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

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

applications

Meereboer, Niels Laurens

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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

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Chapter 4

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&ĞƌƌŽĞůĞĐƚƌŝĐ ƉŽůLJŵĞƌƐ͕ ƐƵĐŚ ĂƐ ƉŽůLJ;ǀŝŶLJůŝĚĞŶĞ ĨůƵŽƌŝĚĞͿ ;Ws&Ϳ͕ ĂƌĞ ĂƚƚƌĂĐƚŝǀĞ electroactive materials that can be integrated in advanced electronic devices. hŶĨŽƌƚƵŶĂƚĞůLJ͕ƚŽŽďƚĂŝŶƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐƉŚĂƐĞŝŶWs&͕ĂĚĚŝƟŽŶĂůƉƌŽĐĞƐƐŝŶŐŵĞƚŚŽĚƐ ŽƌĞdžƉĞŶƐŝǀĞĐŽƉŽůLJŵĞƌŝnjĂƟŽŶƐǁŝƚŚƚƌŝŇƵŽƌŽĞƚŚLJůĞŶĞŚĂǀĞƚŽďĞĞŵƉůŽLJĞĚ͘DŽƌĞŽǀĞƌ͕ ƚŚĞŚŝŐŚůLJŇƵŽƌŝŶĂƚĞĚƉŽůLJŵĞƌƐůĂĐŬĨƵŶĐƟŽŶĂůŝƟĞƐƚŽŐĂŝŶŝŵƉƌŽǀĞĚƉƌŽƉĞƌƟĞƐ͕ƐƵĐŚĂƐ ǁĞƩĂďŝůŝƚLJĂŶĚƉŽƐƐŝďŝůŝƟĞƐĨŽƌĐƌŽƐƐůŝŶŬŝŶŐĂŶĚŶĂŶŽŽďũĞĐƚĚŝƐƉĞƌƐŝŽŶ͘/ŶƚŚŝƐǁŽƌŬ͕ƚŚĞ ƐLJŶƚŚĞƐŝƐĂŶĚĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌŽĨƉŽůLJ;ǀŝŶLJůŝĚĞŶĞŇƵŽƌŝĚĞ-co-ǀŝŶLJůĂůĐŽŚŽůͿ;W;s&-co-sͿͿĐŽƉŽůLJŵĞƌƐĂƌĞĚĞŵŽŶƐƚƌĂƚĞĚƵƐŝŶŐĂĐŚĞĂƉǀŝŶLJůĂĐĞƚĂƚĞͲďĂƐĞĚƉƌĞĐƵƌƐŽƌ͘tĞ ƐŚŽǁƚŚĂƚƚŚĞƐǁŝƚĐŚŝŶŐƉƌŽƉĞƌƟĞƐĐĂŶďĞƚƵŶĞĚďLJǀĂƌLJŝŶŐƚŚĞǀŝŶLJůĂůĐŽŚŽůĐŽŶƚĞŶƚ in the copolymers. Linear dielectric behavior is observed for copolymers with 10 mol йsĚƵĞƚŽĂŵŝdžƚƵƌĞŽĨɲͲĂŶĚɴͲĐƌLJƐƚĂůƐ͘/ŶƚƌŝŐƵŝŶŐůLJ͕ƚŚĞŝŶĐŽƌƉŽƌĂƟŽŶŽĨϭϱŵŽů йsƌĞƐƵůƚƐŝŶƚŚĞĚŝƌĞĐƚĐƌLJƐƚĂůůŝnjĂƟŽŶŝŶƚŽƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐɴͲƉŚĂƐĞĨƌŽŵƚŚĞŵĞůƚ͘ ŽŶƐĞƋƵĞŶƚůLJ͕ ƚŚŝƐ W;s&-co-sͿ ĐŽƉŽůLJŵĞƌ ǁŝƚŚ ŚLJĚƌŽdžLJů ĨƵŶĐƟŽŶĂů ŐƌŽƵƉƐ ŝŶ ƚŚĞ ƉŽůLJŵĞƌďĂĐŬďŽŶĞŝƐĨĞƌƌŽĞůĞĐƚƌŝĐǁŝƚŚŽƵƚĂĚĚŝƟŽŶĂůƉƌŽĐĞƐƐŝŶŐĂŶĚĚĞŵŽŶƐƚƌĂƚĞƐĂ ĐŽĞƌĐŝǀĞĮĞůĚĂŶĚĂƌĞŵŶĂŶƚƉŽůĂƌŝnjĂƟŽŶŽĨϴϬDsŵͲϭ_{ĂŶĚϮ͘ϴђĐŵ}ͲϮ_{ĂƚϮϬϬDsŵ}Ͳϭ_, ƌĞƐƉĞĐƟǀĞůLJ͕ƐŚŽǁŝŶŐŝƚƐŚŝŐŚƉŽƚĞŶƟĂůĨŽƌĂĚǀĂŶĐĞĚĞůĞĐƚƌŽŶŝĐĂƉƉůŝĐĂƟŽŶƐ͘

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

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Introduction

The previous two chapters showed approaches on how we can obtain the ferroelectric ƉŚĂƐĞŝŶƐŵĂůůŝƐŽůĂƚĞĚŶĂŶŽĚŽŵĂŝŶƐ͘/ŶƚŚĞŶĞdžƚĐŚĂƉƚĞƌƐ͕ĂĚŝīĞƌĞŶƚŵĞƚŚŽĚƚŽŝƐŽůĂƚĞ ĨĞƌƌŽĞůĞĐƚƌŝĐ ĐƌLJƐƚĂůƐ ŝƐ ƵƐĞĚ͘ LJ ŝŶƚƌŽĚƵĐŝŶŐ ĨƵŶĐƟŽŶĂůŝƟĞƐ ŝŶ ƚŚĞ Ws& ďĂĐŬďŽŶĞ͕ chemical crosslinking methods can be employed giving isolated crystals in a polymeric network. In this chapter, we demonstrate how these ferroelectric copolymers having ĞĂƐŝůLJĂĐĐĞƐƐŝďůĞĨƵŶĐƟŽŶĂůŝƟĞƐĂƌĞŽďƚĂŝŶĞĚviaĂĨĂĐŝůĞĐŽƉŽůLJŵĞƌŝnjĂƟŽŶ͘ Ɛ ĂůƌĞĂĚLJ ĚŝƐĐƵƐƐĞĚ͕ ĨĞƌƌŽĞůĞĐƚƌŝĐ ƉŽůLJŵĞƌƐ ĂƌĞ Ă ĐůĂƐƐ ŽĨ ŵĂƚĞƌŝĂůƐ ƐŚŽǁŝŶŐ Ă ƐƉŽŶƚĂŶĞŽƵƐ ĞůĞĐƚƌŝĐĂů ƉŽůĂƌŝnjĂƟŽŶ ƚŚĂƚ ĐĂŶ ďĞ ƐǁŝƚĐŚĞĚ ďLJ ƚŚĞ ĂƉƉůŝĐĂƟŽŶ ŽĨ ĂŶ ĞůĞĐƚƌŝĐĮĞůĚ͕ǁŚŝůĞŚĂǀŝŶŐĞdžĐĞůůĞŶƚƉƌŽĐĞƐƐĂďŝůŝƚLJŝŶƚŽůŝŐŚƚ͕ƚŚŽƵŐŚĂŶĚŇĞdžŝďůĞĮůŵƐ͘ϭʹϯ dŚĞƌĞĨŽƌĞ͕ďƵůŬŵĂƚĞƌŝĂůƐĂŶĚƚŚŝŶĮůŵƐŽĨWs&ͲďĂƐĞĚƉŽůLJŵĞƌƐĮŶĚĂƉƉůŝĐĂƟŽŶƐĂŵŽŶŐ ŽƚŚĞƌƐŝŶŵĞŵŽƌLJƐƚŽƌĂŐĞĚĞǀŝĐĞƐ͕ƐĞŶƐŽƌƐ͕ĨĞƌƌŽĞůĞĐƚƌŝĐĮĞůĚ-ĞīĞĐƚƚƌĂŶƐŝƐƚŽƌƐĂŶĚ photovoltaics.ϰ͕ϱ_{dŽŽďƚĂŝŶƚŚĞĚĞƐŝƌĞĚĞůĞĐƚƌŽĂĐƟǀĞƉƌŽƉĞƌƟĞƐ͕ƚŚĞŚŝŐŚůLJŇƵŽƌŝŶĂƚĞĚ} ƉŽůLJŵĞƌƐŚĂǀĞƚŽĐƌLJƐƚĂůůŝnjĞŝŶƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐɴͲƉŚĂƐĞ͕ǁŚĞƌĞŝŶƚŚĞĐŚĂŝŶƐĂĚŽƉƚĂŶĂůůͲ ƚƌĂŶƐĐŽŶĨŽƌŵĂƟŽŶ͘ϲ_{ĞĐĂƵƐĞWs&ĐƌLJƐƚĂůůŝnjĞƐƉƌĞĨĞƌĞŶƟĂůůLJŝŶƚŚĞŶŽŶƉŽůĂƌɲͲƉŚĂƐĞvia} ŵĞůƚĐƌLJƐƚĂůůŝnjĂƟŽŶ͕ŶƵŵĞƌŽƵƐƚĞĐŚŶŝƋƵĞƐƚŽƉƌŽĐĞƐƐWs&ŝŶƚŚĞɴͲƉŚĂƐĞĂƌĞƐƵĐĐĞƐƐĨƵůůLJ ŝŶǀĞƐƟŐĂƚĞĚƚŽĐŽŶƚƌŽůĮůŵƚŚŝĐŬŶĞƐƐ͕ĐƌLJƐƚĂůŽƌŝĞŶƚĂƟŽŶĂŶĚƉŽƌŽƐŝƚLJ͘7,8_{ŶĂĚĚŝƟŽŶĂů} ŵĞƚŚŽĚƚŽĞĂƐŝůLJŽďƚĂŝŶƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐƉŚĂƐĞŝŶWs&ŝƐvias&ĐŽƉŽůLJŵĞƌŝnjĂƟŽŶƐ ǁŝƚŚdƌ&͘9 ZĞŐĂƌĚůĞƐƐ ŽĨ ƚŚĞ ƉƌŽĐĞƐƐŝŶŐ ĐŽŶĚŝƚŝŽŶƐ͕ W;s&-co-dƌ&Ϳ ĐŽƉŽůLJŵĞƌƐ͕ ŝŶ ƚŚĞ ĐŽŵƉŽƐŝƟŽŶƌĂŶŐĞŽĨϱϬͲϴϬŵŽůйs&͕ĂƌĞĂůǁĂLJƐŝŶƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐĐƌLJƐƚĂůůŝŶĞƉŚĂƐĞĂƚ room temperature.10_{,ĞƌĞŝŶ͕ƚŚĞƐůŝŐŚƚůLJďƵůŬŝĞƌdƌ&ƵŶŝƚƐĂĐƚĂƐĚĞĨĞĐƚƐĂŶĚŝŶĐƌĞĂƐĞƚŚĞ}

ƵŶŝƚĐĞůůĚŝŵĞŶƐŝŽŶƐ͕ǁŚŝĐŚƌĞƐƵůƚƐŝŶĞĂƐŝĞƌĐŚĂŝŶƌŽƚĂƟŽŶƐĂƌŽƵŶĚƚŚĞƉŽůLJŵĞƌďĂĐŬďŽŶĞ ůĞĂĚŝŶŐƚŽĐƌLJƐƚĂůůŝnjĂƟŽŶŝŶƚŽƚŚĞƚŚĞƌŵŽĚLJŶĂŵŝĐĂůůLJĨĂǀŽƌĂďůĞĂůůͲƚƌĂŶƐĐŽŶĨŽƌŵĂƟŽŶ͘11 ǀĞŶ ƚŚŽƵŐŚ͕ W;s&-co-dƌ&Ϳ ĐŽƉŽůLJŵĞƌƐ ĂƌĞ ĂůƌĞĂĚLJ ŝŶ ŝŶĚƵƐƚƌŝĂů ƉƌŽĚƵĐƟŽŶ͕ ƚŚĞ ŚĂnjĂƌĚŽƵƐƐƚŽƌĂŐĞĂŶĚƚƌĂŶƐƉŽƌƚĐŽŶĚŝƟŽŶƐŽĨdƌ&ĂŶĚƚŚĞƌŝƐŬŽĨĞdžƉůŽƐŝŽŶƐĚƵƌŝŶŐ ƚŚĞƐLJŶƚŚĞƐŝƐŵĂŬĞdƌ&ĂŶĞdžƉĞŶƐŝǀĞŵŽŶŽŵĞƌ͕ǁŚŝĐŚƌŝƐĞƐƚŚĞĐŽƐƚƐŽĨƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐ polymers.ϰ_{KƚŚĞƌĂƉƉƌŽĂĐŚĞƐ͕ůŝŬĞĂs&ĐŽƉŽůLJŵĞƌŝnjĂƟŽŶǁŝƚŚĐŚůŽƌŽƚƌŝŇƵŽƌŽĞƚŚLJůĞŶĞ} ;d&Ϳ ĨŽůůŽǁĞĚ ďLJ ĚĞĐŚůŽƌŝŶĂƟŽŶ͕ ƉƌŽǀŝĚĞ Ă ƐĂĨĞƌ ĂůƚĞƌŶĂƟǀĞ͕ LJĞƚ ƐƚƌĂƚĞŐŝĞƐ ƚŽ ŐĞƚ ĐŽŵƉůĞƚĞĚĞĐŚůŽƌŝŶĂƟŽŶǁŝƚŚŶŽĚĞŚLJĚƌŽŇƵŽƌŝŶĂƟŽŶŚĂǀĞƚŽďĞĚĞǀĞůŽƉĞĚ͘ϭϮ͕ϭϯ ŽƉŽůLJŵĞƌƐŽĨs&ǁŝƚŚďƵůŬŝĞƌĐŽŶƐƟƚƵĞŶƚƐ͕ƐƵĐŚĂƐŚĞdžĂŇƵŽƌŽƉƌŽƉLJůĞŶĞ;,&WͿ Žƌ ŵŽŶŽŵĞƌƐ ďĞĂƌŝŶŐ ĨƵŶĐƟŽŶĂů ŐƌŽƵƉƐ ;ϮͲƚƌŝŇƵŽƌŽŵĞƚŚĂĐƌLJůŝĐ ĂĐŝĚ͕ ĂůůLJů ĚŝŵĞƚŚLJů phosphonate, etc.ͿƵƐƵĂůůLJLJŝĞůĚƐŵĂůůĞƌĐƌLJƐƚĂůůŝƚĞƐĂŶĚƚŚĞŶŽŶͲĨĞƌƌŽĞůĞĐƚƌŝĐɲͲƉŚĂƐĞ ĐĂƵƐĞĚ ďLJ ƚŚĞ ĞdžĐůƵƐŝŽŶ ŽĨ ƚŚĞ ĐŽŵŽŶŽŵĞƌƐ ŝŶ ƚŚĞ ĐƌLJƐƚĂů ůĂƫĐĞ͘ϭϰʹϭϲ_{ ǀĞŶ ƚŚŽƵŐŚ} ƌĞƉŽƌƚĞĚŝŶƚŚĞůŝƚĞƌĂƚƵƌĞ͕ĐŽƉŽůLJŵĞƌƐŽĨs&ǁŝƚŚŶŽŶͲŇƵŽƌŝŶĂƚĞĚsĐĂƩƌĂĐƚĞĚůŝƩůĞ ĂƩĞŶƟŽŶ͕ƉƌŽďĂďůLJĚƵĞƚŽďƵůŬŝŶĞƐƐĂŶĚƚŚĞŚŝŐŚƌĞĂĐƟǀŝƚLJƌĂƟŽďĞƚǁĞĞŶs&ĂŶĚ sĐĂŶĚƚŚĞƉŽƐƐŝďŝůŝƚLJŽĨĐŚĂŝŶƚƌĂŶƐĨĞƌƚŽŵŽŶŽŵĞƌ͘ϭϳʹϭϵ _{Nevertheless, controlling the}

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

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ĂŶĂƉƉĞĂůŝŶŐŵĞƚŚŽĚƚŽŝŶĐůƵĚĞĚĞĨĞĐƚƐŝŶƚŚĞƉŽůLJŵĞƌďĂĐŬďŽŶĞ͕ǁŚŝůĞƐƟůůŚĂǀŝŶŐ ĐŽĐƌLJƐƚĂůůŝnjĂƟŽŶŽĨs&ĂŶĚsĚƵĞƚŚĞƐŵĂůůƐŝnjĞŽĨƚŚĞsŵŽŶŽŵĞƌ͘/ŶƉĂƌƟĐƵůĂƌ͕ ďĞĐĂƵƐĞsĐŝƐůŽǁͲĐŽƐƚĂŶĚĞĂƐLJŝŶŚĂŶĚůŝŶŐĂŶĚƐƚŽƌĂŐĞ͕ŝƚƉƌŽǀŝĚĞƐŵĂũŽƌĂĚǀĂŶƚĂŐĞƐ ŽǀĞƌŇƵŽƌŝŶĂƚĞĚŵŽŶŽŵĞƌƐ͕ƐƵĐŚĂƐdƌ&ĂŶĚd&͘DŽƌĞŽǀĞƌ͕ƚŚĞŝŶƚƌŽĚƵĐƟŽŶŽĨĂůĐŽŚŽů ŵŽŝĞƟĞƐŝŶƚŚĞWs&ďĂĐŬďŽŶĞŐŝǀĞƐŽƉƉŽƌƚƵŶŝƟĞƐƚŽƉĞƌĨŽƌŵĐŚĞŵŝĐĂůŵŽĚŝĮĐĂƟŽŶƐ (e.g.ŝƐŽĐLJĂŶĂƚĞĐƌŽƐƐůŝŶŬŝŶŐ͕ƐĞĞŚĂƉƚĞƌϱͿ͕ƚŽŝŶĚƵĐĞďĞƩĞƌǁĞƫŶŐƚŽƐƵďƐƚƌĂƚĞƐĂŶĚ ƚŽƐƚƌŽŶŐůLJŝŶƚĞƌĂĐƚǁŝƚŚŶĂŶŽƉĂƌƟĐůĞƐ͘

Materials and Methods

Experimental Materials͗sŝŶLJůĂĐĞƚĂƚĞ;&ůƵŬĂ͕хϵϵйͿǁĂƐĚƌŝĞĚŽǀĞƌĂů₂ĂŶĚĚŝƐƟůůĞĚƵŶĚĞƌƌĞĚƵĐĞĚ ƉƌĞƐƐƵƌĞ͘ĞŶnjŽLJůƉĞƌŽdžŝĚĞ;WKͿǁĂƐƌĞĐƌLJƐƚĂůůŝnjĞĚďLJĂĚĚŝŶŐŵĞƚŚĂŶŽůƚŽĂWKƐŽůƵƟŽŶ ŝŶĐŚůŽƌŽĨŽƌŵ͘sŝŶLJůŝĚĞŶĞŇƵŽƌŝĚĞ;s&͕^LJŶƋƵĞƐƚ>ĂďƐ͕ϵϴйͿ͕ĚŝŵĞƚŚLJůĐĂƌďŽŶĂƚĞ;D͕ ĐƌŽƐ͕хϵϵй͕ĞdžƚƌĂĚƌLJͿ͕ŚLJĚƌŽĐŚůŽƌŝĐĂĐŝĚ;ϯϳй͕ŽŽŵͿǁĞƌĞƵƐĞĚĂƐƌĞĐĞŝǀĞĚ͘ůůŽƚŚĞƌ ƐŽůǀĞŶƚƐǁĞƌĞĂŶĂůLJƟĐĂůŐƌĂĚĞ͘ ^LJŶƚŚĞƐŝƐŽĨƉŽůLJ;ǀŝŶLJůŝĚĞŶĞŇƵŽƌŝĚĞͲĐŽͲǀŝŶLJůĂĐĞƚĂƚĞͿ;W;s&ͲĐŽͲsĐͿͿĐŽƉŽůLJŵĞƌƐ͗ ϲϬϬŵ>WĂƌƌ;ŵŽĚĞůϰϱϲϴͿŚŝŐŚƉƌĞƐƐƵƌĞƌĞĂĐƚŽƌǁĂƐĐŚĂƌŐĞĚǁŝƚŚďĞŶnjŽLJůƉĞƌŽdžŝĚĞ ;ϭϱϬŵŐ͕Ϭ͘ϲϮŵŵŽůͿ͕ĂŶŚLJĚƌŽƵƐĚŝŵĞƚŚLJůĐĂƌďŽŶĂƚĞ;ϯϬϬŵ>Ϳ͕ĂŶĚĨƌĞƐŚůLJĚŝƐƟůůĞĚǀŝŶLJů ĂĐĞƚĂƚĞ;Ϯŵ>͕Ϯϭ͘ϳŵŵŽůͿ͘ŌĞƌƚŚĞƌĞĂĐƟŽŶŵŝdžƚƵƌĞǁĂƐƉƵƌŐĞĚǁŝƚŚE₂ĨŽƌϯϬŵŝŶ͕s& ;ϮϬ͘ϬďĂƌͿǁĂƐƚƌĂŶƐĨĞƌƌĞĚŝŶƚŽƚŚĞƌĞĂĐƚŽƌĂƚƌŽŽŵƚĞŵƉĞƌĂƚƵƌĞ͘dŚĞƌĞĂĐƟŽŶŵŝdžƚƵƌĞ ǁĂƐƌĂƉŝĚůLJŚĞĂƚĞĚƚŽϵϬΣĂŶĚĂůůŽǁĞĚƚŽƐƟƌĂƚϱϬϬƌƉŵĨŽƌϯϬŵŝŶ͘^ƵďƐĞƋƵĞŶƚůLJ͕ƚŚĞ ŚĞĂƟŶŐƐŽƵƌĐĞǁĂƐƌĞŵŽǀĞĚĂŶĚƚŚĞƌĞĂĐƟŽŶŵŝdžƚƵƌĞǁĂƐĐŽŽůĞĚƚŽƌŽŽŵƚĞŵƉĞƌĂƚƵƌĞ ƵƐŝŶŐĂǁĂƚĞƌŇŽǁ͘džĐĞƐƐŽĨs&ǁĂƐƌĞŵŽǀĞĚďLJĚĞƉƌĞƐƐƵƌŝnjŝŶŐƚŚĞƌĞĂĐƟŽŶǀĞƐƐĞů͘ dŚĞƐŽůƵƟŽŶǁĂƐĐŽŶĐĞŶƚƌĂƚĞĚin vacuo in order to precipitate the copolymer in cold ƉĞŶƚĂŶĞ͘dŚĞƉŽůLJŵĞƌǁĂƐĂĚĚŝƟŽŶĂůůLJǁĂƐŚĞĚǁŝƚŚĐŽůĚƉĞŶƚĂŶĞƚŽƌĞŵŽǀĞƵŶƌĞĂĐƚĞĚ ďĞŶnjŽLJůƉĞƌŽdžŝĚĞ͘dŚĞĐŽƉŽůLJŵĞƌǁĂƐĚƌŝĞĚŝŶĂǀĂĐƵƵŵ͘1_{,ͲEDZ;ϰϬϬD,nj͕ĐĞƚŽŶĞͲd}

6Ϳ͗ ɷсϭ͘ϵϬͲϮ͘Ϭϰ;Ɛ͕ͲH₃͕sĐĂŶĚͲH₂Ͳ͕sĐͿ͕Ϯ͘ϮϬͲϮ͘ϱϱ;ŵ͕Ͳ&₂ͲH₂ͲH₂Ͳ&₂Ͳ͕s&Ͳs& ƚĂŝůͲƚŽͲƚĂŝůĂŶĚͲH₂Ͳ͕sĐͿ͕Ϯ͘ϳϬͲϯ͘ϭϬ;ŵ͕Ͳ&₂ͲH₂Ͳ&₂Ͳ͕s&Ͳs&ŚĞĂĚͲƚŽͲƚĂŝůͿ͕ϰ͘ϵϬͲϱ͘ϬϬ ;ŵ͕ͲHͲ͕ͲsĐͲVAcͲsĐͲͿ͕ϱ͘ϭϴͲϱ͘ϯϴ;ŵ͕ͲHͲ͕Ͳs&ͲVAcͲVAcͲs&ͲͿ͕ϱ͘ϰϱͲϱ͘ϳϱ;ŵ͕ͲHͲ͕ Ͳs&ͲVAcͲs&ͲͿ͘

^LJŶƚŚĞƐŝƐŽĨƉŽůLJ;ǀŝŶLJůŝĚĞŶĞŇƵŽƌŝĚĞͲĐŽͲǀŝŶLJůĂůĐŽŚŽůͿ;W;s&ͲĐŽͲsͿĐŽƉŽůLJŵĞƌƐ͗ ƌŽƵŶĚͲďŽƩŽŵŇĂƐŬǁĂƐĐŚĂƌŐĞĚǁŝƚŚϭ͘ϱŐƌĂŵƐŽĨW;s&ͲcoͲsĐͿĐŽƉŽůLJŵĞƌƐ͕ĚŝŽdžĂŶĞ ;ϭϭϬŵ>Ϳ͕ĂŶĚĐŽŶĐĞŶƚƌĂƚĞĚŚLJĚƌŽĐŚůŽƌŝĐĂĐŝĚ;ϲŵ>Ϳ͘dŚĞƌĞĂĐƟŽŶŵŝdžƚƵƌĞǁĂƐƐƟƌƌĞĚ ŽǀĞƌŶŝŐŚƚĂƚϲϬΣ͘dŚĞŵŝdžƚƵƌĞǁĂƐĐŽŶĐĞŶƚƌĂƚĞĚin vacuo, from where the copolymer ǁĂƐƉƌĞĐŝƉŝƚĂƚĞĚďLJĂĚĚŝŶŐĂůĂƌŐĞĞdžĐĞƐƐŽĨǁĂƚĞƌ͘^ƵďƐĞƋƵĞŶƚůLJ͕ƚŚĞĐŽƉŽůLJŵĞƌǁĂƐ ĐŽůůĞĐƚĞĚǀŝĂĮůƚƌĂƟŽŶĨŽůůŽǁĞĚďLJĞdžƚĞŶƐŝǀĞǁĂƐŚŝŶŐǁŝƚŚǁĂƚĞƌƚŽƌĞŵŽǀĞƌĞƐŝĚƵĂůƐŝĚĞ

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: 74PDF page: 74PDF page: 74PDF page: 74

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ƉƌŽĚƵĐƚĂŶĚŚLJĚƌŽĐŚůŽƌŝĐĂĐŝĚ͕LJŝĞůĚŝŶŐϭ͘ϮŐƌĂŵƐŽĨǁŚŝƚĞW;s&ͲcoͲsͿĐŽƉŽůLJŵĞƌƐ͘

1_{,ͲEDZ;ϰϬϬD,nj͕ĐĞƚŽŶĞͲd}

6Ϳ͗ɷсϭ͘ϱϱͲϭ͘ϴϱ;ŵ͕ͲH2Ͳ͕sͿ͕Ϯ͘ϳϬͲϯ͘ϭϬ;ŵ͕Ͳ&2ͲH2Ͳ&2Ͳ͕

s&Ͳs&ƚĂŝůͲƚŽͲƚĂŝůĂŶĚͲH₂Ͳ͕sͿ͕Ϯ͘ϳϬͲϯ͘ϭϬ;ŵ͕Ͳ&₂ͲH₂Ͳ&₂Ͳ͕s&Ͳs&ŚĞĂĚͲƚŽͲƚĂŝůͿ͕ ϯ͘ϵϬͲϰ͘ϱϬ;ŵ͕ͲHͲ͕ͲK,͕sͿ W;s&ͲĐŽͲsͿĐŽƉŽůLJŵĞƌĮůŵƉƌŽĐĞƐƐŝŶŐ͗ƐŽůƵƟŽŶŽĨƚŚĞW;s&-co-sͿĐŽƉŽůLJŵĞƌŝŶ ĐLJĐůŽƉĞŶƚĂŶŽŶĞ;ϱϬŵŐͬŵ>ͿǁĂƐĐĂƐƚŽŶĂŶĂůƵŵŝŶƵŵWĞƚƌŝĚŝƐŚ͘dŚĞƐŽůǀĞŶƚǁĂƐĂůůŽǁĞĚ ƚŽĞǀĂƉŽƌĂƚĞĂƚϭϯϬΣ͕ĨƌŽŵǁŚĞƌĞƚŚĞĮůŵǁĂƐŚĞĂƚĞĚƚŽƚŚĞϭϲϬΣ͘ŌĞƌƌĞŵŽǀŝŶŐ ƚŚĞŚĞĂƟŶŐƐŽƵƌĐĞĂŶĚĐŽŽůŝŶŐĚŽǁŶƚŽĂŵďŝĞŶƚƚĞŵƉĞƌĂƚƵƌĞ͕ĂĨƌĞĞͲƐƚĂŶĚŝŶŐĮůŵǁĂƐ ŽďƚĂŝŶĞĚƵƐŝŶŐĂůŝŌͲŽīŵĞƚŚŽĚŝŶǁĂƚĞƌ͘ Characterization

EƵĐůĞĂƌDĂŐŶĞƟĐZĞƐŽŶĂŶĐĞƐƉĞĐƚƌŽƐĐŽƉLJ͗1_{,ĂŶĚK^zEDZƐƉĞĐƚƌĂ were recorded on}

sĂƌŝĂŶ;syZͿƐƉĞĐƚƌŽŵĞƚĞƌŽƉĞƌĂƟŶŐĂƚϰϬϬD,njĨŽƌƚŚĞ1_{,ŶƵĐůĞƵƐ͘dŚĞŵŽůĂƌĐŽŶƚĞŶƚ}

sĐǁĂƐĐĂůĐƵůĂƚĞĚĂĐĐŽƌĚŝŶŐƚŽĞƋƵĂƟŽŶϰ͘ϭ͘

Fourier Transform Infrared Spectroscopy͗dŚĞ&d/ZƐƉĞĐƚƌĂŽĨƚŚĞĐŽƉŽůLJŵĞƌƐǁĞƌĞ ƌĞĐŽƌĚĞĚŽŶĂƌƵŬĞƌsĞƌƚĞdžϳϬƐƉĞĐƚƌŽƉŚŽƚŽŵĞƚĞƌƵƐŝŶŐϯϮƐĐĂŶƐĂƚĂŶŽŵŝŶĂůƌĞƐŽůƵƟŽŶ ŽĨϰĐŵͲϭ_{ƵƐŝŶŐĂĚŝĂŵŽŶĚƐŝŶŐůĞƌĞŇĞĐƟŽŶĂƩĞŶƵĂƚĞĚƚŽƚĂůƌĞŇĞĐƚĂŶĐĞ;dZͿ͘} tŝĚĞͲĂŶŐůĞyͲƌĂLJƐĐĂƩĞƌŝŶŐ͗ty^ŵĞĂƐƵƌĞŵĞŶƚƐǁĂƐƉĞƌĨŽƌŵĞĚĂƚďĞĂŵůŝŶĞDϮϲ ĂƚƚŚĞƵƌŽƉĞĂŶ^LJŶĐŚƌŽƚƌŽŶZĂĚŝĂƟŽŶ&ĂĐŝůŝƚLJ;^Z&ͿŝŶ'ƌĞŶŽďůĞǁŝƚŚĂǁĂǀĞůĞŶŐƚŚ ʄсϬ͘ϵϳ͘dŚĞty^ƉĂƩĞƌŶǁĂƐĂĐƋƵŝƌĞĚŽǀĞƌĂƟŵĞŝŶƚĞƌǀĂůŽĨϯϬƐĞĐŽŶĚƐƵƐŝŶŐ ĂWŝůĂƚƵƐϯϬϬ<ĚĞƚĞĐƚŽƌ;ϭϰϳϮпϭϵϱƉŝdžĞůƐŽĨϭϳϮʅŵпϭϳϮʅŵƉůĂĐĞĚĂƚĂĚŝƐƚĂŶĐĞŽĨ

Equation 4.1: For the calculation of the molar contents VAc in P(VDF-co-VA) copolymers. It is

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: 75PDF page: 75PDF page: 75PDF page: 75

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4

Ϭ͘Ϯϴŵ͘dŚĞƐĐĂƩĞƌŝŶŐǀĞĐƚŽƌƋŝƐĚĞĮŶĞĚĂƐqсϰʋͬʄ(sin ɽͿǁŝƚŚϮɽďĞŝŶŐƚŚĞƐĐĂƩĞƌŝŶŐ ĂŶŐůĞ͘ĞĐŽŶǀŽůƵƟŽŶŽĨƚŚĞty^ƉƌŽĮůĞƐǁĂƐĂĐŚŝĞǀĞĚƵƐŝŶŐDd>͘dŚĞĞdžƉĞƌŝŵĞŶƚĂů ƉƌŽĮůĞƐǁĞƌĞĚĞĐŽŶǀŽůƵƚĞĚďLJƵƐŝŶŐƚŚĞƐƵŵŽĨĂůŝŶĞĂƌďĂĐŬŐƌŽƵŶĚĂŶĚƉƐĞƵĚŽͲsŽŝŐƚ ƉĞĂŬƐĚĞƐĐƌŝďŝŶŐƚŚĞƐĐĂƩĞƌŝŶŐĨƌŽŵƚŚĞĂŵŽƌƉŚŽƵƐĂŶĚƚŚĞĐƌLJƐƚĂůůŝŶĞƉŚĂƐĞƐ͘ dŚĞƌŵĂůĐŚĂƌĂĐƚĞƌŝnjĂƟŽŶ͗^ƚŚĞƌŵŽŐƌĂŵƐǁĞƌĞƌĞĐŽƌĚĞĚŽŶĂd/ŶƐƚƌƵŵĞŶƚƐ^ YϭϬϬϬ͘d'ƚŚĞƌŵŽŐƌĂŵƐǁĞƌĞƌĞĐŽƌĚĞĚŽŶĂd'ƵŶĚĞƌĂE₂ĂƚŵŽƐƉŚĞƌĞ͘dŚĞŚĞĂƟŶŐ ĂŶĚĐŽŽůŝŶŐƌĂƚĞǁĂƐƐĞƚƚŽďĞϭϬΣŵŝŶͲϭ_. ůĞĐƚƌŝĐĂůĐŚĂƌĂĐƚĞƌŝnjĂƟŽŶ: Ͳ and V-IůŽŽƉƐǁĞƌĞŽďƚĂŝŶĞĚƵƐŝŶŐĂƐƚĂƚĞͲŽĨͲƚŚĞͲĂƌƚ Ăŝdždd&ϮϬϬϬĨĞƌƌŽĞůĞĐƚƌŝĐƚĞƐƚĞƌǁŚĞƌĞĞůĞĐƚƌŝĐĮĞůĚƐ;ƵƉƚŽϭϬŬsͿǁĞƌĞĂƉƉůŝĞĚ ĂĐƌŽƐƐƚŚĞƉŽůLJŵĞƌĮůŵƐǁŝƚŚĂƚƌŝĂŶŐƵůĂƌǁĂǀĞĨŽƌŵĂƚĂĨƌĞƋƵĞŶĐLJŽĨϭϬ,nj͘ŚƌŽŵŝƵŵ ;ϱŶŵͿͬŐŽůĚ;ϭϬϬŶŵͿĞůĞĐƚƌŽĚĞƐǁŝƚŚĂĚŝĂŵĞƚĞƌŽĨϮŵŵǁĞƌĞĚĞƉŽƐŝƚĞĚŽŶďŽƚŚ ƐŝĚĞƐŽĨW;s&-co-sͿĐŽƉŽůLJŵĞƌĮůŵƐďLJǀĂƉŽƌĚĞƉŽƐŝƟŽŶ͘ŚƌŽŵŝƵŵǁĂƐƵƐĞĚŽŶůLJĂƐ ĂĚŚĞƐŝŽŶůĂLJĞƌ͘^ŝůŝĐŽŶŽŝůǁĂƐƵƐĞĚƚŽƉƌĞǀĞŶƚŇĂƐŚŽǀĞƌƐ͘

Results and Discussion

Ɛ ŽƵƚůŝŶĞĚ ŝŶ ^ĐŚĞŵĞ ϰ͘ϭ͕ ƚŚĞ ĐŽƉŽůLJŵĞƌŝnjĂƟŽŶ ŽĨ s& ǁŝƚŚ sĐ ĨŽůůŽǁĞĚ ďLJ ƚŚĞ ŚLJĚƌŽůLJƐŝƐ ƚŽ W;s&-co-sͿ ĐŽƉŽůLJŵĞƌƐ ŝƐ ƐŚŽǁŶ͘ dŚĞ ĐŽƉŽůLJŵĞƌƐ ĚĞƐĐƌŝďĞĚ ŝŶ ƚŚŝƐ ǁŽƌŬĂƌĞĚĞŶŽƚĞĚĂĐĐŽƌĚŝŶŐƚŽƚŚĞĐŽƉŽůLJŵĞƌĐŽŵƉŽƐŝƟŽŶƌĂƟŽĚĞƚĞƌŵŝŶĞĚďLJ1_,EDZ ƐƉĞĐƚƌŽƐĐŽƉLJ͘ƐƉƌŽŽĨŽĨĐŽŶĐĞƉƚ͕ƐŽůƵƟŽŶĐŽƉŽůLJŵĞƌŝnjĂƟŽŶƐŽĨs&ĂŶĚsĐǁĞƌĞ ƉĞƌĨŽƌŵĞĚŝŶĚŝŵĞƚŚLJůĐĂƌďŽŶĂƚĞ;DͿƵƐŝŶŐďĞŶnjŽLJůƉĞƌŽdžŝĚĞĂƐŝŶŝƟĂƚŽƌ͘ƐĂŶĚĂŝĂŶĚ ĐŽͲǁŽƌŬĞƌƐĐŽŵƉĂƌĞĚĂůĂƌŐĞƌĂŶŐĞŽĨƐŽůǀĞŶƚƐĨŽƌƉŚŽƚŽƉŽůLJŵĞƌŝnjĂƟŽŶƐŽĨs&ĂŶĚƚŚĞLJ ĨŽƵŶĚƚŚĂƚDƐŚŽǁƐƚŚĞďĞƐƚƚƌĂĚĞͲŽīďĞƚǁĞĞŶĐŚĂŝŶƚƌĂŶƐĨĞƌĂŶĚŚĂǀŝŶŐĨĂƐƚƌĞĂĐƟŽŶ rates.20_{ĞĐĂƵƐĞƚŚĞƌĞŝƐĂƐƚƌŽŶŐƚĞŶĚĞŶĐLJĨŽƌƚŚĞƉƌŽƉĂŐĂƟŽŶŽĨsĐ͕ƚŚĞĂŵŽƵŶƚŽĨ} sĐĂĚĚĞĚƚŽƉŽůLJŵĞƌŝnjĂƟŽŶŵŝdžƚƵƌĞŝƐůŽǁĂŶĚƚŚĞƌĞĂĐƟŽŶƟŵĞŝƐŬĞƉƚƐŚŽƌƚƚŽĂǀŽŝĚ ĐŽŵƉŽƐŝƟŽŶĂůĚƌŝŌ͘18,19_{ŌĞƌƚŚĞƉŽůLJŵĞƌŝnjĂƟŽŶ͕ƚŚĞƉƌĞƐĞŶĐĞŽĨƵŶƌĞĂĐƚĞĚsĐǁĂƐ} ĐŽŶĮƌŵĞĚƵƐŝŶŐ1_{,EDZƐƉĞĐƚƌŽƐĐŽƉLJ͕ŝŶĚŝĐĂƟŶŐƚŚĞĂďƐĞŶĐĞŽĨWs&ŚŽŵŽƉŽůLJŵĞƌƐ͘} ^ƵďƐĞƋƵĞŶƚůLJ͕ƚŚĞW;s&-co-sĐͿĐŽƉŽůLJŵĞƌƐǁĞƌĞŚLJĚƌŽůLJnjĞĚŝŶĂĚŝŽdžĂŶĞͬŚLJĚƌŽĐŚůŽƌŝĐ ĂĐŝĚŵŝdžƚƵƌĞƚŽLJŝĞůĚW;s&-co-sͿĐŽƉŽůLJŵĞƌƐ͘ǀĞŶƚŚŽƵŐŚ͕ďĂƐĞŚLJĚƌŽůLJƐŝƐŝƐĐŽŵŵŽŶůLJ ƵƐĞĚƚŽŚLJĚƌŽůLJnjĞWsĐ͕ĂĐŝĚŝĐĐŽŶĚŝƟŽŶƐƉƌĞǀĞŶƚĚĞŚLJĚƌŽŇƵŽƌŝŶĂƟŽŶƉƌŽĐĞƐƐĞƐ͕ǁŚŝůĞ ƉƌĞƐĞƌǀŝŶŐƚŚĞǁŚŝƚĞĐŽůŽƌŽĨƚŚĞĮŶĂůƉƌŽĚƵĐƚ͘ǀĞŶƚŚŽƵŐŚĐŚĞĂƉƌĞƐŽƵƌĐĞƐĂƌĞƵƐĞĚ ƚŽƐLJŶƚŚĞƐŝnjĞW;s&-co-sͿĐŽƉŽůLJŵĞƌƐ͕ĨƵƚƵƌĞǁŽƌŬƐŚŽƵůĚďĞĚĞǀŽƚĞĚŝŶŽƉƟŵŝnjŝŶŐƚŚĞ

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: 76PDF page: 76PDF page: 76PDF page: 76

76 ƌĞĂĐƚŽƌĐŽŶĚŝƟŽŶƐ͕ƐƵĐŚĂƐƵƐŝŶŐĂŇŽǁƉƌŽĐĞƐƐŽƌďĂƚĐŚƉŽůLJŵĞƌŝnjĂƟŽŶǁŝƚŚĂĐŽŶƐƚĂŶƚ ŝŶůĞƚŽĨsĐ͕ƚŽŝŶĐƌĞĂƐĞƚŚĞs&ĐŽŶǀĞƌƐŝŽŶ͘ hŶƌĂǀĞůůŝŶŐƚŚĞĐŽŵƉůĞƚĞŵŝĐƌŽƐƚƌƵĐƚƵƌĞŽĨWs&ͲďĂƐĞĚĐŽƉŽůLJŵĞƌƐŝƐĂĐŚĂůůĞŶŐŝŶŐ ƚĂƐŬĚƵĞƚŽƚŚĞůĂƌŐĞŶƵŵďĞƌŽĨƉŽƐƐŝďůĞŵŽŶŽŵĞƌƐĞƋƵĞŶĐĞƐĐĂƵƐĞĚďLJƚŚĞŵŽŶŽŵĞƌ ĚŝƐƚƌŝďƵƟŽŶ͕ ŵŽŶŽŵĞƌ ŝŶǀĞƌƐŝŽŶƐ͕ ŝŶŝƟĂƚŽƌ ĨƌĂŐŵĞŶƚƐ ĂŶĚ ďĂĐŬďŝƟŶŐ ƌĞĂĐƟŽŶƐ͘ϮϭʹϮϯ dŚĞƌĞĨŽƌĞ͕ƚŚĞĨŽĐƵƐŝƐŽŶƉƌŽǀŝŶŐƚŚĞŝŶĐůƵƐŝŽŶŽĨsĐ;ĂŶĚĐŽŶƐĞƋƵĞŶƚůLJsͿƵŶŝƚƐŝŶ the polymer backbone.

/Ŷ&ŝŐƵƌĞϰ͘ϭ͕ƚŚĞ1_{,EDZƐƉĞĐƚƌƵŵŽĨW;s&} 85-co-sĐ15ͿƐŚŽǁƐƚŚĞĐŚĂƌĂĐƚĞƌŝƐƟĐ s& ƐŝŐŶĂůƐ ;ŚĞĂĚͲƚŽͲƚĂŝů ĂĚĚŝƟŽŶͿ ůŽĐĂƚĞĚ ŝŶ ďĞƚǁĞĞŶ Ϯ͘ϳϬͲϯ͘ϭϬ ƉƉŵ͕ ǁŚĞƌĞĂƐ ƚŚĞ ƉƌŽƚŽŶƐĐŽƌƌĞƐƉŽŶĚŝŶŐƚŽƚŚĞƚĂŝůͲƚŽͲƚĂŝůĂĚĚŝƟŽŶƐĂƌĞĂƚϮ͘ϮϬͲϮ͘ϱϱƉƉŵŽǀĞƌůĂƉƉŝŶŐ ǁŝƚŚƚŚĞƐŝŐŶĂůƐĨƌŽŵƚŚĞŵĞƚŚLJůĞŶĞƉƌŽƚŽŶƐĨƌŽŵsĐ͘dŚĞŵĞƚŚLJůƉĞĂŬĂƉƉĞĂƌƐĂƚϮ͘ϬϬ ƉƉŵ͕ǁŚŝĐŚŝƐƐŝŵŝůĂƌƚŽWsĐŚŽŵŽƉŽůLJŵĞƌƐƐŝŶĐĞŶŽƐŝŐŶŝĮĐĂŶƚĐŚĂŶŐĞƐŝŶƚŚĞůŽĐĂů ĞŶǀŝƌŽŶŵĞŶƚŽĨƚŚĞƉƌŽƚŽŶƐĂƌĞĞdžƉĞƌŝĞŶĐĞĚ͘/ŶĐŽŶƚƌĂƐƚ͕ƚŚĞŵĞƚŚŝŶĞŐƌŽƵƉŽĨsĐŝƐ ƐĞƉĂƌĂƚĞĚŝŶƚŚƌĞĞŝƐŽůĂƚĞĚƐŝŐŶĂůƐĂƚϰ͘ϵϬͲϱ͘ϬϬƉƉŵ͕ϱ͘ϭϴͲϱ͘ϯϴƉƉŵĂŶĚϱ͘ϰϱͲϱ͘ϳϱƉƉŵ͕ ƐŚŽǁŝŶŐĚŝīĞƌĞŶƚůŝŶŬĂŐĞƐŝŶƚŚĞW;s&-co-sĐͿƉŽůLJŵĞƌďĂĐŬďŽŶĞ͘dŚĞǁĞĂŬƐŝŐŶĂůĂƚ ϰ͘ϵϬͲϱ͘ϬϬƉƉŵĐŽƌƌĞƐƉŽŶĚƐƚŽŵĞƚŚŝŶĞƉƌŽƚŽŶƐŝŶĐůƵĚĞĚŝŶĂƚůĞĂƐƚƚƌŝĂĚƐŽĨsĐͲsĐͲsĐ ƐĞƋƵĞŶĐĞƐũƵƐƚĂƐĨŽƌWsĐŚŽŵŽƉŽůLJŵĞƌƐ͘/ŶƚĞƌĞƐƟŶŐůLJ͕ƚŚĞĂŵŽƵŶƚŽĨĚLJĂĚƐ;ϱ͘ϭϴͲϱ͘ϯϴ ƉƉŵͿŽƌŝƐŽůĂƚĞĚsĐƵŶŝƚƐ;ϱ͘ϰϱͲϱ͘ϳϱƉƉŵͿŝƐŵƵĐŚŚŝŐŚĞƌ͕ŝŶĚŝĐĂƟŶŐƚŚĞƌĂŶĚŽŵŶĞƐƐ ŽĨƚŚĞĐŽƉŽůLJŵĞƌŝnjĂƟŽŶ͘17_{dŚĞĂŵŽƵŶƚŽĨsĐŝŶƚŚĞĐŽƉŽůLJŵĞƌǁĂƐĚĞƚĞƌŵŝŶĞĚƚŽďĞ} ϭϱŵŽůйďLJŝŶƚĞŐƌĂƟŶŐƚŚĞŵĞƚŚŝŶĞƉƌŽƚŽŶƐĂŶĚĐŽŵƉĂƌĞƚŚĞŵƚŚĞs&ƉƌŽƚŽŶƐŝŶƚŚĞ ďĂĐŬďŽŶĞ;ƋƵĂƟŽŶϰ͘ϭͿ͘1_{,EDZĐŽƌƌĞůĂƟŽŶƐƉĞĐƚƌŽƐĐŽƉLJ;K^zͿ;&ŝŐƵƌĞϰ͘ϮͿǁĂƐƵƐĞĚ} Figure 4.1: 1_{H NMR spectra of P(VDF}

85-co-VAc15) and P(VDF85-co-VA15) showing the successful

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: 77PDF page: 77PDF page: 77PDF page: 77

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4

ƚŽĐŽŶĮƌŵƚŚĞĐŽƌƌĞůĂƟŽŶŽĨƚŚĞďĂĐŬďŽŶĞŵĞƚŚLJůĞŶĞƉƌŽƚŽŶƐƚŽƚŚĞŵĞƚŚŝŶĞƉƌŽƚŽŶƐ ŽĨsĐ͘,ĂǀŝŶŐŝŶŵŝŶĚƚŚĞƐLJŵŵĞƚƌŝĐĂůŶĂƚƵƌĞĂƌŽƵŶĚƚŚĞŵĞƚŚŝŶĞƉƌŽƚŽŶĂƚϱ͘ϰϱͲϱ͘ϳϱ ƉƉŵ͕ŝŶĚĞĞĚ͕ĂƐŝŶŐůĞĐƌŽƐƐƉĞĂŬǁŝƚŚƚŚĞs&ŵĞƚŚLJůĞŶĞƉƌŽƚŽŶƐ;Ϯ͘ϰϭƉƉŵͿŝƐŽďƐĞƌǀĞĚ͕ ƉƌŽǀŝŶŐƚŚĞŝƐŽůĂƟŽŶŽĨŵĞƚŚŝŶĞƉƌŽƚŽŶƐŝŶƚŚĞs&ͲVAcͲs&ƐĞƋƵĞŶĐĞ͘ƐĞdžƉĞĐƚĞĚ͕ ƚŚĞŵĞƚŚŝŶĞƉƌŽƚŽŶƐŝŶƚŚĞͲs&ͲVAc-VAcͲs&ͲĚLJĂĚƐƐŚŽǁƚǁŽĐƌŽƐƐƉĞĂŬƐŝŶƚŚĞ1_, EDZK^z͘^ŝŵŝůĂƌƚŽƚŚĞŝƐŽůĂƚĞĚsĐƵŶŝƚƐ͕ŽŶĞĐŽƌƌĞůĂƟŽŶ;ϱ͘ϯϬͲϮ͘ϯϱƉƉŵͿĐŽŶŶĞĐƚƐ ƚŚĞŵĞƚŚLJůĞŶĞŽĨsĐŶĞdžƚƚŚĞͲ&₂ͲƵŶŝƚƚŽƚŚĞŵĞƚŚŝŶĞƉƌŽƚŽŶƐ͕ǁŚĞƌĞĂƐƚŚĞŽƚŚĞƌ ĐƌŽƐƐƉĞĂŬ;ϱ͘ϯϬͲϭ͘ϵϴͿƉƉŵͿŝƐĐŽƌƌĞůĂƟŶŐƚŚĞŵĞƚŚŝŶĞƉƌŽƚŽŶƚŽƚŚĞŵĞƚŚLJůĞŶĞŽĨƚŚĞ ƐĞƋƵĞŶƟĂůsĐĞŶƟƚLJ͘^ŝŶĐĞƚŚĞŵĞƚŚŝŶĞƉƌŽƚŽŶƐŝŐŶĂůƐůŽĐĂƚĞĚŝŶďĞƚǁĞĞŶϰ͘ϵϬͲϱ͘ϬϬƉƉŵ ĂƌĞƐĂŶĚǁŝĐŚĞĚďĞƚǁĞĞŶsĐƵŶŝƚƐŽŶůLJŽŶĞĐŽƌƌĞůĂƟŽŶƉĞĂŬ;ϰ͘ϵϰͲϭ͘ϵϬƉƉŵͿĂƉƉĞĂƌƐ͘ ŌĞƌĂĐŝĚŝĐƚƌĞĂƚŵĞŶƚŽĨW;s&₈₅-co-sĐ₁₅Ϳ͕ƚŚĞĐŽŵƉůĞƚĞƵƉĮĞůĚƐŚŝŌŽĨƚŚĞŵĞƚŚŝŶĞ ƉƌŽƚŽŶƐ ƚŽ ϯ͘ϵϬͲϰ͘ϱϬ ƉƉŵ ĂŶĚ ƚŚĞ ĚŝƐĂƉƉĞĂƌĂŶĐĞ ŽĨ ƚŚĞ ŵĞƚŚLJů ƉĞĂŬ ŝŶĚŝĐĂƚĞ ƚŚĞ ĐŽŵƉůĞƚĞŚLJĚƌŽůLJƐŝƐƚŽW;s&₈₅-co-s₁₅ͿĂƐƐŚŽǁŶŝŶ&ŝŐƵƌĞϰ͘ϭ͘ƐĂůƌĞĂĚLJŽďƐĞƌǀĞĚĨŽƌ ƚŚĞW;s&₈₅-co-sĐ₁₅ͿĐŽƉŽůLJŵĞƌ͕ƚŚĞƐŝŐŶĂůƐĐŽƌƌĞƐƉŽŶĚŝŶŐƚŽƚŚĞĚŝīĞƌĞŶƚƐĞƋƵĞŶĐĞƐ ŽĨsĐĂŶďĞĚŝƐƟŶŐƵŝƐŚĞĚƵƐŝŶŐ1_{,EDZK^z͘ĐƌŽƐƐƉĞĂŬŝƐŽďƐĞƌǀĞĚĨŽƌƚŚĞŝƐŽůĂƚĞĚ} sƵŶŝƚƐĂƚϰ͘ϯϰͲϮ͘ϮϲƉƉŵĐŽƌƌĞůĂƟŶŐǁŝƚŚƚŚĞŵĞƚŚLJůĞŶĞŶĞdžƚƚŽƚŚĞͲ&₂ͲƵŶŝƚ͘Ɛ ĂďŽǀĞŵĞŶƟŽŶĞĚ͕ƚŚĞĚLJĂĚƐƐŚŽǁƚǁŽĐƌŽƐƐƉĞĂŬƐŽĨŵĞƚŚŝŶĞƉƌŽƚŽŶƐĂƚϰ͘ϮϮͲϮ͘ϭϴƉƉŵ ĂŶĚϰ͘ϮϮͲϭ͘ϲϲƉƉŵ͕ƐŚŽǁŝŶŐƚŚĞŝŶƚĞƌĂĐƟŽŶƐǁŝƚŚƚŚĞŵĞƚŚLJůĞŶĞŶĞdžƚƚŽƚŚĞͲ&₂ͲƵŶŝƚ ĂŶĚǁŝƚŚƚŚĞŵĞƚŚLJůĞŶĞŽĨƚŚĞƐĞƋƵĞŶƟĂůsĐĞŶƟƚLJ͕ƌĞƐƉĞĐƟǀĞůLJ͘

/Ŷ ĂĚĚŝƟŽŶ ƚŽ ƚŚĞ W;s&₈₅-co-s₁₅Ϳ ĐŽƉŽůLJŵĞƌ͕ Ă W;s&₉₀-co-sĐ₁₀Ϳ ĐŽƉŽůLJŵĞƌ ǁŝƚŚϭϬŵŽůйŽĨsĐǁĂƐƉƌĞƉĂƌĞĚĂŶĚƐƵďƐĞƋƵĞŶƚůLJŚLJĚƌŽůLJnjĞĚƚŽW;s&₉₀-co-s₁₀Ϳ͘ /ŶƚĞƌĞƐƟŶŐůLJ͕ƚŚĞůŽǁĞƌĐŽŶƚĞŶƚŽĨsĐŝŶƚŚĞĐŽƉŽůLJŵĞƌŝnjĂƟŽŶƌĞƐƵůƚƐŝŶƚŚĞĂďƐĞŶĐĞ ŽĨsĐƚƌŝĂĚƐŝŶƚŚĞƉŽůLJŵĞƌďĂĐŬďŽŶĞĂƐĚĞŵŽŶƐƚƌĂƚĞĚŝŶƚŚĞ1_{,ͲEDZK^zƐƉĞĐƚƌƵŵ} ;&ŝŐƵƌĞϰ͘ϮďͿ͘ W;s&-co-sͿĐŽƉŽůLJŵĞƌĮůŵƐǁĞƌĞĐĂƐƚĨƌŽŵĐLJĐůŽƉĞŶƚĂŶŽŶĞĂƚϭϯϬΣ͕ǁŚŝĐŚŝƐ ĂďŽǀĞƚŚĞĐƌLJƐƚĂůůŝnjĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞŽĨƚŚĞƉŽůLJŵĞƌƐ͘^ƵďƐĞƋƵĞŶƚůLJ͕ƚŚĞĮůŵƐǁĞƌĞ ŚĞĂƚĞĚƚŽϭϲϬΣĨŽůůŽǁĞĚďLJƋƵĞŶĐŚŝŶŐƚŽĂŵďŝĞŶƚƚĞŵƉĞƌĂƚƵƌĞƚŽĞŶƐƵƌĞĐŽŵƉůĞƚĞ removal of solvent and to obtain the crystalline structure from the melt. Finally, free ƐƚĂŶĚŝŶŐĮůŵƐǁĞƌĞŽďƚĂŝŶĞĚƵƐŝŶŐĂůŝŌͲŽīŵĞƚŚŽĚŝŶǁĂƚĞƌ͘ dŽ ĞŶƐƵƌĞ ƚŚĂƚ ŶŽ ĚĞŐƌĂĚĂƟŽŶ ƉƌŽĐĞƐƐĞƐ ŽĐĐƵƌ ŝŶ ƚŚĞ ĂƉƉůŝĐĂƟŽŶ ƌĂŶŐĞ ŽĨ ƚŚĞ ĨĞƌƌŽĞůĞĐƚƌŝĐ ŵĂƚĞƌŝĂůƐ͕ ŐŽŽĚ ƚŚĞƌŵĂů ƐƚĂďŝůŝƚLJ ŽĨ ƚŚĞ W;s&-co-sͿ ĐŽƉŽůLJŵĞƌƐ ǁĂƐ ĐŽŶĮƌŵĞĚ ǁŝƚŚ ƚŚĞƌŵĂů ŐƌĂǀŝŵĞƚƌŝĐ ĂŶĂůLJƐŝƐ ;&ŝŐƵƌĞ ϰ͘ϯͿ͘ dŚĞ ĚŝīĞƌĞŶƟĂů ƐĐĂŶŶŝŶŐ ĐĂůŽƌŝŵĞƚƌLJ;^ͿƉƌŽĮůĞƐŽĨƚŚĞW;s&-co-sͿĐŽƉŽůLJŵĞƌƐĂƌĞĚĞƉŝĐƚĞĚŝŶ&ŝŐƵƌĞϰ͘ϰď͘Ɛ ĞdžƉĞĐƚĞĚ͕ĚƵĞƚŚĞŝŶƚƌŽĚƵĐƟŽŶŽĨĐŽŵŽŶŽŵĞƌƐŝŶƚŚĞWs&ďĂĐŬďŽŶĞƚŚĞĐƌLJƐƚĂůůŝnjĂƟŽŶ ĂŶĚŵĞůƟŶŐƚĞŵƉĞƌĂƚƵƌĞƐ;d_c and T_mͿĂƌĞƐŝŐŶŝĮĐĂŶƚůLJƌĞĚƵĐĞĚƚŽd_cсϵϯΣĂŶĚd_m = 125 ΣĨŽƌW;s&₈₅-co-s₁₅ͿĂŶĚd_cсϭϬϱΣĂŶĚd_mсϭϯϱΣĨŽƌW;s&₉₀-co-s₁₀Ϳ͕ǁŚĞƌĞĂƐ Ws&ŚŽŵŽƉŽůLJŵĞƌƐƐŚŽǁĐƌLJƐƚĂůůŝnjĂƟŽŶĂŶĚŵĞůƟŶŐƚĞŵƉĞƌĂƚƵƌĞƐƚŚĂƚĂƌĞĂƚůĞĂƐƚ ϯϬΣŚŝŐŚĞƌ͘1_{/ŶƚĞƌĞƐƟŶŐůLJ͕ƚŚĞĐƌLJƐƚĂůůŝnjĂƟŽŶĂŶĚŵĞůƟŶŐƚĞŵƉĞƌĂƚƵƌĞĂƌĞůŽǁĞƌƚŚĂŶ}

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: 78PDF page: 78PDF page: 78PDF page: 78

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Figure 4.2: 1_{H COSY spectrum of (a) P(VDF}

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: 79PDF page: 79PDF page: 79PDF page: 79

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4

ŝƐŽďƐĞƌǀĞĚŝŶĐŽŶƚƌĂƐƚƚŽƚŚĞĐŽƉŽůLJŵĞƌƐǁŝƚŚdƌ&͘EŽƚĞǁŽƌƚŚŝůLJ͕ƚŚĞďƵůŬLJsĐƵŶŝƚƐ ŝŵƉĞĚĞĐƌLJƐƚĂůůŝnjĂƟŽŶŽĨƚŚĞW;s&₈₅-co-sĐ₁₅ͿĐŽƉŽůLJŵĞƌĂŶĚĐŽŶƐĞƋƵĞŶƚůLJĂĐŽŵƉůĞƚĞůLJ ĂŵŽƌƉŚŽƵƐĐŽƉŽůLJŵĞƌŝƐŽďƚĂŝŶĞĚ͕ǁŚĞƌĞĂƐW;s&₉₀-co-sĐ₁₀ͿƐƟůůĐƌLJƐƚĂůůŝnjĞƐĂůďĞŝƚ ĂƚĂůŽǁĞƌƚĞŵƉĞƌĂƚƵƌĞ;&ŝŐƵƌĞϰ͘ϱͿ͘^ŝŵŝůĂƌŽďƐĞƌǀĂƟŽŶƐĂƌĞŵĂĚĞĨŽƌW;s&-co-,&WͿ ĐŽƉŽůLJŵĞƌƐ͕ǁŚĞƌĞŝŶĂŵŽůĂƌĐŽŶƚĞŶƚŽĨхϭϵŵŽůй,&WƉƌĞǀĞŶƚƐĐƌLJƐƚĂůůŝnjĂƟŽŶLJŝĞůĚŝŶŐ a fully amorphous elastomer.ϭϰ

&ŽƵƌŝĞƌ ƚƌĂŶƐĨŽƌŵ ŝŶĨƌĂƌĞĚ ;&d/ZͿ ƐƉĞĐƚƌŽƐĐŽƉLJ ĂŶĚ tŝĚĞͲĂŶŐůĞ yͲƌĂLJ ƐĐĂƩĞƌŝŶŐ ;ty^ͿǁĞƌĞƵƐĞĚƚŽŝĚĞŶƟĨLJƚŚĞĐƌLJƐƚĂůůŝŶĞƉŚĂƐĞƐŝŶƚŚĞW;s&-co-sͿĐŽƉŽůLJŵĞƌƐĂŌĞƌ ŵĞůƚĐƌLJƐƚĂůůŝnjĂƟŽŶ͘/Ŷ&ŝŐƵƌĞϰ͘ϰĂ͕ƚŚĞ&d/ZƐƉĞĐƚƌƵŵŽĨƚŚĞW;s&₈₅-co-s₁₅ͿĐŽƉŽůLJŵĞƌ ĚĞŵŽŶƐƚƌĂƚĞƐƚŚĞĂůůͲƚƌĂŶƐĐŽŶĨŽƌŵĂƟŽŶŽĨƚŚĞƉŽůLJŵĞƌĐŚĂŝŶƐĚƵĞƚŽƚŚĞĂďƐŽƌƉƟŽŶ ďĂŶĚƐůŽĐĂƚĞĚĂƚϱϭϬ͕ϴϰϬ͕ϭϮϳϯĐŵͲϭ_{͕ŝŶĚŝĐĂƟŶŐɴͲƉŚĂƐĞĨŽƌŵĂƟŽŶ͘}ϲ_{/ŶĂĚĚŝƟŽŶ͕ŶŽ}

ĐŚĂƌĂĐƚĞƌŝƐƟĐĂďƐŽƌƉƟŽŶďĂŶĚƐĐŽƌƌĞƐƉŽŶĚŝŶŐƚŽƚŚĞĐƌLJƐƚĂůůŝŶĞɲͲƉŚĂƐĞŽƌɶͲƉŚĂƐĞĂƌĞ ŽďƐĞƌǀĞĚ͕ƉƌŽǀŝŶŐƚŚĂƚW;s&₈₅-co-s₁₅ͿĐƌLJƐƚĂůůŝnjĞĚƐŽůĞůLJŝŶƚŚĞɴͲƉŚĂƐĞ͘&ƵƌƚŚĞƌŵŽƌĞ͕ ƚŚĞty^ƉƌŽĮůĞ;&ŝŐƵƌĞϰ͘ϰĚͿƐŚŽǁƐŽŶĞƉĞĂŬĂƚqсϭϰ͘ϱϱŶŵͲϭ _{(dсϰ͘ϯϮͿŝĚĞŶƟĨLJŝŶŐ} ƚŚĞ;ϭϭϬͬϮϬϬͿĐƌLJƐƚĂůƉůĂŶĞƐ͕ǁŚŝĐŚďĞůŽŶŐƚŽƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐĐƌLJƐƚĂůůŝŶĞƉŚĂƐĞ͘KŶƚŚĞ ĐŽŶƚƌĂƌLJ͕ƚŚĞ&d/ZƐƉĞĐƚƌƵŵŽĨW;s&₉₀-co-s₁₀ͿƐŚŽǁƐ͕ŶĞdžƚƚŽƚŚĞɴͲƉŚĂƐĞĂďƐŽƌƉƟŽŶ ďĂŶĚƐ͕ĐŚĂƌĂĐƚĞƌŝƐƟĐƐŝŐŶĂůƐĐŽƌƌĞƐƉŽŶĚŝŶŐƚŽƚŚĞɲͲƉŚĂƐĞůŽĐĂƚĞĚĂƚϲϭϮ͕ϳϲϬĂŶĚϳϵϲ cmͲϭ_{͘/ŶĂĚĚŝƟŽŶ͕ƚŚĞty^ƉƌŽĮůĞĚĞƉŝĐƚĞĚŝŶ&ŝŐƵƌĞϰ͘ϰĐ͕ĐŽŶĮƌŵƐƚŚĞĐŽĞdžŝƐƚĞŶĐĞŽĨƚŚĞ} ɲͲĂŶĚɴͲƉŚĂƐĞŝŶƚŚĞW;s&₉₀-co-s₁₀ͿĐŽƉŽůLJŵĞƌĚƵĞƚŽĂƉƉĞĂƌĂŶĐĞŽĨƚŚĞ;ϭϬϬͿ͕;ϬϮϬͿ ĂŶĚ;ϭϭϬͿƌĞŇĞĐƟŽŶƐĂƚϭϮ͘ϳϬ͕ϭϯ͘ϮϬĂŶĚϭϰ͘ϮϱŶŵͲϭ_{͕ƌĞƐƉĞĐƟǀĞůLJ͕ďĞƐŝĚĞƐƚŚĞƐĐĂƩĞƌŝŶŐ} ĐŽƌƌĞƐƉŽŶĚŝŶŐƚŽƚŚĞ;ϭϭϬͬϮϬϬͿĐƌLJƐƚĂůƉůĂŶĞƐŽĨƚŚĞɴͲƉŚĂƐĞĂƉƉĞĂƌŝŶŐĂƐƐŚŽƵůĚĞƌƚŽ ƚŚĞ;ϭϭϬͿɲͲƉŚĂƐĞƌĞŇĞĐƟŽŶƐ͘dŚĞĚŝīĞƌĞŶĐĞŝŶĐƌLJƐƚĂůůŝŶĞƉŚĂƐĞƐĨŽƌƚŚĞĐŽƉŽůLJŵĞƌƐŝƐ ĂƐĐƌŝďĞĚƚŽƚŚĞŵŽůĂƌĐŽŶƚĞŶƚŽĨǀŝŶLJůĂůĐŽŚŽů͘dŚĞůĂĐŬŽĨĚĞĨĞĐƚƐŝŶW;s&₉₀-co-s₁₀Ϳ ƌĞƐƵůƚƐŝŶĐƌLJƐƚĂůůŝnjĂƟŽŶŝŶƚŽƚŚĞɲͲƉŚĂƐĞ͕ůŝŬĞƉƵƌĞWs&͕ǁŚĞƌĞĂƐǀŝŶLJůĂůĐŽŚŽůƌŝĐŚƉĂƌƚƐ ƐƟůůĐƌLJƐƚĂůůŝnjĞŝŶƚŚĞɴͲƉŚĂƐĞ͘dŚĞĐŽĞdžŝƐƚĞŶĐĞŽĨƚŚĞɲͲĂŶĚɴͲƉŚĂƐĞŝŶW;s&₉₀-co-s₁₀Ϳ ŝƐĂůƐŽĐůĞĂƌůLJǀŝƐŝďůĞŝŶƚŚĞĚĞĐŽŶǀŽůƵƚĞĚty^ƉƌŽĮůĞƐ͘dŚĞŽǀĞƌĂůůĐƌLJƐƚĂůůŝŶŝƚLJǁĂƐ

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: 80PDF page: 80PDF page: 80PDF page: 80

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Figure 4.5: DSC thermograms of P(VDF90-co-VAc10 ) and P(VDF85-co-VAc15).

Figure 4.4: E *8-6WTIGXVEF (7'XLIVQSKVEQWERH;%<7TVSƼPIWJSVG 4:(*90-co-VA10) and

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: 81PDF page: 81PDF page: 81PDF page: 81

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4

ĚĞƚĞƌŵŝŶĞĚƚŽďĞϱϱйĨƌŽŵǁŚŝĐŚϴϮйĂƌĞɲͲƉŚĂƐĞĐƌLJƐƚĂůƐĂŶĚϭϴйŝƐŝŶƚŚĞɴͲƉŚĂƐĞ͘ W;s&₈₅-co-s₁₅ͿĐƌLJƐƚĂůůŝnjĞĚŝŶƚŚĞɴͲƉŚĂƐĞǁŝƚŚĂĚĞŐƌĞĞŽĨĐƌLJƐƚĂůůŝŶŝƚLJŽĨϯϴй͘DĞůƚ ĐƌLJƐƚĂůůŝnjĂƟŽŶŽĨW;s&-co-sͿĐŽƉŽůLJŵĞƌƐĚŝƌĞĐƚůLJŝŶƚŽƚŚĞɴͲƉŚĂƐĞŝƐƵŶŝƋƵĞĨŽƌWs&Ͳ ďĂƐĞĚĐŽƉŽůLJŵĞƌƐ͘Ws&ƵƐƵĂůůLJĐƌLJƐƚĂůůŝnjĞƐŝŶƚŚĞŬŝŶĞƟĐĂůůLJĨĂǀŽƌĂďůĞɲͲƉŚĂƐĞ͕ǁŚĞƌĞĂƐ W;s&-co-dƌ&ͿĐŽƉŽůLJŵĞƌƐĮƌƐƚĐƌLJƐƚĂůůŝnjĞŝŶƚŽƚŚĞƉĂƌĂĞůĞĐƚƌŝĐƉŚĂƐĞďĞĨŽƌĞƵŶĚĞƌŐŽŝŶŐ Ă ĐƌLJƐƚĂůůŝŶĞ ƉŚĂƐĞ ƚƌĂŶƐŝƟŽŶ ƚŽ ƚŚĞ ĨĞƌƌŽĞůĞĐƚƌŝĐ ƉŚĂƐĞ Ăƚ ůŽǁĞƌ ƚĞŵƉĞƌĂƚƵƌĞƐ͘ /Ŷ ůŝƚĞƌĂƚƵƌĞ͕ƚŽŽǀĞƌĐŽŵĞĐƌLJƐƚĂůůŝnjĂƟŽŶŝŶƚŽƚŚĞɲͲƉŚĂƐĞ͕ƵůƚƌĂĨĂƐƚĐŽŽůŝŶŐĂŶĚĐŽŶĮŶĞĚ ĐƌLJƐƚĂůůŝnjĂƟŽŶĞīĞĐƟǀĞůLJƌĞĚƵĐĞƚŚĞĐƌLJƐƚĂůůŝnjĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞŽĨWs&;ŚĂƉƚĞƌϮͿ͘Ϯϰ͕Ϯϱ /ŶŽƵƌĐĂƐĞ͕ƚŚĞŝŶƚƌŽĚƵĐƟŽŶŽĨĚĞĨĞĐƚƐĂŶĚƚŚĞƐůŝŐŚƚůLJŝŶĐƌĞĂƐĞĚŝŶƚĞƌƉůĂŶĂƌĚŝƐƚĂŶĐĞƐ ŽĨƚŚĞW;s&-co-sͿĐŽƉŽůLJŵĞƌĐŽŵƉĂƌĞĚƚŽWs&ŝŶƚŚĞɴͲƉŚĂƐĞĚƌŝǀĞƐƚŚĞĨŽƌŵĂƟŽŶ of the ferroelectric crystalline phase.

dŚĞĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌŽĨƚŚĞW;s&-co-sͿĐŽƉŽůLJŵĞƌĮůŵƐǁĂƐŝŶǀĞƐƟŐĂƚĞĚďLJ ĂƉƉůLJŝŶŐĂŶĞůĞĐƚƌŝĐĮĞůĚƵƉƚŽϮϬϬDsŵͲϭ_{ŝŶĂƚƌŝĂŶŐƵůĂƌǁĂǀĞĨŽƌŵĂƚĂĨƌĞƋƵĞŶĐLJŽĨϭϬ}

,nj͕ŵĞĂƐƵƌŝŶŐƚŚĞƉŽůĂƌŝnjĂƟŽŶĂƐƚŚĞŝŶƚĞŐƌĂůŽĨƚŚĞƌĞƐƵůƟŶŐĐƵƌƌĞŶƚ͘/ŶĚĞĞĚ͕ĂƚLJƉŝĐĂů ŚLJƐƚĞƌĞƐŝƐůŽŽƉ͕ĚĞŵŽŶƐƚƌĂƚĞĚŝŶ&ŝŐƵƌĞϰ͘ϲď͕ĐŽŶĮƌŵƐƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌŽĨƚŚĞ W;s&₈₅-co-s₁₅ͿĐŽƉŽůLJŵĞƌ͕ǁŚĞƌĞŝŶƚŚĞĐŽĞƌĐŝǀĞĮĞůĚŝƐĨŽƵŶĚƚŽďĞϴϬDsŵͲϭ _{and the}

Figure 4.6: Bipolar Polarization/Current-Electric Field loops for (a) P(VDF90-co-VA10) and (b) P(VDF85 -co-VA₁₅ G (MWGLEVKIIRIVK]HIRWMXMIWERHGLEVKIHMWGLEVKIIƾGMIRGMIWJSVXLI4:(*₉₀-co-VA₁₀)

and P(VDF₈₅-co-VA₁₅) copolymers obtained from unipolar loops. All measurements were obtained

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: 82PDF page: 82PDF page: 82PDF page: 82

82 ƌĞŵŶĂŶƚƉŽůĂƌŝnjĂƟŽŶŝƐϮ͘ϴђĐŵͲϮ ͘WƌŽďĂďůLJ͕ƐŝŶĐĞƚŚĞŝŶƚĞƌƉůĂŶĂƌĚŝƐƚĂŶĐĞŽĨƚŚĞW;s&-co-sͿĐŽƉŽůLJŵĞƌŝƐŝŶďĞƚǁĞĞŶƚŚĞŝŶƚĞƌƉůĂŶĂƌĚŝƐƚĂŶĐĞŽĨWs&ĂŶĚW;s&-co-dƌ&Ϳ͕ƚŚĞ ĐŽĞƌĐŝǀĞĮĞůĚŝƐŝŶďĞƚǁĞĞŶƚŚĂƚŽĨWs&ĂŶĚW;s&-co-dƌ&Ϳ͕ǁŚĞƌĞĂƐƚŚĞůŽǁĞƌĚĞŐƌĞĞŽĨ ĐƌLJƐƚĂůůŝŶŝƚLJĂŶĚƉŚLJƐŝĐĂůƉŝŶŶŝŶŐŽĨsƵŶŝƚƐ;ĚƵĞƚŽƚŚĞůŽǁĞƌĚŝƉŽůĞŵŽŵĞŶƚĐŽŵƉĂƌĞĚ ƚŽs&ĂŶĚdƌ&ͿŝŶƚŚĞĐƌLJƐƚĂůůŝŶĞƐƚƌƵĐƚƵƌĞĞŶŚĂŶĐĞƐĚŝƉŽůĞƌĞǀĞƌƐŝďŝůŝƚLJƌĞƐƵůƟŶŐŝŶĂ ůŽǁĞƌƌĞŵŶĂŶƚƉŽůĂƌŝnjĂƟŽŶ͘Ϯϲ͕Ϯϳ_{/ŶĐŽŶƚƌĂƐƚ͕ĂƐĚĞŵŽŶƐƚƌĂƚĞĚŝŶ&ŝŐƵƌĞϰ͘ϲĂ͕ƚŚĞW;s&} 90 -co-s₁₀ͿĐŽƉŽůLJŵĞƌƐŚŽǁƐůŝŶĞĂƌĚŝĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌ͕ŝŶƐƉŝƚĞŽĨƚŚĞĐŽĞdžŝƐƚĞŶĐĞŽĨƚŚĞ ɲͲĂŶĚɴͲƉŚĂƐĞŝŶƚŚĞĮůŵƐ͘dŚĞůŝŶĞĂƌŝŶĐƌĞĂƐĞŽĨƉŽůĂƌŝnjĂƟŽŶĂƐĨƵŶĐƟŽŶŽĨĞůĞĐƚƌŝĐĮĞůĚ ŝƐĂƌĞƐƵůƚŽĨƚŚĞnjĞƌŽŶĞƚĚŝƉŽůĞŵŽŵĞŶƚɲͲƉŚĂƐĞƉůƵƐƚŚĞŝƐŽůĂƟŽŶĂŶĚƐŵĂůůŶƵŵďĞƌ ŽĨɴͲĐƌLJƐƚĂůƐƌĞƐƵůƟŶŐŝŶĂŵƵĐŚůŽǁĞƌƉŽůĂƌŝnjĂƟŽŶĂƚƐŝŵŝůĂƌĞůĞĐƚƌŝĐĮĞůĚƐƚŚĂŶƚŚĞ ĨĞƌƌŽĞůĞĐƚƌŝĐW;s&₈₅-co-s₁₅ͿĐŽƉŽůLJŵĞƌ͘ ĚĚŝƟŽŶĂůůLJ͕ ƚŚĞ ĐŚĂƌŐĞͲĚŝƐĐŚĂƌŐĞ ĞĸĐŝĞŶĐLJ ǁĂƐ ĐĂůĐƵůĂƚĞĚ ĨƌŽŵ ƚŚĞ ƵŶŝƉŽůĂƌ ƉŽůĂƌŝnjĂƟŽŶͲĞůĞĐƚƌŝĐĮĞůĚůŽŽƉƐĂƐĚĞŵŽŶƐƚƌĂƚĞĚŝŶ&ŝŐƵƌĞϰ͘ϲĐ͘ƐĞdžƉĞĐƚĞĚ͕ĨĞƌƌŽĞůĞĐƚƌŝĐ W;s&₈₅-co-s₁₅ͿƐŚŽǁƐŵƵĐŚůŽǁĞƌĞĸĐŝĞŶĐŝĞƐ;ϰϳйǀƐϳϮй͕ƌĞƐƉĞĐƟǀĞůLJͿĂďŽǀĞƚŚĞ ĐŽĞƌĐŝǀĞĮĞůĚƚŚĂŶůŝŶĞĂƌĚŝĞůĞĐƚƌŝĐW;s&₉₀-co-s₁₀ͿĚƵĞƚŽƚŚĞŚŝŐŚƌĞŵŶĂŶƚƉŽůĂƌŝnjĂƟŽŶ͘ EĞǀĞƌƚŚĞůĞƐƐ͕ƐŝŵŝůĂƌĚŝƐĐŚĂƌŐĞĞŶĞƌŐLJĚĞŶƐŝƟĞƐĂƌĞŽďƚĂŝŶĞĚĚƵĞƚŽƚŚĞŶŽŶͲůŝŶĞĂƌ ďĞŚĂǀŝŽƌŽĨĨĞƌƌŽĞůĞĐƚƌŝĐŵĂƚĞƌŝĂůƐƌĞƐƵůƟŶŐŝŶĂŚŝŐŚƉŽůĂƌŝnjĂƟŽŶ͘/ŶƚĞƌĞƐƟŶŐůLJ͕ƚŚĞ ŚŝŐŚĞĸĐŝĞŶĐŝĞƐĨŽƌW;s&₉₀-co-s₁₀ͿƐŚŽǁƐŝƚƐƉŽƚĞŶƟĂůƚŽďĞƵƐĞĚŝŶĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJ ƐƚŽƌĂŐĞƐĂƉƉůŝĐĂƟŽŶƐ͘ƚϯϬϬDsŵͲϭ_{͕ƚŚĞĚŝƐĐŚĂƌŐĞĚĞŶĞƌŐLJĚĞŶƐŝƚLJŝƐĚĞƚĞƌŵŝŶĞĚƚŽϱ͘ϰ:} cmͲϯ_{ĨŽƌW;s&} 90-co-s10Ϳ͕ǁŚĞƌĞĂƐƚŚĞŐŽůĚĞŶƐƚĂŶĚĂƌĚ͕ďŝĂdžŝĂůůLJŽƌŝĞŶƚĞĚƉŽůLJƉƌŽƉLJůĞŶĞ͕ ĚŝƐƉůĂLJƐĂĚŝƐĐŚĂƌŐĞĚĞŶĞƌŐLJĚĞŶƐŝƚLJŽĨϭ͘ϯ:ĐŵͲϯ_{ĂƚƚŚĞƐĂŵĞĮĞůĚ͘}28

Conclusions

dŚĞĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌŽĨW;s&-co-sͿĐŽƉŽůLJŵĞƌƐǁĂƐĚĞŵŽŶƐƚƌĂƚĞĚ͘dŚĞƵƐĞŽĨ sĐĂƐĂĐŚĞĂƉĐŽŵŽŶŽŵĞƌĂŶĚĂŶĞĂƐLJĨƌĞĞƌĂĚŝĐĂůƉŽůLJŵĞƌŝnjĂƟŽŶŝŶƐŽůƵƟŽŶ͕W;s&-co- sĐͿĐŽƉŽůLJŵĞƌƐǁĞƌĞƐƵĐĐĞƐƐĨƵůůLJƐLJŶƚŚĞƐŝnjĞĚĂŶĚƐƵďƐĞƋƵĞŶƚůLJŚLJĚƌŽůLJnjĞĚƚŽW;s&-co-sͿ͘tŚĞŶϭϱŵŽůйsǁĂƐŝŶĐůƵĚĞĚŝŶƚŚĞĐŽƉŽůLJŵĞƌ͕ŵĞůƚĐƌLJƐƚĂůůŝnjĂƟŽŶĚŝƌĞĐƚůLJ ŝŶƚŽƚŚĞɴͲƉŚĂƐĞƌĞƐƵůƚƐŝŶĨĞƌƌŽĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌ͕ĞdžĐůƵĚŝŶŐƚŚĞƌĞƋƵŝƌĞŵĞŶƚŽĨƚŚĞĞdžƚƌĂ ƉƌŽĐĞƐƐŝŶŐŵĞƚŚŽĚƐ͘dŚĞĐŽĞƌĐŝǀĞĮĞůĚĂŶĚƌĞŵŶĂŶƚƉŽůĂƌŝnjĂƟŽŶǁĞƌĞĚĞƚĞƌŵŝŶĞĚƚŽ ďĞϴϬDsŵͲϭ_{ĂŶĚϮ͘ϴђĐŵ}ͲϮ_{ĂƚϮϬϬDsŵ}Ͳϭ_{͕ƌĞƐƉĞĐƟǀĞůLJ͘/ŶĐŽŶƚƌĂƐƚ͕ƚŚĞŝŶĐůƵƐŝŽŶ} ŽĨϭϬŵŽůйsůĞĂĚƐƚŽĂŵŝdžƚƵƌĞƚŚĞɲͲĂŶĚĂƐŵĂůůĂŵŽƵŶƚŽĨɴͲĐƌLJƐƚĂůƐƌĞƐƵůƟŶŐŝŶ ůŝŶĞĂƌĚŝĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌǁŝƚŚŚŝŐŚĐŚĂƌŐĞͲĚŝƐĐŚĂƌŐĞĞĸĐŝĞŶĐŝĞƐĂŶĚĂĚŝƐĐŚĂƌŐĞĚĞŶĞƌŐLJ ĚĞŶƐŝƚLJŽĨϱ͘ϰ:ĐŵͲϯ_{ĂƚϯϬϬDsŵ}Ͳϭ_{͕ƐŚŽǁŝŶŐƚŚĞǀĞƌƐĂƟůŝƚLJŝŶĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌŽĨ} W;s&-co-sͿĐŽƉŽůLJŵĞƌƐďLJƐŝŵƉůLJĐŚĂŶŐŝŶŐƚŚĞsĐŽŶƚĞŶƚ͘/ƚŝƐĞŶǀŝƐŝŽŶĞĚƚŚĂƚW;s&-co-sͿĐŽƉŽůLJŵĞƌƐ͕ĚƵĞƚŽƚŚĞŝŶƚƌŽĚƵĐƟŽŶŽĨŚLJĚƌŽdžLJůŐƌŽƵƉƐŝŶƚŚĞƉŽůLJŵĞƌďĂĐŬďŽŶĞ͕ ƉƌŽǀŝĚĞƐĂƉůĂƞŽƌŵĨŽƌĂĚǀĂŶĐĞĚŵĂƚĞƌŝĂůƐǁŝƚŚƚƵŶĂďůĞĞůĞĐƚƌŽĂĐƟǀĞƉƌŽƉĞƌƟĞƐŝŶďƵůŬ ĂŶĚƚŚŝŶĮůŵĂƉƉůŝĐĂƟŽŶƐ͘dŚŝƐŝƐĨƵƌƚŚĞƌĚŝƐĐƵƐƐĞĚŝŶŚĂƉƚĞƌϱĂŶĚϲ͘

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: 83PDF page: 83PDF page: 83PDF page: 83

83

4

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B ϮϬϬϵ, 48;ϯͿ͕ϱϭϰʹϱϮϱ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϴϬͬϬϬϮϮϮϯϰϬϵϬϮϴϯϳϱϮϳ͘

;ϵͿ &ƵƌƵŬĂǁĂ͕ d͖͘ ĂƚĞ͕ D͖͘ &ƵŬĂĚĂ͕ ͖͘ dĂũŝƚƐƵ͕ z͖͘ ŚŝďĂ͕ ͘ &ĞƌƌŽĞůĞĐƚƌŝĐ ĞŚĂǀŝŽƌ ŝŶ ƚŚĞ ŽƉŽůLJŵĞƌŽĨsŝŶLJůŝĚĞŶĞŇƵŽƌŝĚĞĂŶĚdƌŝŇƵŽƌŽĞƚŚLJůĞŶĞ͘Jpn. J. Appl. Phys. ϭϵϴϬ, 19;ϮͿ͕>ϭϬϵ͘ ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϭϰϯͬ::W͘ϭϵ͘>ϭϬϵ͘

;ϭϬͿ zĂŐŝ͕ d͖͘ dĂƚĞŵŽƚŽ͕ D͖͘ ^ĂŬŽ͕ :͘ dƌĂŶƐŝƚŝŽŶ ĞŚĂǀŝŽƌ ĂŶĚ ŝĞůĞĐƚƌŝĐ WƌŽƉĞƌƚŝĞƐ ŝŶ dƌŝŇƵŽƌŽĞƚŚLJůĞŶĞĂŶĚsŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞŽƉŽůLJŵĞƌƐ͘Polymer Journal ϭϵϴϬ, 12;ϰͿ͕ϮϬϵʹ ϮϮϯ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϮϵϱͬƉŽůLJŵũ͘ϭϮ͘ϮϬϵ͘

;ϭϭͿ &ƵƌƵŬĂǁĂ͕ d͘ ^ƚƌƵĐƚƵƌĞ ĂŶĚ &ƵŶĐƟŽŶĂů WƌŽƉĞƌƟĞƐ ŽĨ &ĞƌƌŽĞůĞĐƚƌŝĐ WŽůLJŵĞƌƐ͘ Advances

in Colloid and Interface Science ϭϵϵϳ, 71ʹ72͕ ϭϴϯʹϮϬϴ͘ ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϭϲͬ^ϬϬϬϭͲ

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

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;ϭϮͿ dĂŶ͕ ^͖͘ >ŝ͕ :͖͘ 'ĂŽ͕ '͖͘ >ŝ͕ ,͖͘ ŚĂŶŐ͕ ͘ ^LJŶƚŚĞƐŝƐ ŽĨ &ůƵŽƌŽƉŽůLJŵĞƌ ŽŶƚĂŝŶŝŶŐ dƵŶĂďůĞ hŶƐĂƚƵƌĂƟŽŶďLJĂŽŶƚƌŽůůĞĚĞŚLJĚƌŽĐŚůŽƌŝŶĂƟŽŶŽĨW;s&ͲŽͲd&ͿĂŶĚ/ƚƐƵƌŝŶŐĨŽƌ ,ŝŐŚWĞƌĨŽƌŵĂŶĐĞZƵďďĞƌƉƉůŝĐĂƟŽŶƐ͘J. Mater. Chem. ϮϬϭϮ, 22;ϯϱͿ͕ϭϴϰϵϲʹϭϴϱϬϰ͘ŚƩƉƐ͗ͬͬ ĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϯϵͬϮ:Dϯϯϭϯϯ<͘

;ϭϯͿ >Ƶ͕ z͖͘ ůĂƵĚĞ͕ :͖͘ EĞĞƐĞ͕ ͖͘ ŚĂŶŐ͕ Y͖͘ tĂŶŐ͕ Y͘  DŽĚƵůĂƌ ƉƉƌŽĂĐŚ ƚŽ &ĞƌƌŽĞůĞĐƚƌŝĐ Polymers with Chemically Tunable Curie Temperatures and Dielectric Constants. J. Am. Chem.

Soc. ϮϬϬϲ, 128;ϮϱͿ͕ϴϭϮϬʹϴϭϮϭ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬũĂϬϲϮϯϬϲdž͘

;ϭϰͿ ŚŵĞĚ͕d͘^͖͘Ğ^ŝŵŽŶĞ͕:͘D͖͘ZŽďĞƌƚƐ͕'͘t͘ŽŶƟŶƵŽƵƐŽƉŽůLJŵĞƌŝnjĂƟŽŶŽĨsŝŶLJůŝĚĞŶĞ &ůƵŽƌŝĚĞǁŝƚŚ,ĞdžĂŇƵŽƌŽƉƌŽƉLJůĞŶĞŝŶ^ƵƉĞƌĐƌŝƟĐĂůĂƌďŽŶŝŽdžŝĚĞ͗>Žǁ,ĞdžĂŇƵŽƌŽƉƌŽƉLJůĞŶĞ Content Semicrystalline Copolymers. Macromolecules ϮϬϬϳ, 40;ϮϲͿ͕ϵϯϮϮʹϵϯϯϭ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ ŽƌŐͬϭϬ͘ϭϬϮϭͬŵĂϬϳϭϯϲϭϯ͘

;ϭϱͿ ĂŶĞƌũĞĞ͕^͖͘tĞŚďŝ͕D͖͘DĂŶƐĞƌŝ͕͖͘DĞŚĚŝ͕͖͘ůĂĂĞĚĚŝŶĞ͕͖͘,ĂĐŚĞŵ͕͖͘ŵĞĚƵƌŝ͕͘ WŽůLJ;sŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞͿŽŶƚĂŝŶŝŶŐWŚŽƐƉŚŽŶŝĐĐŝĚĂƐŶƟĐŽƌƌŽƐŝŽŶŽĂƟŶŐĨŽƌ^ƚĞĞů͘ACS

Appl. Mater. Interfaces ϮϬϭϳ, 9;ϳͿ͕ϲϰϯϯʹϲϰϰϯ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬĂĐƐĂŵŝ͘ϲďϭϱϰϬϴ͘

;ϭϲͿ tĞŚďŝ͕D͖͘ĂŶĞƌũĞĞ͕^͖͘DĞŚĚŝ͕͖͘ůĂĂĞĚĚŝŶĞ͕͖͘,ĂĐŚĞŵ͕͖͘ŵĞĚƵƌŝ͕͘sŝŶLJůŝĚĞŶĞ &ůƵŽƌŝĚĞͲĂƐĞĚWŽůLJŵĞƌEĞƚǁŽƌŬǀŝĂƌŽƐƐͲ>ŝŶŬŝŶŐŽĨWĞŶĚĂŶƚdƌŝĞƚŚŽdžLJƐŝůĂŶĞ&ƵŶĐƟŽŶĂůŝƚLJ ĨŽƌWŽƚĞŶƟĂůƉƉůŝĐĂƟŽŶƐŝŶŽĂƟŶŐƐ͘Macromolecules ϮϬϭϳ, 50;ϮϯͿ͕ϵϯϮϵʹϵϯϯϵ͘ŚƩƉƐ͗ͬͬ ĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬĂĐƐ͘ŵĂĐƌŽŵŽů͘ϳďϬϮϭϯϴ͘ ;ϭϳͿ WĂŶĐŚĂůŝŶŐĂŵ͕s͖͘ZĞLJŶŽůĚƐ͕:͘Z͘EĞǁsŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞŽƉŽůLJŵĞƌƐ͗WŽůLJ;sŝŶLJůĐĞƚĂƚĞͲĐŽͲ ǀŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞͿ͘:ŽƵƌŶĂůŽĨWŽůLJŵĞƌ^ĐŝĞŶĐĞWĂƌƚ͗WŽůLJŵĞƌ>ĞƩĞƌƐ ϭϵϴϵ, 27;ϲͿ͕ϮϬϭʹϮϬϴ͘ ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϬϮͬƉŽů͘ϭϵϴϵ͘ϭϰϬϮϳϬϲϬϱ͘ ;ϭϴͿ ƌĂŶĚƌƵƉ͕:͖͘/ŵŵĞƌŐƵƚ͕͘,͖͘'ƌƵůŬĞ͕͘͘WŽůLJŵĞƌ,ĂŶĚŬ͕ϰƚŚĚŝƟŽŶ͖tŝůĞLJ͕ϮϬϬϰ͘ ;ϭϵͿ ĂƌĂĚŝĞ͕ ͖͘ ^ŚŽŝĐŚĞƚ͕ D͘ ^͘ ^LJŶƚŚĞƐŝƐ ŽĨ &ůƵŽƌŽĐĂƌďŽŶоsŝŶLJů ĐĞƚĂƚĞ ŽƉŽůLJŵĞƌƐ ŝŶ ^ƵƉĞƌĐƌŝƟĐĂůĂƌďŽŶŝŽdžŝĚĞ͗/ŶƐŝŐŚƚŝŶƚŽƵůŬWƌŽƉĞƌƟĞƐ͘Macromolecules ϮϬϬϮ, 35;ϵͿ͕ ϯϱϲϵʹϯϱϳϱ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬŵĂϬϭϬϰϲϭŬ͘ ;ϮϬͿ ƐĂŶĚĞŝ͕͖͘͘ĚĞďŽůƵ͕K͘/͖͘^ŝŵƉƐŽŶ͕͘W͘DŝůĚͲdĞŵƉĞƌĂƚƵƌĞDŶϮ;KͿϭϬͲWŚŽƚŽŵĞĚŝĂƚĞĚ ŽŶƚƌŽůůĞĚZĂĚŝĐĂůWŽůLJŵĞƌŝnjĂƟŽŶŽĨsŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞĂŶĚ^LJŶƚŚĞƐŝƐŽĨtĞůůͲĞĮŶĞĚ WŽůLJ;sŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞͿůŽĐŬŽƉŽůLJŵĞƌƐ͘J. Am. Chem. Soc. ϮϬϭϮ, 134;ϭϰͿ͕ϲϬϴϬʹϲϬϴϯ͘ ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬũĂϯϬϬϭϳϴƌ͘ ;ϮϭͿ dǁƵŵ͕͖͘͘'ĂŽ͕͖͘>ŝ͕y͖͘DĐŽƌĚ͕͘&͖͘&Ždž͕W͖͘͘>LJŽŶƐ͕͘&͖͘ZŝŶĂůĚŝ͕W͘>͘ŚĂƌĂĐƚĞƌŝnjĂƟŽŶ ŽĨƚŚĞŚĂŝŶͲŶĚƐĂŶĚƌĂŶĐŚŝŶŐ^ƚƌƵĐƚƵƌĞƐŝŶWŽůLJǀŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞǁŝƚŚDƵůƟĚŝŵĞŶƐŝŽŶĂů EDZ͘Macromolecules ϮϬϭϮ, 45;ϭϯͿ͕ϱϱϬϭʹϱϱϭϮ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬŵĂϯϬϬϴϯϱƐ͘ ;ϮϮͿ 'ƵĞƌƌĞ͕D͖͘ĂŵƉĂŐŶĞ͕͖͘'ŝŵĞůůŽ͕K͖͘WĂƌƌĂ͕<͖͘ŵĞĚƵƌŝ͕͖͘>ĂĚŵŝƌĂů͕s͘ĞĞƉĞƌ/ŶƐŝŐŚƚŝŶƚŽ ƚŚĞD/yWŽůLJŵĞƌŝnjĂƟŽŶŽĨsŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞ͘Macromolecules ϮϬϭϱ, 48;ϮϭͿ͕ϳϴϭϬʹϳϴϮϮ͘ ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬĂĐƐ͘ŵĂĐƌŽŵŽů͘ϱďϬϭϱϮϴ͘ ;ϮϯͿ WŝĂŶĐĂ͕D͖͘ĂƌĐŚŝĞƐŝ͕͖͘ƐƉŽƐƚŽ͕'͖͘ZĂĚŝĐĞ͕^͘ŶĚ'ƌŽƵƉƐŝŶ&ůƵŽƌŽƉŽůLJŵĞƌƐ͘Journal of Fluorine Chemistry ϭϵϵϵ, 95;ϭͿ͕ϳϭʹϴϰ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϭϲͬ^ϬϬϮϮͲϭϭϯϵ;ϵϴͿϬϬϯϬϰͲϮ͘

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

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;ϮϰͿ 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 ;ϮϱͿ DĞĞƌĞďŽĞƌ͕E͘>͖͘dĞƌnjŝđ͕/͖͘^ĂŝĚŝ͕^͖͘,ĞƌŵŝĚĂDĞƌŝŶŽ͕͖͘>ŽŽƐ͕<͘EĂŶŽĐŽŶĮŶĞŵĞŶƚͲ/ŶĚƵĐĞĚ ɴͲWŚĂƐĞ&ŽƌŵĂƟŽŶ/ŶƐŝĚĞWŽůLJ;sŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞͿͲĂƐĞĚůŽĐŬŽƉŽůLJŵĞƌƐ͘ACS Macro >ĞƩ͘ ϮϬϭϴ͕ϴϲϯʹϴϲϳ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬĂĐƐŵĂĐƌŽůĞƩ͘ϴďϬϬϰϭϴ͘ ;ϮϲͿ dƐƵƚƐƵŵŝ͕E͖͘<ŽƐƵŐŝ͕Z͖͘<ŝŶĂƐŚŝ͕<͖͘^ĂŬĂŝ͕t͘EĂƚƵƌĞŽĨƚŚĞŶŚĂŶĐĞŵĞŶƚŝŶ&ĞƌƌŽĞůĞĐƚƌŝĐ WƌŽƉĞƌƟĞƐďLJ'ŽůĚEĂŶŽƉĂƌƟĐůĞƐŝŶsŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞĂŶĚdƌŝŇƵŽƌŽĞƚŚLJůĞŶĞŽƉŽůLJŵĞƌ͘ACS

Appl. Mater. Interfaces ϮϬϭϲ, 8;ϮϲͿ͕ϭϲϴϭϲʹϭϲϴϮϮ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬĂĐƐĂŵŝ͘ϲďϬϱϴϵϳ͘

;ϮϳͿ ŚƵ͕>͘džƉůŽƌŝŶŐ^ƚƌĂƚĞŐŝĞƐĨŽƌ,ŝŐŚŝĞůĞĐƚƌŝĐŽŶƐƚĂŶƚĂŶĚ>Žǁ>ŽƐƐWŽůLJŵĞƌŝĞůĞĐƚƌŝĐƐ͘

:͘WŚLJƐ͘ŚĞŵ͘>ĞƩ͘ ϮϬϭϰ, 5;ϮϭͿ͕ϯϲϳϳʹϯϲϴϳ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬũnjϱϬϭϴϯϭƋ͘

;ϮϴͿ ŚĂŽ͕ z͖͘ >ŝ͕ Y͖͘ ŚĂŶŐ͕ y͖͘ >ŝ͕ ,͖͘ >Ƶ͕ :͖͘ ŚĂŶŐ͕ ͘ ,ŝŐŚ ŶĞƌŐLJ ĞŶƐŝƚLJ ĂŶĚ ŝƐĐŚĂƌŐŝŶŐ ĸĐŝĞŶĐLJĐŚŝĞǀĞĚŝŶŚůŽƌŝŶĂƚĞĚWŽůLJĞƚŚLJůĞŶĞ&ŝůŵƐĨŽƌ,ŝŐŚŶĞƌŐLJͲ^ƚŽƌĂŐĞƉƉůŝĐĂƟŽŶƐ͘

Macromolecular Chemistry and Physics ϮϬϭϴ, 219;ϴͿ͕ϭϳϬϬϲϮϭ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϬϮͬ