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: 31PDF page: 31PDF page: 31PDF page: 31

Chapter 2

2ERSGSRƼRIQIRXMRHYGIH¼TLEWIJSVQEXMSRMR4:(*

dŚĞĞůĞĐƚƌŽĂĐƟǀĞƉƌŽƉĞƌƟĞƐŽĨƉŽůǇ;ǀŝŶǇůŝĚĞŶĞŇƵŽƌŝĚĞͿ;Ws&ͿĂƌĞĂĚŝƌĞĐƚĐŽŶƐĞƋƵĞŶĐĞ ŽĨŝƚƐĐƌǇƐƚĂůůŝŶĞƉŚĂƐĞƐ͘ůƚŚŽƵŐŚƉŽŽƌůǇƵŶĚĞƌƐƚŽŽĚ͕ŶĂŶŽƐƚƌƵĐƚƵƌŝŶŐWs&ŝŶĐŽŶĮŶĞĚ ŐĞŽŵĞƚƌŝĞƐĐĂŶĚƌĂƐƟĐĂůůǇĐŚĂŶŐĞŝƚƐĐƌǇƐƚĂůůŝǌĂƟŽŶďĞŚĂǀŝŽƌ͘dŚĞƌĞĨŽƌĞ͕ǁĞƐǇŶƚŚĞƐŝǌĞĚ ĂǀĂƌŝĞƚǇŽĨWs&ͲďĂƐĞĚƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐƚŽŐĂŝŶĂďĞƩĞƌƵŶĚĞƌƐƚĂŶĚŝŶŐŽĨƚŚĞŵĞůƚ ĐƌǇƐƚĂůůŝǌĂƟŽŶĂŶĚĞǆƉůŽƌĞŚŽǁĐƌǇƐƚĂůůŝǌĂƟŽŶŝƐĂīĞĐƚĞĚďǇƚŚĞŵŽƌƉŚŽůŽŐǇĂŶĚĐŚĞŵŝĐĂů ŶĂƚƵƌĞ ŽĨ ƚŚĞ ĂŵŽƌƉŚŽƵƐ ďůŽĐŬ͘ ŝīĞƌĞŶƟĂů ƐĐĂŶŶŝŶŐ ĐĂůŽƌŝŵĞƚƌǇ͕ ƐŵĂůůͬǁŝĚĞͲĂŶŐůĞ yͲƌĂǇƐĐĂƩĞƌŝŶŐ͕ĂŶĚƚƌĂŶƐŵŝƐƐŝŽŶĞůĞĐƚƌŽŶŵŝĐƌŽƐĐŽƉǇŐĂǀĞĞǆĐĞůůĞŶƚŝŶƐŝŐŚƚƐŝŶƚŚĞ ŵŽƌƉŚŽůŽŐǇĂŶĚƚŚĞĐŽƌƌĞƐƉŽŶĚŝŶŐĐƌǇƐƚĂůůŝŶĞƉŚĂƐĞƐ͘tĞĮŶĚƚŚĂƚĐƌǇƐƚĂůůŝǌĂƟŽŶŽĨ Ws&ŝŶƐŝĚĞƐƉŚĞƌŝĐĂůŶĂŶŽĚŽŵĂŝŶƐŽĐĐƵƌƐviaĂŚŽŵŽŐĞŶĞŽƵƐŶƵĐůĞĂƟŽŶŵĞĐŚĂŶŝƐŵ ůĞĂĚŝŶŐƚŽĂůĂƌŐĞƵŶĚĞƌĐŽŽůŝŶŐĂŶĚƚŚĞĨŽƌŵĂƟŽŶŽĨƚŚĞƚŚĞƌŵŽĚǇŶĂŵŝĐĂůůǇĨĂǀŽƌĂďůĞ ĨĞƌƌŽĞůĞĐƚƌŝĐɴͲƉŚĂƐĞ͘KŶƚŚĞĐŽŶƚƌĂƌǇ͕ǁŚĞŶĐŽŶĮŶĞĚĐƌǇƐƚĂůůŝǌĂƟŽŶŝŶƐŝĚĞĂůĂŵĞůůĂƌ ŵŽƌƉŚŽůŽŐǇŽĐĐƵƌƐŽƌŝŶƚŚĞĐĂƐĞŽĨďƌĞĂŬͲŽƵƚĐƌǇƐƚĂůůŝǌĂƟŽŶ͕ĂŚĞƚĞƌŽŐĞŶĞŽƵƐŶƵĐůĞĂƟŽŶ ƉƌŽĐĞƐƐůĞĂĚƐƚŽƚŚĞĨŽƌŵĂƟŽŶŽĨƚŚĞŶŽŶͲĨĞƌƌŽĞůĞĐƚƌŝĐɲͲƉŚĂƐĞ͘&ƵƌƚŚĞƌŵŽƌĞ͕ĨĂǀŽƌĂďůĞ ŵĞůƚŝŶƚĞƌĂĐƟŽŶƐďĞƚǁĞĞŶďŽƚŚďůŽĐŬƐŝŶĚƵĐĞĐƌǇƐƚĂůůŝǌĂƟŽŶŝŶƚŽƚŚĞƉŽůĂƌɶͲƉŚĂƐĞĂƚ moderate cooling rates.

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32

Introduction

ƐĞǆƉůĂŝŶĞĚŝŶŚĂƉƚĞƌϭ͕ŽďƚĂŝŶŝŶŐŝƐŽůĂƚĞĚƐŵĂůůƉŽůĂƌɴͲĐƌǇƐƚĂůƐŝŶWs&ŝƐďĞŶĞĮĐŝĂů ĨŽƌƌĞĚƵĐŝŶŐĐŽƵƉůŝŶŐŝŶƚĞƌĂĐƟŽŶƐďĞƚǁĞĞŶĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶƐǁŚŝůĞŵĂŝŶƚĂŝŶŝŶŐ ůĂƌŐĞƉŽůĂƌŝǌĂƟŽŶƐŝŶĚŝĞůĞĐƚƌŝĐŵĂƚĞƌŝĂůƐ͘,ŽǁĞǀĞƌ͕ǁŚĞŶWs&ŝƐƉƌŽĐĞƐƐĞĚĨƌŽŵƚŚĞ ŵĞůƚ͕ƚŚĞŶŽŶƉŽůĂƌɲͲƉŚĂƐĞŝƐƉƌĞĚŽŵŝŶĂŶƚƵŶůĞƐƐĐĞƌƚĂŝŶƉƌŽĐĞƐƐŝŶŐĐŽŶĚŝƟŽŶƐĂƌĞ applied (i.e.ƵůƚƌĂĨĂƐƚĐŽŽůŝŶŐ͕ĂĚĚŝƟŽŶŽĨŶƵĐůĞĂƟŽŶĂŐĞŶƚƐ͕ŵĞĐŚĂŶŝĐĂůƐƚƌĞƚĐŚŝŶŐ͕etc.Ϳ͘1 dŚĞƐĞĂĚĚŝƟŽŶĂůƉƌŽĐĞƐƐŝŶŐĐŽŶĚŝƟŽŶƐƐƟůůŐŝǀĞůĂƌŐĞĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶƐ͕ƌĞƐƵůƟŶŐŝŶ ĨĞƌƌŽĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌ͘dŚĞƌĞĨŽƌĞ͕ĂŶŝŶĐƌĞĂƐŝŶŐĂŵŽƵŶƚŽĨƌĞƐĞĂƌĐŚĂƩĞŶƟŽŶŝƐĨŽĐƵƐĞĚ on breaking up these domains viaŶĂŶŽĐŽŶĮŶĞŵĞŶƚĂƉƉƌŽĂĐŚĞƐ͕ǁŚŝůĞƐƟůůƉƌŽĐĞƐƐŝŶŐ Ws&ĨƌŽŵƚŚĞŵĞůƚ͘

DĞůƚĐƌǇƐƚĂůůŝǌĂƟŽŶŽĨƉŽůǇŵĞƌƐŝŶŶĂŶŽĐŽŶĮŶĞĚĚŽŵĂŝŶƐĐĂŶĚƌĂƐƟĐĂůůǇĐŚĂŶŐĞƚŚĞ ĐƌǇƐƚĂůůŝǌĂƟŽŶďĞŚĂǀŝŽƌ͕ĐƌǇƐƚĂůŽƌŝĞŶƚĂƟŽŶ͕ĐƌǇƐƚĂůůŝŶŝƚǇ͕ŝŶĚƵĐĞƉŚĂƐĞƚƌĂŶƐĨŽƌŵĂƟŽŶƐ͕ and polymorphism.2_{&ŽƌĞǆĂŵƉůĞ͕ƚŚĞĐƌǇƐƚĂůŽƌŝĞŶƚĂƟŽŶŽĨWs&ŝƐĐŚĂŶŐĞĚĨƌŽŵŽŶͲ}

ĞĚŐĞɲͲƉŚĂƐĞƚŽŝŶͲƉůĂŶĞɲͲƉŚĂƐĞǁŚĞŶƚŚĞĚŝŵĞŶƐŝŽŶƐŽĨůĂŵŝŶĂƚĞĚWs&ͬƉŽůǇ;ƐƵůĨŽŶĞͿ are reduced from 225 nm to 28 nm.ϯ_{dǁŽĚŝŵĞŶƐŝŽŶĂůŶĂŶŽĐŽŶĮŶĞŵĞŶƚŝƐĂĐŚŝĞǀĞĚ}

ǁŚĞŶWs&ǁĂƐŵĞůƚͲǁĞƩĞĚŝŶƚŽŶĂŶŽƉŽƌĞƐŽĨŽƌĚĞƌĞĚĂŶŽĚŝĐĂůƵŵŝŶƵŵŽǆŝĚĞ͘dŚĞ ƉŽůǇŵĞƌƐƟůůĐƌǇƐƚĂůůŝǌĞƐŝŶƚŚĞŶŽŶͲĨĞƌƌŽĞůĞĐƚƌŝĐɲͲƉŚĂƐĞĂůƚŚŽƵŐŚƚŚĞŐƌŽǁƚŚŽĨƚŚĞ ďͲĂǆŝƐŽĨƚŚĞĐƌǇƐƚĂůŝƐůŝŵŝƚĞĚƚŽďĞƉĂƌĂůůĞůƚŽƚŚĞĐǇůŝŶĚƌŝĐĂůĂǆŝƐ͘ϰ_{ZĞĐĞŶƚůǇ͕WĂŶet. al.} ŚĂǀĞĞŵďĞĚĚĞĚWs&ŶĂŶŽƉĂƌƟĐůĞƐŝŶϭϴϬŶŵƉŽůǇƐƚǇƌĞŶĞ;W^ͿŶĂŶŽƐƉŚĞƌĞƐĨŽůůŽǁĞĚ ďǇŵĞůƚƌĞĐƌǇƐƚĂůůŝǌĂƟŽŶ͘5_{/ŶƚĞƌĞƐƟŶŐůǇ͕ƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐɴͲƉŚĂƐĞŝƐŽďƚĂŝŶĞĚŝŶƐƚĞĂĚ} ŽĨƚŚĞŬŝŶĞƟĐĂůůǇĨĂǀŽƌĂďůĞɲͲƉŚĂƐĞ͘dŚŝƐŝƐĞǆƉůĂŝŶĞĚďǇĂĐŚĂŶŐĞŽĨƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶ ŵĞĐŚĂŶŝƐŵ ĨƌŽŵ ŚĞƚĞƌŽŐĞŶĞŽƵƐ ŶƵĐůĞĂƟŽŶ ŝŶ ǌĞƌŽ͕ ŽŶĞ ĂŶĚ ƚǁŽ ĚŝŵĞŶƐŝŽŶƐ ƚŽ ŚŽŵŽŐĞŶĞŽƵƐŶƵĐůĞĂƟŽŶŝŶƚŚƌĞĞĚŝŵĞŶƐŝŽŶƐ͘ϲ dŚĞĂďŽǀĞŵĞŶƟŽŶĞĚĞǆĂŵƉůĞƐŽĨĐŽŶĮŶĞĚĐƌǇƐƚĂůůŝǌĂƟŽŶŽĨWs&ĂƌĞĂůůĂĐŚŝĞǀĞĚvia ƚŽƉͲĚŽǁŶĂƉƉƌŽĂĐŚĞƐ͘ŽƩŽŵͲƵƉĂƉƉƌŽĂĐŚĞƐ͕ƐƵĐŚĂƐďůŽĐŬĐŽƉŽůǇŵĞƌƐĞůĨͲĂƐƐĞŵďůǇ͕ ƉƌŽǀŝĚĞĂĐŽƐƚͲĞĸĐŝĞŶƚŵĞƚŚŽĚƚŽŵĂŬĞŶĂŶŽƐƚƌƵĐƚƵƌĞĚĨĞƌƌŽĞůĞĐƚƌŝĐƐ͕ƐŝŶĐĞŶŽĞǆƉĞŶƐŝǀĞ ĞƋƵŝƉŵĞŶƚŝƐƌĞƋƵŝƌĞĚ͘7_{hƐŝŶŐƚŚŝƐĂƉƉƌŽĂĐŚ͕ĨĞĂƚƵƌĞƐŝǌĞƐďĞǇŽŶĚƚŚĞůŝŵŝƚĂƟŽŶƐŽĨ} ƚŽƉͲĚŽǁŶ ĂƉƉƌŽĂĐŚĞƐ ĂƌĞ ĞĂƐŝůǇ ĂĐĐĞƐƐŝďůĞ ďǇ ƚƵŶŝŶŐ ƚŚĞ ůĞŶŐƚŚ ƐĐĂůĞ ŽĨ ƚŚĞ ďůŽĐŬ copolymers.8_{/ŶĂĚĚŝƟŽŶ͕ĚŝīĞƌĞŶƚƚǇƉĞƐŽĨĐŽŶĮŶĞŵĞŶƚĂƌĞƌĞĂůŝǌĞĚďǇƐŝŵƉůǇĐŚĂŶŐŝŶŐ} ƚŚĞƌĂƟŽďĞƚǁĞĞŶƚŚĞďůŽĐŬƐ͕ǁŚŝĐŚŵĂŬĞƐďůŽĐŬĐŽƉŽůǇŵĞƌƐĞůĨͲĂƐƐĞŵďůǇĂŶĂƉƉĞĂůŝŶŐ ŵĞƚŚŽĚƚŽƐƚƵĚǇƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶŽĨƐĞŵŝͲĐƌǇƐƚĂůůŝŶĞƉŽůǇŵĞƌƐŝŶƐŝĚĞŶĂŶŽĚŽŵĂŝŶƐ͘9 ƌǇƐƚĂůůŝǌĂƟŽŶĨƌŽŵƚŚĞŵĞůƚǁŝƚŚŝŶƚŚĞƐĞŶĂŶŽĚŽŵĂŝŶƐĐĂŶŐŝǀĞĚŝīĞƌĞŶƚŽƵƚĐŽŵĞƐ͘2 &ŝƌƐƚ͕ďƌĞĂŬŽƵƚĐƌǇƐƚĂůůŝǌĂƟŽŶŽĐĐƵƌƐǁŚĞŶƚŚĞŝŶƚĞƌďůŽĐŬƐĞŐƌĞŐĂƟŽŶƐƚƌĞŶŐƚŚďĞƚǁĞĞŶ ƚŚĞĚŝƐƟŶĐƚďůŽĐŬƐŝƐůŽǁĂŶĚĐƌǇƐƚĂůůŝǌĂƟŽŶĚƌŝǀĞŶƐĞůĨͲĂƐƐĞŵďůǇǁŝůůƚƌĂŶƐĨŽƌŵƚŚĞ ŵĞůƚŵŽƌƉŚŽůŽŐǇƚŽĂůĂŵĞůůĂƌŵŽƌƉŚŽůŽŐǇǁŝƚŚĂůƚĞƌŶĂƟŶŐĐƌǇƐƚĂůůŝŶĞĂŶĚĂŵŽƌƉŚŽƵƐ domains.10_{^ĞĐŽŶĚůǇ͕ĐŽŶĮŶĞĚĐƌǇƐƚĂůůŝǌĂƟŽŶĐĂŶŽĐĐƵƌŝĨƚŚĞŝŶƚĞƌďůŽĐŬƐĞŐƌĞŐĂƟŽŶ} ƐƚƌĞŶŐƚŚŝƐƐƵĸĐŝĞŶƚůǇŚŝŐŚ͘/ŶƚŚŝƐĐĂƐĞ͕ƚŚĞŵĞůƚŵŽƌƉŚŽůŽŐǇǁŝůůďĞƉƌĞƐĞƌǀĞĚĂŌĞƌ ĐƌǇƐƚĂůůŝǌĂƟŽŶŝŶƐŝĚĞƚŚĞŶĂŶŽƐŝǌĞĚĚŽŵĂŝŶƐ͘Ϯ͕ϲ

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2

ZĞĐĞŶƚůǇ͕ŝƚŝƐƐŚŽǁŶƚŚĂƚĂǁŝĚĞǀĂƌŝĞƚǇŽĨWs&ͲďĂƐĞĚƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐĐĂŶďĞ prepared viaĂĐŽƉƉĞƌ;/ͿʹĐĂƚĂůǇǌĞĚĂǌŝĚĞͲĂůŬǇŶĞĐǇĐůŽĂĚĚŝƟŽŶ;ƵͿƌĞĂĐƟŽŶ͘11,12 /ŶŽƌĚĞƌƚŽƐƚƵĚǇƚŚĞĞīĞĐƚŽĨƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶŵŽĚĞŽŶƚŚĞĐƌǇƐƚĂůůŝŶĞƉŚĂƐĞŝŶWs& ďůŽĐŬĐŽƉŽůǇŵĞƌƐ͕ǀĂƌŝŽƵƐWs&ͲďĂƐĞĚƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐĂƌĞƉƌĞƉĂƌĞĚǁŝƚŚĚŝīĞƌĞŶƚ ǁĞŝŐŚƚƌĂƟŽƐĐŽŵƉĂƌĞĚƚŽƚŚĞWs&ďůŽĐŬ͘

Materials and Methods

Experimental Materials. ϮͲsŝŶǇůƉǇƌŝĚŝŶĞ ;^ŝŐŵĂͲůĚƌŝĐŚ͕ ϵϳйͿ ǁĂƐ ĚƌŝĞĚ ŽǀĞƌŶŝŐŚƚ ŽǀĞƌ Ă,₂ and ĚŝƐƟůůĞĚ ƵŶĚĞƌ ƌĞĚƵĐĞĚ ƉƌĞƐƐƵƌĞ͘ Ϯ͕Ϯ഻ͲǌŽďŝƐ;ϮͲŵĞƚŚǇůƉƌŽƉŝŽŶŝƚƌŝůĞͿ ;/E͕ &ůƵŬĂ͕ ϵϴнйͿǁĂƐƌĞĐƌǇƐƚĂůůŝǌĞĚƚǁŝĐĞĨƌŽŵŵĞƚŚĂŶŽů͘ŽƉƉĞƌ;/ͿďƌŽŵŝĚĞ;Ƶƌ͕^ŝŐŵĂͲůĚƌŝĐŚ͕ ϵϴйͿǁĂƐƐƟƌƌĞĚĨŽƌϭŚŽƵƌŝŶŐůĂĐŝĂůĂĐĞƟĐĂĐŝĚĂŶĚƚŚĞŶĮůƚĞƌĞĚĂŶĚǁĂƐŚĞĚǁŝƚŚ ĂĐĞƟĐ ĂĐŝĚ ĂŶĚ ĞƚŚĂŶŽů ďĞĨŽƌĞ ĚƌǇŝŶŐ ƵŶĚĞƌ Ă ǀĂĐƵƵŵ͘ ϰͲ;;ƚƌŝŵĞƚŚǇůƐŝůǇůͿĞƚŚǇŶǇůͿ ďĞŶǌŽǇů ƉĞƌŽǆŝĚĞ͕ ϮͲ;ĚŽĚĞĐǇůƚŚŝŽĐĂƌďŽŶŽƚŚŝŽǇůƚŚŝŽͿͲϮͲŵĞƚŚǇůƉƌŽƉŝŽŶŝĐ ĂĐŝĚ ϯͲĂǌŝĚŽͲ ϭͲƉƌŽƉĂŶŽů ĞƐƚĞƌ ;Z&d ĂŐĞŶƚͿ͕ ĂŶĚ ƚŚĞ WtͲbͲWs&ͲbͲWt ďůŽĐŬ ĐŽƉŽůǇŵĞƌ ǁĞƌĞ prepared according to literature procedures.ϭϮʹϭϰ_{sŝŶǇůŝĚĞŶĞ ŇƵŽƌŝĚĞ ;s&͕ ^ǇŶƋƵĞƐƚ}

>ĂďƐ͕ ϵϴйͿ͕ ϭ͕ϭ͕ϰ͕ϳ͕ϳͲƉĞŶƚĂŵĞƚŚǇůĚŝĞƚŚǇůĞŶĞƚƌŝĂŵŝŶĞ ;WDd͕ ĐƌŽƐ͕ ϵϵнйͿ͕ N,NͲ ĚŝŵĞƚŚǇůĨŽƌŵĂŵŝĚĞ;D&͕ĐƌŽƐKƌŐĂŶŝĐƐ͕ĂŶŚǇĚƌŽƵƐ͕ϵϵ͘ϴйͿ͕ǁĞƌĞƵƐĞĚĂƐƌĞĐĞŝǀĞĚ͘ ůůŽƚŚĞƌƐŽůǀĞŶƚƐǁĞƌĞĂŶĂůǇƟĐĂůŐƌĂĚĞ͘ ^ǇŶƚŚĞƐŝƐŽĨ;dD^ͲĂůŬǇŶĞͿͲƚĞƌŵŝŶĂƚĞĚWs&͘ƐŽůƵƟŽŶŽĨϰͲ;;ƚƌŝŵĞƚŚǇůƐŝůǇůͿĞƚŚǇŶǇůͿ ďĞŶǌŽǇůƉĞƌŽǆŝĚĞ;ϳϱϬŵŐ͕ϭ͘ϳϮŵŵŽů͕WKͿŝŶϯϬϬŵ>ŽĨĂŶŚǇĚƌŽƵƐĂĐĞƚŽŶŝƚƌŝůĞǁĂƐ ŝŶƚƌŽĚƵĐĞĚŝŶĂϲϬϬŵ>WĂƌƌ;ŵŽĚĞůϰϱϲϴͿŚŝŐŚƉƌĞƐƐƵƌĞƌĞĂĐƚŽƌĂŶĚƉƵƌŐĞĚǁŝƚŚE₂for 0.5 ŚŽƵƌƐ͘^ƵďƐĞƋƵĞŶƚůǇ͕ϮϬďĂƌŽĨs&ǁĂƐŝŶƚƌŽĚƵĐĞĚŝŶƚŽƚŚĞƌĞĂĐƚŽƌĂƚƌŽŽŵƚĞŵƉĞƌĂƚƵƌĞ͘ The temperature inside the reactor was increased to 90 o_{ĂŶĚƚŚĞƌĞĂĐƟŽŶŵŝǆƚƵƌĞ}

ǁĂƐƐƟƌƌĞĚĂƚϱϬϬƌƉŵĨŽƌĂĚĚŝƟŽŶĂůϰŚŽƵƌƐ͘dŚĞƌĞĂĐƚŽƌǁĂƐĐŽŽůĞĚĚŽǁŶďǇǁĂƚĞƌƚŽ room temperature and depressurized to remove unreacted monomer. The solvent was removed in vacuo ĂŶĚƚŚĞƌĞŵĂŝŶŝŶŐƐŽůŝĚǁĂƐǁĂƐŚĞĚŵƵůƟƉůĞƟŵĞƐǁŝƚŚĐŚůŽƌŽĨŽƌŵƚŽ ƌĞŵŽǀĞŝŶŝƟĂƚŽƌƌĞƐŝĚƵĞƐ͘dŚĞƉŽůǇŵĞƌǁĂƐĮŶĂůůǇĚƌŝĞĚin vacuo at room temperature to ŽďƚĂŝŶĂůŝŐŚƚͲǇĞůůŽǁƉƌŽĚƵĐƚ͘1_{,EDZ;ϰϬϬD,ǌ͕D^KͲd}

6Ϳ͗ɷсϬ͘ϮϮ;Ɛ͕Ͳ^ŝ;H3ͿϯͿ͕Ϯ͘ϮϬͲ

Ϯ͘ϰϬ;ŵ͕Ͳ&₂ͲH₂ͲH₂Ͳ&₂Ͳ͕s&Ͳs&ƚĂŝůͲƚŽͲƚĂŝůͿ͕Ϯ͘ϳϬͲϯ͘ϭϬ;ŵ͕Ͳ&₂ͲH₂Ͳ&₂Ͳ͕s&Ͳs& ŚĞĂĚͲƚŽͲƚĂŝůͿ͕ϰ͘ϲϲ;ƚ͕ͲKKͲH₂CF₂ͲͿ͕ϲ͘ϯϰ;ƚ͕Ͳ&₂CHͿ͕ϳ͘ϲϯ;Ě͕ƌHͿ͕ϳ͘ϵϵ;Ě͕ƌHͿ͘

^ǇŶƚŚĞƐŝƐŽĨĂůŬǇŶĞͲƚĞƌŵŝŶĂƚĞĚWs&͘h;ϴϳ͘Ϯђ>͕Ϭ͘ϱϴŵŵŽůͿǁĂƐĂĚĚĞĚƚŽĂƐŽůƵƟŽŶ

ŽĨ;dD^ͲĂůŬǇŶĞͿͲƚĞƌŵŝŶĂƚĞĚWs&;ϯ͘ϱŐ͕Ϭ͘ϮϵŵŵŽůͿŝŶϯϱϬŵ>ŽĨĂŶĂĐĞƚŽŶŝƚƌŝůĞ͗ǁĂƚĞƌ ;ϭϵ͗ϭͿŵŝǆƚƵƌĞ͘dŚĞƌĞĂĐƟŽŶŵŝǆƚƵƌĞǁĂƐƐƟƌƌĞĚĨŽƌϮŚŽƵƌƐĂƚϲϬo_{C. The solvent was}

removed in vacuo ĂŶĚƚŚĞƉŽůǇŵĞƌǁĂƐƉƌĞĐŝƉŝƚĂƚĞĚĨƌŽŵD&ŝŶĂŵŝǆƚƵƌĞDĞK,͗ǁĂƚĞƌ ;ϭ͗ϭͿ͘ŌĞƌĮůƚƌĂƟŽŶƚŚĞƉŽůǇŵĞƌǁĂƐƚŚŽƌŽƵŐŚůǇǁĂƐŚĞĚǁŝƚŚŵĞƚŚĂŶŽůĂŶĚĐŚůŽƌŽĨŽƌŵ

(5)

34

ĂŶĚĮŶĂůůǇĚƌŝĞĚin vacuoĂƚƌŽŽŵƚĞŵƉĞƌĂƚƵƌĞƚŽǇŝĞůĚĂůŝŐŚƚͲďƌŽǁŶƉŽůǇŵĞƌ͘1_,EDZ

;ϰϬϬD,ǌ͕D^KͲd₆Ϳ͗ɷсϮ͘ϮϬͲϮ͘ϰϬ;ŵ͕Ͳ&₂ͲH₂ͲH₂Ͳ&₂Ͳs&Ͳs&ƚĂŝůͲƚŽͲƚĂŝůͿ͕Ϯ͘ϳϬͲϯ͘ϭϬ ;ŵ͕Ͳ&₂ͲH₂Ͳ&Ͳ͕s&Ͳs&ŚĞĂĚͲƚŽͲƚĂŝůͿ͕ϰ͘ϱϭ;Ɛ͕Ͳ,ĂůŬǇŶĞͿ͕ϰ͘ϲϲ;ƚ͕ͲKKͲH₂CF₂ͲͿ͕ϲ͘ϯϰ ;ƚ͕Ͳ&₂CHͿ͕ϳ͘ϲϲ;Ě͕ƌHͿ͕ϴ͘Ϭϭ;Ě͕ƌHͿ͘

Synthesis of azide-terminated P2VP.ƚǇƉŝĐĂůƉƌŽĐĞĚƵƌĞĨŽƌZ&dƉŽůǇŵĞƌŝǌĂƟŽŶ

ŽĨϮͲǀŝŶǇůƉǇƌŝĚŝŶĞŝƐĂƐĨŽůůŽǁƐ͘ϮͲsŝŶǇůƉǇƌŝĚŝŶĞŵŽŶŽŵĞƌ;ϱŵ>͕ϴϰŵŵŽůͿ͕Z&dĂŐĞŶƚ ĂŶĚ/EŝŶĂƌĂƟŽϯϳϬ͗ϭ͗Ϭ͘ϭǁĞƌĞĚŝƐƐŽůǀĞĚŝŶϰ͘ϱŵ>ŽĨĂŶŚǇĚƌŽƵƐD&ŝŶĂƉƌĞͲĚƌŝĞĚ ^ĐŚůĞŶŬƚƵďĞ͘dŚĞŵŝǆƚƵƌĞǁĂƐƐƵďũĞĐƚĞĚƚŽĂƚůĞĂƐƚƚŚƌĞĞĨƌĞĞǌĞͲƉƵŵƉͲƚŚĂǁĐǇĐůĞƐ and placed in an oil bath preheated to 70 o_{͘ŌĞƌƌĞĂĐƟŶŐĨŽƌϲŚŽƵƌƐ͕ƚŚĞƌĞĂĐƟŽŶ}

ǁĂƐƚĞƌŵŝŶĂƚĞĚďǇĐŽŽůŝŶŐŝŶůŝƋƵŝĚE₂͘^ƵďƐĞƋƵĞŶƚůǇ͕D&ǁĂƐƌĞŵŽǀĞĚin vacuo and ƚŚĞƉŽůǇŵĞƌǁĂƐĚŝƐƐŽůǀĞĚŝŶd,&ĂŶĚƐƵďƐĞƋƵĞŶƚůǇƉƌĞĐŝƉŝƚĂƚĞĚŝŶĂůĂƌŐĞĞǆĐĞƐƐŽĨ ŶͲŚĞǆĂŶĞ͘dŚĞƉŽůǇŵĞƌǁĂƐĐŽůůĞĐƚĞĚviaĮůƚƌĂƟŽŶĂŶĚƌĞƉƌĞĐŝƉŝƚĂƚĞĚƚǁŽŵŽƌĞƟŵĞƐ ĨƌŽŵd,&ŝŶnͲŚĞǆĂŶĞĂŶĚĮŶĂůůǇĚƌŝĞĚŽǀĞƌŶŝŐŚƚin vacuo at room temperature to remove ƌĞƐŝĚƵĂůǀŽůĂƟůĞƐ͘1_{,EDZ;ϰϬϬD,ǌ͕D^KͲd} 6Ϳ͗ɷсϬ͘ϲϱͲϬ͘ϵϱ;ŵ͕ͲĂůŬǇůͿ͕ϭ͘ϰͲϮ͘ϰ;ŵ͕ ͲH₂CH;ƌͿͲͿ͕ϯ͘ϲϯ;ŵ͕;ͲKKͲH₂ͲͿ͕ϰ͘ϴϯ;ŵ͕Ͳ^;с^Ϳ^ͲH;ƌͿͲͿ͕ϲ͘ϭϬͲϲ͘ϳϱ;ŵ͕ƌHͿ͕ϲ͘ϴϬͲ ϳ͘ϮϬ;ŵ͕ƌHͿ͕ϳ͘ϮϮͲϳ͘ϲϱ;ŵ͕ƌHͿ͕ϴ͘ϭϬͲϴ͘ϱϱ;ŵ͕ƌHͿ͘ 'ĞŶĞƌĂůƉƌŽĐĞĚƵƌĞĨŽƌƚŚĞƉƌĞƉĂƌĂƟŽŶŽĨWs&ͲďĂƐĞĚďůŽĐŬĐŽƉŽůǇŵĞƌƐ͘ŐĞŶĞƌĂů ƌŽƵƚĞĨŽƌƚŚĞƵͲĐĂƚĂůǇǌĞĚĂůŬǇŶĞĂǌŝĚĞĐǇĐůŽĂĚĚŝƟŽŶ;ƵͿƵƐĞĚĨŽƌƚŚĞƉƌĞƉĂƌĂƟŽŶ ŽĨďůŽĐŬĐŽƉŽůǇŵĞƌƐŝƐĚĞƐĐƌŝďĞĚďĞůŽǁ͘dŚĞĂůŬǇŶĞͲƚĞƌŵŝŶĂƚĞĚWs&;ϯϬϬŵŐ͕Ϭ͘ϬϮϱ ŵŵŽůͿ͕ WϮsW ĂŶĚ Ƶƌ ǁĞƌĞ ĂĚĚĞĚ ŝŶƚŽ Ă ƉƌĞͲĚƌŝĞĚ ^ĐŚůĞŶŬ ƚƵďĞ ŝŶ Ă ŵŽůĂƌ ƌĂƟŽ ΀Ws&΁͗΀WϮsW΁͗΀Ƶƌ΁сϭ͗Ϯ͘ϲ͗ϰ͘ŌĞƌƉĞƌĨŽƌŵŝŶŐĚĞŐĂƐƐŝŶŐƉƌŽĐĞĚƵƌĞƐ;ƚŚƌĞĞƌĞƉĞƟƟǀĞ ĐǇĐůĞƐŽĨĞǀĂĐƵĂƟŶŐĂŶĚďĂĐŬĮůůŝŶŐǁŝƚŚE₂Ϳ͕ϰŵ>ŽĨĂŶŚǇĚƌŽƵƐD&ǁĂƐĂĚĚĞĚ͕ĨŽůůŽǁĞĚ ďǇWDd;ϯϬђů͕Ϭ͘ϭϰŵŵŽůͿ͘dŚĞƌĞĂĐƟŽŶǁĂƐĂůůŽǁĞĚƚŽƐƟƌĨŽƌϰĚĂǇƐĂƚϲϬo_{C and} ĂŌĞƌǁĂƌĚƐƚĞƌŵŝŶĂƚĞĚďǇĞǆƉŽƐŝŶŐƚŽƚŚĞĂŝƌ͘dŚĞƌĞĂĐƟŽŶŵŝǆƚƵƌĞǁĂƐĮůƚĞƌĞĚƚŚƌŽƵŐŚ ĂƐŚŽƌƚŶĞƵƚƌĂůĂůƵŵŝŶĂĐŽůƵŵŶŝŶŽƌĚĞƌƚŽƌĞŵŽǀĞĐŽƉƉĞƌĐĂƚĂůǇƐƚǁŝƚŚd,&ĂƐĞůƵĞŶƚ͘ The solvents were removed in vacuoĂŶĚƚŚĞŵŝǆƚƵƌĞǁĂƐĚŝƐƐŽůǀĞĚŝŶd,&ĂŐĂŝŶ͘dŚĞ ƉŽůǇŵĞƌƐǁĞƌĞƉƌĞĐŝƉŝƚĂƚĞĚŝŶŶͲŚĞǆĂŶĞ͘ŌĞƌĮůƚƌĂƟŽŶƚŚĞƉƌŽĚƵĐƚǁĂƐĐŽůůĞĐƚĞĚvia ĮůƚƌĂƟŽŶĂŶĚƚŚĞƵŶƌĞĂĐƚĞĚŚŽŵŽƉŽůǇŵĞƌǁĂƐǁĂƐŚĞĚĂǁĂǇǁŝƚŚŵĞƚŚĂŶŽůƵƐŝŶŐĂ ĨĞǁĐŽŶƐĞĐƵƟǀĞĐĞŶƚƌŝĨƵŐĂƟŽŶƐƚĞƉƐ;ϱŵŝŶ͕ϰϱϬϬƌƉŵͿ͘dŚĞƉŽůǇŵĞƌǁĂƐƉƌĞĐŝƉŝƚĂƚĞĚ ĨƌŽŵd,&ŝŶŶͲŚĞǆĂŶĞƐŽŶĐĞŵŽƌĞƚŽŽďƚĂŝŶĂůŝŐŚƚďƌŽǁŶƉŽǁĚĞƌ͘1_{,EDZ;ϰϬϬD,ǌ͕}

D^KͲd₆Ϳ͗ɷсϬ͘ϲϱͲϬ͘ϵϱ;ŵ͕ͲĂůŬǇůͿ͕ϭ͘ϰϬͲϮ͘ϮϬ;ŵ͕ͲH₂CH;ƌͿͲͿ͕Ϯ͘ϮϬͲϮ͘ϰϬ;ŵ͕Ͳ&₂ͲH₂Ͳ CH₂Ͳ&₂Ͳ͕s&Ͳs&ƚĂŝůͲƚŽͲƚĂŝůͿ͕Ϯ͘ϳϬͲϯ͘ϭϬ;ŵ͕Ͳ&₂ͲH₂Ͳ&Ͳ͕s&Ͳs&ŚĞĂĚͲƚŽͲƚĂŝůͿ͕ϰ͘ϯϴ ;ŵ͕ͲEͲH₂Ͳ,₂ͲͿ͕ϰ͘ϲϲ;ƚ͕ͲKKͲH₂CF₂ͲͿ͕ϲ͘ϭϬͲϲ͘ϳϱ;ŵ͕ƌHͿ͕ϲ͘ϴϬͲϳ͘ϮϬ;ŵ͕ƌHͿ͕ϳ͘ϮϮͲϳ͘ϲϱ ;ŵ͕ƌHͿ͕ϴ͘Ϭϯ;Ě͕ƌH WKͿ͕ϴ͘Ϭϴ;Ě͕ƌH WKͿ͕ϴ͘ϭϬͲϴ͘ϱϱ;ŵ͕ƌHͿ͕ϴ͘ϳϰ;Ɛ͕ͲHͲƚƌŝĂǌŽůĞͿ͘ ůŽĐŬĐŽƉŽůǇŵĞƌĮůŵƉƌĞƉĂƌĂƟŽŶ͘ůůƚŚĞďůŽĐŬĐŽƉŽůǇŵĞƌƐ͕WϮsWͲbͲWs&ͲbͲWϮsWĂŶĚ PtͲbͲWs&ͲbͲWt͕ǁĞƌĞĚŝƐƐŽůǀĞĚŝŶϰŵ>D&;ϭϬŵŐͬŵ>Ϳ͘dŚĞƐŽůƵƟŽŶǁĂƐĮůƚĞƌĞĚ ŽǀĞƌĂϬ͘ϰϱђŵWd&ĮůƚĞƌĂŶĚƐƵďƐĞƋƵĞŶƚůǇƉŽƵƌĞĚŝŶĂŐůĂƐƐWĞƚƌŝĚŝƐŚ͘dŚĞƐŽůǀĞŶƚ ǁĂƐĂůůŽǁĞĚƚŽĞǀĂƉŽƌĂƚĞĂƚϰϱΣŽǀĞƌƚǁŽĚĂǇƐ͘dŽƐƚƵĚǇƚŚĞƐĞůĨͲĂƐƐĞŵďůǇĨƌŽŵƚŚĞ ŵĞůƚĂŶĚƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶďĞŚĂǀŝŽƌ͕ƚŚĞďůŽĐŬĐŽƉŽůǇŵĞƌĮůŵƐǁĞƌĞŚĞĂƚĞĚƚŽϭϵϬΣ

(6)

35

2

ĂƚϰϬΣͬŵŝŶ͕ƚŚĞƌŵĂůůǇĂŶŶĞĂůĞĚĨŽƌϯϬŵŝŶĂƚϭϵϬΣ͕ĂŶĚƐƵďƐĞƋƵĞŶƚůǇĐŽŽůĞĚƚŽƌŽŽŵ ƚĞŵƉĞƌĂƚƵƌĞĂƚϭϬΣͬŵŝŶĚƵƌŝŶŐĂůůŵĞĂƐƵƌĞŵĞŶƚƐƵŶůĞƐƐŽƚŚĞƌǁŝƐĞŶŽƟĐĞĚ͘

Characterization

EƵĐůĞĂƌDĂŐŶĞƟĐZĞƐŽŶĂŶĐĞ;1_{H NMR) spectra ǁĞƌĞƌĞĐŽƌĚĞĚŽŶϰϬϬD,ǌsĂƌŝĂŶ;syZͿ}

spectrometer at room temperature.

'ĞůWĞƌŵĞĂƟŽŶŚƌŽŵĂƚŽŐƌĂƉŚǇ;'WͿŽĨWs&ĂŶĚƚŚĞWϮsWͲbͲWs&ͲbͲWϮsWďůŽĐŬ ĐŽƉŽůǇŵĞƌƐǁĞƌĞƉĞƌĨŽƌŵĞĚŝŶD&;ĐŽŶƚĂŝŶŝŶŐϬ͘ϬϭD>ŝƌͿƵƐŝŶŐsŝƐĐŽƚĞŬ'WŵĂǆ ĞƋƵŝƉƉĞĚ ǁŝƚŚ ŵŽĚĞů ϯϬϮ d ĚĞƚĞĐƚŽƌƐ ĂŶĚ ƚǁŽ ĐŽůƵŵŶƐ ;ŐŝůĞŶƚ dĞĐŚŶŽůŽŐŝĞƐͲ WŽůĂƌ'ĞůͲ>ĂŶĚD͕ϴђŵϯϬĐŵͿĂƚĂŇŽǁƌĂƚĞŽĨϭ͘Ϭŵ>ͼŵŝŶͲϭ_{ĂŶĚϱϬΣ͘EĂƌƌŽǁĚŝƐƉĞƌƐŝƚǇ} WDD ƐƚĂŶĚĂƌĚƐ ;WŽůǇŵĞƌ >ĂďŽƌĂƚŽƌŝĞƐͿ ǁĞƌĞ ƵƐĞĚ ĨŽƌ ĐŽŶƐƚƌƵĐƟŶŐ ĂŶ ƵŶŝǀĞƌƐĂů ĐĂůŝďƌĂƟŽŶĐƵƌǀĞĂƉƉůŝĞĚĨŽƌĚĞƚĞƌŵŝŶŝŶŐŵŽůĞĐƵůĂƌǁĞŝŐŚƚƐ͘ƚƌŝƉůĞĚĞƚĞĐƟŽŶŵĞƚŚŽĚ ǁŝƚŚd,&͕ƐƚĂďŝůŝǌĞĚǁŝƚŚ,d͕ĂƐĞůƵĞŶƚĂŶĚĂŇŽǁƌĂƚĞŽĨϭ͘Ϭŵ>ŵŝŶͲϭ_{ĂƚϯϱΣǁĂƐ} ƵƐĞĚƚŽĚĞƚĞƌŵŝŶĞƚŚĞŵŽůĞĐƵůĂƌǁĞŝŐŚƚĂŶĚƚŚĞƉŽůǇĚŝƐƉĞƌƐŝƚǇŝŶĚĞǆ;W/ͿŽĨWϮsW͘dŚĞ ƐĞƉĂƌĂƟŽŶǁĂƐĐĂƌƌŝĞĚŽƵƚďǇƵƟůŝǌŝŶŐƚǁŽW>ŐĞůϱђŵD/yͲ͕ϯϬϬŵŵĐŽůƵŵŶƐ;ŐŝůĞŶƚ dĞĐŚŶŽůŽŐŝĞƐͿĐĂůŝďƌĂƚĞĚǁŝƚŚŶĂƌƌŽǁDtƉŽůǇƐƚǇƌĞŶĞƐƚĂŶĚĂƌĚƐ;ŐŝůĞŶƚdĞĐŚŶŽůŽŐŝĞƐ ĂŶĚWŽůǇŵĞƌ>ĂďŽƌĂƚŽƌŝĞƐͿ͘ƉƌĞĚĞƚĞƌŵŝŶĞĚƌĞĨƌĂĐƟǀĞŝŶĚĞǆŝŶĐƌĞŵĞŶƚ;ĚŶͬĚĐͿŽĨϬ͘ϭϲϳ ŵ>ͼŐͲϭ_{ǁĂƐƵƐĞĚƚŽĐĂůĐƵůĂƚĞƚŚĞŵŽůĞĐƵůĂƌǁĞŝŐŚƚĐŚĂƌĂĐƚĞƌŝƐƟĐƐĨŽƌWϮsW͘}

Fourier transform infrared spectroscopy (FTIR)͘dŚĞ&d/ZƐƉĞĐƚƌĂŽĨƚŚĞƌŵĂůůǇĂŶŶĞĂůĞĚ

ďůŽĐŬĐŽƉŽůǇŵĞƌƐĂŵƉůĞƐǁĞƌĞƌĞĐŽƌĚĞĚŽŶĂƌƵŬĞƌsĞƌƚĞǆϳϬƐƉĞĐƚƌŽƉŚŽƚŽŵĞƚĞƌƵƐŝŶŐ ϯϮƐĐĂŶƐĂƚĂŶŽŵŝŶĂůƌĞƐŽůƵƟŽŶŽĨϰĐŵͲϭ_{ƵƐŝŶŐĂĚŝĂŵŽŶĚƐŝŶŐůĞƌĞŇĞĐƟŽŶĂƩĞŶƵĂƚĞĚ} ƚŽƚĂůƌĞŇĞĐƚĂŶĐĞ;dZͿ͘ ŝīĞƌĞŶƟĂů ^ĐĂŶŶŝŶŐ ĂůŽƌŝŵĞƚƌǇ ;^Ϳ ƚŚĞƌŵŽŐƌĂŵƐ ǁĞƌĞ ƌĞĐŽƌĚĞĚ ŽŶ Ă d /ŶƐƚƌƵŵĞŶƚƐ^YϭϬϬϬďǇŚĞĂƟŶŐĂƐĂŵƉůĞƚŽϭϵϬΣ͘^ƵďƐĞƋƵĞŶƚůǇ͕ƚŚĞƐĂŵƉůĞǁĂƐ ĂŶŶĞĂůĞĚĂƚϭϵϬΣĨŽƌϯϬŵŝŶďĞĨŽƌĞĐŽŽůŝŶŐƚŽƌŽŽŵƚĞŵƉĞƌĂƚƵƌĞĂƚϭϬΣͼŵŝŶͲϭ_. /Ŷ ƐŝƚƵ yͲƌĂǇ ^ĐĂƩĞƌŝŶŐ͘ dŝŵĞͲƚĞŵƉĞƌĂƚƵƌĞ ƌĞƐŽůǀĞĚ ƐŵĂůůͲĂŶŐůĞ yͲƌĂǇ ƐĐĂƩĞƌŝŶŐ ĂŶĚǁŝĚĞͲĂŶŐůĞyͲƌĂǇƐĐĂƩĞƌŝŶŐ;^y^ĂŶĚty^ͿŵĞĂƐƵƌĞŵĞŶƚƐǁĞƌĞƉĞƌĨŽƌŵĞĚĂƚ ďĞĂŵůŝŶĞDϮϲĂƚƚŚĞƵƌŽƉĞĂŶ^ǇŶĐŚƌŽƚƌŽŶZĂĚŝĂƟŽŶ&ĂĐŝůŝƚǇ;^Z&ͿŝŶ'ƌĞŶŽďůĞǁŝƚŚ ĂǁĂǀĞůĞŶŐƚŚʄсϬ͘ϵϳ͘ϭϱ͕ϭϲ_{ĐƋƵŝƐŝƟŽŶŽĨƐŝŵƵůƚĂŶĞŽƵƐůǇ^y^ĂŶĚty^ƉĂƩĞƌŶƐǁĂƐ} ƉĞƌĨŽƌŵĞĚŽǀĞƌƟŵĞŝŶƚĞƌǀĂůƐŽĨϯϬƐĞĐŽŶĚƐƵƐŝŶŐĂWŝůĂƚƵƐϭDĚĞƚĞĐƚŽƌ;ϵϴϭпϭϬϰϯ ƉŝǆĞůƐŽĨϭϳϮʅŵпϭϳϮʅŵƉůĂĐĞĚĂƚĂĚŝƐƚĂŶĐĞŽĨϯ͘ϱŵͿĂŶĚĂWŝůĂƚƵƐϯϬϬ<ĚĞƚĞĐƚŽƌ ;ϭϰϳϮпϭϵϱƉŝǆĞůƐŽĨϭϳϮʅŵпϭϳϮʅŵƉůĂĐĞĚĂƚĂĚŝƐƚĂŶĐĞŽĨϬ͘ϮϴŵͿ͕ƌĞƐƉĞĐƟǀĞůǇ͘ dŚĞƐĐĂƩĞƌŝŶŐǀĞĐƚŽƌƋŝƐĚĞĮŶĞĚĂƐƋсϰʋͬʄ;ƐŝŶɽ) with 2ɽďĞŝŶŐƚŚĞƐĐĂƩĞƌŝŶŐĂŶŐůĞ͘ dĞŵƉĞƌĂƚƵƌĞͲƌĞƐŽůǀĞĚŵĞĂƐƵƌĞŵĞŶƚƐǁĞƌĞƉĞƌĨŽƌŵĞĚƵƐŝŶŐĂ>ŝŶŬĂŵ^ϲϬϬĐĞůů͘

Transmission Electron Microscopy (TEM) was performed on a Philips CM12

ƚƌĂŶƐŵŝƐƐŝŽŶ ĞůĞĐƚƌŽŶ ŵŝĐƌŽƐĐŽƉĞ ŽƉĞƌĂƟŶŐ Ăƚ ĂŶ ĂĐĐĞůĞƌĂƟŶŐ ǀŽůƚĂŐĞ ŽĨ ϭϮϬ Ŭs͘ ƐĞĐƟŽŶŽĨƚŚĞƚŚĞƌŵĂůůǇĂŶŶĞĂůĞĚ;^ͿďůŽĐŬĐŽƉŽůǇŵĞƌĮůŵǁĂƐĞŵďĞĚĚĞĚŝŶĞƉŽǆǇ

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36 ƌĞƐŝŶ ;ƉŽĮǆ͕ ůĞĐƚƌŽŶ DŝĐƌŽƐĐŽƉǇ ^ĐŝĞŶĐĞƐͿ ĂŶĚ ƐƵďƐĞƋƵĞŶƚůǇ ŵŝĐƌŽƚŽŵĞĚ ƵƐŝŶŐ Ă >ĞŝĐĂhůƚƌĂĐƵƚhdͲƵůƚƌĂŵŝĐƌŽƚŽŵĞŝŶŽƌĚĞƌƚŽƉƌĞƉĂƌĞƵůƚƌĂƚŚŝŶƐĞĐƟŽŶƐ;ĐĂ͘ϴϬŶŵͿ͘ EŽĂĚĚŝƟŽŶĂůƐƚĂŝŶŝŶŐŽĨƚŚĞƐĂŵƉůĞƐǁĂƐƌĞƋƵŝƌĞĚ͘ WŽůĂƌŝǌĞĚKƉƟĐĂůDŝĐƌŽƐĐŽƉǇ;WKDͿŝŵĂŐĞƐǁĞƌĞƌĞĐŽƌĚĞĚƵƐŝŶŐĂĞŝƐƐǆŝŽƉŚŽƚ ƉŽůĂƌŝǌŝŶŐŵŝĐƌŽƐĐŽƉĞĞƋƵŝƉƉĞĚǁŝƚŚĂ^ŽŶǇ/ͲϱϬϬĐĂŵĞƌĂĨŽƌŝŵĂŐĞĂĐƋƵŝƐŝƟŽŶ͘ dŚĞŝŵĂŐĞƐǁĞƌĞƌĞĐŽƌĚĞĚƵƐŝŶŐ<^ϯϬϬϬƐŽŌǁĂƌĞ;ĞŝƐƐͿ͘dŚĞďůŽĐŬĐŽƉŽůǇŵĞƌƐĂŵƉůĞƐ ǁĞƌĞŚĞĂƚĞĚŽŶĂDĞƩůĞƌdŽůĞĚŽ&WϴϮ,dŚŽƚƐƚĂŐĞƵƐŝŶŐĂDĞƩůĞƌ&WϵϬĐŽŶƚƌŽůƉĂŶĞů ƵŶƟůŵĞůƟŶŐǁĂƐŽďƐĞƌǀĞĚ͘ŌĞƌƚŚĞƌŵĂůĂŶŶĞĂůŝŶŐĨŽƌϱŵŝŶ͕ƚŚĞƐĂŵƉůĞƐǁĞƌĞƐůŽǁůǇ ĐŽŽůĞĚĚŽǁŶďǇƚƵƌŶŝŶŐŽīƚŚĞŚŽƚƐƚĂŐĞ͘

Results and Discussion

ƐĚŝƐƉůĂǇĞĚŝŶ^ĐŚĞŵĞϮ͘ϭ͕ĂůŬǇŶĞƚĞƌŵŝŶĂƚĞĚƚĞůĞĐŚĞůŝĐWs&;ϭϮϲϬϬŐŵŽůͲϭ_͕DǁͬDŶ ϭ͘ϱͿǁĂƐƉƌĞƉĂƌĞĚviaĨƌĞĞƌĂĚŝĐĂůƉŽůǇŵĞƌŝǌĂƟŽŶ͘ǌŝĚĞƚĞƌŵŝŶĂƚĞĚƉŽůǇ;ϮͲǀŝŶǇůƉǇƌŝĚŝŶĞͿ ;WϮsWͿ ĂŶĚ ƉŽůǇ;tertͲďƵƚǇůĂĐƌǇůĂƚĞͿ ;WtͿ ǁĞƌĞ ƉƌĞƉĂƌĞĚ via ƌĞǀĞƌƐŝďůĞ ĂĚĚŝƟŽŶ ĨƌĂŐŵĞŶƚĂƟŽŶĐŚĂŝŶƚƌĂŶƐĨĞƌ;Z&dͿƉŽůǇŵĞƌŝǌĂƟŽŶ͘^ƵďƐĞƋƵĞŶƚůǇ͕ĂƵƌĞĂĐƟŽŶ ǁĂƐƉĞƌĨŽƌŵĞĚƚŽŽďƚĂŝŶƚŚĞƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐ͕ǁŚĞƌĞŝŶĂŶĞǆĐĞƐƐŽĨĞŝƚŚĞƌWϮsW or PtǁĂƐĂĚĚĞĚƚŽĞŶƐƵƌĞĐŽŵƉůĞƚĞĐŽŶǀĞƌƐŝŽŶŽĨƚŚĞĂůŬǇŶĞŵŽŝĞƟĞƐ͘ǆĐĞƐƐŽĨWϮsW or PtǁĂƐǁĂƐŚĞĚĂǁĂǇǁŝƚŚĂƐĞůĞĐƟǀĞƐŽůǀĞŶƚĂŌĞƌƚŚĞƌĞĂĐƟŽŶ͘&ƵůůĐŽŶǀĞƌƐŝŽŶŽĨ ƚŚĞĂůŬǇŶĞĨƵŶĐƟŽŶĂůŝǌĞĚWs&ǁĂƐĐŽŶĮƌŵĞĚǁŝƚŚĂĚŽǁŶĮĞůĚƐŚŝŌŽĨƚŚĞĂƌŽŵĂƟĐ ƉƌŽƚŽŶƐŽƌŝŐŝŶĂƟŶŐĨƌŽŵƚŚĞŝŶŝƟĂƚŽƌĨƌĂŐŵĞŶƚƐĂŶĚƚŚĞĚŝƐĂƉƉĞĂƌĂŶĐĞŽĨƚŚĞĂůŬǇŶĞ proton in the 1_{,ͲEDZƐƉĞĐƚƌƵŵ;&ŝŐƵƌĞϮ͘ϮͿ͘^ŝǌĞĞǆĐůƵƐŝŽŶĐŚƌŽŵĂƚŽŐƌĂƉŚǇǁĂƐƵƐĞĚ}

ƚŽĐŽŶĮƌŵĐŽŵƉůĞƚĞƌĞŵŽǀĂůŽĨƚŚĞŚŽŵŽƉŽůǇŵĞƌƐĂŶĚƚŚƵƐƚŚĞƐƵĐĐĞƐƐĨƵůĨŽƌŵĂƟŽŶ ŽĨƚŚĞƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐ͘dŚĞWs&ͲďĂƐĞĚƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐĂƌĞůŝƐƚĞĚŝŶdĂďůĞϮ͘ϭ͘ dŚĞƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌĮůŵƐǁĞƌĞĐĂƐƚĨƌŽŵĚŝŵĞƚŚǇůĨŽƌŵĂŵŝĚĞ;D&ͿĂƚϰϱΣ͘ŌĞƌ ĐŽŵƉůĞƚĞĞǀĂƉŽƌĂƟŽŶŽĨD&͕ƚŚĞďůŽĐŬĐŽƉŽůǇŵĞƌƐǁĞƌĞŚĞĂƚĞĚƚŽƚŚĞŵĞůƚĂŶĚĐŽŽůĞĚ ĚŽǁŶǁŝƚŚϭϬΣŵŝŶͲϭ_{ŝŶŽƌĚĞƌƚŽƐƚƵĚǇƚŚĞŝƌŵŽƌƉŚŽůŽŐǇĂŶĚĐƌǇƐƚĂůůŝǌĂƟŽŶďĞŚĂǀŝŽƌ͘}

Figure 2.1: Representive GPC eluograms for PVDF and P2VP_0.17-b-PVDF_0.66-b-P2VP_0.17 block copolymers.

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37

2

Scheme 2.1: Synthetic route towards P2VP-b-PVDF-b-P2VP.

polymer DŶ;ŬŐŵŽůͲϭ_ͿĂ b ǁĂŵŽƌƉŚ͘ ďůŽĐŬc WÖò¥ c _X c;йͿ d Ws& ϭϮ͘ϲe _ϭ͘ϱϯe ₀ ₁ _ϰϵ PtϬ͘ϯͲbͲWs&Ϭ͘ϰͲbͲWtϬ͘ϯ ϯϬ͘Ϭf ϭ͘ϱϲg Ϭ͘ϲ Ϭ͘ϰ ϰϲ WϮsW0.27ͲbͲWs&Ϭ͘ϰϲͲbͲWϮsW0.27 28.0f _ϭ͘ϵϲg _0.55 _Ϭ͘ϰϱ ₁₅ WϮsW0.17ͲbͲWs&Ϭ͘ϲϲͲbͲWϮsW0.17 ϭϵ͘ϰf _n.d. _Ϭ͘ϯϱ _Ϭ͘ϲϱ _ϯϳ WϮsWϬ͘ϬϲͲbͲWs&0.88ͲbͲWϮsWϬ͘Ϭϲ ϭϰ͘ϯf _ϭ͘ϱϯg _0.12 _0.88 _ϯϳ

Table 2.2: Molecular Characteristics and Crystallinity of the Block Copolymers.

a_{Number-average molecular weight (M}

n). bDispersity (ɺ = Mw/Mn) cThe weight fractions were

determined by 1_{H-NMR spectroscopy.}d_{The degree of crystallinity of the PVDF block was determined}

JVSQXLI[IMKLXJVEGXMSRWXLIGV]WXEPPM^EXMSRI\SXLIVQSFXEMRIHJVSQ(7'ERHXLIXLISVIXMGEP QIPXMRKIRXLEPT]SJ»TLEWI4:(*.K-1_{ERH¼TLEWI4:(*.K}-1_).17e_{The molecular}

weight characteristics of PVDF were calculated using GPC with DMF (0.01 M LiBr) as eluent and monodisperse PMMA standards. f_{The block copolymer molecular weights were calculated using the}

Mn of PVDF and weight fractions of the distinct blocks. gThe ɺ of the block copolymers is determined

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38

&ŝŐƵƌĞϮ͘ϯƐŚŽǁƐƚŚĞƐŵĂůůͲĂŶŐůĞyͲƌĂǇƐĐĂƩĞƌŝŶŐ;^y^ͿƉƌŽĮůĞƐŝŶƚŚĞŵĞůƚĂŶĚĂŌĞƌ ĐƌǇƐƚĂůůŝǌĂƟŽŶ͕ƚŚĞƚƌĂŶƐŵŝƐƐŝŽŶĞůĞĐƚƌŽŶŵŝĐƌŽƐĐŽƉǇ;dDͿŝŵĂŐĞĂŶĚƚŚĞǁŝĚĞͲĂŶŐůĞ yͲƌĂǇƐĐĂƩĞƌŝŶŐ;ty^ͿƉƌŽĮůĞĨŽƌWϮsW_0.27-b-Ws&_Ϭ͘ϰϲ-b-WϮsW_0.27 at room temperature.ϭϱ͕ϭϲ

dŚĞ^y^ƉƌŽĮůĞƌĞǀĞĂůƐŽŶůǇŽŶĞƉĞĂŬ;q сϬ͘ϭϴϰŶŵͲϭ_{, dсϯϰŶŵͿ͕ǁŚŝĐŚŝƐŝŶƐƵĸĐŝĞŶƚ}

ƚŽĐŽŶĐůƵĚĞĂŶǇƚŚŝŶŐĂďŽƵƚƚŚĞŵĞůƚŵŽƌƉŚŽůŽŐǇ͘,ŽǁĞǀĞƌ͕ĨƌŽŵƚŚĞdDŝŵĂŐĞǁĞ ĐŽŶĐůƵĚĞƚŚĂƚĂĚŝƐŽƌĚĞƌĞĚƐƉŚĞƌŝĐĂůŵŽƌƉŚŽůŽŐǇŝƐŽďƚĂŝŶĞĚĂŌĞƌĐƌǇƐƚĂůůŝǌĂƟŽŶǁŝƚŚ an interdomain distance that is in agreement with the interdomain distance calculated ĨƌŽŵ^y^͘dŚĞƌĞůĂƟǀĞůǇŚŝŐŚƉŽůǇĚŝƐƉĞƌƐŝƚǇŽĨƚŚĞWs&ďůŽĐŬƉƌĞǀĞŶƚƐƚŚĞĂƉƉĞĂƌĂŶĐĞ ŽĨŚŝŐŚĞƌŽƌĚĞƌƐĐĂƩĞƌŝŶŐŵĂǆŝŵĂŝŶƚŚĞ^y^ƉƌŽĮůĞ͘9_{,ŽǁĞǀĞƌ͕ŶŽĐŚĂŶŐĞŽĨƐŚĂƉĞ}

ĂŶĚƉŽƐŝƟŽŶŽĨƚŚĞ^y^ƐŝŐŶĂůŝƐŽďƐĞƌǀĞĚĂŌĞƌĐŽŽůŝŶŐĚŽǁŶƚŽƌŽŽŵƚĞŵƉĞƌĂƚƵƌĞ͕ ǁŚŝĐŚ ĚĞŵŽŶƐƚƌĂƚĞƐ ƚŚĂƚ WϮsW_0.27-b-Ws&_Ϭ͘ϰϲ-b-WϮsW_0.27 ĐĂŶ ďĞ ƵƐĞĚ ƚŽ ĐŽŶĮŶĞ ƚŚĞ ĐƌǇƐƚĂůůŝǌĂƟŽŶŽĨWs&͘

Figure 2.2: (a) 1_{,216WTIGXVEJSVE^MHIXIVQMREXIH4:4
4:4b-PVDF-b4:4
ERHEPO]RI}

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39

2

ŝīĞƌĞŶƟĂů ƐĐĂŶŶŝŶŐ ĐĂůŽƌŝŵĞƚƌǇ ;^Ϳ ǁĂƐ ƉĞƌĨŽƌŵĞĚ ƚŽ ŐĂŝŶ ďĞƩĞƌ ŝŶƐŝŐŚƚƐ ŝŶ ƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶŵĞĐŚĂŶŝƐŵ͘dŚĞƚŚĞƌŵŽŐƌĂŵƐŽĨWs&ĂŶĚƚŚĞƚƌŝďůŽĐŬĐŽƉŽůǇŵĞƌƐ͕ ĚĞƉŝĐƚĞĚŝŶ&ŝŐƵƌĞϮ͘ϰ͕ƐŚŽǁƚŚĂƚĐƌǇƐƚĂůůŝǌĂƟŽŶŽĨWϮsW_0.27-b-Ws&_Ϭ͘ϰϲ-b-WϮsW_0.27 takes place at lower temperatures compared to the parent homopolymer. The large number ŽĨŶƵĐůĞŝƚŚĂƚĂƌĞŶĞĞĚĞĚĨŽƌƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶŝŶƐŝĚĞƚŚĞƐƉŚĞƌŝĐĂůĚŽŵĂŝŶƐƌĞƐƵůƚƐŝŶĂ ŚŽŵŽŐĞŶĞŽƵƐŶƵĐůĞĂƟŽŶƉƌŽĐĞƐƐ͕ƐŝŶĐĞƚŚĞŶƵŵďĞƌŽĨƐƉŚĞƌĞƐŽƵƚŶƵŵďĞƌƚŚĞŝŵƉƵƌŝƟĞƐ ƚŚĂƚĐĂŶŝŶŝƟĂƚĞĐƌǇƐƚĂůůŝǌĂƟŽŶďǇƐĞǀĞƌĂůŽƌĚĞƌƐŽĨŵĂŐŶŝƚƵĚĞ͘2_{/ŶĂĚĚŝƟŽŶ͕ǀŝƚƌŝĮĐĂƟŽŶ}

ŽĨƚŚĞWϮsWŵĂƚƌŝǆƵƉŽŶĐŽŽůŝŶŐŝƐŽďƐĞƌǀĞĚďĞĨŽƌĞĐƌǇƐƚĂůůŝǌĂƟŽŶŽĨWs&͕ǁŚŝĐŚůĞĂĚƐ to a low degree of crystallinity due to a strongly reduced mobility of the polymer chains ŝŶƚŚĞĞĂƌůǇƐƚĂŐĞŽĨĐƌǇƐƚĂůůŝǌĂƟŽŶ͘

Figure 2.3: 7%<7TVSƼPIWE 8)1MQEKIF ERH;%<7TVSƼPIG JSV4:40.27-b-PVDF0.46-b-P2VP0.27.

Scalebar in (b) corresponds to 100 nm.

Figure 2.4: DSC cooling scans from the melt for P2VP_0.27-b-PVDF_0.46-b-P2VP_0.27 WLS[MRKGSRƼRIH GV]WXEPPM^EXMSRMRWTLIVIW4tBA0.3-b-PVDF0.4-b-PtBA0.3 WLS[MRKFVIEOSYXGV]WXEPPM^EXMSR4:40.17

-b-PVDF_0.66-b-P2VP_0.17 WLS[MRKGSRƼRIHGV]WXEPPM^EXMSRMRPEQIPPEI4:4_0.06-b-PVDF_0.88-b-P2VP_0.06 WLS[MRKFVIEOSYXGV]WXEPPM^EXMSRERHJSVTYVI4:(*

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^ƚƌŝŬŝŶŐůǇ͕ ƚŚĞ ty^ ƉƌŽĨŝůĞ ŽĨ WϮsW_0.27-b-Ws&_Ϭ͘ϰϲ-b-WϮsW_0.27 reveals that ŶĂŶŽĐŽŶĮŶĞŵĞŶƚ ŚĂƐ Ă ƉƌŽĨŽƵŶĚ ĞīĞĐƚ ŽŶ ƚŚĞ ĐƌǇƐƚĂůůŝǌĂƟŽŶ ŽĨ Ws&͕ ŝŶĚƵĐŝŶŐ ƚŚĞĨŽƌŵĂƟŽŶŽĨƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐɴͲƉŚĂƐĞ͘dŚĞƐĐĂƩĞƌŝŶŐƉĞĂŬŝŶƚŚĞty^ƉƌŽĮůĞ ŽĨƚŚĞ;ϭϭϬͬϮϬϬͿĐƌǇƐƚĂůƉůĂŶĞƐĂƚqсϭϰ͘ϲŶŵͲϭ_{ŝƐĞĂƐǇƚŽĚŝƐƟŶŐƵŝƐŚĨƌŽŵƚŚĞƉĞĂŬƐ} ĐŽƌƌĞƐƉŽŶĚŝŶŐƚŽŽƚŚĞƌĐƌǇƐƚĂůůŝŶĞƉŚĂƐĞƐ͘/ŶĂĚĚŝƟŽŶ͕ƚŚĞ&ŽƵƌŝĞƌƚƌĂŶƐĨŽƌŵŝŶĨƌĂƌĞĚ ƐƉĞĐƚƌŽƐĐŽƉǇ;&d/ZͿƐƉĞĐƚƌƵŵ;&ŝŐƵƌĞϮ͘ϱͿƐŚŽǁƐƚŚĞĂďƐŽƌƉƟŽŶďĂŶĚƐĂƚϴϰϬĐŵͲϭ_and 1279 cmͲϭ_{ĐŽŶĮƌŵŝŶŐƚŚĞĂůůͲƚƌĂŶƐĐŽŶĨŽƌŵĂƟŽŶŽĨƚŚĞƉŽůǇŵĞƌĐŚĂŝŶƐŝŶƐŝĚĞƚŚĞĐƌǇƐƚĂů͘}1 KŶƚŚĞĐŽŶƚƌĂƌǇ͕ƉƵƌĞWs&ĐƌǇƐƚĂůůŝǌĞƐĨƌŽŵƚŚĞŵĞůƚŝŶƚŚĞɲͲƉŚĂƐĞĂƚŵŽĚĞƌĂƚĞ ĐƌǇƐƚĂůůŝǌĂƟŽŶƌĂƚĞƐ͘18_{'ƌĞŐŽƌŝŽĂŶĚĞƐƚĂƌŝĚĞŵŽŶƐƚƌĂƚĞĚƚŚĂƚƚŚĞŵĂǆŝŵƵŵƌĂƚĞŽĨ} ĐƌǇƐƚĂůůŝǌĂƟŽŶĨŽƌƚŚĞɴͲƉŚĂƐĞŚĂƉƉĞŶƐĂƚϲϬΣ͕ǁŚĞƌĞĂƐĂŵĂǆŝŵƵŵĐƌǇƐƚĂůůŝǌĂƟŽŶ ƌĂƚĞĨŽƌƚŚĞɲͲƉŚĂƐĞŝƐŽĐĐƵƌƌŝŶŐĂƚϭϯϬΣ͘19_{This suggests that at lower temperatures}

the thermodynamically favorable crystalline structure is formed probably as a result of ĂŚŝŐŚĞƌƉĂĐŬŝŶŐĚĞŶƐŝƚǇŽĨƚŚĞɴͲƉŚĂƐĞĐŽŵƉĂƌĞĚƚŽƚŚĞɲͲƉŚĂƐĞ͕ǁŚŝĐŚƌĞĚƵĐĞƐƚŚĞ ĨƌĞĞĞŶĞƌŐǇŽĨƚŚĞƐǇƐƚĞŵďǇůĞƐƐƐƚĞƌŝĐŝŶƚĞƌĂĐƟŽŶ͘20_{ǇĐŽŶĮŶŝŶŐƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶ}

in spherical domains and forcing crystallization via a homogeneous nucleation ŵĞĐŚĂŶŝƐŵ͕ǁĞŵĂŶĂŐĞĚƚŽƐŚŝŌƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞƚŽǀĂůƵĞƐĂƚǁŚŝĐŚĂ ŵĂǆŝŵƵŵĐƌǇƐƚĂůůŝǌĂƟŽŶƌĂƚĞŽĨƚŚĞɴŝƐŽďƐĞƌǀĞĚ͘^ŝŵŝůĂƌƌĞƐƵůƚƐǁĞƌĞŽďƚĂŝŶĞĚǁŚĞŶ Ws& ŶĂŶŽƉĂƌƟĐůĞƐ ǁĞƌĞ ĞŵďĞĚĚĞĚ ŝŶ ƉŽůǇƐƚǇƌĞŶĞ ŶĂŶŽƐƉŚĞƌĞƐ ĂŶĚ ƐƵďƐĞƋƵĞŶƚůǇ recrystallized from the melt or viaƵůƚƌĂͲĨĂƐƚƋƵĞŶĐŚŝŶŐŽĨWs&ĮůŵƐ͕ǁŚŝĐŚůĞĂĚƐƚŽĂ ůŽǁĐƌǇƐƚĂůůŝǌĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞ;ĂƌŽƵŶĚϯϬΣͿĂŶĚƚŚĞĨŽƌŵĂƟŽŶŽĨƚŚĞɴͲƉŚĂƐĞ͘5,21,22

/Ŷ ĐŽŶƚƌĂƐƚ ƚŽ ƚŚĞƐĞ ƉƌŽĐĞĚƵƌĞƐ ƵƐŝŶŐ ĞǆƚĞƌŶĂů ƉƌŽĐĞƐƐŝŶŐ ĞƋƵŝƉŵĞŶƚ͕ ĐŽŶĨŝŶĞĚ ĐƌǇƐƚĂůůŝǌĂƟŽŶŽĨWs&ĂŌĞƌďůŽĐŬĐŽƉŽůǇŵĞƌƐĞůĨͲĂƐƐĞŵďůǇƉƌŽǀĞƐƚŽďĞĂŶĞĂƐǇŵĞƚŚŽĚ ƚŽŽďƚĂŝŶƚŚĞɴͲƉŚĂƐĞ͘

Figure 2.5: FTIR spectra for P2VP_0.27-b-PVDF_0.46-b-P2VP_0.27 4tBA_0.3-b-PVDF_0.4-b-PtBA_0.3 P2VP_0.17-b-PVDF_0.66-b-P2VP_0.17 4:4_0.06-b-PVDF_0.88-b-P2VP_0.06 ERHJSVTYVI4:(*

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2

dŽǀĞƌŝĨǇƚŚĂƚƚŚĞɴͲƉŚĂƐĞĨŽƌŵĂƟŽŶŝƐĂĐŽŶƐĞƋƵĞŶĐĞŽĨƚŚĞƐƚƌŽŶŐƌĞĚƵĐƟŽŶŝŶ ĐƌǇƐƚĂůůŝǌĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞ͕ǁĞƉƌĞƉĂƌĞĚĂWt_Ϭ͘ϯ-b-Ws&_Ϭ͘ϰ-b-Pt_Ϭ͘ϯ triblock copolymer ǁŝƚŚĂƐŝŵŝůĂƌǁĞŝŐŚƚĨƌĂĐƟŽŶŽĨWtĂƐŝŶWϮsW_0.27-b-Ws&_Ϭ͘ϰϲ-b-WϮsW_0.27͘/ŶƚĞƌĞƐƟŶŐůǇ͕Ă ƉŚĂƐĞƐĞƉĂƌĂƚĞĚŵĞůƚŝƐĨŽƌŵĞĚĂŌĞƌŵĞůƟŶŐŽĨWs&;&ŝŐƵƌĞϮ͘ϲĂͿ͘WƌŽďĂďůǇ͕ƚŚĞďƵůŬǇ tertͲďƵƚǇůŐƌŽƵƉƐŽĨWtĚŝƐƌƵƉƚŚǇĚƌŽŐĞŶďŽŶĚŝŶŐďĞƚǁĞĞŶƚŚĞĐĂƌďŽŶǇůŐƌŽƵƉƐŽĨt ĂŶĚƚŚĞŚǇĚƌŽŐĞŶĂƚŽŵƐŽĨs&͘Ϯϯ_{,ŽǁĞǀĞƌ͕ƚŚĞŐůĂƐƐƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞŽĨWtǁĂƐ} ƚŽŽůŽǁƚŽƉƌĞƐĞƌǀĞĐƌǇƐƚĂůůŝǌĂƟŽŶŝŶƐŝĚĞƚŚĞŵĞůƚŵŽƌƉŚŽůŽŐǇ͘ƐĂƌĞƐƵůƚ͕ďƌĞĂŬͲŽƵƚ ĐƌǇƐƚĂůůŝǌĂƟŽŶĐŽŵƉůĞƚĞůǇĞƌĂƐĞƐƚŚĞŵĞůƚƐƚƌƵĐƚƵƌĞŵĂŬŝŶŐĂĚŝƐŽƌĚĞƌĞĚĂůƚĞƌŶĂƟŶŐ ĐƌǇƐƚĂůůŝŶĞͲĂŵŽƌƉŚŽƵƐŵŽƌƉŚŽůŽŐǇĂƐĚĞƉŝĐƚĞĚŝŶƚŚĞdDŝŵĂŐĞ;&ŝŐƵƌĞϮ͘ϲĐͿ͘dŚĞ ĚŝīĞƌĞŶĐĞďĞƚǁĞĞŶƚŚĞƚǁŽĐƌǇƐƚĂůůŝǌĂƟŽŶŵŽĚĞƐ͕ĐŽŶĮŶĞĚĂŶĚďƌĞĂŬͲŽƵƚĐƌǇƐƚĂůůŝǌĂƟŽŶ͕ ŝƐŽďƐĞƌǀĞĚĂƐǁĞůůƵŶĚĞƌĂƉŽůĂƌŝǌĞĚŽƉƟĐĂůŵŝĐƌŽƐĐŽƉĞ;WKDͿ͘ In Pt_Ϭ͘ϯ-b-Ws&_Ϭ͘ϰ-b-Pt_Ϭ͘ϯ͕ǁĞŽďƐĞƌǀĞĂĐůĞĂƌďŝƌĞĨƌŝŶŐĞŶĐĞƉĂƩĞƌŶƐŚŽǁŝŶŐƚŚĞ ƐƉŚĞƌƵůŝƟĐƐƵƉĞƌƐƚƌƵĐƚƵƌĞ͕ǁŚĞƌĞĂƐƚŚĞĂďƐĞŶĐĞŽĨŵĂĐƌŽƐĐŽƉŝĐĐƌǇƐƚĂůůŝǌĂƟŽŶƌĞƐƵůƚƐ ŝŶĂŶŽƉƟĐĂůůǇŚŽŵŽŐĞŶĞŽƵƐWKDŝŵĂŐĞŽĨWϮsW_0.27-b-Ws&_Ϭ͘ϰϲ-b-WϮsW_0.27;&ŝŐƵƌĞϮ͘ϳͿ͘Ϯϰ

The high molecular weight of the PtďůŽĐŬƐŝŐŶŝĮĐĂŶƚůǇƌĞĚƵĐĞƐƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶ ƚĞŵƉĞƌĂƚƵƌĞ ĨƌŽŵ ϭϯϮ͘ϱ ƚŽ ϭϭϬ͘ϱ Σ͘ ,ŽǁĞǀĞƌ͕ ƚŚĞ ĐƌǇƐƚĂůůŝǌĂƟŽŶ ƚĞŵƉĞƌĂƚƵƌĞ ŝƐ ŵƵĐŚ ŚŝŐŚĞƌ ƚŚĂŶ ĨŽƌ ƚŚĞ ĐƌǇƐƚĂůůŝǌĂƟŽŶ ŽĨ Ws& ŝŶƐŝĚĞ ƐƉŚĞƌŝĐĂů ŶĂŶŽĚŽŵĂŝŶƐ͘ Ɛ ĂďŽǀĞŵĞŶƟŽŶĞĚ͕ĂƚŚŝŐŚƚĞŵƉĞƌĂƚƵƌĞƐƚŚĞŬŝŶĞƟĐĂůůǇĨĂǀŽƌĂďůĞɲͲƉŚĂƐĞŝƐĨŽƌŵĞĚ͕ ǁŚŝĐŚ ŝƐ ŝŶ ĞǆĐĞůůĞŶƚ ĂŐƌĞĞŵĞŶƚ ǁŝƚŚ ƚŚĞ ty^ ĚĂƚĂ ĚĞƉŝĐƚĞĚ ŝŶ &ŝŐƵƌĞ Ϯ͘ϲĐ͘ dŚĞ ƉĞĂŬƉŽƐŝƟŽŶƐqĂƚϭϮ͘ϲ͕ϭϯ͘ϭ͕ϭϰ͘Ϯ͕ĂŶĚϭϴ͘ϴŶŵͲϭ_{ĨƌŽŵƚŚĞty^ƉƌŽĮůĞŽĨƚŚŝƐďůŽĐŬ} ĐŽƉŽůǇŵĞƌĐŽƌƌĞƐƉŽŶĚƚŽƚŚĞ;ϭϬϬͿ͕;ϬϮϬͿ͕;ϭϭϬͿ͕ĂŶĚ;ϬϮϭͿĐƌǇƐƚĂůƉůĂŶĞƐŽĨƚŚĞĂůĨĂ ĐƌǇƐƚĂůƐ͕ƌĞƐƉĞĐƟǀĞůǇ͘1_{DŽƌĞŽǀĞƌ͕ƚŚĞĂďƐŽƌƉƟŽŶďĂŶĚƐŝŶƚŚĞ&d/ZƐƉĞĐƚƌƵŵ;&ŝŐƵƌĞ}

Figure 2.6: E 7%<7 TVSƼPIW F 8)1 MQEKI G ;%<7 TVSƼPI JSV 4tBA_0.3-b-PVDF_0.4-b-PtBA_0.3. Scalebar corresponds to 100 nm.

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42 Ϯ͘ϱͿƚŚĂƚďĞůŽŶŐĞǆĐůƵƐŝǀĞůǇƚŽƚŚĞɲƉŚĂƐĞĂƌĞĐůĞĂƌůǇǀŝƐŝďůĞ͘ƐĂůƌĞĂĚǇĞǆƉůĂŝŶĞĚ͕ƚŚĞ ĐƌǇƐƚĂůůŝǌĂƟŽŶƌĂƚĞĨŽƌɲͲƉŚĂƐĞĨŽƌŵĂƟŽŶĂƚϭϭϬ͘ϱΣŝƐƐƟůůŚŝŐŚ͕ǁŚĞƌĞĂƐƚŚĞƌĂƚĞŽĨ ĐƌǇƐƚĂůůŝǌĂƟŽŶĨŽƌƚŚĞɴͲƉŚĂƐĞŝƐƉƌĂĐƟĐĂůůǇǌĞƌŽ͘19_{&ƵƌƚŚĞƌŵŽƌĞ͕ĐƌǇƐƚĂůůŝǌĂƟŽŶŽĨWs&} ĚƵƌŝŶŐďƌĞĂŬͲŽƵƚŝƐďĂƌĞůǇŚĂŵƉĞƌĞĚƌĞƐƵůƟŶŐŝŶĂĚĞŐƌĞĞŽĨĐƌǇƐƚĂůůŝŶŝƚǇƚŚĂƚĐůŽƐĞůǇ ŵĂƚĐŚĞƐƉƵƌĞWs&͕ǁŚŝĐŚŝƐĐŽŵƉůĞƚĞůǇĚŝīĞƌĞŶƚĨƌŽŵWϮsW_0.27-b-Ws&_Ϭ͘ϰϲ-b-WϮsW_0.27 ǁŚĞƌĞƚŚƌĞĞĚŝŵĞŶƐŝŽŶĂůĐŽŶĮŶĞŵĞŶƚƌĞĚƵĐĞƐƚŚĞĚĞŐƌĞĞŽĨĐƌǇƐƚĂůůŝŶŝƚǇƚŽϭϱй;dĂďůĞ Ϯ͘ϭͿ͘/ŶŽƌĚĞƌƚŽĞǆĂŵŝŶĞƚŚĞŝŶŇƵĞŶĐĞŽĨĐŽŶĮŶĞŵĞŶƚƚǇƉĞŽŶWs&ĐƌǇƐƚĂůůŝǌĂƟŽŶ͕ ǁĞƐǇŶƚŚĞƐŝǌĞĚĂWϮsW_0.17-b-Ws&_Ϭ͘ϲϲ-b-WϮsW_0.17 block copolymer with a similar volume ĨƌĂĐƟŽŶŽĨƚŚĞĚŝƐƟŶĐƚďůŽĐŬƐ͘ ƐĂĐŽŶƐĞƋƵĞŶĐĞ͕ĂůĂŵĞůůĂƌŵŽƌƉŚŽůŽŐǇŝŶƚŚĞŵĞůƚŝƐŽďƐĞƌǀĞĚĂƐƉƌŽǀĞŶďǇƚŚĞ ^y^ƉƌŽĮůĞ;&ŝŐƵƌĞϮ͘ϴĂͿĂŶĚdDŝŵĂŐĞ;&ŝŐƵƌĞϮ͘ϴĐͿŽĨƚŚĞďůŽĐŬĐŽƉŽůǇŵĞƌ͘dŚĞ^y^ ƉƌŽĮůĞŽĨƚŚĞŵŽůƚĞŶƐƚĂƚĞƐŚŽǁƐƚǁŽƐŝŐŶĂůƐǁŝƚŚĂƌĂƟŽ1q:2q (qсϬ͘ϮϲϭŶŵͲϭ_{, dсϮϰ} ŶŵͿ͘ǀĞŶƚŚŽƵŐŚ͕ŶŽĐŽŶĐůƵƐŝŽŶĂďŽƵƚƚŚĞŵŽƌƉŚŽůŽŐǇĐĂŶďĞĚƌĂǁŶ͕ƚŚĞdDŝŵĂŐĞ ĚĞŵŽŶƐƚƌĂƚĞƐƚŚĂƚĂƐǇŵŵĞƚƌŝĐĂůůĂŵĞůůĂĞŵŽƌƉŚŽůŽŐǇŝƐĂĐƋƵŝƌĞĚ͘dŚĞĚŽŵĂŝŶƐƉĂĐŝŶŐ ĐĂůĐƵůĂƚĞĚĨƌŽŵƚŚĞ^y^ƉƌŽĮůĞĂŶĚŽďƐĞƌǀĞĚĨƌŽŵdDǁĞƌĞŝŶŐŽŽĚĂĐĐŽƌĚĂŶĐĞ͘ dŚĞĨĂĐƚƚŚĂƚƚŚĞƉŽƐŝƟŽŶŽĨƚŚĞĮƌƐƚŽƌĚĞƌƉĞĂŬĚŝĚŶŽƚĐŚĂŶŐĞƵƉŽŶĐŽŽůŝŶŐƚŽƌŽŽŵ ƚĞŵƉĞƌĂƚƵƌĞŝŶĚŝĐĂƚĞƐƚŚĂƚƚŚĞůĂŵĞůůĂƌŵŽƌƉŚŽůŽŐǇĨƌŽŵƚŚĞŵĞůƚƌĞƚĂŝŶĞĚƵƉŽŶWs& ĐƌǇƐƚĂůůŝǌĂƟŽŶĚƵĞƚŽĂƉƉĂƌĞŶƚůǇƚŚĞƐƚƌŽŶŐŝŶƚĞƌďůŽĐŬƐĞŐƌĞŐĂƟŽŶďĞƚǁĞĞŶWs&ĂŶĚ WϮsWĂŶĚĂŚŝŐŚŐůĂƐƐƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞŽĨWϮsW͘ĚĚŝƟŽŶĂůůǇ͕ƚŚĞWKDŝŵĂŐĞŽĨ ƚŚĞďůŽĐŬĐŽƉŽůǇŵĞƌĚŝĚŶŽƚƐŚŽǁďŝƌĞĨƌŝŶŐĞŶĐĞĐŽŶĮƌŵŝŶŐƚŚĞĐŽŶĮŶĞĚĐƌǇƐƚĂůůŝǌĂƟŽŶ ;&ŝŐƵƌĞϮ͘ϳͿ͘ ƌǇƐƚĂůůŝǌĂƟŽŶǁŝƚŚŝŶĂůƚĞƌŶĂƟŶŐůĂŵĞůůĂƌĚŽŵĂŝŶƐŽĐĐƵƌƌĞĚƐŽůĞůǇŝŶƚŚĞɲͲƉŚĂƐĞĂƐ ƐŚŽǁŶŝŶƚŚĞty^;&ŝŐƵƌĞϮ͘ϴďͿĂŶĚ&d/ZƐƉĞĐƚƌĂ;&ŝŐƵƌĞϮ͘ϱͿ͕ǁŚŝĐŚĐĂŶďĞĞůƵĐŝĚĂƚĞĚ ďǇĂŶĂůǇǌŝŶŐƚŚĞƚŚĞƌŵĂůďĞŚĂǀŝŽƌ͘/ŶƚŚĞ^ƚŚĞƌŵŽŐƌĂŵǁĞƐĞĞĂƐŵĂůůƌĞĚƵĐƟŽŶŝŶ ƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞĐŽŵƉĂƌĞĚƚŽƚŚĞŚŽŵŽƉŽůǇŵĞƌĂŶĚŶŽůĂƌŐĞƵŶĚĞƌĐŽŽůŝŶŐ ŝƐŽďƐĞƌǀĞĚĨŽƌWϮsW_0.17-b-Ws&_Ϭ͘ϲϲ-b-WϮsW_0.17;&ŝŐƵƌĞϮ͘ϰͿ͘/ŶƚŚŝƐĐĂƐĞ͕ƐŵĂůůŝŵƉƵƌŝƟĞƐ ƚŚĂƚ ĨŽƌŵ ŶƵĐůĞŝ ƚŚĂƚ ŝŶŝƟĂƚĞ ĐƌǇƐƚĂůůŝǌĂƟŽŶ ĂƌĞ ƉƌĞƐĞŶƚ ŝŶ ĞǀĞƌǇ ůĂŵĞůůĂƌ ĚŽŵĂŝŶ ĂŶĚƚŚĞƌĞĨŽƌĞĂŚĞƚĞƌŽŐĞŶĞŽƵƐŶƵĐůĞĂƟŽŶƉƌŽĐĞƐƐŝƐŽďƐĞƌǀĞĚ͘/ŶůŝƚĞƌĂƚƵƌĞ͕ƐŝŵŝůĂƌ ŽďƐĞƌǀĂƟŽŶƐĂƌĞŵĂĚĞĨŽƌĂůĂƌŐĞǀĂƌŝĞƚǇŽĨďůŽĐŬĐŽƉŽůǇŵĞƌƐǇƐƚĞŵƐ͕ƐƵĐŚĂƐŝƐŽƚĂĐƟĐ ƉŽůǇ;ƉƌŽƉǇůĞŶĞͿͲblockͲĂƚĂĐƚŝĐ ƉŽůǇ;ƐƚǇƌĞŶĞͿ͕ ƉŽůǇ;ĞƚŚǇůĞŶĞ ŽǆŝĚĞͿͲblockͲƉŽůǇ;ϭ͕ϰͲ ďƵƚĂĚŝĞŶĞͿĂŶĚŵĂŶǇŵŽƌĞ͘Ϯϱ͕Ϯϲ_{ŽŶƐĞƋƵĞŶƚůǇ͕ĂƚƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞ;ϭϮϴ} ΣͿƚŚĞƌĂƚĞŽĨĐƌǇƐƚĂůůŝǌĂƟŽŶŽĨƚŚĞɲͲƉŚĂƐĞŝƐŚŝŐŚĞƐƚĂƐĂďŽǀĞŵĞŶƟŽŶĞĚ͕ǁŚŝĐŚƌĞƐƵůƚƐ ŝŶƚŚĞĨŽƌŵĂƟŽŶŽĨƚŚĞĐƌǇƐƚĂůůŝŶĞɲͲƉŚĂƐĞ͘ /ŶWϮsW_Ϭ͘Ϭϲ-b-Ws&_0.88-b-WϮsW_Ϭ͘ϬϲƚŚĞĨƌĂĐƟŽŶŽĨWϮsWŝŶƚŚĞďůŽĐŬĐŽƉŽůǇŵĞƌŝƐůŽǁ͕ ǁŚŝĐŚůĞĂĚƐƚŽĂĚŝƐŽƌĚĞƌĞĚŵĞůƚƐŝŶĐĞƚŚĞƐĞŐƌĞŐĂƟŽŶƐƚƌĞŶŐƚŚ;ʖEͿďĞƚǁĞĞŶƚŚĞĚŝƐƟŶĐƚ ďůŽĐŬƐŝƐůŽǁ͘dŚŝƐŝƐŵĂŶŝĨĞƐƚĞĚŝŶƚŚĞ^y^ƉƌŽĮůĞŝŶ&ŝŐƵƌĞϮ͘ϵĂ͕ǁŚĞƌĞŝŶĂĐŽƌƌĞůĂƟŽŶ ŚŽůĞĚƵĞƚŽĚĞŶƐŝƚǇŇƵĐƚƵĂƟŽŶƐŝŶƚŚĞŵĞůƚŝƐŽďƐĞƌǀĞĚ͘/Ŷ&ŝŐƵƌĞϮ͘ϵĐ͕ƚŚĞdDŝŵĂŐĞ ƐŚŽǁƐ ƚŚĂƚ ďƌĞĂŬͲŽƵƚ ĐƌǇƐƚĂůůŝǌĂƟŽŶ ŽĨ WϮsW_Ϭ͘Ϭϲ-b-Ws&_0.88-b-WϮsW_Ϭ͘Ϭϲ leads to the

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43

2

ĨŽƌŵĂƟŽŶŽĨůĂŵĞůůĂĞ͘/ŶĂĚĚŝƟŽŶ͕ƚŚĞWKDŝŵĂŐĞƌĞĐŽƌĚĞĚĂŌĞƌĐƌǇƐƚĂůůŝǌĂƟŽŶƐŚŽǁƐ ĂĐůĞĂƌďŝƌĞĨƌŝŶŐĞŶĐĞƉĂƩĞƌŶƚŚĂƚŝƐĐŚĂƌĂĐƚĞƌŝƐƟĐĨŽƌƚŚĞƐƉŚĞƌƵůŝƟĐƐƵƉĞƌƐƚƌƵĐƚƵƌĞ͘ /ŶƚĞƌĞƐƟŶŐůǇ͕ƚŚĞ^ƐĐĂŶŽĨWϮsW_Ϭ͘Ϭϲ-b-Ws&_0.88-b-WϮsW_Ϭ͘Ϭϲ;&ŝŐƵƌĞϮ͘ϰͿĚĞŵŽŶƐƚƌĂƚĞƐ ĂŚŝŐŚĞƌĐƌǇƐƚĂůůŝǌĂƟŽŶĂŶĚŵĞůƟŶŐƚĞŵƉĞƌĂƚƵƌĞĐŽŵƉĂƌĞĚƚŽƚŚĞŚŽŵŽƉŽůǇŵĞƌWs&͘ /Ŷ ĂĚĚŝƟŽŶ͕ ƚŚĞ ĐƌǇƐƚĂůůŝǌĂƟŽŶ ĞǆŽƚŚĞƌŵ ƐŚŽǁƐ Ă ĚŽƵďůĞ ĐƌǇƐƚĂůůŝǌĂƟŽŶ ƉƌŽĐĞƐƐ͘ dŽ ŝŶǀĞƐƟŐĂƚĞƚŚĞŶĂƚƵƌĞŽĨƚŚĞĚŽƵďůĞĐƌǇƐƚĂůůŝǌĂƟŽŶĞǆŽƚŚĞƌŵ͕ǁĞƌĞĐŽƌĚĞĚty^ƉƌŽĮůĞƐ ;&ŝŐƵƌĞϮ͘ϵďͿĂƚĚŝīĞƌĞŶƚƚĞŵƉĞƌĂƚƵƌĞƐĚƵƌŝŶŐĐƌǇƐƚĂůůŝǌĂƟŽŶ͘/ƚŝƐŽďƐĞƌǀĞĚƚŚĂƚWs& ĮƌƐƚĐƌǇƐƚĂůůŝǌĞƐŝŶƚŚĞɶͲƉŚĂƐĞ͕ǁŚŝůĞĨƵƌƚŚĞƌƌĞĚƵĐƟŽŶŽĨƚŚĞƚĞŵƉĞƌĂƚƵƌĞƌĞƐƵůƚĞĚ ŝŶƚŚĞɲͲƉŚĂƐĞĨŽƌŵĂƟŽŶ͘dŚŝƐŝƐƐƵƉƉŽƌƚĞĚďǇƚŚĞ&d/ZƐƉĞĐƚƌƵŵƌĞĐŽƌĚĞĚĂƚƌŽŽŵ

Figure 2.7: (a) POM images for P2VP_0.25-b-PVDF_0.5-b-P2VP_0.25F 4tBA_0.3-b-PVDF_0.4-b-PtBA_0.3G P2VP0.15-b-PVDF0.7-b-P2VP0.15H 4:40.06-b-PVDF0.88-b-P2VP0.06ERHJSVTYVII 4:(*7GEPIFEV

corresponds to 50 μm.

Figure 2.8: 7%<7TVSƼPIWE ;%<7TVSƼPIF ERH8)1MQEKIG JSV4:4_0.17-b-PVDF_0.66-b-P2VP_0.17. Scalebar corresponds to 50 nm.

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44

ƚĞŵƉĞƌĂƚƵƌĞǁŚĞƌĞƚŚĞĐŚĂƌĂĐƚĞƌŝƐƟĐĂďƐŽƌƉƟŽŶďĂŶĚƐŽĨďŽƚŚƚŚĞɲͲĂŶĚɶͲƉŚĂƐĞĂƌĞ ŽďƐĞƌǀĞĚ;&ŝŐƵƌĞϮ͘ϱͿ͘dŚĞɶͲƉŚĂƐĞĨƌŽŵƚŚĞŵĞůƚŝƐƵƐƵĂůůǇŽďƚĂŝŶĞĚvia slow cooling, ĂŶŶĞĂůŝŶŐŽĨƚŚĞɲͲƉŚĂƐĞĂƚŚŝŐŚƚĞŵƉĞƌĂƚƵƌĞŽƌviaƚŚĞĂĚĚŝƟŽŶŽĨƉŽůĂƌĮůůĞƌƐ͕ƐƵĐŚĂƐ zeolite, clay and KBr powder.ϭ͕ϮϳʹϮϵ_{/ƚŝƐďĞůŝĞǀĞĚƚŚĂƚƚŚĞĂĚĚŝƟŽŶŽĨƚŚĞƐĞĮůůĞƌƐƌĞƐƵůƚƐŝŶ}

ĨĂǀŽƌĂďůĞŝŶƚĞƌĂĐƟŽŶƐďĞƚǁĞĞŶƚŚĞƉŽůĂƌƐƵƌĨĂĐĞĂŶĚWs&ĐŚĂŝŶƐĚƌŝǀŝŶŐƚŚĞĨŽƌŵĂƟŽŶ ŽĨƚŚĞƉŽůĂƌɶͲƉŚĂƐĞ͘dŚŝƐŵŝŐŚƚĞǆƉůĂŝŶƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶŽĨWs&ŝŶƚŽƚŚĞɶͲƉŚĂƐĞďǇ ŝŶƚĞƌĂĐƟŽŶďĞƚǁĞĞŶƚŚĞƌĞůĂƟǀĞůǇƉŽůĂƌWϮsWĂŶĚs&ƵŶŝƚƐŝŶƚŚĞŵĞůƚ͘

Conclusions

dŚĞ ŵĞůƚ ĐƌǇƐƚĂůůŝǌĂƟŽŶ ŽĨ ƐĞůĨͲĂƐƐĞŵďůĞĚ Ws&ͲďĂƐĞĚ ďůŽĐŬ ĐŽƉŽůǇŵĞƌƐ ƉƌŽǀĞƐ ƚŽ ďĞĂŶĂƉƉĞĂůŝŶŐŵĞƚŚŽĚƚŽƐƚƵĚǇĐŽŶĮŶĞŵĞŶƚĞīĞĐƚŽŶƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶŵŽĚĞĂŶĚ ĐƌǇƐƚĂůůŝŶĞƉŚĂƐĞƐŝŶWs&͘tĞƐŚŽǁƚŚĂƚƉŚĂƐĞďĞŚĂǀŝŽƌ͕ĐƌǇƐƚĂůůŝǌĂƟŽŶŵĞĐŚĂŶŝƐŵ͕ĂŶĚ ƚŚĞĐŚĞŵŝĐĂůŶĂƚƵƌĞŽĨƚŚĞĂŵŽƌƉŚŽƵƐďůŽĐŬƐŚĂǀĞĂŐƌĞĂƚŝŵƉĂĐƚŽŶƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶ ďĞŚĂǀŝŽƌŽĨWs&ŝŶŝƚƐďůŽĐŬĐŽƉŽůǇŵĞƌƐ͘dŚĞĨĞƌƌŽĞůĞĐƚƌŝĐɴͲƉŚĂƐĞŝƐĨŽƌŵĞĚǁŚĞŶ ƚŚĞĐƌǇƐƚĂůůŝǌĂƟŽŶŽĨWs&ŝƐĐŽŶĮŶĞĚŝŶƚŚƌĞĞĚŝŵĞŶƐŝŽŶĂůƐƉŚĞƌŝĐĂůŶĂŶŽĚŽŵĂŝŶƐ͘ ŽŶǀĞƌƐĞůǇ͕Ws&ĐƌǇƐƚĂůůŝǌĂƟŽŶǁŝƚŚŝŶĂůĂŵĞůůĂƌŵŽƌƉŚŽůŽŐǇŽƌĂŌĞƌďƌĞĂŬͲŽƵƚƌĞƐƵůƚƐ ŝŶƚŚĞĨŽƌŵĂƟŽŶŽĨƚŚĞɲͲƉŚĂƐĞ͕ƵŶůĞƐƐĨĂǀŽƌĂďůĞƉŽůĂƌŝŶƚĞƌĂĐƟŽŶƐďĞƚǁĞĞŶƚŚĞĚŝƐƟŶĐƚ ďůŽĐŬƐĚƵƌŝŶŐŵĞůƚƌĞĐƌǇƐƚĂůůŝǌĂƟŽŶŝŶŝƟĂƚĞƚŚĞĨŽƌŵĂƟŽŶŽĨƚŚĞƉŽůĂƌɶͲƉŚĂƐĞ͘dŚĞƐĞ ĮŶĚŝŶŐƐƉƌŽǀŝĚĞŐƵŝĚĞůŝŶĞƐŽĨŚŽǁ͕ŝŶĂŶĞĂƐǇǁĂǇ͕ƚŽŽďƚĂŝŶWs&ĐƌǇƐƚĂůůŝŶĞƉŚĂƐĞƐ ĚĞƐŝƌĂďůĞĨŽƌĂĚǀĂŶĐĞĚĂƉƉůŝĐĂƟŽŶƐ͘

Figure 2.9: 7%<7 TVSƼPIW E ;%<7 TVSƼPIW F ERH 8)1 MQEKI G JSV 4:40.06-b-PVDF0.88

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2 References

;ϭͿ DĂƌƟŶƐ͕ W͖͘ >ŽƉĞƐ͕ ͘ ͖͘ >ĂŶĐĞƌŽƐͲDĞŶĚĞǌ͕ ^͘ ůĞĐƚƌŽĂĐƟǀĞ WŚĂƐĞƐ ŽĨ WŽůǇ;sŝŶǇůŝĚĞŶĞ &ůƵŽƌŝĚĞͿ͗ĞƚĞƌŵŝŶĂƟŽŶ͕WƌŽĐĞƐƐŝŶŐĂŶĚƉƉůŝĐĂƟŽŶƐ͘Progress in Polymer Science ϮϬϭϰ, 39;ϰͿ͕ϲϴϯʹϳϬϲ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϭϲͬũ͘ƉƌŽŐƉŽůǇŵƐĐŝ͘ϮϬϭϯ͘Ϭϳ͘ϬϬϲ͘

;ϮͿ EĂŬĂŐĂǁĂ͕^͖͘DĂƌƵďĂǇĂƐŚŝ͕,͖͘EŽũŝŵĂ͕^͘ƌǇƐƚĂůůŝǌĂƟŽŶŽĨWŽůǇŵĞƌŚĂŝŶƐŽŶĮŶĞĚŝŶ Nanodomains. European Polymer Journal ϮϬϭϱ, 70͕ ϮϲϮʹϮϳϱ͘ ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϭϲͬũ͘ ĞƵƌƉŽůǇŵũ͘ϮϬϭϱ͘Ϭϳ͘Ϭϭϴ͘

;ϯͿ DĂĐŬĞǇ͕D͖͘&ůĂŶĚŝŶ͕>͖͘,ŝůƚŶĞƌ͕͖͘ĂĞƌ͕͘ŽŶĮŶĞĚƌǇƐƚĂůůŝǌĂƟŽŶŽĨWs&ĂŶĚĂWs&Ͳd& Copolymer in Nanolayered Films. Journal of Polymer Science Part B: Polymer Physics ϮϬϭϭ, 49;ϮϰͿ͕ϭϳϱϬʹϭϳϲϭ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϬϮͬƉŽůď͘ϮϮϯϳϱ͘

;ϰͿ Ăŝ͕y͖͘EŝƵ͕:͖͘ZĞŶ͕͖͘^ƵŶ͕y͖͘zĂŶ͕^͘īĞĐƚƐŽĨEĂŶŽƉŽƌŽƵƐŶŽĚŝĐůƵŵŝŶĂKǆŝĚĞŽŶƚŚĞ ƌǇƐƚĂůůŝǌĂƟŽŶĂŶĚDĞůƟŶŐĞŚĂǀŝŽƌŽĨWŽůǇ;sŝŶǇůŝĚĞŶĞ&ůƵŽƌŝĚĞͿ͘J. Phys. Chem. B ϮϬϭϲ, 120 ;ϰͿ͕ϴϰϯʹϴϱϬ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬĂĐƐ͘ũƉĐď͘ϱďϭϭϭϳϴ͘

;ϱͿ WĂŶ͕D͖͘zĂŶŐ͕>͖͘tĂŶŐ͕:͖͘dĂŶŐ͕^͖͘ŚŽŶŐ͕'͖͘^Ƶ͕Z͖͘^ĞŶ͕D͘<͖͘ŶĚŽŚ͕D͘<͖͘<ŽŐĂ͕d͖͘ŚƵ͕>͘ ŽŵƉŽƐŝƚĞWŽůǇ;sŝŶǇůŝĚĞŶĞ&ůƵŽƌŝĚĞͿͬWŽůǇƐƚǇƌĞŶĞ>ĂƚĞǆWĂƌƟĐůĞƐĨŽƌŽŶĮŶĞĚƌǇƐƚĂůůŝǌĂƟŽŶ ŝŶ ϭϴϬ Eŵ EĂŶŽƐƉŚĞƌĞƐ ǀŝĂ ŵƵůƐŝĮĞƌͲ&ƌĞĞ ĂƚĐŚ ^ĞĞĚĞĚ ŵƵůƐŝŽŶ WŽůǇŵĞƌŝǌĂƟŽŶ͘ Macromolecules ϮϬϭϰ, 47;ϴͿ͕ϮϲϯϮʹϮϲϰϰ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬŵĂϱϬϬϮϰϵƉ͘

;ϲͿ >ŽŽ͕z͘Ͳ>͖͘ZĞŐŝƐƚĞƌ͕Z͖͘͘ZǇĂŶ͕͘:͖͘ĞĞ͕'͘d͘WŽůǇŵĞƌƌǇƐƚĂůůŝǌĂƟŽŶŽŶĮŶĞĚŝŶKŶĞ͕dǁŽ͕ or Three Dimensions. Macromolecules ϮϬϬϭ, 34;ϮϲͿ͕ϴϵϲϴʹϴϵϳϳ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬ ma011521p. ;ϳͿ ,ĂǁŬĞƌ͕͘:͖͘ZƵƐƐĞůů͕d͘W͘ůŽĐŬŽƉŽůǇŵĞƌ>ŝƚŚŽŐƌĂƉŚǇ͗DĞƌŐŝŶŐ͞ŽƩŽŵͲhƉ͟ǁŝƚŚ͞dŽƉͲ ŽǁŶ͟WƌŽĐĞƐƐĞƐ͘DZ^ƵůůĞƟŶ ϮϬϬϱ, 30;ϭϮͿ͕ϵϱϮʹϵϲϲ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϱϱϳͬŵƌƐϮϬϬϱ͘Ϯϰϵ͘ ;ϴͿ ĂƚĞƐ͕&͘^͖͘&ƌĞĚƌŝĐŬƐŽŶ͕'͘,͘ůŽĐŬŽƉŽůǇŵĞƌƐͶĞƐŝŐŶĞƌ^ŽŌDĂƚĞƌŝĂůƐ͘Physics Today ϮϬϬϴ, 52;ϮͿ͕ϯϮ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϲϯͬϭ͘ϴϴϮϱϮϮ͘ ;ϵͿ tŝĚŝŶ͕ :͘ D͖͘ ^ĐŚŵŝƩ͕ ͘ <͖͘ ^ĐŚŵŝƩ͕ ͘ >͖͘ /ŵ͕ <͖͘ DĂŚĂŶƚŚĂƉƉĂ͕ D͘ <͘ hŶĞǆƉĞĐƚĞĚ ŽŶƐĞƋƵĞŶĐĞƐŽĨůŽĐŬWŽůǇĚŝƐƉĞƌƐŝƚǇŽŶƚŚĞ^ĞůĨͲƐƐĞŵďůǇŽĨdƌŝďůŽĐŬŽƉŽůǇŵĞƌƐ͘J. Am. Chem. Soc. ϮϬϭϮ, 134;ϴͿ͕ϯϴϯϰʹϯϴϰϰ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬũĂϮϭϬϱϰϴĞ͘

;ϭϬͿ >ŽŽ͕ z͘Ͳ>͖͘ ZĞŐŝƐƚĞƌ͕ Z͘ ͖͘ ZǇĂŶ͕ ͘ :͘ DŽĚĞƐ ŽĨ ƌǇƐƚĂůůŝǌĂƚŝŽŶ ŝŶ ůŽĐŬ ŽƉŽůǇŵĞƌ DŝĐƌŽĚŽŵĂŝŶƐ͗ƌĞĂŬŽƵƚ͕dĞŵƉůĂƚĞĚ͕ĂŶĚŽŶĮŶĞĚ͘Macromolecules ϮϬϬϮ, 35;ϲͿ͕Ϯϯϲϱʹ Ϯϯϳϰ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬŵĂϬϭϭϴϮϰũ͘ ;ϭϭͿ sŽĞƚ͕s͘^͖͘͘ŬĞŶƐƚĞŝŶ͕'͘K͘Z͘͘ǀĂŶ͖DĞĞƌĞďŽĞƌ͕E͘>͖͘,ŽĨŵĂŶ͕͘,͖͘ƌŝŶŬĞ͕'͘ƚĞŶ͖ >ŽŽƐ͕ <͘ ŽƵďůĞͲƌǇƐƚĂůůŝŶĞ W>>ͲďͲWs&ͲďͲW>> dƌŝďůŽĐŬ ŽƉŽůǇŵĞƌƐ͗ WƌĞƉĂƌĂƟŽŶ ĂŶĚ ƌǇƐƚĂůůŝǌĂƟŽŶ͘Polym. Chem. ϮϬϭϰ, 5;ϳͿ͕ϮϮϭϵʹϮϮϯϬ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϯϵͬϯWzϬϭϱϲϬ͘ ;ϭϮͿ dĞƌǌŝĐ͕/͖͘DĞĞƌĞďŽĞƌ͕E͘>͖͘>ŽŽƐ͕<͘ƵůŝĐŬŚĞŵŝƐƚƌǇ͗sĞƌƐĂƟůĞƉƉƌŽĂĐŚƚŽǁĂƌĚƐ

Ws&ͲĂƐĞĚ ůŽĐŬ ŽƉŽůǇŵĞƌƐ͘ Polym. Chem. ϮϬϭϴ, 9 ;ϮϳͿ͕ ϯϳϭϰʹϯϳϮϬ͘ ŚƚƚƉƐ͗ͬͬĚŽŝ͘ ŽƌŐͬϭϬ͘ϭϬϯϵͬϴWzϬϬϳϰϮ:͘

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;ϭϯͿ ZĂŶũĂŶ͕Z͖͘ƌŝƩĂŝŶ͕t͘:͘dĂŶĚĞŵZ&dWŽůǇŵĞƌŝǌĂƟŽŶĂŶĚůŝĐŬŚĞŵŝƐƚƌǇ͗ŶĸĐŝĞŶƚ ƉƉƌŽĂĐŚƚŽ^ƵƌĨĂĐĞDŽĚŝĮĐĂƟŽŶ͘DĂĐƌŽŵŽůĞĐƵůĂƌZĂƉŝĚŽŵŵƵŶŝĐĂƟŽŶƐ ϮϬϬϳ, 28;ϮϭͿ͕ ϮϬϴϰʹϮϬϴϵ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϬϮͬŵĂƌĐ͘ϮϬϬϳϬϬϰϮϴ͘

;ϭϰͿ >Ăŝ͕ :͘ d͖͘ &ŝůůĂ͕ ͖͘ ^ŚĞĂ͕ Z͘ &ƵŶĐƚŝŽŶĂů WŽůǇŵĞƌƐ ĨƌŽŵ EŽǀĞů ĂƌďŽǆǇůͲdĞƌŵŝŶĂƚĞĚ dƌŝƚŚŝŽĐĂƌďŽŶĂƚĞƐĂƐ,ŝŐŚůǇĸĐŝĞŶƚZ&dŐĞŶƚƐ͘Macromolecules ϮϬϬϮ, 35;ϭϴͿ͕ϲϳϱϰʹϲϳϱϲ͘ ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬŵĂϬϮϬϯϲϮŵ͘ ;ϭϱͿ ŽƌƐďŽŽŵ͕D͖͘ƌĂƐ͕t͖͘ĞƌũĂŬ͕/͖͘ĞƚŽůůĞŶĂĞƌĞ͕͖͘'ůĂƐƚƌĂǀĂŶ>ŽŽŶ͕͖͘'ŽĞĚƚŬŝŶĚƚ͕W͖͘ <ŽŶŝũŶĞŶďƵƌŐ͕D͖͘>ĂƐƐŝŶŐ͕W͖͘>ĞǀŝŶĞ͕z͘<͖͘DƵŶŶĞŬĞ͕͖͘ĞƚĂů͘dŚĞƵƚĐŚʹĞůŐŝĂŶĞĂŵůŝŶĞ ĂƚƚŚĞ^Z&͘:ŽƵƌŶĂůŽĨ^ǇŶĐŚƌŽƚƌŽŶZĂĚŝĂƟŽŶ ϭϵϵϴ, 5;ϯͿ͕ϱϭϴʹϱϮϬ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϭϬϳͬ ^ϬϵϬϵϬϰϵϱϵϳϬϭϯϰϴϰ͘ ;ϭϲͿ ƌĂƐ͕t͖͘ŽůďŶǇĂ͕/͘W͖͘ĞƚŽůůĞŶĂĞƌĞ͕͖͘dŽů͕Z͘ǀĂŶ͖DĂůĨŽŝƐ͕D͖͘'ƌĞĂǀĞƐ͕'͘E͖͘ZǇĂŶ͕ ͘:͖͘,ĞĞůĞǇ͕͖͘/hƌ͘ZĞĐĞŶƚǆƉĞƌŝŵĞŶƚƐŽŶĂ^ŵĂůůͲŶŐůĞͬtŝĚĞͲŶŐůĞyͲZĂǇ^ĐĂƩĞƌŝŶŐ ĞĂŵ>ŝŶĞĂƚƚŚĞ^Z&͘Journal of Applied Crystallography ϮϬϬϯ, 36͕ϳϵϭʹϳϵϰ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ ŽƌŐͬϭϬ͘ϭϭϬϳͬ^ϬϬϮϭϴϴϵϴϬϯϬϬϰϬϬy͘ ;ϭϳͿ 'ƌĂĚǇƐ ƌŬĂĚŝƵƐǌ͖ ^ĂũŬŝĞǁŝĐǌ WĂǁĞů͘ ĞƚĞƌŵŝŶĂƚŝŽŶ ŽĨ ƚŚĞ DĞůƚŝŶŐ ŶƚŚĂůƉǇ ŽĨ ɴ WŚĂƐĞ ŽĨ WŽůǇ;sŝŶǇůŝĚĞŶĞ &ůƵŽƌŝĚĞͿ͘ epoly ϮϬϭϯ, 13 ;ϭͿ͕ ϮϬϯ͘ ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϱϭϱͬ ĞƉŽůǇ͘ϮϬϭϯ͘ϭϯ͘ϭ͘ϮϬϯ͘ ;ϭϴͿ >ŽǀŝŶŐĞƌ͕͘:͘ƌǇƐƚĂůůŝǌĂƟŽŶĂŶĚDŽƌƉŚŽůŽŐǇŽĨDĞůƚͲ^ŽůŝĚŝĮĞĚWŽůǇ;sŝŶǇůŝĚĞŶĞ&ůƵŽƌŝĚĞͿ͘ :ŽƵƌŶĂů ŽĨ WŽůǇŵĞƌ ^ĐŝĞŶĐĞ͗ WŽůǇŵĞƌ WŚǇƐŝĐƐ ĚŝƟŽŶ ϭϵϴϬ, 18 ;ϰͿ͕ ϳϵϯʹϴϬϵ͘ ŚƩƉƐ͗ͬͬĚŽŝ͘ ŽƌŐͬϭϬ͘ϭϬϬϮͬƉŽů͘ϭϵϴϬ͘ϭϴϬϭϴϬϰϭϮ͘ ;ϭϵͿ 'ƌĞŐŽƌŝŽ͕Z͘:͖͘ĞƐƚĂƌŝ͕D͘īĞĐƚŽĨƌǇƐƚĂůůŝǌĂƟŽŶdĞŵƉĞƌĂƚƵƌĞŽŶƚŚĞƌǇƐƚĂůůŝŶĞWŚĂƐĞ ŽŶƚĞŶƚĂŶĚDŽƌƉŚŽůŽŐǇŽĨWŽůǇ;sŝŶǇůŝĚĞŶĞ&ůƵŽƌŝĚĞͿ͘Journal of Polymer Science Part B: Polymer Physics ϭϵϵϰ, 32;ϱͿ͕ϴϱϵʹϴϳϬ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϬϮͬƉŽůď͘ϭϵϵϰ͘ϬϵϬϯϮϬϱϬϵ͘ ;ϮϬͿ 'ƵŽ͕͖͘ĞŶŐ͕&͖͘ŬŚŝů͕͘&ĞƌƌŽĞůĞĐƚƌŝĐWŽůǇŵĞƌEĂŶŽƐƚƌƵĐƚƵƌĞƐ͗&ĂďƌŝĐĂƟŽŶ͕^ƚƌƵĐƚƵƌĂů

ŚĂƌĂĐƚĞƌŝƐƟĐƐĂŶĚWĞƌĨŽƌŵĂŶĐĞƵŶĚĞƌŽŶĮŶĞŵĞŶƚ͘J Nanosci Nanotechnol ϮϬϭϰ, 14;ϮͿ͕ ϮϬϴϲʹϮϭϬϬ͘

;ϮϭͿ ,ƐƵ͕ ͘ ͖͘ 'Ğŝů͕ W͘ ,͘ DŽƌƉŚŽůŽŐǇͲƐƚƌƵĐƚƵƌĞͲƉƌŽƉĞƌƚǇ ZĞůĂƟŽŶƐŚŝƉƐ ŝŶ hůƚƌĂƋƵĞŶĐŚĞĚ WŽůǇ;sŝŶǇůŝĚĞŶĞ&ůƵŽƌŝĚĞͿ͘Journal of Applied Physics ϭϵϴϰ, 56;ϵͿ͕ϮϰϬϰʹϮϰϭϭ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ ŽƌŐͬϭϬ͘ϭϬϲϯͬϭ͘ϯϯϰϯϬϮ͘ ;ϮϮͿ KŬĂ͕z͖͘<ŽŝǌƵŵŝ͕E͘&ŽƌŵĂƟŽŶŽĨhŶŽƌŝĞŶƚĞĚ&Žƌŵ/WŽůǇ;sŝŶǇůŝĚĞŶĞ&ůƵŽƌŝĚĞͿďǇ,ŝŐŚͲZĂƚĞ YƵĞŶĐŚŝŶŐĂŶĚ/ƚƐůĞĐƚƌŝĐĂůWƌŽƉĞƌƟĞƐ͘ϭϵϴϱ, 63;ϯͿ͕ϭϵϮʹϮϬϲ͘ ;ϮϯͿ ŽůĞŵĂŶ͕D͘D͖͘ĂƌŝĂŶ͕:͖͘sĂƌŶĞůů͕͘&͖͘WĂŝŶƚĞƌ͕W͘͘&ŽƵƌŝĞƌdƌĂŶƐĨŽƌŵ/ŶĨƌĂƌĞĚ^ƚƵĚǇŽĨ WŽůǇŵĞƌůĞŶĚƐ͘/͘WŽůǇ;sŝŶǇůŝĚĞŶĞ&ůƵŽƌŝĚĞͿͶWŽůǇ;DĞƚŚǇůDĞƚŚĂĐƌǇůĂƚĞͿ^ǇƐƚĞŵ͘Journal ŽĨWŽůǇŵĞƌ^ĐŝĞŶĐĞ͗WŽůǇŵĞƌ>ĞƩĞƌƐĚŝƟŽŶ ϭϵϳϳ, 15;ϭϮͿ͕ϳϰϱʹϳϱϬ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϬϮͬ ƉŽů͘ϭϵϳϳ͘ϭϯϬϭϱϭϮϬϳ͘

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;ϮϰͿ ^ŚŝŽŵŝ͕d͖͘dĂŬĞƐŚŝƚĂ͕,͖͘<ĂǁĂŐƵĐŚŝ͕,͖͘EĂŐĂŝ͕D͖͘dĂŬĞŶĂŬĂ͕<͖͘DŝǇĂ͕D͘ƌǇƐƚĂůůŝǌĂƟŽŶĂŶĚ ^ƚƌƵĐƚƵƌĞ&ŽƌŵĂƟŽŶŽĨůŽĐŬŽƉŽůǇŵĞƌƐŽŶƚĂŝŶŝŶŐĂZƵďďĞƌǇŵŽƌƉŚŽƵƐŽŵƉŽŶĞŶƚ͘ Macromolecules ϮϬϬϮ, 35;ϮϭͿ͕ϴϬϱϲʹϴϬϲϱ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬŵĂϬϮϬϬϭϭϴ͘ ;ϮϱͿ >ŝŶ͕ D͘Ͳ͖͘ ŚĞŶ͕ ,͘Ͳ>͖͘ >ŝŶ͕ t͘Ͳ&͖͘ ,ƵĂŶŐ͕ W͘Ͳ^͖͘ dƐĂŝ͕ :͘Ͳ͘ ƌǇƐƚĂůůŝǌĂƟŽŶ ŽĨ /ƐŽƚĂĐƟĐ WŽůǇƉƌŽƉǇůĞŶĞƵŶĚĞƌƚŚĞ^ƉĂƟĂůŽŶĮŶĞŵĞŶƚdĞŵƉůĂƚĞĚďǇůŽĐŬŽƉŽůǇŵĞƌDŝĐƌŽĚŽŵĂŝŶƐ͘ J. Phys. Chem. B ϮϬϭϮ, 116;ϰϬͿ͕ϭϮϯϱϳʹϭϮϯϳϭ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬũƉϯϬϲϰϭϬũ͘ ;ϮϲͿ ŚĞŶ͕,͘Ͳ>͖͘tƵ͕:͘Ͳ͖͘>ŝŶ͕d͘Ͳ>͖͘>ŝŶ͕:͘^͘ƌǇƐƚĂůůŝǌĂƟŽŶ<ŝŶĞƟĐƐŝŶDŝĐƌŽƉŚĂƐĞͲ^ĞƉĂƌĂƚĞĚ WŽůǇ;ƚŚǇůĞŶĞKǆŝĚĞͿͲůŽĐŬͲWŽůǇ;ϭ͕ϰͲƵƚĂĚŝĞŶĞͿ͘Macromolecules ϮϬϬϭ, 34;ϮϬͿ͕ϲϵϯϲʹϲϵϰϰ͘ ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬŵĂϬϭϬϱϱϮŚ͘ ;ϮϳͿ DŝǇĂǌĂŬŝ͕d͖͘dĂŬĞĚĂ͕z͖͘ŬĂƐĂŬĂ͕D͖͘^ĂŬĂŝ͕D͖͘,ŽƐŚŝŬŽ͕͘WƌĞƉĂƌĂƟŽŶŽĨ/ƐŽƚŚĞƌŵĂůůǇ ƌǇƐƚĂůůŝǌĞĚɶͲ&ŽƌŵWŽůǇ;sŝŶǇůŝĚĞŶĞ&ůƵŽƌŝĚĞͿ&ŝůŵƐďǇĚĚŝŶŐĂ<ƌWŽǁĚĞƌĂƐĂEƵĐůĞĂƟŶŐ ŐĞŶƚ͘Macromolecules ϮϬϬϴ, 41;ϳͿ͕ϮϳϰϵʹϮϳϱϯ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬŵĂϳϬϮϲϵϭĐ͘ ;ϮϴͿ >ŽƉĞƐ͕͖͘͘ŽƐƚĂ͕͘D͖͘dĂǀĂƌĞƐ͕͘:͖͘EĞǀĞƐ͕/͖͘͘>ĂŶĐĞƌŽƐͲDĞŶĚĞǌ͕^͘EƵĐůĞĂƟŽŶŽĨƚŚĞ ůĞĐƚƌŽĂĐƟǀĞɶWŚĂƐĞĂŶĚŶŚĂŶĐĞŵĞŶƚŽĨƚŚĞKƉƟĐĂůdƌĂŶƐƉĂƌĞŶĐǇŝŶ>Žǁ&ŝůůĞƌŽŶƚĞŶƚ WŽůǇ;sŝŶǇůŝĚĞŶĞͿͬůĂǇEĂŶŽĐŽŵƉŽƐŝƚĞƐ͘J. Phys. Chem. C ϮϬϭϭ, 115;ϯϳͿ͕ϭϴϬϳϲʹϭϴϬϴϮ͘ŚƩƉƐ͗ͬͬ ĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬũƉϮϬϰϱϭϯǁ͘

;ϮϵͿ >ŽƉĞƐ͕͖͘͘ĂƉĂƌƌŽƐ͕͖͘'ſŵĞǌZŝďĞůůĞƐ͕:͘>͖͘EĞǀĞƐ͕/͖͘͘>ĂŶĐĞƌŽƐͲDĞŶĚĞǌ͕^͘ůĞĐƚƌŝĐĂů ĂŶĚ dŚĞƌŵĂů ĞŚĂǀŝŽƌ ŽĨ ɶͲWŚĂƐĞ WŽůǇ;sŝŶǇůŝĚĞŶĞ &ůƵŽƌŝĚĞͿͬEĂz ĞŽůŝƚĞ ŽŵƉŽƐŝƚĞƐ͘ Microporous and Mesoporous Materials ϮϬϭϮ, 161͕ ϵϴʹϭϬϱ͘ ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϭϲͬũ͘ micromeso.2012.05.019.

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