŝŶĚĞǆ ƐŝŐŶĂůƚŽĂƐŝŐŶĂůǁŝƚŚĂƉŽƐŝƟǀĞǀĂůƵĞĨŽƌƚŚĞďůŽĐŬĐŽƉŽůǇŵĞƌ͘/ŶĂĚĚŝƟŽŶ͕ƚŚĞƵŶŝŵŽĚĂů ƐǇŵŵĞƚƌŝĐĂůƐŚĂƉĞŽĨƚŚĞƉƌŽĚƵĐƚĞůƵŐƌĂŵƐĂƚůŽǁĞƌƌĞƚĞŶƟŽŶǀŽůƵŵĞƐĐŽŵƉĂƌĞĚƚŽ ďŽƚŚW;s&-co-dƌ&ͿĂŶĚƚŚĞĂůŬǇŶĞƚĞƌŵŝŶĂƚĞĚŚŽŵŽƉŽůǇŵĞƌƐ͕W^ĂŶĚWtBOS, prove ƚŚĞĨŽƌŵĂƟŽŶŽĨƚŚĞƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐ͘

Curie transition temperature in P(VDF-co-TrFE) copolymers

dŽƵŶĚĞƌƐƚĂŶĚƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞŝŶƚŚĞƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌĮůŵƐ͕ǁĞĮƌƐƚ

ĂŶĂůǇǌĞĚƚŚĞĂƐͲƐǇŶƚŚĞƐŝǌĞĚW;s&-co-dƌ&ͿĐŽƉŽůǇŵĞƌƐƵƐĞĚŝŶƚŚŝƐƐƚƵĚǇ͘dŚĞW;s&-co-dƌ&ͿĐŽƉŽůǇŵĞƌƐĂƌĞĚĞƐŝŐŶĂƚĞĚĂĐĐŽƌĚŝŶŐƚŽƚŚĞŝƌŵŽůĂƌƌĂƟŽs&ĂŶĚdƌ&;e.g.

W;s&₈₂-co-dƌ&₁₈ͿĐŽŶƚĂŝŶƐϭϴŵŽůйdƌ&Ϳ͘dŚĞ^ƉƌŽĮůĞƐĚĞƉŝĐƚĞĚŝŶ&ŝŐƵƌĞϯ͘ϯƐŚŽǁ ƚŚĂƚW;s&₈₂-co-dƌ&₁₈ͿŚĂƐĂƐůŝŐŚƚůǇŚŝŐŚĞƌĐƌǇƐƚĂůůŝǌĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞƚŚĂŶW;s&₇₂ -co-dƌ&₂₈Ϳ͘&ƵƌƚŚĞƌŵŽƌĞ͕ƚŚĞƉĂƌĂĞůĞĐƚƌŝĐͲƚŽͲĨĞƌƌŽĞůĞĐƚƌŝĐƉŚĂƐĞƚƌĂŶƐŝƟŽŶĨŽƌW;s&₈₂ -co-dƌ&₁₈ͿƵƉŽŶĐŽŽůŝŶŐŝƐĚĞƚĞƌŵŝŶĞĚƚŽďĞϳϱΣ͕ǁŚĞƌĞĂƐW;s&₇₂-co-dƌ&₂₈ͿƐŚŽǁƐ ƚǁŽƵƌŝĞƚƌĂŶƐŝƟŽŶƐĂƚϱϱΣĂŶĚϰϮΣ;&ŝŐƵƌĞϯ͘ϯĚͿ͘/ŶƚŚĞ^ŚĞĂƟŶŐƐĐĂŶƚŚĞƌĞŝƐ ŶŽƵƌŝĞƚƌĂŶƐŝƟŽŶĚĞƚĞĐƚĞĚǁŚĞŶŽŶůǇϭϴŵŽůйdƌ&ŝƐŝŶĐŽƌƉŽƌĂƚĞĚŝŶƚŚĞĐŽƉŽůǇŵĞƌ ;&ŝŐƵƌĞϯ͘ϯďͿ͘,ŽǁĞǀĞƌ͕ǁĞŽďƐĞƌǀĞĂĐůĞĂƌďƌŽĂĚĮƌƐƚŽƌĚĞƌƚĞŵƉĞƌĂƚƵƌĞƚƌĂŶƐŝƟŽŶĨŽƌ W;s&₇₂-co-dƌ&₂₈ͿƵƉŽŶŚĞĂƟŶŐ;&ŝŐƵƌĞϯ͘ϯĞͿ͘dŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶŽĨW;s&-co-dƌ&Ϳ ĐŽƉŽůǇŵĞƌƐǁŝƚŚǀĂƌǇŝŶŐdƌ&ĐŽŶƚĞŶƚŝƐǁĞůůĚĞƐĐƌŝďĞĚŝŶƚŚĞůŝƚĞƌĂƚƵƌĞ͘ϭϰ_{The increased} ďƵůŬŝŶĞƐƐŽĨƚŚĞdƌ&ƵŶŝƚƐĂŶĚƚŚĞŝŶƚƌŽĚƵĐƟŽŶŽĨ͚ĚĞĨĞĐƚƐ͛ŝŶƚŚĞƉŽůǇŵĞƌďĂĐŬďŽŶĞ ƌĞƐƵůƚƐŝŶĂůŽǁĞƌĐƌǇƐƚĂůůŝǌĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞĂŶĚĂůŽǁĞƌĞŶĞƌŐǇƌĞƋƵŝƌĞĚĨŽƌƚŚĞƉŚĂƐĞ ƚƌĂŶƐŝƟŽŶƐƚŽŽĐĐƵƌ͘ DŽƌĞŝŶĨŽƌŵĂƟŽŶŽŶƚŚĞĐƌǇƐƚĂůůŝŶĞƉŚĂƐĞĂŶĚƉŚĂƐĞƚƌĂŶƐŝƟŽŶǁĂƐĚĞƌŝǀĞĚĨƌŽŵƚŚĞ ƚĞŵƉĞƌĂƚƵƌĞͲƌĞƐŽůǀĞĚty^ƉƌŽĮůĞƐŽĨƚŚĞĐŽƉŽůǇŵĞƌƐ͘ϯϭ͕ϯϮ_{ϮƐƵƌĨĂĐĞƉůŽƚǁĂƐĐŚŽƐĞŶ} ƚŽǀŝƐƵĂůŝǌĞƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶĂŶĚƵƌŝĞƚƌĂŶƐŝƟŽŶŽĨƚŚĞƉŽůǇŵĞƌƐĂŵƉůĞƐ͕͘ǁŚĞƌĞŝŶƚŚĞ Figure 3.2: GPC elugrams of the block copolymers indicating removal of unreacted homopolymers.

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58 ƐĐĂƩĞƌŝŶŐǀĞĐƚŽƌ;qͿŝƐƉůŽƩĞĚǀĞƌƐƵƐƚĞŵƉĞƌĂƚƵƌĞ;ΣͿŚĂǀŝŶŐƚŚĞƌĞůĂƟǀĞŝŶƚĞŶƐŝƟĞƐ ŽŶƚŚĞƐƵƌĨĂĐĞ͘ŽƚŚĐŽƉŽůǇŵĞƌƐĮƌƐƚĐƌǇƐƚĂůůŝǌĞŝŶƚŚĞŚŝŐŚƚĞŵƉĞƌĂƚƵƌĞƉĂƌĂĞůĞĐƚƌŝĐ ;,dWͿƉŚĂƐĞ͘ϭϯ_{,ŽǁĞǀĞƌ͕ĂŌĞƌƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶ͕W;s&} 82-co-dƌ&18ͿĚĞŵŽŶƐƚƌĂƚĞƐƚǁŽ ĚŝƐƟŶĐƚĐƌǇƐƚĂůůŝŶĞƉŚĂƐĞƐ;,dWĂŶĚƚŚĞůŽǁƚĞŵƉĞƌĂƚƵƌĞĨĞƌƌŽĞůĞĐƚƌŝĐ;>d&ͿͿĂƚƌŽŽŵ ƚĞŵƉĞƌĂƚƵƌĞ&ŝŐƵƌĞϯ͘ϯĂĂŶĚϯ͘ϯĞͿ͕ǁŚĞƌĞĂƐW;s&₇₂-co-dƌ&₂₈ͿƐŚŽǁƐũƵƐƚƚŚĞ>d&ƉŚĂƐĞƐ ;&ŝŐƵƌĞϯ͘ϯĚĂŶĚϯ͘ϯĨͿ͘ĞĐĂƵƐĞƚŚĞůŽǁĂŵŽƵŶƚŽĨdƌ&ŝŶƐŝĚĞƚŚĞW;s&₈₂-co-dƌ&₁₈Ϳ copolymer leads to small interplanar distances and therefore restricts chain mobility, ĂŵŝǆƚƵƌĞŽĨƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐĂŶĚƉĂƌĂĞůĞĐƚƌŝĐƉŚĂƐĞŝƐŽďƚĂŝŶĞĚƵƉŽŶĐŽŽůŝŶŐ͘hƉŽŶ ŚĞĂƟŶŐ͕ƚŚĞty^ƉƌŽĮůĞƐŽĨW;s&₈₂-co-dƌ&₁₈ͿƌĞǀĞĂůƚŚĂƚƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶĂŶĚƚŚĞ ŵĞůƟŶŐĞŶĚŽƚŚĞƌŵĐŽŝŶĐŝĚĞ͕ĂůƚŚŽƵŐŚƚŚĞƌĞŝƐŶŽƉŚĂƐĞƚƌĂŶƐŝƟŽŶŽďƐĞƌǀĞĚĨŽƌW;s&₈₂ -co-dƌ&₁₈ͿŝŶƚŚĞ^ƉƌŽĮůĞ;&ŝŐƵƌĞϯ͘ϯďͿ͘&ŽƌW;s&₇₂-co-dƌ&₂₈Ϳ͕ƚŚĞǀĂůƵĞƐŽĨƚŚĞT_cr and

ŵĞůƟŶŐƚĞŵƉĞƌĂƚƵƌĞĂƌĞŝŶŐŽŽĚĂŐƌĞĞŵĞŶƚŝŶďŽƚŚty^ĂŶĚ^͘

'YVMIXVERWMXMSRYRHIVRERSGSRƼRIQIRX

&ŽƌƚŚĞĞīĞĐƚŽĨŶĂŶŽĐŽŶĮŶĞŵĞŶƚŽŶƚŚĞT_cr, the block copolymers were designed to ĨŽƌŵƐƉŚĞƌŝĐĂůŶĂŶŽĚŽŵĂŝŶƐŽĨĐƌǇƐƚĂůůŝŶĞW;s&-co-dƌ&ͿŝŶƐŝĚĞĂŶĂŵŽƌƉŚŽƵƐĐŽŶĮŶŝŶŐ ŵĂƚƌŝǆ͘/ŶƚŚŝƐǁĂǇ͕ƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶŽĐĐƵƌƐviaĂŚŽŵŽŐĞŶĞŽƵƐŶƵĐůĞĂƟŽŶŵĞĐŚĂŶŝƐŵ͕ ǁŚĞƌĞƐƵƌĨĂĐĞĞīĞĐƚƐŽŶƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶĂƌĞŵŝŶŝŵŝǌĞĚĚƵĞƚŽƵŶĨĂǀŽƌĂďůĞŝŶƚĞƌĂĐƟŽŶƐ Figure 3.3: (7'ERHXIQTIVEXYVIVIWSPZIH;%<7TVSƼPIWSJ4:(*₈₂-co-TrFE₁₈) (a) cooled from the melt at 10 °C min-1_{F
LIEXIHEXq'QMR}-1_{ERHG
XLIHIGSRZSPYXIH;%<7TVSƼPIVIGSVHIHEXVSSQ} XIQTIVEXYVI(7'ERHXIQTIVEXYVIVIWSPZIH;%<7TVSƼPIWSJ4:(*₇₂-co-TrFE₂₈) (d) cooled from the melt at 10 °C min-1_{I
LIEXIHEXq'QMR}-1_{ERHJ
XLIHIGSRZSPYXIH;%<7TVSƼPIVIGSVHIHEX} room temperature.

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ďĞƚǁĞĞŶĚŝƐƟŶĐƚďůŽĐŬƐƌĞƐƵůƟŶŐŝŶĐŚĂŝŶƐƚƌĞƚĐŚŝŶŐĂƚƚŚĞŝŶƚĞƌĨĂĐĞĂŶĚĐƌǇƐƚĂůůŝǌĂƟŽŶ inside the core of the spheres.ϯϯ

Two PS-b-W;s&-co-dƌ&Ϳ-b-PS triblock copolymers, PS-b-W;s&₈₂-co-dƌ&₁₈Ϳ-b-PS and PS-b-W;s&₇₂-co-dƌ&₂₈Ϳ-b-W^ŐŝǀŝŶŐĂƐƉŚĞƌŝĐĂůŵŽƌƉŚŽůŽŐǇ͕ďƵƚǁŝƚŚĂĚŝīĞƌĞŶƚ ŵŽůĂƌƌĂƟŽs&ĂŶĚdƌ&ǁĞƌĞƐĞůĞĐƚĞĚĨŽƌƚŚŝƐƐƚƵĚǇ͘dŚĞƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐǁĞƌĞ ƐŽůǀĞŶƚͲĐĂƐƚĨƌŽŵĚŝŵĞƚŚǇůĨŽƌŵĂŵŝĚĞ;D&ͿĂƚϰϱΣ͘^ƵďƐĞƋƵĞŶƚůǇ͕ƚŚĞĮůŵƐǁĞƌĞ thermally annealed in the melt followed by cooling to room temperature at a rate of 10 ΣŵŝŶͲϭ_{͘dŚĞƐƚƌƵĐƚƵƌĞĨŽƌŵĂƟŽŶǁĂƐŝĚĞŶƟĮĞĚƵƐŝŶŐƐŵĂůůͲĂŶŐůĞyͲƌĂǇƐĐĂƩĞƌŝŶŐ;^y^Ϳ} ĂŶĚƚƌĂŶƐŵŝƐƐŝŽŶĞůĞĐƚƌŽŶŵŝĐƌŽƐĐŽƉǇ;dDͿ͘ŌĞƌƚŚĞƌŵĂůĂŶŶĞĂůŝŶŐŝŶƚŚĞŵĞůƚĂŶĚ ƐƵďƐĞƋƵĞŶƚĐŽŽůŝŶŐƚŽƌŽŽŵƚĞŵƉĞƌĂƚƵƌĞĚŝƐŽƌĚĞƌĞĚŵŝĐĞůůĂƌƐƉŚĞƌĞƐĂƌĞĨŽƌŵĞĚŝŶďŽƚŚ PS-b-W;s&-co-dƌ&Ϳ-b-W^ƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐĂƐĚĞŵŽŶƐƚƌĂƚĞĚŝŶƚŚĞdDŝŵĂŐĞ;&ŝŐƵƌĞ ϯ͘ϰĂĂŶĚϯ͘ϰĐͿ͘ŽƚŚW^Ͳb-W;s&-co-dƌ&Ϳ-b-W^ƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐƐŚŽǁĂĮƌƐƚŽƌĚĞƌ ƐĐĂƩĞƌŝŶŐŵĂǆŝŵƵŵůŽĐĂƚĞĚĂƚq = 0.15 nmͲϭ_{;&ŝŐƵƌĞϯ͘ϰďĂŶĚϯ͘ϰĚͿ͕ŝŶĚŝĐĂƟŶŐƐŝŵŝůĂƌ} ĚŽŵĂŝŶƐƉĂĐŝŶŐƐ͘dŚĞůĂĐŬŽĨůŽŶŐͲƌĂŶŐĞƉĞƌŝŽĚŝĐŝƚǇ͕ƉƌŽďĂďůǇĐĂƵƐĞĚďǇƚŚĞƌĞůĂƟǀĞůǇ high ÐŽĨƚŚĞƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐĂŶĚĐƌǇƐƚĂůůŝǌĂƟŽŶ͕ŝƐŽďƐĞƌǀĞĚĨŽƌǀĂƌŝŽƵƐƐƉŚĞƌŝĐĂů micellar nanomorphologies in literature.ϯϰ͕ϯϱ_{Due to similar sphere diameters and since} ƚŚĞƐĂŵĞW^ŚŽŵŽƉŽůǇŵĞƌǁĂƐƵƐĞĚĨŽƌƚŚĞĐůŝĐŬƌĞĂĐƟŽŶ͕ƚŚĞĞīĞĐƚŽĨdƌ&ĐŽŶƚĞŶƚŝŶ W;s&-co-dƌ&ͿͲďĂƐĞĚďůŽĐŬĐŽƉŽůǇŵĞƌƐĐĂŶĞīĞĐƟǀĞůǇďĞƐƚƵĚŝĞĚ͘ ƐĞǆƉĞĐƚĞĚ͕ĂƐƚƌŽŶŐůǇƌĞĚƵĐĞĚĐƌǇƐƚĂůůŝǌĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞĨŽƌďŽƚŚW^-b-W;s&-co-dƌ&Ϳ-b-W^ ƚƌŝďůŽĐŬ ĐŽƉŽůǇŵĞƌƐ ŝƐ ŽďƐĞƌǀĞĚ &ŝŐƵƌĞ ϯ͘ϱĂ ĂŶĚ ϯ͘ϱĚͿ͘ ZĞĐĞŶƚůǇ͕ ǁĞ ŶŽƟĐĞĚƚŚĂƚŶĂŶŽĐŽŶĮŶĞŵĞŶƚŚĂƐĂƉƌŽĨŽƵŶĚĞīĞĐƚŽŶƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶďĞŚĂǀŝŽƌŽĨ Ws&ͲďĂƐĞĚďůŽĐŬĐŽƉŽůǇŵĞƌƐ͘Ϯϲ_{,ĂƌĚĐŽŶĮŶĞŵĞŶƚŝŶƐƉŚĞƌŝĐĂůŶĂŶŽĚŽŵĂŝŶƐƌĞƐƵůƚƐ} ŝŶĂƐƚƌŽŶŐůǇƌĞĚƵĐĞĚĐƌǇƐƚĂůůŝǌĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞĂŶĚƚŚĞĞǆĐůƵƐŝǀĞĨŽƌŵĂƟŽŶŽĨƚŚĞ ĨĞƌƌŽĞůĞĐƚƌŝĐɴͲƉŚĂƐĞ͘/ŶĂƐŝŵŝůĂƌǁĂǇ͕ĚƵĞƚŽĂŚŽŵŽŐĞŶĞŽƵƐŶƵĐůĞĂƟŽŶŵĞĐŚĂŶŝƐŵ͕ ƚŚĞůĂƌŐĞĚƌŽƉŝŶĐƌǇƐƚĂůůŝǌĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞĨŽƌW^-b-W;s&₈₂-co-dƌ&₁₈Ϳ-b-PS leads to ƚŚĞĐŽŶĐƵƌƌĞŶĐĞŽĨƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞǁŝƚŚƚŚĞT_cr͘dŚĞty^ƉƌŽĮůĞƐŝŶ &ŝŐƵƌĞϯ͘ϱĂĂŶĚ&ŝŐƵƌĞϯ͘ϱĐƐŚŽǁƚŚĂƚW;s&₈₂-co-dƌ&₁₈ͿĐƌǇƐƚĂůůŝǌĞƐŝŶƐŝĚĞƚŚĞƐƉŚĞƌŝĐĂů ŶĂŶŽĚŽŵĂŝŶƐŝŶĂŵŝǆƚƵƌĞŽĨƚŚƌĞĞĐƌǇƐƚĂůůŝŶĞƉŚĂƐĞƐ͘ ƚϭϰ͘ϭŶŵͲϭ_{͕ƚŚĞĐŚĂƌĂĐƚĞƌŝƐƟĐ;ϭϭϬͬϮϬϬͿƌĞŇĞĐƟǀĞƉůĂŶĞƐŝŐŶĂůĐŽƌƌĞƐƉŽŶĚŝŶŐƚŽƚŚĞ} >d&ƉŚĂƐĞĂƉƉĞĂƌƐ͕ĐŽŶƐŝƐƟŶŐŽĨĂůůͲƚƌĂŶƐŽƌŐĂŶŝǌĞĚW;s&ͲcoͲdƌ&ͿĐŚĂŝŶƐ͘dŚĞ>& ;ĐŽŽůĞĚĨĞƌƌŽĞůĞĐƚƌŝĐƉŚĂƐĞͿŝƐŽďƐĞƌǀĞĚĂƚϭϯ͘ϱŶŵͲϭ_{͕ŚĂǀŝŶŐƚƌĂŶƐƐĞƋƵĞŶĐĞƐǁŝƚŚŐĂƵĐŚĞ} ĚĞĨĞĐƚƐŝŶƚŚĞĐƌǇƐƚĂůƐ͕ǁŚĞƌĞĂƐƚŚĞŚŝŐŚƚĞŵƉĞƌĂƚƵƌĞ,dWƉŚĂƐĞŝƐůŽĐĂƚĞĚĂƚϭϯ͘ϭŶŵͲϭ_. ĂƌŐĂŝŶĞƚ͘Ăů͘ĂůƌĞĂĚǇĚĞŵŽŶƐƚƌĂƚĞĚƚŚĞĐŽĞǆŝƐƚĞŶĐĞŽĨƚŚĞ>&ĂŶĚƚŚĞ>d&ŝŶ W;s&-co-dƌ&ͿĐŽƉŽůǇŵĞƌƐǁŝƚŚŚŝŐŚdƌ&;хϯϬŵŽůйͿĐŽŶƚĞŶƚ͘ϭϯ_{,ŽǁĞǀĞƌ͕ƚŚĞĂƉƉĞĂƌĂŶĐĞ} ŽĨƚŚĞ>&ŝƐ͕ĨŽƌƚŚĞĮƌƐƚƟŵĞ͕ĚĞŵŽŶƐƚƌĂƚĞĚŝŶĂĐŽƉŽůǇŵĞƌǁŝƚŚůŽǁdƌ&ĐŽŶƚĞŶƚ͘ ƵĞƚŽƚŚĞŝŶĐƌĞĂƐĞĚƐƵƌĨĂĐĞĂƌĞĂŝŶƐƉŚĞƌŝĐĂůŶĂŶŽĚŽŵĂŝŶƐ͕ƚŚĞŵŽďŝůŝƚǇŽĨƚŚĞW;s&-co-dƌ&ͿĐŚĂŝŶƐĂƚƚŚĞďŽƵŶĚĂƌǇŝƐƐƚƌŽŶŐůǇƌĞĚƵĐĞĚƌĞƐƵůƟŶŐŝŶŵŽƌĞŐĂƵĐŚĞĚĞĨĞĐƚƐ͘ /ŶĂĚĚŝƟŽŶ͕ƚŚĞůŽǁĞƌĐƌǇƐƚĂůůŝǌĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞĨĂǀŽƌƐƚŚĞĨŽƌŵĂƟŽŶŽĨĐƌǇƐƚĂůƐŝŶ ƚŚĞĂůůͲƚƌĂŶƐĐŽŶĨŽƌŵĂƟŽŶ͕ďƵƚŝƐŚĂŵƉĞƌĞĚďǇƚŚĞĐŚĂŝŶŵŽďŝůŝƚǇ͕ƌĞƐƵůƟŶŐŝŶƚŚĞ>&͘

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hƉŽŶŚĞĂƟŶŐƚŚĞďůŽĐŬĐŽƉŽůǇŵĞƌ͕ĮƌƐƚƚŚĞ>&ƚƌĂŶƐĨŽƌŵƐƚŽƚŚĞ,dWďĞĨŽƌĞŵĞůƟŶŐ͕ ǁŚĞƌĞĂƐŶŽƚƌĂŶƐŝƟŽŶŽĨƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐƉŚĂƐĞŝƐŽďƐĞƌǀĞĚ͕ƉƌŽďĂďůǇĚƵĞƚŽƚŚĞƐůŝŐŚƚůǇ ůŽǁĞƌŵĞůƟŶŐƚĞŵƉĞƌĂƚƵƌĞĐĂƵƐĞĚďǇƚŚĞŶĂŶŽĐŽŶĮŶĞŵĞŶƚĞīĞĐƚ͘

dŚĞďůŽĐŬĐŽƉŽůǇŵĞƌǁŝƚŚŚŝŐŚĞƌdƌ&ĐŽŶƚĞŶƚ͕W^-b-W;s&₇₂-co-dƌ&₂₈Ϳ-b-PS, shows a ĐƌǇƐƚĂůůŝǌĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞĂƚϴϱΣ;&ŝŐƵƌĞϯ͘ϱĚͿ͕ĞǀĞŶƚŚŽƵŐŚƚŚĞƐĂŵĞĚŽŵĂŝŶƐƉĂĐŝŶŐƐ ǁĞƌĞŽďƚĂŝŶĞĚĨƌŽŵƚŚĞdDŝŵĂŐĞƐĂŶĚ^y^ĞǆƉĞƌŝŵĞŶƚƐ͘dŚĞŚŝŐŚĞƌdƌ&ĐŽŶƚĞŶƚ ĂƉƉĂƌĞŶƚůǇĨĂǀŽƌƐƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶĂƚŚŝŐŚĞƌƚĞŵƉĞƌĂƚƵƌĞ͕ƐŝŶĐĞĚĞĨĞĐƚƐŝŶƚŚĞƉŽůǇŵĞƌ ďĂĐŬďŽŶĞĂƌĞĨƵŶĐƟŽŶŝŶŐĂƐŶƵĐůĞĂƟŽŶƉŽŝŶƚƐ͘ƐŝŶĚŝĐĂƚĞĚďǇƚŚĞty^ƉƌŽĮůĞƐŝŶ &ŝŐƵƌĞϯ͘ϱĚ͕ƚŚĞŚŝŐŚĞƌĐƌǇƐƚĂůůŝǌĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞƌĞƐƵůƚƐŝŶƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶŝŶƚŽƚŚĞ ŬŝŶĞƟĐĂůůǇĨĂǀŽƌĂďůĞ,dW͘^ƵďƐĞƋƵĞŶƚůǇ͕ƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚŽƚŚĞ>d&ŝƐŝŶĐƌĞĂƐĞĚ ĐŽŵƉĂƌĞĚƚŽƉƌŝƐƟŶĞW;s&₇₂-co-dƌ&₂₈Ϳ͘/ŶĂĚĚŝƟŽŶ͕Ă>&ŶĞǆƚƚŽƚŚĞ>d&ĂƉƉĞĂƌƐ͕ ŝŶĚŝĐĂƟŶŐƚŚĞƌĞĚƵĐĞĚŵŽďŝůŝƚǇŽĨƚŚĞW;s&₇₂-co-dƌ&₂₈ͿĐŽƉŽůǇŵĞƌĂƚƚŚĞŝŶƚĞƌĨĂĐĞŽĨ ƚŚĞŶĂŶŽƐƉŚĞƌĞƐ͘ƐƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶŝƐĂĐŽŶƐĞƋƵĞŶĐĞŽĨĐŽŽƉĞƌĂƟǀĞŵŽǀĞŵĞŶƚŽĨ ƚŚĞƉŽůǇŵĞƌĐŚĂŝŶƐŝŶƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶ͕ƚŚĞƌĞĚƵĐƟŽŶŝŶĐƌǇƐƚĂůůŝƚĞƐŝǌĞƌĞƐƵůƚƐŝŶ

Figure 3.4: TEM image of thermally annealed (a) PS-b-P(VDF₈₂-co-TrFE₁₈)-b-PS and (c) PS-b-P(VDF₇₂

-co-TrFE28)-b47VIGSVHIHEXVSSQXIQTIVEXYVI7GEPIFEVGSVVIWTSRHWXSRQ7%<7TVSƼPIWSJF PS-b-P(VDF₈₂-co-TrFE₁₈)-b-PS and (d) PS-b-P(VDF₇₂-co-TrFE₂₈)-b-PS recorded at room temperature and in the melt.

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ƐŵĂůůĞƌĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶƐ͕ůĞĂĚŝŶŐƚŽĂůŽǁĞƌĞŶĞƌŐǇďĂƌƌŝĞƌĨŽƌƚŚĞƉŚĂƐĞƚƌĂŶƐŝƟŽŶ ƚŽŽĐĐƵƌ͘/ŶĚĞĞĚ͕ĂƐŽďƐĞƌǀĞĚĨƌŽŵƚŚĞƐƚƌŽŶŐƌĞĚƵĐƟŽŶŽĨƚŚĞĞŶƚŚĂůƉǇǀĂůƵĞƐĨŽƌƚŚĞ ƵƌŝĞƚƌĂŶƐŝƟŽŶŝŶƐŝĚĞƚŚĞďůŽĐŬĐŽƉŽůǇŵĞƌƐ͕ĐƌǇƐƚĂůůŝǌĂƟŽŶŝŶƐŝĚĞƐƉŚĞƌŝĐĂůŶĂŶŽĚŽŵĂŝŶƐ ƌĞƐƵůƚƐŝŶĂƌĞĚƵĐƟŽŶŽĨĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶƐŝǌĞĐŽŵƉĂƌĞĚƚŽƉƌŝƐƟŶĞŚŽŵŽƉŽůǇŵĞƌ͘ >ƵƚŬĞŶŚĂƵƐ Ğƚ͘ Ăů͘ ƉŽƐƚƵůĂƚĞĚ ƚŚĂƚ ƉŽůĂƌ ƐƵƌĨĂĐĞƐ ŝŶ ĐŽŶƚĂĐƚ ǁŝƚŚ W;s&-co-dƌ&Ϳ ŵĂǇ ƌĞĚƵĐĞ ƚŚĞ ƵƌŝĞ ƚƌĂŶƐŝƟŽŶ ŝŶ ĐŽŶĮŶĞĚ ŐĞŽŵĞƚƌŝĞƐ ǁŝƚŚ ůŽǁ ĨĞĂƚƵƌĞ ƐŝǌĞƐ ;ϭϱ ŶŵͿ͘ 19_{To prove this, we designed a block copolymer system that phase separates in a} ƐƉŚĞƌŝĐĂůŵŽƌƉŚŽůŽŐǇǁŝƚŚĂƉŽůĂƌŵĂƚƌŝǆ͘,ŽǁĞǀĞƌ͕ƚŚĞƉƌĞƉĂƌĂƟŽŶŽĨďůŽĐŬĐŽƉŽůǇŵĞƌƐ ƚŚĂƚĚŝƌĞĐƚůǇƐĞůĨͲĂƐƐĞŵďůĞŝŶƚŽƚŚĞĚĞƐŝƌĞĚŵŽƌƉŚŽůŽŐǇŝƐĚŝĸĐƵůƚĚƵĞƚŽĨĂǀŽƌĂďůĞ ŝŶƚĞƌĂĐƟŽŶƐďĞƚǁĞĞŶƚŚĞĚŝƐƟŶĐƚďůŽĐŬƐ͘dŚĞƌĞĨŽƌĞ͕ƚŚĞĚĞƐŝƌĞĚƐǇƐƚĞŵŝƐƉƌĞƉĂƌĞĚŝŶ ƚǁŽƐƚĞƉƐ͗ŵŝĐƌŽƉŚĂƐĞƐĞƉĂƌĂƟŽŶŽĨW;s&-co-dƌ&ͿďůŽĐŬĐŽƉŽůǇŵĞƌƐƵƐŝŶŐŚǇĚƌŽůǇƐĂďůĞ nonpolar blocks with a high T_g into a spherical morphology followed by in situ hydrolysis ƚŽƚŚĞƉŽůĂƌŵĂƚƌŝǆ͘ǀĞŶƚŚŽƵŐŚƉŽůǇ;ĂůŬǇůŵĞƚŚĂĐƌǇůĂƚĞƐͿĂƌĞĂƚĮƌƐƚƐŝŐŚƚƚŚĞŵŽƐƚ ůŽŐŝĐĂůĐŚŽŝĐĞ͕ƚŚĞŝƌŚǇĚƌŽůǇƐŝƐŝƐĂĐĐŽŵƉĂŶŝĞĚǁŝƚŚƐƚƌŽŶŐƐǁĞůůŝŶŐĚƵĞƚŽƐĂůƚĨŽƌŵĂƟŽŶ͕ ǁŚŝĐŚĚŝƐƌƵƉƚƐƚŚĞŵŽƌƉŚŽůŽŐǇ͘dŚĞĂŵŽƌƉŚŽƵƐďůŽĐŬƚŚĂƚĨƵůĮůůĞĚĂůůƌĞƋƵŝƌĞŵĞŶƚƐ (i.e.ŶĂŶŽƐƉŚĞƌĞĨŽƌŵĂƟŽŶ͕ŚŝŐŚ T_gĂŶĚŶŽƐǁĞůůŝŶŐĚƵƌŝŶŐŚǇĚƌŽůǇƐŝƐͿŝƐƉŽůǇ;ϰͲtertͲ ďƵƚŽǆǇƐƚǇƌĞŶĞͿ;WtK^Ϳ͘

dŚĞdDŝŵĂŐĞŽĨWtBOS-b-W;s&₇₂-co-dƌ&₂₈Ϳ-b-PtK^;&ŝŐƵƌĞϯ͘ϲďͿƌĞǀĞĂůƐƚŚĂƚĂ ĚŝƐŽƌĚĞƌĞĚƐƉŚĞƌŝĐĂůŶĂŶŽŵŽƌƉŚŽůŽŐǇŝƐŽďƚĂŝŶĞĚĂŌĞƌƚŚĞƌŵĂůĂŶŶĞĂůŝŶŐŝŶƚŚĞŵĞůƚ͕ ǁŝƚŚĂĮƌƐƚŽƌĚĞƌƐĐĂƩĞƌŝŶŐŵĂǆŝŵĂůŽĐĂƚĞĚĂƚq = 0.22 nmͲϭ

, as is observed for the PS-b-W;s&-co-dƌ&Ϳ-b-W^ƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐ;&ŝŐƵƌĞϯ͘ϳͿ͘ǀĞŶƚŚŽƵŐŚƚŚĞƐĂŵĞW;s&₇₂

-co-Figure 3.5: (7'ERHXIQTIVEXYVIVIWSPZIH;%<7TVSƼPIWSJ47b-P(VDF₈₂-co-TrFE₁₈)-b-PS after (a) cooling from the melt at 10 °C min-1_{and (b) heating at 10 °C min}-1_{(IGSRZSPYXIH;%<7TVSƼPIWSJ} (c) PS-b-P(VDF82-co-TrFE18)-b-PS recorded at room temperature. DSC and temperature-resolved ;%<7TVSƼPIWSJ47b-P(VDF₇₂-co-TrFE₂₈)-b-PS after (d) cooling from the melt at 10 °C min-1_{and (e)} heating at 10 °C min-1_{(IGSRZSPYXIH;%<7TVSƼPIWSJJ
47b-P(VDF}

72-co-TrFE28)-b-PS recorded at room temperature.

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dƌ&₂₈ͿŝƐƵƐĞĚĨŽƌƚŚĞƐǇŶƚŚĞƐŝƐĂŶĚĂƐůŝŐŚƚůǇŚŝŐŚĞƌŵŽůĞĐƵůĂƌǁĞŝŐŚƚŽĨWtBOS, the lower ĚŽŵĂŝŶƐƉĂĐŝŶŐŵŝŐŚƚďĞĂƌĞƐƵůƚŽĨŚŝŐŚŵŽůĞĐƵůĂƌǁĞŝŐŚƚůŽƐƐĞƐĚƵƌŝŶŐƚŚĞǁŽƌŬͲƵƉ ƉƌŽĐĞĚƵƌĞ͘ƐĞǆƉĞĐƚĞĚ͕ũƵƐƚĂƐĨŽƌW^ͲďĂƐĞĚƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐ͕ŚŝŐŚĞƌŽƌĚĞƌƉĞĂŬƐŝŶ ƚŚĞ^y^ƉƌŽĮůĞƐĂƌĞĂďƐĞŶƚĂŶĚƚŚĞĮƌƐƚŽƌĚĞƌƐĐĂƩĞƌŝŶŐŵĂǆŝŵĂƌĞŵĂŝŶƐĂƚƚŚĞƐĂŵĞ qͲǀĂůƵĞƵƉŽŶĐŽŽůŝŶŐŝŶĚŝĐĂƟŶŐƚŚĂƚƚŚĞŵĞůƚƐƚƌƵĐƚƵƌĞŝƐƌĞƚĂŝŶĞĚĂƚƌŽŽŵƚĞŵƉĞƌĂƚƵƌĞ͘ EŽƚĞǁŽƌƚŚǇ͕ƐŝŵŝůĂƌďĞŚĂǀŝŽƌƌĞŐĂƌĚŝŶŐƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶĨŽƌWtBOS-b-W;s&-co-dƌ&Ϳ-b-PtK^ĂŶĚƚŚĞW^ͲďĂƐĞĚƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐŝƐŽďƐĞƌǀĞĚŚĂǀŝŶŐŝŶŵŝŶĚƚŚĂƚWtBOS is also nonpolar.

Figure 3.6: (7'ERHXIQTIVEXYVIVIWSPZIH;%<7TVSƼPIWSJ47b-P(VDF₈₂-co-TrFE₁₈)-b-PS after (a) cooling from the melt at 10 °C min-1_{and (b) heating at 10 °C min}-1_{(IGSRZSPYXIH;%<7TVSƼPIWSJ} (c) PS-b-P(VDF₈₂-co-TrFE₁₈)-b-PS recorded at room temperature. DSC and temperature-resolved ;%<7TVSƼPIWSJ47b-P(VDF₇₂-co-TrFE₂₈)-b-PS after (d) cooling from the melt at 10 °C min-1_and (e) heating at 10 °C min-1_{(IGSRZSPYXIH;%<7TVSƼPIWSJJ
47b-P(VDF}

72-co-TrFE28)-b-PS recorded at room temperature.

Figure 3.7: 7%<7TVSƼPIWSJE 4tBOS-b-P(VDF₇₂-co-TrFE₂₈)-b-PtBOS and (b) PHS-b-P(VDF₇₂ -co-TrFE₂₈)-b-PHS.

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To transfer PtK^ŝŶƚŽĂŵŽƌĞƉŽůĂƌŵĂƚƌŝǆĨŽƌƚŚĞW;s&-co-dƌ&ͿŶĂŶŽƐƉŚĞƌĞƐ͕ ƚŚĞƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌĮůŵƐǁĞƌĞŚǇĚƌŽůǇǌĞĚin situǁŝƚŚƚƌŝŇƵŽƌŽĂĐĞƟĐĂĐŝĚ;d&ͿƚŽ ƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐǁŝƚŚƉŽůǇ;ϰͲŚǇĚƌŽǆǇƐƚǇƌĞŶĞͿ;W,^Ϳ͘/ŶĚĞĞĚ͕ƌĞŵŽǀĂůŽĨƚŚĞƚĞƌƚͲďƵƚǇů ƉƌŽƚĞĐƟŶŐŐƌŽƵƉƐ;&ŝŐƵƌĞϯ͘ϭͿĂŶĚŵĞůƟŶŐŽĨW;s&-co-dƌ&ͿŝŶƐŝĚĞƚŚĞW,^ŵĂƚƌŝǆĂƚ ϭϱϬΣŝŶĚŝĐĂƚĞŶŽƐŝŐŶŝĮĐĂŶƚĐŚĂŶŐĞƐŝŶƚŚĞŵŽƌƉŚŽůŽŐǇĂƐŽďƐĞƌǀĞĚŝŶƚŚĞ^y^ƉƌŽĮůĞ ĂŶĚdDŝŵĂŐĞ;&ŝŐƵƌĞϯ͘ϲĐĂŶĚ&ŝŐƵƌĞϯ͘ϳͿ͘dŽƉƌĞǀĞŶƚĐƌŽƐƐůŝŶŬŝŶŐĂŶĚŵŝǆŝŶŐŽĨW,^ ĂŶĚW;s&-co-dƌ&Ϳ͕ƚŚĞƚĞŵƉĞƌĂƚƵƌĞǁĂƐƐĞůĞĐƚĞĚƚŽďĞďĞůŽǁƚŚĞd_gŽĨW,^;ϭϴϬΣͿ͘ϯϲ The in situŚǇĚƌŽůǇǌĞĚW,^-b-W;s&-co-dƌ&Ϳ-b-W,^ƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌ͕ƐŝŵŝůĂƌƚŽ ƚŚĞW^ͲĂŶĚWtK^ͲďĂƐĞĚƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐ͕ƐŚŽǁƐĂůĂƌŐĞƌĞĚƵĐƟŽŶŝŶĐƌǇƐƚĂůůŝǌĂƟŽŶ temperature due to crystallization in strongly confined spherical nanodomains. /ŶƚƌŝŐƵŝŶŐůǇ͕ ĂƐ ƐŚŽǁŶ ŝŶ &ŝŐƵƌĞ ϯ͘ϴĨ͕ ƚŚĞ ,dW ƉŚĂƐĞ ŝƐ ĂůƐŽ ŽďƐĞƌǀĞĚ Ăƚ ƌŽŽŵ temperature, which can be due to a reduced chain mobility at lower temperature, ŚĂŵƉĞƌŝŶŐƚŚĞĐƌǇƐƚĂůůŝŶĞƉŚĂƐĞƚƌĂŶƐŝƟŽŶǁŚĞŶĐŽŽůŝŶŐ͘ĚĚŝƟŽŶĂůůǇ͕ŝŶƐƚĞĂĚŽĨĂƐůŝŐŚƚ ŝŶĐƌĞĂƐĞ͕ĂƐƚƌŽŶŐƌĞĚƵĐƟŽŶŝŶƚŚĞT_crŝƐŽďƐĞƌǀĞĚƵƉŽŶĐŽŽůŝŶŐ͘^ƵďƐĞƋƵĞŶƚŚĞĂƟŶŐůĞĂĚƐ ƚŽĂƌĞĚƵĐĞĚƉŚĂƐĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞĐŽŵƉĂƌĞĚƚŽƚŚĞWtK^ͲbͲW;s&-co-dƌ&ͿͲbͲ PtBOS triblock copolymer. Because there are no large changes in the structure and the domain size (ȴ,_crǀĂůƵĞƐŝŶdĂďůĞϬͲϭͿŽďƐĞƌǀĞĚ͕ƚŚĞŵĂŝŶĐĂƵƐĞĨŽƌƚŚĞƌĞĚƵĐƟŽŶŽĨƚŚĞ

T_crĐĂŶďĞĂƐĐƌŝďĞĚƚŽƉŽůĂƌŝŶƚĞƌĂĐƟŽŶƐďĞƚǁĞĞŶW;s&-co-dƌ&ͿĂŶĚW,^͘dŚĞƐƚƌŽŶŐ ƌĞĚƵĐƟŽŶŝŶƚŚĞT_cr;ϭϬΣͿŚĂƐĂůƌĞĂĚǇďĞĞŶĚĞŵŽŶƐƚƌĂƚĞĚŝŶĂůƵŵŝŶŝƵŵŽǆŝĚĞŶĂŶŽƉŽƌĞƐ͘ 19_{/ŶƚĞƌĂĐƟŽŶƐŽĨƚŚĞƐƵƌĨĂĐĞǁŝƚŚW;s&-co-dƌ&ͿƌĞĚƵĐĞĚƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶǁŝƚŚϭϬ}

Figure 3.8:E (7'TVSƼPIERH;%<7WYVJEGITPSXJVSQ4tBOS-b-P(VDF₇₂-co-TrFE₂₈)-b-PtBOS cooled from the melt at 10 °C min-1_{F
(7'TVSƼPIERH;%<7WYVJEGITPSXJVSQ4tBOS-b-P(VDF}

72-co-TrFE28

)-b-PtBOS heated at 10 °C min-1_{G
(IGSRZSPYXIH;%<7TVSƼPISJ4tBOS-b-P(VDF}

72-co-TrFE28 )-b-Pt&37VIGSVHIHEXVSSQXIQTIVEXYVI[LIRGSSPIHJVSQXLIQIPXH (7'TVSƼPIERH;%<7WYVJEGI plot from PHS-b-P(VDF72-co-TrFE28)-b-PHS cooled from 150 °C at 10 °C min-1I (7'TVSƼPIERH ;%<7WYVJEGITPSXJVSQ4,7b-P(VDF₇₂-co-TrFE₂₈)-b-PHS heated at 10 °C min-1_{.(f) Deconvoluted} ;%<7TVSƼPISJ4,7b-P(VDF₇₂-co-TrFE₂₈)-b-PHS recorded at room temperature when cooled from 150 °C.

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64 Σ͕ǁŚĞƌĞĂƐW;s&-co-dƌ&ͿĨƵƌƚŚĞƌĂǁĂǇĨƌŽŵƚŚĞŝŶƚĞƌĨĂĐĞƐŚŽǁĞĚƐŝŵŝůĂƌďĞŚĂǀŝŽƌ ĐŽŵƉĂƌĞĚƚŽƚŚĞďƵůŬŵĂƚĞƌŝĂů͘ǇƵƐĞŽĨƚŚĞƐĂŵĞƌĂƟŽŶĂůĞ͕ƐƵƌĨĂĐĞĞīĞĐƚƐƌĞƐƵůƚĞĚŝŶ ĂŶĞĂƌƌŽŽŵƚĞŵƉĞƌĂƚƵƌĞƵƌŝĞƚƌĂŶƐŝƟŽŶŝŶƵůƚƌĂƚŚŝŶĮůŵƐŽĨƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐĐŽƉŽůǇŵĞƌ obtained viaĂ>ĂŶŐŵƵŝƌͲůŽĚŐĞƩŵĞƚŚŽĚ͕ǁŚĞƌĞĂƐƚŚĞƉŚĂƐĞƚƌĂŶƐŝƟŽŶŽĨƚŚĞŝŶƚĞƌŝŽƌ ŽĨƚŚĞĮůŵŝƐƌĞĚƵĐĞĚǁŝƚŚϭϬΣ͘ϯϳ_{dŚĞĂďƐĞŶĐĞŽĨƚǁŽƵƌŝĞƚƌĂŶƐŝƟŽŶƐŝŶƚŚĞďůŽĐŬ} ĐŽƉŽůǇŵĞƌƐŝƐĂƌĞƐƵůƚŽĨƐƚƌŽŶŐĞƌƚŚƌĞĞĚŝŵĞŶƐŝŽŶĂůĐŽŶĮŶĞŵĞŶƚ͘ dŽƌĂƟŽŶĂůŝǌĞƚŚĞĐŚĂŶŐĞŽĨƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞƵƉŽŶƚŚƌĞĞͲĚŝŵĞŶƐŝŽŶĂů ĐŽŶĮŶĞŵĞŶƚ͕ ǁĞ ƐŚŽƵůĚ ŚŝŐŚůŝŐŚƚ ƚŚĞ ĚŝīĞƌĞŶĐĞƐ ďĞƚǁĞĞŶ ŶĞĂƚ W;s&ͲcoͲdƌ&Ϳ ĂŶĚ ƚŚĞĚŝƐƟŶĐƚďůŽĐŬĐŽƉŽůǇŵĞƌƐ͕ŝŶĐůƵĚŝŶŐĐƌǇƐƚĂůƐŝǌĞ͕ĐƌǇƐƚĂůůŝǌĂƟŽŶŵĞĐŚĂŶŝƐŵ͕ĂŶĚ ŝŶƚĞƌĂĐƟŽŶƐǁŝƚŚW;s&ͲcoͲdƌ&ͿĐŚĂŝŶƐ͘ĞĐĂƵƐĞƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶŵĞĐŚĂŶŝƐŵĂŶĚ ƚĞŵƉĞƌĂƚƵƌĞĂƌĞƐŝŵŝůĂƌƌĞŐĂƌĚůĞƐƐŽĨƚŚĞƐƵƌƌŽƵŶĚŝŶŐŵĂƚƌŝǆ͕ǁĞĐĂŶĞǆĐůƵĚĞƚŚĞƐĞ ƉŚĞŶŽŵĞŶĂ ĂƐ ĚƌŝǀĞŶ ĨŽƌĐĞ ĨŽƌ ƚŚĞ ĐŚĂŶŐĞ ŽĨ ƚŚĞ ƵƌŝĞ ƚƌĂŶƐŝƟŽŶ͘ ĚĚŝƟŽŶĂůůǇ͕ ĂƐ ŝŶĚŝĐĂƚĞĚďǇƚŚĞƐŝŵŝůĂƌĞŶƚŚĂůƉǇǀĂůƵĞƐĨŽƌƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶ;dĂďůĞϯ͘ϮͿ͕ƚŚĞĐƌǇƐƚĂůůŝƚĞ ƐŝǌĞ ŽĨ W;s&ͲcoͲdƌ&Ϳ ŝŶ ƚŚĞ ĚŝƐƟŶĐƚ ďůŽĐŬ ĐŽƉŽůǇŵĞƌ ƐǇƐƚĞŵƐ ŝƐ ĐŽŵƉĂƌĂďůĞ͕ ďƵƚ ĐŽŵƉůĞƚĞůǇĚŝīĞƌĞŶƚďĞŚĂǀŝŽƌŝƐŽďƐĞƌǀĞĚĨŽƌƚŚĞĚŝƐƟŶĐƚďůŽĐŬĐŽƉŽůǇŵĞƌƐ͘ĞĐĂƵƐĞ ĨŽƌ ƚŚĞ ĐƌǇƐƚĂůůŝŶĞ ƉŚĂƐĞ ƚƌĂŶƐŝƟŽŶ ŽĨ ƐŵĂůů ƐŝǌĞĚ W;s&ͲcoͲdƌ&Ϳ ĐƌǇƐƚĂůƐ ŶŽ ůĂƌŐĞ ĚŝƐƉůĂĐĞŵĞŶƚŽĨƚŚĞƉŽůǇŵĞƌĐŚĂŝŶƐŝƐƌĞƋƵŝƌĞĚ͕ƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞŝƐ increased.ϯϴ_{,ŽǁĞǀĞƌ͕ƚĂŬŝŶŐŝŶƚŽĂĐĐŽƵŶƚƚŚĞůĂƌŐĞŶƵŵďĞƌŽĨŚǇĚƌŽǆǇůŐƌŽƵƉƐŝŶW,^ĂŶĚ} ƚŚĞƉŽƐƐŝďŝůŝƚǇƚŽĨŽƌŵŚǇĚƌŽŐĞŶͲďŽŶĚŝŶŐŝŶƚĞƌĂĐƟŽŶƐǁŝƚŚW;s&ͲcoͲdƌ&ͿĂƐŝƐŐĞŶĞƌĂůůǇ ĂĐĐĞƉƚĞĚŝŶƚŚĞůŝƚĞƌĂƚƵƌĞ͕ǁĞƌĞůĂƚĞƚŚĞƌĞĚƵĐƟŽŶŽĨƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞ ƚŽŚǇĚƌŽŐĞŶďŽŶĚĨŽƌŵĂƟŽŶďĞƚǁĞĞŶĂŵŽƌƉŚŽƵƐW;s&ͲcoͲdƌ&ͿĐŚĂŝŶƐĂŶĚW,^͘ϯϵʹϰϯ ,ĞƌĞ͕ƚŚĞŚǇĚƌŽŐĞŶďŽŶĚĨŽƌŵĂƟŽŶŝƐĚĞƐĐƌŝďĞĚĂƐŝŶƚĞƌĂĐƟŽŶƐďĞƚǁĞĞŶƚŚĞŇƵŽƌŝŶĞ ĂƚŽŵƐĂŶĚƚŚĞŚǇĚƌŽǆǇůŐƌŽƵƉƐ͘ĞĐĂƵƐĞĚƵƌŝŶŐƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶĐŽŽƉĞƌĂƟǀĞŵŽƟŽŶ ŽĨƚŚĞƉŽůǇŵĞƌĐŚĂŝŶƐƚĂŬĞƐƉůĂĐĞ͕ďƵƚƚŚĞĐŚĂŝŶŵŽďŝůŝƚǇŽĨĂŵŽƌƉŚŽƵƐW;s&ͲcoͲdƌ&Ϳ ŝƐŚĂŵƉĞƌĞĚĚƵĞƚŽŚǇĚƌŽŐĞŶďŽŶĚŝŶƚĞƌĂĐƟŽŶƐ͕ƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶŝƐƌĞĚƵĐĞĚƚŽůŽǁĞƌ

temperatures.ϯϴ_{Future work should provide deeper insights into morphological and}

ĐƌǇƐƚĂůůŝƚĞƐŝǌĞĞīĞĐƚƐ͘

Table 3.2: Enthalpy values for the Curie transition.

Polymer ȴ,_{Đƌ͕ĐŽŽůŝŶŐ}Ă _ȴ, Đƌ͕ŚĞĂƟŶŐ ď W;s&82-co-dƌ&18Ϳ ϴ͘ϯϱ Ͳ W;s&72-co-dƌ&28Ϳ ϴ͘ϳϭͬϰ͘ϱϱ ϭϰ͘ϵ W^ͲbͲW;s&₈₂-co-dƌ&₁₈ͿͲbͲW^ Ͳ Ͳ W^ͲbͲW;s&₇₂-co-dƌ&₂₈ͿͲbͲW^ 1.92 5.98

PtK^ͲbͲW;s&₇₂-co-dƌ&₂₈ͿͲbͲWtBOS ϯ͘Ϯϯ ϰ͘ϴϱ

W,^-b-W;s&₇₂-co-dƌ&₂₈ͿͲbͲW,^ Ϯ͘ϲϰ ϯ͘ϴϵ

a_²,

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65

3 Conclusions

dŚĞĞīĞĐƚŽĨƚŚĞƐƵƌƌŽƵŶĚŝŶŐŵĂƚƌŝǆŽŶƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶǁŚĞŶW;s&-co-dƌ&ͿŝƐ ĐŽŶĮŶĞĚ ŝŶ ƐƉŚĞƌŝĐĂů ŶĂŶŽĚŽŵĂŝŶƐ ŚĂƐ ďĞĞŶ ĞǆĂŵŝŶĞĚ͘ dŚĞƌĞĨŽƌĞ͕ W;s&-co-dƌ&ͿͲ ďĂƐĞĚƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐǁĞƌĞĚĞƐŝŐŶĞĚƚŽŚĂǀĞĂŚĂƌĚĐŽŶĮŶĞŵĞŶƚĞīĞĐƚŽŶƚŚĞ ĐƌǇƐƚĂůůŝǌĂƟŽŶǁŝƚŚƚŚĞƉŽƐƐŝďŝůŝƚǇƚŽƚƵŶĞƚŚĞƉŽůĂƌŝƚǇŽĨƚŚĞĂŵŽƌƉŚŽƵƐďůŽĐŬin situ. hƐŝŶŐĞĂƐŝůǇĂĐĐĞƐƐŝďůĞĞǆƉĞƌŝŵĞŶƚĂůƚĞĐŚŶŝƋƵĞƐ͕ƐƵĐŚĂƐ^ĂŶĚty^͕ƚŚĞĐƌǇƐƚĂůůŝŶĞͲ ƚŽͲĐƌǇƐƚĂůůŝŶĞƉŚĂƐĞƚƌĂŶƐŝƟŽŶƐǁĞƌĞĨŽůůŽǁĞĚƐŚŽǁŝŶŐƚŚĞƉŽǁĞƌŽĨďůŽĐŬĐŽƉŽůǇŵĞƌƐ ĨŽƌ ĨƵŶĚĂŵĞŶƚĂů ƐƚƵĚŝĞƐ͘ tŚĞŶ Ă ŶŽŶƉŽůĂƌ ŵĂƚƌŝǆ ŝƐ ƵƐĞĚ͕ Ă ƐůŝŐŚƚ ŝŶĐƌĞĂƐĞ ŝŶ ƚŚĞ ƵƌŝĞ ƚƌĂŶƐŝƟŽŶ ŝƐ ŽďƐĞƌǀĞĚ ĂƐ Ă ƌĞƐƵůƚ ŽĨ ƚŚĞ ĐƌǇƐƚĂůůŝƚĞ ƐŝǌĞ ƌĞĚƵĐƟŽŶ͘ /Ŷ ĐŽŶƚƌĂƐƚ͕ ĂƐǁŝƚĐŚƚŽĂŵŽƌĞƉŽůĂƌƐƵƌƌŽƵŶĚŝŶŐ͕ƐƚƌŽŶŐůǇĂīĞĐƚĞĚƚŚĞT_cr͘WŽůĂƌŝŶƚĞƌĂĐƟŽŶƐĂƚ ƚŚĞĐƌǇƐƚĂůůŝŶĞͲĂŵŽƌƉŚŽƵƐŝŶƚĞƌĨĂĐĞůĞĂĚƚŽĂƐƚƌŽŶŐƌĞĚƵĐƟŽŶŝŶƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶ ƚĞŵƉĞƌĂƚƵƌĞ͘dŚĞƌĞĨŽƌĞ͕ǁŚĞŶĐŽŶĮŶŝŶŐW;s&-co-dƌ&ͿƚŽĮŶŝƚĞŶĂŶŽĚŝŵĞŶƐŝŽŶƐ͕ĐĂƌĞĨƵů ĐŽŶƐŝĚĞƌĂƟŽŶƐŚĂǀĞƚŽďĞŵĂĚĞƚŽƐĞůĞĐƚƚŚĞƉŽůĂƌŝƚǇŽĨƚŚĞƐƵƌƌŽƵŶĚŝŶŐŵĂƚƌŝǆ͘/Ŷ ĂĚĚŝƟŽŶ͕ƚŽƚƵŶĞƚŚĞT_crĨŽƌƚŚĞĚĞƐŝƌĞĚĂƉƉůŝĐĂƟŽŶ͕ďůŽĐŬĐŽƉŽůǇŵĞƌƐƉƌŽǀĞƚŽďĞĂŶ appealing candidate due to the large variety in polymer blocks available.