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

Processed on: 21-3-2019 PDF page: 105PDF page: 105PDF page: 105PDF page: 105

Chapter 6

6IPE\SVJIVVSIPIGXVMGFILEZMSVMR4:(*ter8V*)ter:% 

XIVTSP]QIVW

ZĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐƉŽůLJŵĞƌƐ͕ŚĂǀŝŶŐĂŚŝŐŚĞŶĞƌŐLJƐƚŽƌĂŐĞĚĞŶƐŝƚLJĂŶĚĞĸĐŝĞŶĐLJ͕ĂƌĞ ƌĂƉŝĚůLJĚĞǀĞůŽƉŝŶŐĨŽƌƌĞůŝĂďůĞĂŶĚĐŽŵƉĂĐƚĚŝĞůĞĐƚƌŝĐĮůŵĐĂƉĂĐŝƚŽƌƐ͘hŶƟůŶŽǁ͕ƚŚĞLJ ŚĂǀĞďĞĞŶďĂƐĞĚŽŶŚŝŐŚůLJŇƵŽƌŝŶĂƚĞĚŵŽŶŽŵĞƌƐůĂĐŬŝŶŐĨƵŶĐƟŽŶĂůŝƟĞƐĨŽƌĨƵƌƚŚĞƌ ŵŽĚŝĮĐĂƟŽŶƐ͕ƐƵĐŚĂƐŐŽŽĚĚŝƐƉĞƌƐŝŽŶŽĨŶĂŶŽƉĂƌƟĐůĞƐŽƌĨĂĐŝůĞĐƌŽƐƐůŝŶŬŝŶŐ͕ƚŽŐĂŝŶ ĞŶŚĂŶĐĞĚƉƌŽƉĞƌƟĞƐ͘/ŶƚŚŝƐǁŽƌŬ͕ǁĞƐƚƵĚLJƚŚĞĞůĞĐƚƌŽĂĐƟǀĞƉƌŽƉĞƌƟĞƐŽĨĂŶŽǀĞůĐůĂƐƐ ŽĨƉŽůLJ;ǀŝŶLJůŝĚĞŶĞŇƵŽƌŝĚĞ-ter-ƚƌŝŇƵŽƌŽĞƚŚLJůĞŶĞ-ter-ǀŝŶLJůĂůĐŽŚŽůͿ;W;s&-ter-dƌ&-ter-sͿͿƚĞƌƉŽůLJŵĞƌƐĨŽƌĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJƐƚŽƌĂŐĞĂƉƉůŝĐĂƟŽŶƐ͘ĚĚŝƟŽŶĂůůLJ͕ǁĞƐŚŽǁƚŚĂƚ ƚŚĞsƵŶŝƚƐŝŶƚŚĞƐĞƚĞƌƉŽůLJŵĞƌƐĐĂŶďĞĐƌŽƐƐůŝŶŬĞĚƵƐŝŶŐĨĂĐŝůĞƵƌĞƚŚĂŶĞĐŚĞŵŝƐƚƌLJ͘/ƚ ŝƐĨŽƵŶĚƚŚĂƚŝŶƚƌŽĚƵĐŝŶŐsŝŶƚŚĞƚĞƌƉŽůLJŵĞƌďĂĐŬďŽŶĞůĞĂĚƐƚŽĐŽĐƌLJƐƚĂůůŝnjĂƟŽŶǁŝƚŚ ƚŚĞŇƵŽƌŝŶĂƚĞĚŵŽŶŽŵĞƌŝĐĐŽŶƐƟƚƵĞŶƚƐ͘dŚĞsĚĞĨĞĐƚƐƉƌŽŵŽƚĞƚŚĞĨŽƌŵĂƟŽŶŽĨddd' ŵŽŶŽŵĞƌƐĞƋƵĞŶĐĞƐĨĂǀŽƌŝŶŐƌĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌ͘ŽŶƐĞƋƵĞŶƚůLJ͕ƚŚĞƵƌŝĞ ƚƌĂŶƐŝƟŽŶŝƐƐƚƌŽŶŐůLJƌĞĚƵĐĞĚĐŽŵƉĂƌĞĚƚŽW;s&ͲcoͲdƌ&ͿĂŶĂůŽŐƵĞƐ͘DŽƌĞŽǀĞƌ͕ĐŚĞŵŝĐĂů ĐƌŽƐƐůŝŶŬŝŶŐŽĨW;s&-ter-dƌ&-ter-sͿƚĞƌƉŽůLJŵĞƌƐƌĞƐƵůƚƐŝŶĞdžƚƌĞŵĞůLJƐůŝŵŚLJƐƚĞƌĞƐŝƐ ůŽŽƉƐĚƵĞƚŽƚŚĞŝŶĐƌĞĂƐĞŝŶƚŚĞƌĞůĂƟǀĞĂŵŽƵŶƚŽĨƚŚĞĚŝƐŽƌĚĞƌĞĚƉĂƌĂĞůĞĐƚƌŝĐƉŚĂƐĞ ĂŶĚƵůƚƌĂĮŶĞĐƌLJƐƚĂůůŝƚĞƐ͕ůĞĂĚŝŶŐƚŽĞŶŚĂŶĐĞĚĐŚĂƌŐĞͲĚŝƐĐŚĂƌŐĞĞĸĐŝĞŶĐŝĞƐ͘dŚĞƌĞĨŽƌĞ͕ ƚŚŝƐŶĞǁĐůĂƐƐŽĨƌĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐƉŽůLJŵĞƌƐ͕ǁŚĞƌĞŝŶƉŚLJƐŝĐĂůƉŝŶŶŝŶŐĂŶĚĐŚĞŵŝĐĂů ĐƌŽƐƐůŝŶŬŝŶŐĂƌĞĐŽŵďŝŶĞĚ͕ƐŚŽǁƐŐƌĞĂƚƉƌŽŵŝƐĞĨŽƌĨƵƚƵƌĞĂĚǀĂŶĐĞĚĂƉƉůŝĐĂƟŽŶƐ͘

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

ĚǀĂŶĐĞĚ ĞůĞĐƚƌŽŶŝĐ ĚĞǀŝĐĞƐ ĂŶĚ ĐŝƌĐƵŝƚƐ͕ ƉƵůƐĞĚ ƉŽǁĞƌ ƚĞĐŚŶŽůŽŐŝĞƐ ĂŶĚ ĞůĞĐƚƌŝĐ ǀĞŚŝĐůĞƐĂƌĞĂŵŽŶŐŽƚŚĞƌƐĂƉƉůŝĐĂƟŽŶƐƚŚĂƚŶĞĞĚŚŝŐŚĞŶĞƌŐLJĚĞŶƐŝƚLJĚŝĞůĞĐƚƌŝĐƐĨŽƌ ĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJƐƚŽƌĂŐĞ͘ϭʹϯ_{EŽǁĂĚĂLJƐ͕ďLJƐĞůĞĐƟŶŐƉŽůLJŵĞƌƐĂƐƚŚĞŵĂƚĞƌŝĂůŽĨĐŚŽŝĐĞ͕} ŵĂŝŶƌĞƋƵŝƌĞŵĞŶƚƐƐƵĐŚĂƐůŝŐŚƚǁĞŝŐŚƚŶĂƚƵƌĞ͕ůŽǁĐŽƐƚ͕ĞĂƐĞŽĨƉƌŽĐĞƐƐŝŶŐ͕ƐĞůĨͲŚĞĂůŝŶŐ ĐĂƉĂďŝůŝƚLJĂŶĚŚŝŐŚďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚƐĂƌĞĞĂƐŝůLJĨƵůĮůůĞĚ͘hŶĨŽƌƚƵŶĂƚĞůLJ͕ŝŶŚĞƌĞŶƚƚŽ commercially available high breakdown strength polymers are low dielectric constants, ƐƵƉƉƌĞƐƐŝŶŐ ƚŚĞ ŵĂdžŝŵƵŵ ĞŶĞƌŐLJ ĚĞŶƐŝƟĞƐ ƚŽ ďĞ ƐƚŽƌĞĚ ŝŶƐŝĚĞ ƚŚĞ ĚŝĞůĞĐƚƌŝĐƐ͘ &Žƌ ŝŶƐƚĂŶĐĞ͕ƐƚĂƚĞͲŽĨͲƚŚĞͲĂƌƚKWWƐŚŽǁƐĂŶĞŶĞƌŐLJĚĞŶƐŝƚLJŽĨũƵƐƚΕϰ:ĐŵͲϯ _{at an electric} ĮĞůĚŽĨϲϬϬDsŵͲϭ_{͘dŚĞƌĞĨŽƌĞ͕ƚŽŝŵƉƌŽǀĞƚŚĞĞŶĞƌŐLJƐƚŽƌĂŐĞŝŶĚŝĞůĞĐƚƌŝĐƐ͕ƚŚĞLJƌĞƋƵŝƌĞ} both a high dielectric constant (ɸͿĂŶĚŚŝŐŚďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚ͕ƐŝŶĐĞƚŚĞƐƚŽƌĞĚĞŶĞƌŐLJ density (UͿŝƐƉƌŽƉŽƌƟŽŶĂůƚŽƚŚĞĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚĂŶĚƚŚĞĞůĞĐƚƌŝĐĮĞůĚ;EͿƐƋƵĂƌĞĚĂƐ ĚŝƐƉůĂLJĞĚŝŶƋƵĂƟŽŶϲ͘ϭ͕ǁŚĞƌĞŝŶɸ₀ŝƐƚŚĞƉĞƌŵŝƫǀŝƚLJŝŶĨƌĞĞƐƉĂĐĞ͘  ;ϲ͘ϭͿ /ŶĐŽŶƚƌĂƐƚ͕ƉŽůLJ;ǀŝŶLJůŝĚĞŶĞŇƵŽƌŝĚĞͿ;Ws&ͿŚĂƐďŽƚŚĂŚŝŐŚĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚ;ΕϭϬͿ ĂŶĚďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚ;ΕϲϬϬDsŵͲϭ_{Ϳ͕ŵĂŬŝŶŐŝƚĂŶĞdžĐĞůůĞŶƚĐŚŽŝĐĞƚŽďĞƵƐĞĚĂƐ} dielectric material.ϰ͕ϱ_{,ŽǁĞǀĞƌ͕ĂŶŝƌƌĞǀĞƌƐŝďůĞĐƌLJƐƚĂůůŝŶĞƉŚĂƐĞƚƌĂŶƐĨŽƌŵĂƟŽŶĨƌŽŵ} ƚŚĞɲͲƚŽƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐɴͲƉŚĂƐĞĂƚŚŝŐŚĞůĞĐƚƌŝĐĮĞůĚƐƌĞƐƵůƚƐŝŶĨĞƌƌŽĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌ͕ ǁŚŝĐŚƐƵīĞƌƐĨƌŽŵůĂƌŐĞŚLJƐƚĞƌĞƐŝƐůŽƐƐĞƐ͘ϲ_{ĐĐŽƌĚŝŶŐůLJ͕ƌĞƐĞĂƌĐŚĞīŽƌƚƐĨŽĐƵƐŽŶƚƵŶŝŶŐ} ƚŚĞĐƌLJƐƚĂůŝƐŽŵŽƌƉŚŝƐŵ͕ĐƌLJƐƚĂůůŝƚĞƐŝnjĞĂŶĚĐƌLJƐƚĂůůŝŶĞͲĂŵŽƌƉŚŽƵƐŝŶƚĞƌĨĂĐĞŽĨWs&Ͳ ďĂƐĞĚ;ĐŽͿƉŽůLJŵĞƌƐƚŽLJŝĞůĚƐůŝŵŚLJƐƚĞƌĞƐŝƐůŽŽƉƐ;i.e.ƌĞůĂdžŽƌŽƌĚŽƵďůĞŚLJƐƚĞƌĞƐŝƐůŽŽƉ ;,>ͿďĞŚĂǀŝŽƌͿǁŚŝůĞƐƟůůŚĂǀŝŶŐůĂƌŐĞƉŽůĂƌŝnjĂƟŽŶƐ͘ϱ͕ϳʹϭϱ ƐƐƵĐŚ͕ĐŽͲĂŶĚƚĞƌƉŽůLJŵĞƌŝnjĂƟŽŶƐŽĨs&ǁŝƚŚŽƚŚĞƌŇƵŽƌŝŶĂƚĞĚĐŽŵŽŶŽŵĞƌƐ͕ůŝŬĞ ƚƌŝŇƵŽƌŽĞƚŚLJůĞŶĞ;dƌ&Ϳ͕ĐŚůŽƌŽƚƌŝŇƵŽƌŽĞƚŚLJůĞŶĞ;d&ͿĂŶĚĐŚůŽƌŽŇƵŽƌŽĞƚŚLJůĞŶĞ;&Ϳ͕ ŚĂǀĞďĞĞŶĞŵƉůŽLJĞĚƚŽŐƌĂĚƵĂůůLJŝŶĐƌĞĂƐĞƚŚĞĐƌLJƐƚĂůůĂƫĐĞƐƉĂĐŝŶŐ͘ϭϲ͕ϭϳ _{Dependent on} ƚŚĞƉƌŽĐĞƐƐŝŶŐĐŽŶĚŝƟŽŶƐ͕ŝŶĐŽƌƉŽƌĂƟŶŐƚŚĞƐĞĐŽŵŽŶŽŵĞƌƐǁŝƚŚĂůŽǁĞƌĚŝƉŽůĞŵŽŵĞŶƚ ůĞĂĚƐƚŽƚŚĞĨŽƌŵĂƟŽŶŽĨƉŚLJƐŝĐĂůƉŝŶŶŝŶŐƐƉŽƚƐ͕ĚĞƐƚĂďŝůŝnjŝŶŐƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐƉŚĂƐĞ ĂŶĚĞŶŚĂŶĐŝŶŐƚŚĞĚŝƉŽůĞƌĞǀĞƌƐŝďŝůŝƚLJ͕ǁŚŝĐŚƌĞƐƵůƚƐŝŶƌĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌ͘ DŽƌĞŽǀĞƌ͕ŝŶĂW;s&-ter-dƌ&-ter-d&ͿƚĞƌƉŽůLJŵĞƌ͕ĂƐƉĞĐŝĮĐŵŽŶŽŵĞƌĐŽŵƉŽƐŝƟŽŶ ůĞĂĚƐƚŽĂŶĞĂƌƌŽŽŵƚĞŵƉĞƌĂƚƵƌĞƵƌŝĞƚƌĂŶƐŝƟŽŶĂĐĐŽŵƉĂŶŝĞĚǁŝƚŚůĂƌŐĞĚŝĞůĞĐƚƌŝĐ ĐŽŶƐƚĂŶƚƐ;ɸсϱϬͿ͕ƌĞŶĚĞƌŝŶŐƚŚĞƐĞŵĂƚĞƌŝĂůƐƐƵŝƚĂďůĞĨŽƌĞůĞĐƚƌŽĐĂůŽƌŝĐĐŽŽůŝŶŐĚĞǀŝĐĞƐ as well.18,19_{ /ŶƚĞƌĞƐƟŶŐůLJ͕ ƚŚĞ tĂŶŐ ŐƌŽƵƉ ƌĞǀĞĂůĞĚ ƚŚĂƚ ƚĂĐƟĐŝƚLJ ŝŶ W;s&-co-dƌ&Ϳ} ĐŽƉŽůLJŵĞƌƐƉůĂLJƐĂĐƌƵĐŝĂůƌŽůĞŝŶƚŚĞĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌ͘20_{,ĞƌĞ͕ƐƚĞƌĞŽĐŚĞŵŝĐĂů} ĐŚĂŶŐĞƐ;ĨƌŽŵŵĂŝŶůLJƐLJŶĚŝŽƚĂĐƟĐƚŽŝƐŽƚĂĐƟĐƐĞƋƵĞŶĐĞƐͿŝŶĚƵĐĞĚďLJƐƚĞƌĞŽƐƉĞĐŝĮĐdƌ& ŵŽŶŽŵĞƌƐůĞĂĚƐƚŽĂŶŽƌĚĞƌͲƚŽͲĚŝƐŽƌĚĞƌĞǀŽůƵƟŽŶŝŶƚŚĞĐƌLJƐƚĂůůŝŶĞƉŚĂƐĞĂƚхϰϱŵŽůй dƌ&͕ǁŚŝĐŚƌĞƐƵůƚƐŝŶĂŶŝŶĐƌĞĂƐŝŶŐĂŵŽƵŶƚƐϯͬϭŚĞůŝĐĞƐĂƐŽƉƉŽƐĞĚƚŽƚŚĞĂůůͲƚƌĂŶƐ

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: 107PDF page: 107PDF page: 107PDF page: 107

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ƉůĂŶĂƌĐŽŶĨŽƌŵĂƟŽŶƐͲĐŚĂŶŐŝŶŐŝƚƐďĞŚĂǀŝŽƌĨƌŽŵĨĞƌƌŽĞůĞĐƚƌŝĐƚŽƌĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐ behavior.20_{ĚĚŝƟŽŶĂůůLJ͕ĂŌĞƌŵĞĐŚĂŶŝĐĂůƐƚƌĞƚĐŚŝŶŐ͕ďƵůŬLJŚĞdžĂŇƵŽƌŽƉƌŽƉLJůĞŶĞ;,&WͿ} ŵŽŶŽŵĞƌŝĐĐŽŶƐƟƚƵĞŶƚƐĂƌĞŝŶĐŽƌƉŽƌĂƚĞĚŝŶƚŚĞƉŽůLJŵĞƌĐƌLJƐƚĂůƐůĞĂĚŝŶŐƚŽƌĞůĂdžŽƌ ferroelectric behavior, which is caused by a break up of large ferroelectric nanodomains into smaller nonpolar regions.21_{W;s&-co-d&ͿĐŽƉŽůLJŵĞƌƐŐƌĂŌĞĚǁŝƚŚƉŽůLJƐƚLJƌĞŶĞ;W^Ϳ} ŽƌƉŽůLJ;ĂůŬLJůŵĞƚŚĂĐƌLJůĂƚĞͿ;WDͿĂƌĞĂŶŽƚŚĞƌŵĞĂŶƐƚŽĂǀĞƌƚĨĞƌƌŽĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌŝŶ Ws&͘ϳ͕ϮϮ͕Ϯϯ_{,ĞƌĞ͕W^ŽƌWDƐŝĚĞĐŚĂŝŶƐƐĞŐƌĞŐĂƚĞƚŽƚŚĞĐƌLJƐƚĂůůŝŶĞͲĂŵŽƌƉŚŽƵƐŝŶƚĞƌĨĂĐĞ͕} ĐƌĞĂƟŶŐĂŶŽŶƉŽůĂƌĐŽŶĮŶŝŶŐůĂLJĞƌƚŚĂƚĞīĞĐƟǀĞůLJĚĞƐƚĂďŝůŝnjĞƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶƐ͕ ƌĞƐƵůƟŶŐŝŶ,>ďĞŚĂǀŝŽƌ͘dŚĞƐĞƐƚƌĂƚĞŐŝĞƐĐŚĂŶŐĞƚŚĞĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌŽĨWs& ĚƌĂƐƟĐĂůůLJĂŶĚƐŚŽǁŝŶĐƌĞĂƐĞĚƌĞůĞĂƐĞĚĞŶĞƌŐLJĚĞŶƐŝƟĞƐĂŶĚĞĸĐŝĞŶĐŝĞƐ͘ ůƚĞƌŶĂƟǀĞƐƚƌĂƚĞŐŝĞƐƚŽŵŽĚŝĨLJWs&ƚŽƌĞŶĚĞƌĚŝĞůĞĐƚƌŝĐŵĂƚĞƌŝĂůƐŝŶĐůƵĚĞĐŚĞŵŝĐĂů ĐƌŽƐƐůŝŶŬŝŶŐ͘/ŶƚŚŝƐǁĂLJ͕ƐŵĂůůŶĂŶŽĐƌLJƐƚĂůƐĂƌĞĨŽƌŵĞĚǁŚŝůĞĂĚĚŝƟŽŶĂůůLJŝŶĐƌĞĂƐŝŶŐƚŚĞ dielectric breakdown strength of the material due to an enhancement of the mechanical ƉƌŽƉĞƌƟĞƐ͘Ϯϰ͕Ϯϱ_{hŶĨŽƌƚƵŶĂƚĞůLJ͕ĞīĞĐƟǀĞǁĂLJƐƚŽŐĂŝŶĐŽŶƚƌŽůŽǀĞƌƚŚĞĐƌŽƐƐůŝŶŬŝŶŐƐŝƚĞƐ} ŝŶŇƵŽƌŝŶĂƚĞĚƉŽůLJŵĞƌƐĂƌĞƌĂƌĞĚƵĞƚŽƚŚĞůĂĐŬŽĨĨƵŶĐƟŽŶĂůŝƟĞƐŝŶƚŚĞŇƵŽƌŝŶĂƚĞĚ ďĂĐŬďŽŶĞƐ͘EĞǀĞƌƚŚĞůĞƐƐ͕ĐŚĞŵŝĐĂůĐƌŽƐƐůŝŶŬŝŶŐŝƐƉĞƌĨŽƌŵĞĚƵƐŝŶŐƉĞƌŽdžŝĚĞƐĂŶĚƚƌŝĂůůLJů ŝƐŽĐLJĂŶƵƌĂƚĞ ;d/Ϳ͕ ĚŝĂŵŝŶĞƐ Žƌ ĞůĞĐƚƌŽďĞĂŵ ŝƌƌŝĚĂƟŽŶ͘Ϯϰ͕Ϯϲ͕Ϯϳ_{ /Ŷ ƉĂƌƟĐƵůĂƌ͕ ƚŚĞ ƵƐĞ ŽĨ} ƉĞƌŽdžŝĚĞƐĂŶĚd/ƚŽĐƌŽƐƐůŝŶŬW;s&-co-d&ͿƌĞƐƵůƚƐŝŶĞdžĐĞůůĞŶƚĚŝĞůĞĐƚƌŝĐƉĞƌĨŽƌŵĂŶĐĞ ŚĂǀŝŶŐŚŝŐŚĞĸĐŝĞŶĐŝĞƐĂŶĚůĂƌŐĞƌĞůĞĂƐĞĚĞŶĞƌŐLJĚĞŶƐŝƟĞƐ;ϴϯйĂŶĚϭϳ:ĐŵͲϯ_{ĂƚϰϬϬ} DsŵͲϭ_{͕ƌĞƐƉĞĐƟǀĞůLJͿ͕ƐŚŽǁŝŶŐƚŚĞŐƌĞĂƚƉŽƚĞŶƟĂůŽĨĐŚĞŵŝĐĂůůLJĐƌŽƐƐůŝŶŬĞĚWs&ĨŽƌ} ĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJƐƚŽƌĂŐĞĂƉƉůŝĐĂƟŽŶƐ͘ ZĞĐĞŶƚůLJ͕ǁĞŚĂǀĞƐŚŽǁŶŚŽǁǀŝŶLJůĂůĐŽŚŽů;sͿƵŶŝƚƐĐĂŶĞĂƐŝůLJďĞŝŶƚƌŽĚƵĐĞĚŝŶƚŚĞ Ws&ďĂĐŬďŽŶĞ͘28 _{Due to the small size of the monomeric units, they can be included in} ƚŚĞWs&ĐƌLJƐƚĂůƐ͕ŝŶĐƌĞĂƐŝŶŐƚŚĞĐƌLJƐƚĂůůĂƫĐĞƐŝnjĞĂŶĚĂĐƚĂƐƉŝŶŶŝŶŐƐƉŽƚƐ͘DŽƌĞŽǀĞƌ͕ ƚŚĞƐĞŚLJĚƌŽdžLJůĨƵŶĐƟŽŶĂůŝƟĞƐ͕ďĞŝŶŐǁĞůůĚŝƐƚƌŝďƵƚĞĚŽǀĞƌƚŚĞƉŽůLJŵĞƌďĂĐŬďŽŶĞ͕ĐĂŶďĞ ƵƐĞĚƚŽĚŽĞĂƐLJĂĚĚŝƟŽŶĂůĐŚĞŵŝƐƚƌŝĞƐƚŽŝŵƉƌŽǀĞĨŽƌĞdžĂŵƉůĞŶĂŶŽŽďũĞĐƚĚŝƐƉĞƌƐŝŽŶ͕ adhesion to interfaces, and crosslinking. In this work, physical pinning and chemical ĐƌŽƐƐůŝŶŬŝŶŐĂƌĞĐŽŵďŝŶĞĚƚŽŽďƚĂŝŶŶĂƌƌŽǁŚLJƐƚĞƌĞƐŝƐůŽŽƉƐǁŝƚŚŚŝŐŚƉŽůĂƌŝnjĂƟŽŶ͘ tĞ ĚĞŵŽŶƐƚƌĂƚĞ ƚŚĞ ƐLJŶƚŚĞƐŝƐ ĂŶĚ ĐŚĞŵŝĐĂů ĐƌŽƐƐůŝŶŬŝŶŐ ŽĨ W;s&-ter-dƌ&-ter-sͿ ƚĞƌƉŽůLJŵĞƌƐĂŶĚƐŚŽǁŝƚƐĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌ͘/ŶĂĚĚŝƟŽŶ͕ƚŚĞĞīĞĐƚŽĨsƵŶŝƚƐŽŶ ƚŚĞƚŚĞƌŵĂůďĞŚĂǀŝŽƌŝŶƚŚĞƚĞƌƉŽůLJŵĞƌƐŝƐŝŶǀĞƐƟŐĂƚĞĚ͕ƐŚŽǁŝŶŐŚŽǁsƵŶŝƚƐĐŚĂŶŐĞ ƉƌŽƉĞƌƟĞƐ ƐƵĐŚ ĂƐ ƚŚĞ ƵƌŝĞ ƚƌĂŶƐŝƟŽŶ ƚĞŵƉĞƌĂƚƵƌĞ͘ ^ƚƌŽŶŐ ƌĞĚƵĐƟŽŶƐ ŝŶ ƚŚĞ ƵƌŝĞ ƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞŽĨƚŚĞW;s&-ter-dƌ&-ter-sͿƚĞƌƉŽůLJŵĞƌƐĂƌĞĨŽƵŶĚ͕ǁŚŝůĞƚŚĞ ĐƌŽƐƐůŝŶŬĞĚ ŵĂƚĞƌŝĂůƐ ĚŝƐƉůĂLJ ŶĂƌƌŽǁ ŚLJƐƚĞƌĞƐŝƐ ůŽŽƉ ƌĞůĂdžŽƌ ĨĞƌƌŽĞůĞĐƚƌŝĐ ďĞŚĂǀŝŽƌ͕ ŵĂŬŝŶŐƚŚĞŵŚŝŐŚůLJƐƵŝƚĂďůĞĨŽƌĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJƐƚŽƌĂŐĞĂƉƉůŝĐĂƟŽŶƐ͘

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: 108PDF page: 108PDF page: 108PDF page: 108

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Materials and Methods

Experimental Materials: ĞŶnjŽLJůƉĞƌŽdžŝĚĞǁĂƐƌĞĐƌLJƐƚĂůůŝnjĞĚƉƌŝŽƌƚŽƵƐĞ͘sŝŶLJůĂĐĞƚĂƚĞǁĂƐĚƌŝĞĚŽǀĞƌ Ă,₂ĂŶĚĚŝƐƟůůĞĚƵŶĚĞƌƌĞĚƵĐĞĚƉƌĞƐƐƵƌĞ͘sŝŶLJůŝĚĞŶĞŇƵŽƌŝĚĞ;s&͕^LJŶƋƵĞƐƚ>ĂďƐ͕ϵϴйͿ͕ ƚƌŝŇƵŽƌŽĞƚŚLJůĞŶĞ;dƌ&͕^LJŶƋƵĞƐƚ>ĂďƐ͕ϵϴйͿ͕,ĞdžĂŵĞƚŚLJůĞŶĞĚŝŝƐŽĐLJĂŶĂƚĞ;,D/͕d/͕ ϵϴйͿĂŶĚĐLJĐůŽƉĞŶƚĂŶŽŶĞ;d/͕хϵϵйͿǁĞƌĞƵƐĞĚĂƐƌĞĐĞŝǀĞĚ͘ůůƐŽůǀĞŶƚĂƌĞŽďƚĂŝŶĞĚ ĨƌŽŵĐŽŵŵĞƌĐŝĂůƌĞƐŽƵƌĐĞƐĂŶĚƵƐĞĚǁŝƚŚŽƵƚĨƵƌƚŚĞƌƉƵƌŝĮĐĂƟŽŶ͘ ^LJŶƚŚĞƐŝƐŽĨW;s&ͲƚĞƌͲdƌ&ͲƚĞƌͲsĐͿƚĞƌƉŽůLJŵĞƌƐ͗ϲϬϬŵ>WĂƌƌ;ŵŽĚĞůϰϱϲϴͿŚŝŐŚ ƉƌĞƐƐƵƌĞƌĞĂĐƚŽƌǁĂƐĐŚĂƌŐĞĚǁŝƚŚďĞŶnjŽLJůƉĞƌŽdžŝĚĞ;ϭϱϬŵŐ͕Ϭ͘ϲϮŵŵŽůͿ͕ĂŶŚLJĚƌŽƵƐ ĚŝŵĞƚŚLJůĐĂƌďŽŶĂƚĞ;ϯϬϬŵ>Ϳ͕ĂŶĚĨƌĞƐŚůLJĚŝƐƟůůĞĚǀŝŶLJůĂĐĞƚĂƚĞ;sĐ͕ϭŵ>͕ϭϬ͘ϵŵŵŽůͿ͘ ŌĞƌƚŚĞƌĞĂĐƟŽŶŵŝdžƚƵƌĞǁĂƐƉƵƌŐĞĚǁŝƚŚE₂ĨŽƌϯϬŵŝŶ͕dƌ&;Ϯ͘ϱďĂƌͿĂŶĚs&;ƚŽϭϱ ďĂƌͿǁĞƌĞƚƌĂŶƐĨĞƌƌĞĚŝŶƚŽƚŚĞƌĞĂĐƚŽƌĂƚƌŽŽŵƚĞŵƉĞƌĂƚƵƌĞ͘dŚĞƌĞĂĐƟŽŶŵŝdžƚƵƌĞǁĂƐ ƌĂƉŝĚůLJŚĞĂƚĞĚƚŽϵϬΣĂŶĚĂůůŽǁĞĚƚŽƐƟƌĂƚϱϬϬƌƉŵĨŽƌϯϬŵŝŶ͘^ƵďƐĞƋƵĞŶƚůLJ͕ƚŚĞ ŚĞĂƟŶŐƐŽƵƌĐĞǁĂƐƌĞŵŽǀĞĚĂŶĚƚŚĞƌĞĂĐƟŽŶŵŝdžƚƵƌĞǁĂƐĐŽŽůĞĚƚŽƌŽŽŵƚĞŵƉĞƌĂƚƵƌĞ ƵƐŝŶŐĂǁĂƚĞƌŇŽǁ͘džĐĞƐƐŽĨdƌ&ĂŶĚs&ǁĞƌĞƌĞŵŽǀĞĚďLJĚĞƉƌĞƐƐƵƌŝnjŝŶŐƚŚĞƌĞĂĐƟŽŶ ǀĞƐƐĞů͘dŚĞƐŽůƵƟŽŶǁĂƐĐŽŶĐĞŶƚƌĂƚĞĚŝŶǀĂĐƵŽŝŶŽƌĚĞƌƚŽƉƌĞĐŝƉŝƚĂƚĞƚŚĞĐŽƉŽůLJŵĞƌŝŶ ĂǁĂƚĞƌͬŵĞƚŚĂŶŽůŵŝdžƚƵƌĞ͘džĐĞƐƐŽĨŝŶŝƟĂƚŽƌǁĂƐƌĞŵŽǀĞĚďLJĞdžƚĞŶƐŝǀĞůLJǁĂƐŚŝŶŐǁŝƚŚ chloroform. Finally, the copolymer was dried in a vacuum.

^LJŶƚŚĞƐŝƐŽĨW;s&ͲƚĞƌͲdƌ&ͲƚĞƌͲsͿƚĞƌƉŽůLJŵĞƌƐ͗ŐĞŶĞƌĂůƐLJŶƚŚĞƟĐƉƌŽĐĞĚƵƌĞŝƐ ĚĞƐĐƌŝďĞĚĂƐĨŽůůŽǁƐ͗ĂƌŽƵŶĚͲďŽƩŽŵŇĂƐŬǁĂƐĐŚĂƌŐĞĚǁŝƚŚϭ͘ϬŐƌĂŵƐŽĨW;s&-ter-dƌ&-ter-sĐͿƚĞƌƉŽůLJŵĞƌƐ͕ĚŝŽdžĂŶĞ;ϴϬŵ>Ϳ͕ĂŶĚĐŽŶĐĞŶƚƌĂƚĞĚŚLJĚƌŽĐŚůŽƌŝĐĂĐŝĚ;ϴŵ>Ϳ͘ dŚĞƌĞĂĐƟŽŶŵŝdžƚƵƌĞǁĂƐƐƟƌƌĞĚŽǀĞƌŶŝŐŚƚĂƚϲϬΣ͘dŚĞŵŝdžƚƵƌĞǁĂƐĐŽŶĐĞŶƚƌĂƚĞĚŝŶ ǀĂĐƵŽ͕ĂŌĞƌǁŚŝĐŚƚŚĞĐŽƉŽůLJŵĞƌǁĂƐƉƌĞĐŝƉŝƚĂƚĞĚďLJĂĚĚŝŶŐĂůĂƌŐĞĞdžĐĞƐƐŽĨǁĂƚĞƌ͘ ^ƵďƐĞƋƵĞŶƚůLJ͕ƚŚĞĐŽƉŽůLJŵĞƌǁĂƐĐŽůůĞĐƚĞĚviaĮůƚƌĂƟŽŶĨŽůůŽǁĞĚďLJĞdžƚĞŶƐŝǀĞǁĂƐŚŝŶŐ with water to remove residual side product and hydrochloric acid, yielding 0.8 grams of ǁŚŝƚĞW;s&-ter-dƌ&-ter-sͿƚĞƌƉŽůLJŵĞƌƐ͘ ƌŽƐƐůŝŶŬŝŶŐ ŽĨ W;s&ͲƚĞƌͲdƌ&ͲƚĞƌͲsͿ ƚĞƌƉŽůLJŵĞƌƐ͗ W;s&-ter-dƌ&-ter-sͿ ;Ϯϱ ŵŐ͕ŵŵŽůsͿĂŶĚ,D/;ϭ͕ђ>͕ŵŵŽůŽƌϮ͕ђ>͕ŵŵŽůͿǁĞƌĞĐŽŵďŝŶĞĚŝŶϭ͘ϱŵ> ĐLJĐůŽƉĞŶƚĂŶŽŶĞĂŶĚĂůůŽǁĞĚƚŽŵŝdžĂƚϴϬΣĨŽƌϯϬŵŝŶ͘ŌĞƌĐŽŽůŝŶŐĚŽǁŶƚŽƌŽŽŵ ƚĞŵƉĞƌĂƚƵƌĞ͕ƚŚĞƐŽůƵƟŽŶǁĂƐƉĂƐƐĞĚƚŚƌŽƵŐŚĂϬ͘ϰϱђŵWd&ĮůƚĞƌŝŶƚŽĂŶĂůƵŵŝŶƵŵ ƉĂŶ ;Ɔ ϯ ŵŵͿ͘ WƌŝƐƟŶĞ W;s&-ter-dƌ&-ter-sͿ ƚĞƌƉŽůLJŵĞƌƐ ǁĞƌĞ ĂŌĞƌ ĚŝƐƐŽůǀŝŶŐ ŝŶ ĐLJĐůŽƉĞŶƚĂŶŽŶĞ;ϰϬŵŐŝŶϭ͘ϱŵ>ͿĚŝƌĞĐƚůLJƚƌĂŶƐĨĞƌƌĞĚŝŶĂŶĂůƵŵŝŶƵŵƉĂŶƵƐŝŶŐĂϬ͘ϰϱ ђŵWd&ĮůƚĞƌ͘dŚĞĂůƵŵŝŶƵŵƉĂŶǁĂƐƚƌĂŶƐĨĞƌƌĞĚƚŽĂŚĞĂƟŶŐƉůĂƚĞƐĞƚĂƚϭϯϬΣƚŽ ŝŶĚƵĐĞĐƌŽƐƐůŝŶŬŝŶŐĂŶĚĞǀĂƉŽƌĂƟŽŶŽĨƐŽůǀĞŶƚ͘dŚĞŶĞdžƚĚĂLJ͕ƚŚĞ;ĐƌŽƐƐůŝŶŬĞĚͿƐĂŵƉůĞƐ ǁĞƌĞŚĞĂƚĞĚƚŽϭϲϬΣƚŽĞƌĂƐĞƚŚĞƌŵĂůŚŝƐƚŽƌLJĂŶĚƐƵďƐĞƋƵĞŶƚůLJƋƵĞŶĐŚĞĚĂƚƌŽŽŵ ƚĞŵƉĞƌĂƚƵƌĞ͘^ƵďƐĞƋƵĞŶƚůLJ͕ΕϭϬђŵƚŚŝĐŬĨƌĞĞͲƐƚĂŶĚŝŶŐĮůŵƐĂƌĞŽďƚĂŝŶĞĚviaĂůŝŌͲŽī ŵĞƚŚŽĚŝŶǁĂƚĞƌ͘ůůƐĂŵƉůĞƐǁĞƌĞĚƌŝĞĚŽǀĞƌŶŝŐŚƚƵŶĚĞƌĂǀĂĐƵƵŵ͘

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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6

Characterization

NMR spectroscopy: 1_{, ĂŶĚ}19_{& EDZ ;K^zͿ ƐƉĞĐƚƌĂ ǁĞƌĞ ƌĞĐŽƌĚĞĚ ŽŶ sĂƌŝĂŶ ;syZͿ} ƐƉĞĐƚƌŽŵĞƚĞƌŽƉĞƌĂƟŶŐĂƚϰϬϬD,njĨŽƌƚŚĞ1_{,ŶƵĐůĞƵƐĂŶĚϯϳϲD,njĨŽƌƚŚĞ}19_{F nucleus.} dŚĞĐŽŵƉŽƐŝƟŽŶǁĂƐĚĞƚĞƌŵŝŶĞĚviaƚŚĞĨŽůůŽǁŝŶŐŵĞƚŚŽĚ͘&ŝƌƐƚ͕ƚŚĞƌĂƟŽďĞƚǁĞĞŶs& ĂŶĚdƌ&;ƌ_s&ͬdƌ&ͿǁĂƐĐĂůĐƵůĂƚĞĚƵƐŝŶŐ19_{&EDZƐƉĞĐƚƌŽƐĐŽƉLJ͘}20_{dŚĞƌĂƟŽŽĨdƌ&ĂŶĚs} was determined using 1_{,EDZƐƉĞĐƚƌŽƐĐŽƉLJĂĐĐŽƌĚŝŶŐƚŽƚŚĞĨŽůůŽǁŝŶŐĞƋƵĂƟŽŶ͗}

ŽŶƐĞƋƵĞŶƚůLJ͕ƵƐŝŶŐƚŚĞƌĂƟŽƐƌ_s&ͬdƌ& and r_dƌ&ͬs͕ƚŚĞƚĞƌƉŽůLJŵĞƌĐŽŵƉŽƐŝƟŽŶǁĂƐ obtained.

Fourier Transform Infrared Spectroscopy: dŚĞ&d/ZƐƉĞĐƚƌĂŽĨƚŚĞĐŽƉŽůLJŵĞƌƐǁĞƌĞ

ƌĞĐŽƌĚĞĚŽŶĂƌƵŬĞƌsĞƌƚĞdžϳϬƐƉĞĐƚƌŽƉŚŽƚŽŵĞƚĞƌƵƐŝŶŐϯϮƐĐĂŶƐĂƚĂŶŽŵŝŶĂůƌĞƐŽůƵƟŽŶ ŽĨϰĐŵͲϭ_{ƵƐŝŶŐĂĚŝĂŵŽŶĚƐŝŶŐůĞƌĞŇĞĐƟŽŶĂƩĞŶƵĂƚĞĚƚŽƚĂůƌĞŇĞĐƚĂŶĐĞ;dZͿ͘}

ŝīĞƌĞŶƟĂůƐĐĂŶŶŝŶŐĐĂůŽƌŝŵĞƚƌLJ;^Ϳ͗^ƚŚĞƌŵŽŐƌĂŵƐǁĞƌĞƌĞĐŽƌĚĞĚŽŶĂd

/ŶƐƚƌƵŵĞŶƚƐ^YϭϬϬϬ͘dŚĞŚĞĂƟŶŐĂŶĚĐŽŽůŝŶŐƌĂƚĞǁĂƐƐĞƚƚŽďĞϭϬΣŵŝŶͲϭ_.

tŝĚĞͲĂŶŐůĞ yͲƌĂLJ ƐĐĂƩĞƌŝŶŐ ;ty^Ϳ͗ ty^ ŵĞĂƐƵƌĞŵĞŶƚƐ ǁĂƐ ƉĞƌĨŽƌŵĞĚ Ăƚ

ďĞĂŵůŝŶĞDϮϲĂƚƚŚĞƵƌŽƉĞĂŶ^LJŶĐŚƌŽƚƌŽŶZĂĚŝĂƟŽŶ&ĂĐŝůŝƚLJ;^Z&ͿŝŶ'ƌĞŶŽďůĞǁŝƚŚĂ ǁĂǀĞůĞŶŐƚŚʄсϬ͘ϵϳ͘dŚĞty^ƉĂƩĞƌŶǁĂƐĂĐƋƵŝƌĞĚŽǀĞƌĂƟŵĞŝŶƚĞƌǀĂůŽĨϯϬƐĞĐŽŶĚƐ ƵƐŝŶŐĂWŝůĂƚƵƐϯϬϬ<ĚĞƚĞĐƚŽƌ;ϭϰϳϮпϭϵϱƉŝdžĞůƐŽĨϭϳϮʅŵпϭϳϮʅŵƉůĂĐĞĚĂƚĂĚŝƐƚĂŶĐĞ ŽĨϬ͘Ϯϴŵ͘dŚĞƐĐĂƩĞƌŝŶŐǀĞĐƚŽƌƋŝƐĚĞĮŶĞĚĂƐqсϰʋͬʄ(sin ɽͿǁŝƚŚϮɽďĞŝŶŐƚŚĞƐĐĂƩĞƌŝŶŐ ĂŶŐůĞ͘ĞĐŽŶǀŽůƵƟŽŶŽĨƚŚĞty^ƉƌŽĮůĞƐǁĂƐĂĐŚŝĞǀĞĚƵƐŝŶŐDd>͘dŚĞĞdžƉĞƌŝŵĞŶƚĂů ƉƌŽĮůĞƐǁĞƌĞĚĞĐŽŶǀŽůƵƚĞĚďLJƵƐŝŶŐƚŚĞƐƵŵŽĨĂůŝŶĞĂƌďĂĐŬŐƌŽƵŶĚĂŶĚƉƐĞƵĚŽͲsŽŝŐƚ ƉĞĂŬƐĚĞƐĐƌŝďŝŶŐƚŚĞƐĐĂƩĞƌŝŶŐĨƌŽŵƚŚĞĂŵŽƌƉŚŽƵƐĂŶĚƚŚĞĐƌLJƐƚĂůůŝŶĞƉŚĂƐĞƐ͘ ůĞĐƚƌŝĐĂůĐŚĂƌĂĐƚĞƌŝnjĂƟŽŶ͗Ͳ and I-EůŽŽƉƐǁĞƌĞŽďƚĂŝŶĞĚƵƐŝŶŐĂƐƚĂƚĞͲŽĨͲƚŚĞͲĂƌƚ Ăŝdždd&ϮϬϬϬĨĞƌƌŽĞůĞĐƚƌŝĐƚĞƐƚĞƌǁŚĞƌĞĞůĞĐƚƌŝĐĮĞůĚƐ;ƵƉƚŽϭϬŬsͿǁĞƌĞĂƉƉůŝĞĚ ĂĐƌŽƐƐƚŚĞƉŽůLJŵĞƌĮůŵƐǁŝƚŚĂƚƌŝĂŶŐƵůĂƌǁĂǀĞĨŽƌŵĂƚĂĨƌĞƋƵĞŶĐLJŽĨϭϬ,nj͘ŚƌŽŵŝƵŵ ;ϱŶŵͿͬŐŽůĚ;ϭϬϬŶŵͿĞůĞĐƚƌŽĚĞƐǁŝƚŚĂĚŝĂŵĞƚĞƌŽĨϮŵŵǁĞƌĞĚĞƉŽƐŝƚĞĚŽŶďŽƚŚ ƐŝĚĞƐŽĨW;s&-co-sͿĐŽƉŽůLJŵĞƌĮůŵƐďLJǀĂƉŽƌĚĞƉŽƐŝƟŽŶ͘ŚƌŽŵŝƵŵǁĂƐƵƐĞĚŽŶůLJĂƐ ĂĚŚĞƐŝŽŶůĂLJĞƌ͘^ŝůŝĐŽŶŽŝůǁĂƐƵƐĞĚƚŽƉƌĞǀĞŶƚŇĂƐŚŽǀĞƌƐ͘

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: 110PDF page: 110PDF page: 110PDF page: 110

110

Results and Discussion

dŚĞƐLJŶƚŚĞƐŝƐĂŶĚĐƌŽƐƐůŝŶŬŝŶŐŽĨW;s&-ter-dƌ&-ter-sͿƚĞƌƉŽůLJŵĞƌƐŝƐŽƵƚůŝŶĞĚŝŶ^ĐŚĞŵĞ ϲ͘ϭ͘dŽƐŚŽǁƚŚĞŝŵƉĂĐƚŽĨƚŚĞŝŶƚƌŽĚƵĐƟŽŶŽĨsƵŶŝƚƐŝŶƚŚĞW;s&-ter-dƌ&-ter-sͿ ƚĞƌƉŽůLJŵĞƌƐŽŶƚŚĞƚŚĞƌŵĂůĂŶĚĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌ͕ǁĞƐLJŶƚŚĞƐŝnjĞĚƚǁŽĚŝīĞƌĞŶƚ ƚĞƌƉŽůLJŵĞƌƐŚĂǀŝŶŐĂƐŝŵŝůĂƌdƌ&ͬsƌĂƟŽ͘W;s&_0.78-ter-dƌ&_0.17-ter-s_0.05ͿĂŶĚW;s&_Ϭ͘ϱϯ -ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10Ϳ͘ĞĐĂƵƐĞW;s&-co-dƌ&ͿĐŽƉŽůLJŵĞƌƐĐŽŶƚĂŝŶŝŶŐϱϬŽƌϴϬŵŽůйs& ĂƌĞŽŶƚŚĞǀĞƌŐĞŽĨƐŽůĞůLJĐƌLJƐƚĂůůŝnjŝŶŐŝŶƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐƉŚĂƐĞ͕ƌĞƉůĂĐŝŶŐdƌ&ƵŶŝƚƐĨŽƌ s͕ǁŚŝůĞŚĂǀŝŶŐĂƐŝŵŝůĂƌĂŵŽƵŶƚŽĨs&͕ĂůůŽǁƐĨŽƌĂŐŽŽĚĐŽŵƉĂƌŝƐŽŶƚŽůŝƚĞƌĂƚƵƌĞ reports.20,29 ĞĐĂƵƐĞƚŚĞƚĂƵƚŽŵĞƌŝnjĂƟŽŶĞƋƵŝůŝďƌŝƵŵŽĨǀŝŶLJůĂůĐŽŚŽůůŝĞƐŽŶƚŚĞĂĐĞƚĂůĚĞŚLJĚĞ ƐŝĚĞ͕W;s&-ter-dƌ&-ter-sͿǁĂƐƐLJŶƚŚĞƐŝnjĞĚŝŶĚŝƌĞĐƚůLJƵƐŝŶŐǀŝŶLJůĂĐĞƚĂƚĞ;sĐͿŝŶƚŚĞ ƚĞƌƉŽůLJŵĞƌŝnjĂƟŽŶƌĞĂĐƟŽŶ͘ϯϬ_{ƐƐƵĐŚ͕viaĂĨƌĞĞƌĂĚŝĐĂůƉŽůLJŵĞƌŝnjĂƟŽŶ͕s&͕dƌ&ĂŶĚ} sĐǁĞƌĞƚĞƌƉŽůLJŵĞƌŝnjĞĚŝŶĚŝŵĞƚŚLJůĐĂƌďŽŶĂƚĞ;DͿƵƐŝŶŐďĞŶnjŽLJůƉĞƌŽdžŝĚĞ;WKͿĂƐ ŝŶŝƟĂƚŽƌ͘DǁĂƐƐĞůĞĐƚĞĚĂƐƐŽůǀĞŶƚĚƵĞƚŽĂŐŽŽĚƚƌĂĚĞͲŽīďĞƚǁĞĞŶƌĞĂĐƟŽŶƌĂƚĞĂŶĚ chain transfer to solvent.ϯϭ_{/ƚŝƐƵŶĚĞƌƐƚŽŽĚĨƌŽŵƚŚĞůŝƚĞƌĂƚƵƌĞƚŚĂƚƚĞƌƉŽůLJŵĞƌŝnjĂƟŽŶƐ} ŽĨǀŝŶLJůŵŽŶŽŵĞƌƐ͕ƐƵĐŚĂƐϯ͕ϯ͕ϯͲƚƌŝŇƵŽƌŽƉƌŽƉĞŶĞ;d&WͿ͕ǁŝƚŚs&ĂŶĚdƌ&ůĞĂĚƚŽ ĐŽŵƉŽƐŝƟŽŶĂů ŚĞƚĞƌŽŐĞŶĞŝƚLJ ǁŚĞŶ ŚŝŐŚ ĐŽŶǀĞƌƐŝŽŶƐ ĂƌĞ ĂĐŚŝĞǀĞĚ ĂƐ d&W ƉƌĞĨĞƌƐ ƚŽ ŚŽŵŽƉƌŽƉĂŐĂƚĞ ĚƵĞ ƚŽ ůĂƌŐĞ ĚŝīĞƌĞŶĐĞƐ ŝŶ ƌĞĂĐƟǀŝƚLJ ƌĂƟŽƐ͘ϯϮ_{ dŽ ŵŝƟŐĂƚĞ ĐŽŶĐĞƌŶƐ} ƌĞŐĂƌĚŝŶŐĐŽŵƉŽƐŝƟŽŶĂůŚĞƚĞƌŽŐĞŶĞŝƚLJ͕ƚŚĞƌĞĂĐƟŽŶƟŵĞƐĂƌĞŬĞƉƚƐŚŽƌƚ;ǁŝƚŚŵŝŶŝŵĂů ƉƌĞƐƐƵƌĞĚƌŽƉфϮďĂƌƚŽƉƌĞǀĞŶƚůĂƌŐĞǀĂƌŝĂƟŽŶƐŝŶs&ĂŶĚdƌ&ĐŽŶĐĞŶƚƌĂƟŽŶƐͿĂŶĚƚŚĞ sĐĐŽŶƚĞŶƚŝƐŬĞƉƚůŽǁƚŽŵŝŶŝŵŝnjĞƚŚĞĐŽŵƉŽƐŝƟŽŶĂůĚƌŝŌĚƵĞƚŽƚŚĞůĂƌŐĞĚŝīĞƌĞŶĐĞƐ ŝŶƌĞĂĐƟǀŝƚLJƌĂƟŽƐďĞƚǁĞĞŶs&ĂŶĚsĐůĞĂĚŝŶŐƚŽƚŚĞƉƌĞĨĞƌĞŶƟĂůĐŽŶƐƵŵƉƟŽŶŽĨsĐ ĚƵƌŝŶŐƚŚĞƉŽůLJŵĞƌŝnjĂƟŽŶ͘Ϯϴ͕ϯϯ͕ϯϰ ŌĞƌƚŚĞƉŽůLJŵĞƌŝnjĂƟŽŶ͕ƚŚĞƉƌĞƐĞŶĐĞŽĨƵŶƌĞĂĐƚĞĚsĐǁĂƐĐŽŶĮƌŵĞĚďLJ1_,EDZ ƐƉĞĐƚƌŽƐĐŽƉLJŝŶĚŝĐĂƟŶŐƚŚĂƚŶŽW;s&-co-dƌ&ͿĐŽƉŽůLJŵĞƌƐǁĞƌĞĨŽƌŵĞĚ͘^ƵďƐĞƋƵĞŶƚůLJ͕ ŚLJĚƌŽůLJƐŝƐŽĨƚŚĞW;s&-ter-dƌ&-ter-sĐͿƚĞƌƉŽůLJŵĞƌƐŝŶĂĚŝŽdžĂŶĞͬ,ůŵŝdžƚƵƌĞLJŝĞůĚĞĚ W;s&-ter-dƌ&-ter-sͿ͘ EŽƚĞǁŽƌƚŚLJ͕ ĂĐŝĚŝĐ ĐŽŶĚŝƟŽŶƐ ǁĞƌĞ ƵƐĞĚ ƚŽ ŚLJĚƌŽůLJnjĞ ƚŚĞ ƚĞƌƉŽůLJŵĞƌƐƚŽƉƌĞǀĞŶƚĚĞŚLJĚƌŽŇƵŽƌŝŶĂƟŽŶƌĞĂĐƟŽŶƐ͘ /Ŷ&ŝŐƵƌĞϲ͘ϭ͕ƚŚĞ1_{,EDZƐƉĞĐƚƌĂĚĞŵŽŶƐƚƌĂƚĞƚŚĞĐŽŵƉůĞƚĞƌĞŵŽǀĂůŽĨƚŚĞĂĐĞƚLJů} groups by the disappearance corresponding methyl protons located at 2.00 ppm, proving ĂƐƵĐĐĞƐƐĨƵůĨƵůůĐŽŶǀĞƌƐŝŽŶƚŽƚŚĞŚLJĚƌŽdžLJůĨƵŶĐƟŽŶĂůŝnjĞĚƚĞƌƉŽůLJŵĞƌƐ͘ĚĚŝƟŽŶĂůůLJ͕ĂŶ ƵƉĮĞůĚƐŚŝŌŽĨƚŚĞŵĞƚŚŝŶĞƉƌŽƚŽŶƐ;ͲH;K,ͿͲͿƚŽϰ͘ϭϭͲϰ͘ϲϬƉƉŵĐŽŶĮƌŵƐƚŚĞĨŽƌŵĂƟŽŶ ŽĨŚLJĚƌŽdžLJůŐƌŽƵƉƐ͕ǁŚŝĐŚƉƌŽƚŽŶƐĂƌĞůŽĐĂƚĞĚŝŶďĞƚǁĞĞŶϰ͘ϭϭͲϱ͘ϬϬƉƉŵ͘DŽƌĞŽǀĞƌ͕ ƚŚĞŵƵůƟƉůĞĐŽƌƌĞůĂƟŽŶƐŝŐŶĂůƐŝŶƚŚĞ1_{,EDZĐŽƌƌĞůĂƟŽŶƐƉĞĐƚƌƵŵ;&ŝŐƵƌĞϲ͘ϮͿƌĞǀĞĂů} ƚŚĂƚƚŚĞŵĞƚŚŝŶĞƉƌŽƚŽŶŽĨƚŚĞǀŝŶLJůĂůĐŽŚŽůƵŶŝƚƐĐŽƌƌĞůĂƚĞǁŝƚŚĚŝīĞƌĞŶƚŵŽŶŽŵĞƌ ƐĞƋƵĞŶĐĞƐŽĨďŽƚŚs&;ͲH₂CF₂Ͳ͕ΕϮ͘ϮϲƉƉŵͿĂŶĚdƌ&;ͲHFCF₂Ͳ͕ϱ͘ϭϱ͕ϱ͘ϲϱ͕ϲ͘ϯƉƉŵͿ͕ ŝŶĚŝĐĂƟŶŐƚŚĞŐŽŽĚĚŝƐƚƌŝďƵƟŽŶŽĨsƵŶŝƚƐŝŶƚŚĞďĂĐŬďŽŶĞ͘WƌĞǀŝŽƵƐǁŽƌŬŝŶŽƵƌŐƌŽƵƉ

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: 111PDF page: 111PDF page: 111PDF page: 111

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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: 112PDF page: 112PDF page: 112PDF page: 112

112 ĂůƌĞĂĚLJĚĞŵŽŶƐƚƌĂƚĞĚƚŚĞĞdžĐĞůůĞŶƚĚŝƐƉĞƌƐŝŽŶŽĨsƵŶŝƚƐ;ƵƉƚŽϭϱŵŽůйͿŝŶW;s&-co-sͿĐŽƉŽůLJŵĞƌƐ͕ǁŚĞƌĞƐŝŵŝůĂƌƌĞĂĐƟŽŶĐŽŶĚŝƟŽŶƐǁĞƌĞĂƉƉůŝĞĚ͘28 ,ŽǁĞǀĞƌ͕ĚŝīĞƌĞŶƚĨƌŽŵƚŚŽƐĞŽĨW;s&ͲcoͲsͿĐŽƉŽůLJŵĞƌƐ͕ƚŚĞ1_{,EDZƐƉĞĐƚƌĂ} ;&ŝŐƵƌĞϲ͘ϭͿŽĨƚŚĞW;s&-ter-dƌ&-ter-sͿƚĞƌƉŽůLJŵĞƌƐƐŚŽǁĂŶĂĚĚŝƟŽŶĂůƐŝŐŶĂůƚŚĂƚ ĂƉƉĞĂƌƐĂƌŽƵŶĚϰ͘ϴϬƉƉŵ͘dŚŝƐŝƐĂƩƌŝďƵƚĞĚƚŽƚŚĞʹK,ƉƌŽƚŽŶƐŽĨsƵŶŝƚƐĂĚũĂĐĞŶƚ ƚŽdƌ&ƵŶŝƚƐĂŶĚƚŚĞƐŝŐŶĂůďĞĐŽŵĞƐŵŽƌĞƉƌŽŶŽƵŶĐĞĚǁŚĞŶƚŚĞdƌ&ĐŽŶƚĞŶƚŝŶƚŚĞ ƚĞƌƉŽůLJŵĞƌĐŽŵƉŽƐŝƟŽŶŝƐŝŶĐƌĞĂƐĞĚ͕ŚŝŐŚůŝŐŚƟŶŐƚŚĞĚŝīĞƌĞŶĐĞŽĨƚŚĞŵŝĐƌŽƐƚƌƵĐƚƵƌĞ ďĞƚǁĞĞŶ ƚŚĞ ƚǁŽ ƚĞƌƉŽůLJŵĞƌƐ ƵƐĞĚ ŝŶ ƚŚŝƐ ƐƚƵĚLJ͘ ,ĞƌĞ͕ ƚŚĞ ŇƵŽƌŝŶĞ ĂƚŽŵ dƌ& ŝŶ ʹ ,;K,ͿHFCF₂ʹĐĂƵƐĞƐŵŽƌĞĚĞƐŚŝĞůĚŝŶŐůĞĂĚŝŶŐƚŽĂĚŽǁŶĮĞůĚƐŚŝŌĐŽŵƉĂƌĞĚƚŽƚŚĞ ŚLJĚƌŽdžLJůŐƌŽƵƉŽĨsŶĞdžƚƚŽĂs&ƵŶŝƚ͘28_{ĞĐĂƵƐĞƚŚĞƌĞŝƐĂĐůĞĂƌĚŝƐƟŶĐƟŽŶďĞƚǁĞĞŶ} ƚŚĞsƉƌŽƚŽŶƐĂŶĚƚŚĞʹH&ʹƉƌŽƚŽŶƐĐŽƌƌĞƐƉŽŶĚŝŶŐƚŽdƌ&;ϱ͘ϭϬʹϲ͘ϬϬƉƉŵͿ͕ƚŚĞƌĂƟŽ ďĞƚǁĞĞŶdƌ&ĂŶĚsĐĂŶďĞĞĂƐŝůLJĚĞƚĞƌŵŝŶĞĚ͘&ƌŽŵƚŚĞ19_{&EDZƐƉĞĐƚƌĂ;&ŝŐƵƌĞϲ͘ϯͿ͕} ƚŚĞƌĂƟŽďĞƚǁĞĞŶs&ĂŶĚdƌ&ŝƐŽďƚĂŝŶĞĚ͕ĂůůŽǁŝŶŐƚŚĞƚĞƌƉŽůLJŵĞƌĐŽŵƉŽƐŝƟŽŶƚŽďĞ calculated.

dŽĞdžĂŵŝŶĞƚŚĞƚŚĞƌŵĂůĐŚĂƌĂĐƚĞƌŝƐƟĐƐŽĨƚŚĞƚĞƌƉŽůLJŵĞƌƐ͕W;s&_0.78-ter-dƌ&_0.17

-ter-s_0.05ͿĂŶĚW;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10Ϳ͕ǁĞƉĞƌĨŽƌŵĞĚĚŝīĞƌĞŶƟĂůƐĐĂŶŶŝŶŐĐĂůŽƌŝŵĞƚƌLJ ;^ͿŵĞĂƐƵƌĞŵĞŶƚƐ͘ƐƐŚŽǁŶŝŶ&ŝŐƵƌĞϲ͘ϰ͕ƌĞƉůĂĐŝŶŐdƌ&ƵŶŝƚƐĨŽƌsŝŶƚŚĞƉŽůLJŵĞƌ ďĂĐŬďŽŶĞŚĂƐĂƉƌŽĨŽƵŶĚŝŶŇƵĞŶĐĞŽŶƚŚĞƚŚĞƌŵĂůďĞŚĂǀŝŽƌŽĨƚŚĞƚĞƌƉŽůLJŵĞƌƐ͘ϮϬ͕ϯϱ dŚĞ ĐƌLJƐƚĂůůŝnjĂƟŽŶ ƚĞŵƉĞƌĂƚƵƌĞ ;T_crͿ ŽĨ W;s&_0.78-ter-dƌ&_0.17-ter-s_0.05Ϳ ŝƐ ĚĞƚĞƌŵŝŶĞĚ ƚŽďĞϵϯΣ͕ǁŚŝůĞƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞ;T_CͿĚƌŽƉƉĞĚƚŽϱϱΣ͕ĂďŽƵƚϮϱ ΣůŽǁĞƌƚŚĂŶW;s&-co-dƌ&ͿǁŝƚŚĞƋƵĂůs&ĐŽŶƚĞŶƚ͘^ŝŵŝůĂƌďĞŚĂǀŝŽƌŝƐŽďƐĞƌǀĞĚŝŶ ƚŚĞŵĞůƟŶŐƐĐĂŶ͘/ŶŚĞƌĞ͕ĂƐŚĂƌƉƵƌŝĞƚƌĂŶƐŝƟŽŶŝƐŚĂǀŝŶŐĂŵĂdžŝŵƵŵĂƚϳϵΣĂŶĚ ƚŚĞƉŽůLJŵĞƌŝƐĐŽŵƉůĞƚĞůLJŵŽůƚĞŶĂƚϭϮϬΣ͕ďŽƚŚǀĂůƵĞƐƐƚƌŽŶŐůLJƌĞĚƵĐĞĚĐŽŵƉĂƌƚĞĚ ƚŽW;s&ͲcoͲdƌ&ͿǁŝƚŚϮϮŵŽůйdƌ&ŝŶƐŝĚĞ;T_CΕϭϬϬΣ͕T_mΕϭϰϴΣͿ͘ϯϱ_W;s& Ϭ͘ϱϯ -ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10Ϳ͕ĐŽŶƚĂŝŶŝŶŐůĞƐƐs&ĂŶĚĂĐŽŵƉĂƌĂďůĞƌĂƟŽdƌ&ͬs͕ĚĞŵŽŶƐƚƌĂƚĞƐ ĂƐŝŵŝůĂƌĐƌLJƐƚĂůůŝnjĂƟŽŶƚĞŵƉĞƌĂƚƵƌĞĂƐW;s&_0.78-ter-dƌ&_0.17-ter-s_0.05Ϳ͕ǁŚŝůĞƚŚĞƵƌŝĞ

Figure 6.1: (a) 1_{H NMR spectra of P(VDF}

0.53-ter-TrFE0.37-ter-VAc0.10) and P(VDF0.53-ter-TrFE0.37-ter-VA0.10 

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: 113PDF page: 113PDF page: 113PDF page: 113

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ƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞŝƐůŽǁĞƌĞĚƚŽϰϬΣ͘hƉŽŶŚĞĂƟŶŐ͕ƚŚĞƌĞǀĞƌƐĞƉƌŽĐĞƐƐŝŶǀŽůǀĞƐ ĂƵƌŝĞƚƌĂŶƐŝƟŽŶĂƚϰϲΣĂŶĚƚŚĞƚĞƌƉŽůLJŵĞƌŝƐĐŽŵƉůĞƚĞůLJŵŽůƚĞŶĂƚϭϰϵΣ͘dŚĞůĂƌŐĞ ĚŝīĞƌĞŶĐĞŝŶŵĞůƟŶŐƚĞŵƉĞƌĂƚƵƌĞŽĨƚŚĞƚĞƌƉŽůLJŵĞƌƐŝƐĂŶĂůŽŐŽƵƐƚŽƚŚĂƚŽĨW;s&-co-dƌ&ͿĐŽƉŽůLJŵĞƌƐ͘,ĞƌĞ͕ƚŚĞT_mƚĂŬĞƐĂŵŝŶŝŵƵŵǀĂůƵĞǁŝƚŚϵϬŵŽůйs&ŝŶƐŝĚĞĂŶĚŝƐ ƐŚŝŌĞĚƚŽŚŝŐŚĞƌǀĂůƵĞƐǁŚĞŶƚŚĞs&Žƌdƌ&ĐŽŶƚĞŶƚŝƐŝŶĐƌĞĂƐĞĚ͕ŵŽǀŝŶŐƚŽǁĂƌĚƐƚŚĞT_m of its parent homopolymers.ϯϱ_{ƐĞdžƉĞĐƚĞĚ͕ĂŶŝŶĐƌĞĂƐŝŶŐdƌ&ĐŽŶƚĞŶƚŝŶƚŚĞƚĞƌƉŽůLJŵĞƌƐ} ůŽǁĞƌƐƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞ͘ǀĞŶƚŚŽƵŐŚƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞ

Figure 6.2: 1_{H NMR COSY spectrum of (a) P(VDF}

0.78-ter-TrFE0.17-ter-VA0.05) and (b) P(VDF0.53-ter-TrFE0.37

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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ŝŶW;s&-co-dƌ&ͿĐŽƉŽůLJŵĞƌƐĐĂŶďĞƐůŝŐŚƚůLJǀĂƌŝĞĚďLJƚƵŶŝŶŐƚŚĞƉƌŽĐĞƐƐŝŶŐĐŽŶĚŝƟŽŶƐ ŽƌƉŽůLJŵĞƌŝnjĂƟŽŶŵĞƚŚŽĚ͕ƚŚĞƚĞƌƉŽůLJŵĞƌƐƐŚŽǁĂT_C much lower than obtained for W;s&-co-dƌ&ͿŚĂǀŝŶŐĂƐŝŵŝůĂƌs&ĐŽŶƚĞŶƚ͘ϯϲʹϯϴ_{dŚŝƐƌĞƐƵůƚŝƐƋƵŝƚĞƌĞŵĂƌŬĂďůĞ͕ƐŝŶĐĞŝƚ} ŝƐŐĞŶĞƌĂůůLJďĞůŝĞǀĞĚƚŚĂƚŵŽŶŽŵĞƌƐŚĂǀŝŶŐĂůĂƌŐĞƌƐŝnjĞ;dƌ&хsͿĨĂĐŝůŝƚĂƚĞŝŶƌĞĚƵĐŝŶŐ ƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞ͘8_{/ŶĐŽŵƉĂƌŝƐŽŶ͕W;s&-ter-dƌ&-ter-d&ͿƚĞƌƉŽůLJŵĞƌƐ͕} ǁŚĞƌĞŝŶd&ĂůƐŽĐŽĐƌLJƐƚĂůůŝnjĞƐǁŝƚŚs&ĂŶĚdƌ&ƌĞŐĂƌĚůĞƐƐŽĨƚŚĞŵĞůƚĐƌLJƐƚĂůůŝnjĂƟŽŶ

Figure 6.3:19_{F NMR spectrum of the terpolymers.}

Figure 6.4: (a) DSC thermograms and (b) FTIR spectra of the P(VDF-ter-TrFE-ter-VA) terpolymers.

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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ĐŽŶĚŝƟŽŶƐ͕ƐŚŽǁĂůƐŽĂƌĞĚƵĐƟŽŶŝŶƵƌŝĞƚƌĂŶƐŝƟŽŶǁŚĞŶdƌ&ƵŶŝƚƐĂƌĞƌĞƉůĂĐĞĚďLJ d&͘ϭϵ͕ϯϵ_{  ƚŚŝƌĚ ŵŽŶŽŵĞƌ ŝŶƚƌŽĚƵĐĞĚ ŝŶƚŽ ƚŚĞ ƉŽůLJŵĞƌ ďĂĐŬďŽŶĞ ĂĐƚƐ ĂƐ Ă ĚĞĨĞĐƚ} ĂůůŽǁŝŶŐĂŶŝŶĐƌĞĂƐĞŝŶƚŚĞĐƌLJƐƚĂůůĂƫĐĞƐƉĂĐŝŶŐĂŶĚŵŽƌĞddd'н_TTTGͲ_{ĐŽŶĨŽƌŵĂƟŽŶƐ} (T = trans and G = gaucheͿ͕ĂƐŽƉƉŽƐĞĚƚŽƚŚĞĚĞŶƐĞůLJƉĂĐŬĞĚĂůůͲƚƌĂŶƐĐŽŶĨŽƌŵĂƟŽŶŝŶ ĨĞƌƌŽĞůĞĐƚƌŝĐW;s&-co-dƌ&Ϳ͘dŚŝƐŝŶĐƌĞĂƐĞŝŶƚŚĞĚŝƐŽƌĚĞƌĞĚƉĂƌĂĞůĞĐƚƌŝĐƉŚĂƐĞĐŽŶƚĞŶƚ ĂŶĚƚŚĞŝŶĐƌĞĂƐĞĚŝŶƚĞƌĐŚĂŝŶĚŝƐƚĂŶĐĞŝŶƚŚĞĐƌLJƐƚĂůƐůŽǁĞƌƐƚŚĞƌĞƋƵŝƌĞĚĞŶĞƌŐLJďĂƌƌŝĞƌ ĨŽƌƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶ͕ůĞĂĚŝŶŐƚŽĂƌŽŽŵƚĞŵƉĞƌĂƚƵƌĞƉŚĂƐĞƚƌĂŶƐŝƟŽŶĨŽƌW;s&_0.79 -ter-dƌ&_0.07-ter-d&_Ϭ͘ϭϰͿ͘ dŽĨƵƌƚŚĞƌĞůƵĐŝĚĂƚĞƚŚĞĞīĞĐƚŽĨsŝŶĐŽƌƉŽƌĂƟŽŶŝŶƚŚĞƚĞƌƉŽůLJŵĞƌďĂĐŬďŽŶĞŽŶ ƚŚĞĐƌLJƐƚĂůůŝnjĂƟŽŶďĞŚĂǀŝŽƌ͕ǁŝĚĞͲĂŶŐůĞyͲƌĂLJƐĐĂƩĞƌŝŶŐ;ty^ͿĂŶĚ&ŽƵƌŝĞƌƚƌĂŶƐĨŽƌŵ ŝŶĨƌĂƌĞĚƐƉĞĐƚƌŽƐĐŽƉLJ;&d/ZͿĂƌĞƉĞƌĨŽƌŵĞĚ;&ŝŐƵƌĞϲ͘ϰͿ͘ďƐŽƌďĂŶĐĞƉĞĂŬƐďĞůŽŶŐŝŶŐƚŽ ƚŚĞƐƉĞĐŝĮĐŵŽŶŽŵĞƌĐŽŶĨŽƌŵĂƟŽŶƐĂƌĞůŽĐĂƚĞĚĂƌŽƵŶĚϱϬϳ;ddd'Ϳ͕ϲϭϰ;d'Ϳ͕ϴϰϬ;d_ŵхϰͿ and 1280 cmͲϭ_(T ŵхϰͿŝŶƚŚĞ&d/ZƐƉĞĐƚƌĂ͘ ϮϬ͕ϰϬ_{dŚĞW;s&} Ϭ͘ϱϯ-ter-dƌ&Ϭ͘ϯϳ-ter-s0.10ͿƐŚŽǁƐ͕ ŶĞdžƚƚŽƚŚĞd_ŵхϰĐŽŶĨŽƌŵĂƟŽŶƐ͕ƚŚĞĐŚĂƌĂĐƚĞƌŝƐƟĐddd'ĂŶĚd'ĂďƐŽƌƉƟŽŶďĂŶĚĂƚϱϬϲ cmͲϭ_{ĂŶĚϲϭϮĐŵ}Ͳϭ_{͘ǀĞŶƚŚŽƵŐŚƚŚĞĂďƐŽƌƉƟŽŶďĂŶĚƐĂƐƐŽĐŝĂƚĞĚǁŝƚŚƚŚĞddd'ĂƌĞĂďƐĞŶƚ} ŝŶW;s&_0.78-ter-dƌ&_0.17-ter-s_0.05Ϳ͕ƚŚĞƉĞĂŬƐĐŽƌƌĞƐƉŽŶĚŝŶŐƚŽƚŚĞd_ŵхϰĐŽŶĨŽƌŵĂƟŽŶƐ ĂƌĞƉƌĞƐĞŶƚĂůďĞŝƚůĞƐƐŝŶƚĞŶƐĞũƵƐƚĂƐƚŚĞd'ĂďƐŽƌƉƟŽŶďĂŶĚƐ͘/ŶƚĞƌĞƐƟŶŐůLJ͕ĂƌĞĐĞŶƚ study using 19_{&EDZƐƉĞĐƚƌŽƐĐŽƉLJĂŶĚĐŽŵƉƵƚĂƟŽŶĂůĚĂƚĂƐŚŽǁĞĚƚŚĂƚŝƐŽƚĂĐƟĐdƌ&Ͳ} dƌ& ƐĞŐŵĞŶƚƐ ƉƌĞĨĞƌĞŶƟĂůůLJ ĐƌLJƐƚĂůůŝnjĞ ŝŶ ĂŶ ϯͬϭ ŚĞůŝĐĂů ĐŽŶĨŽƌŵĂƟŽŶ ŚĂǀŝŶŐ ddd' ĐŽŶĨŽƌŵĂƟŽŶƐ͘ϮϬ͕ϰϭ _{Indeed, comparing the} 19_{&EDZƐƉĞĐƚƌĂŽĨƚŚĞsͲďĂƐĞĚƚĞƌƉŽůLJŵĞƌƐ} ƵƐĞĚŝŶƚŚŝƐƐƚƵĚLJ͕W;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10ͿƐŚŽǁƐĂůĂƌŐĞŝŶĐƌĞĂƐĞŝŶƚŚĞƐŝŐŶĂůƐŝŶ ƚŚĞƌĞŐŝŽŶĂƌŽƵŶĚͲϮϭϮƉƉŵĐŽŶĮƌŵŝŶŐŝƐŽƚĂĐƟĐdƌ&Ͳdƌ&ůŝŶŬĂŐĞƐ͘

ƐĞdžƉĞĐƚĞĚ͕W;s&_0.78-ter-dƌ&_0.17-ter-s_0.05ͿŝƐŝŶƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐƉŚĂƐĞĂƚƌŽŽŵ ƚĞŵƉĞƌĂƚƵƌĞ͕ĂƐĞǀŝĚĞŶĐĞĚďLJƚŚĞĐŽŶĐŽŵŝƚĂŶƚ;ϭϭϬͬϮϬϬͿty^ƉĞĂŬƐůŽĐĂƚĞĚĂƚϭϰ͘ϭϱ nmͲϭ_{;&ŝŐƵƌĞϲ͘ϰĐͿ͘DŽƌĞŽǀĞƌ͕ƉĞĂŬĚĞĐŽŶǀŽůƵƟŽŶƌĞǀĞĂůƐĂŶĂĚĚŝƟŽŶĂůĐƌLJƐƚĂůůŝŶĞƉŚĂƐĞ} Ăƚϭϯ͘ϳŶŵͲϭ_{, which is recognized as a ferroelectric phase having gauche defects.}ϰϮ͕ϰϯ _In ĐŽŶƚƌĂƐƚ͕ĂƐ^ĂŶĚ&d/ZƐƉĞĐƚƌŽƐĐŽƉLJĂůƌĞĂĚLJƐƵŐŐĞƐƚĞĚ͕W;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10Ϳ ƐŚŽǁƐĂĐŽŵƉůĞƚĞůLJĚŝīĞƌĞŶƚĐƌLJƐƚĂůůŝnjĂƟŽŶďĞŚĂǀŝŽƌ͘/ŶƚŚĞty^ƉƌŽĮůĞĚĞƉŝĐƚĞĚŝŶ &ŝŐƵƌĞϲ͘ϰĚ͕ƚŚĞĐŽĞdžŝƐƚĞŶĐĞŽĨƚǁŽĐƌLJƐƚĂůůŝŶĞƉŚĂƐĞƐĐŚĂƌĂĐƚĞƌŝnjĞĚďLJƚǁŽĚŝīĞƌĞŶƚ ƉĞĂŬƐůŽĐĂƚĞĚĂƚϭϯ͘ϮϰĂŶĚϭϯ͘ϰϴŶŵͲϭ_{ŝƐƌĞǀĞĂůĞĚ͘EĞdžƚƚŽƚŚĞĐŚĂƌĂĐƚĞƌŝƐƟĐĨĞƌƌŽĞůĞĐƚƌŝĐ} ƉŚĂƐĞƉĞĂŬůŽĐĂƚĞĚĂƚϭϯ͘ϰϴŶŵͲϭ_{͕ĂƐĞĐŽŶĚƉĞĂŬůŽĐĂƚĞĚĂƚϭϯ͘ϮϰŶŵ}Ͳϭ _{is present and it is} ĂƐƐŽĐŝĂƚĞĚǁŝƚŚƚŚĞĞdžŝƐƚĞŶĐĞŽĨĂĚŝƐŽƌĚĞƌĞĚƉĂƌĂĞůĞĐƚƌŝĐƐƚƌƵĐƚƵƌĞ͕ŝŶĂŐƌĞĞŵĞŶƚǁŝƚŚ many literature reports.ϮϬ͕ϰϰʹϰϳ_{dŚĞůĂƌŐĞƐŚŝŌƚŽůŽǁĞƌƋͲǀĂůƵĞƐŝŶW;s&}

Ϭ͘ϱϯ-ter-dƌ&Ϭ͘ϯϳ -ter-s_0.10ͿŝƐĂƩƌŝďƵƚĞĚƚŽƚŚĞŝŶĐůƵƐŝŽŶŽĨŵŽƌĞdƌ&ƵŶŝƚƐŝŶĐƌĞĂƐŝŶŐƚŚĞƐƉĂĐŝŶŐďĞƚǁĞĞŶƚŚĞ ƌĞŇĞĐƟǀĞƉůĂŶĞƐ͘ĚĚŝƟŽŶĂůůLJ͕ƐŝŶĐĞƚŚĞϭϬϬйŵĞůƟŶŐĞŶƚŚĂůƉŝĞƐĂƌĞƵŶŬŶŽǁŶ͕ty^ŝƐ ƵƐĞĚƚŽĚĞƚĞƌŵŝŶĞƚŚĞĐƌLJƐƚĂůůŝŶŝƚLJŽĨƚŚĞƚĞƌƉŽůLJŵĞƌƐ͘/ŶƚĞƌĞƐƟŶŐůLJ͕ĂŶŝŶĐƌĞĂƐŝŶŐƚƌĞŶĚ ŝƐŽďƐĞƌǀĞĚƵƉŽŶŚŝŐŚĞƌdƌ&ĐŽŶƚĞŶƚŝŶƚŚĞŇƵŽƌŝŶĂƚĞĚsͲďĂƐĞĚƉŽůLJŵĞƌƐƐĂŵƉůĞƐ͘ &ƌŽŵĂƉƌĞǀŝŽƵƐƐƚƵĚLJ͕W;s&-co-sͿƐŚŽǁƐĂĚĞŐƌĞĞŽĨĐƌLJƐƚĂůůŝŶŝƚLJŽĨϯϴй͕ǁŚĞƌĞĂƐ ƚŚĞĐƌLJƐƚĂůůŝŶŝƚLJŝŶW;s&_0.78-ter-dƌ&_0.17-ter-s_0.05ͿĂŶĚW;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10ͿŝƐ

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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ĐĂůĐƵůĂƚĞĚƚŽďĞϰϴйĂŶĚϲϯй͕ƌĞƐƉĞĐƟǀĞůLJ͘28_{/ƚŝƐďĞůŝĞǀĞĚƚŚĂƚƚŚĞŝŶĐƌĞĂƐŝŶŐƐŝnjĞŽĨdƌ&} ŵŽŶŽŵĞƌƐŽǀĞƌĐŽŵĞƐƐƚƌƵĐƚƵƌĂůŝŵƉĞƌĨĞĐƟŽŶƐŝŶĚƵĐĞĚďLJsƵŶŝƚƐĂůůŽǁŝŶŐŵŽƌĞsƚŽ ďĞŝŶĐůƵĚĞĚŝŶƚŚĞĐƌLJƐƚĂůůĂƫĐĞƐ͘EŽƚĞǁŽƌƚŚŝůLJ͕ŝŶƚŚĞsͲďĂƐĞĚƚĞƌƉŽůLJŵĞƌƐ͕ƐŝŵŝůĂƌŽƌ ŚŝŐŚĞƌĚĞŐƌĞĞŽĨĐƌLJƐƚĂůůŝŶŝƟĞƐĂƌĞŽďƚĂŝŶĞĚĂƐĐŽŵƉĂƌĞĚƚŽW;s&_Ϭ͘ϱϯ-co-dƌ&_Ϭ͘ϰϳ

Ϳ͕W;s&-ter-dƌ&-ter-d&ͿĂŶĚW;s&-ter-dƌ&-ter-&ͿƚŚĂƚĚĞŵŽŶƐƚƌĂƚĞĂƉƉĞĂůŝŶŐĞůĞĐƚƌŽĂĐƟǀĞ ďĞŚĂǀŝŽƌĨŽƌĚŝĞůĞĐƚƌŝĐĂƉƉůŝĐĂƟŽŶƐ͘ϴ͕ϮϬ͕ϯϵ KŶĞ ŵĂũŽƌ ĂĚǀĂŶƚĂŐĞ ŽĨ ƚŚĞ W;s&-ter-dƌ&-ter-sͿ ƚĞƌƉŽůLJŵĞƌƐ ŝƐ ŚĂǀŝŶŐ ĞĂƐŝůLJ ĂĐĐĞƐƐŝďůĞ ŚLJĚƌŽdžLJů ĨƵŶĐƟŽŶĂů ŐƌŽƵƉƐ ƚŚĂƚ ĂůůŽǁƐ ĨĂĐŝůĞ ŵŽĚŝĮĐĂƟŽŶƐ͘ hƐŝŶŐ ƚŚĞƐĞ ŚLJĚƌŽdžLJů ĨƵŶĐƟŽŶĂůŝƟĞƐ ĨŽƌ ĐƌŽƐƐůŝŶŬŝŶŐ ŽīĞƌƐ ĂŶ ŽƉƉŽƌƚƵŶŝƚLJ ƚŽ ďƌĞĂŬ ƵƉ ůĂƌŐĞ ĨĞƌƌŽĞůĞĐƚƌŝĐĐƌLJƐƚĂůůŝŶĞĚŽŵĂŝŶƐƐŽƚŚĂƚƐůŝŵŚLJƐƚĞƌĞƐŝƐůŽŽƉƐĐĂŶďĞŽďƚĂŝŶĞĚ͕ǁŚŝůĞƐƟůů ŚĂǀŝŶŐŚŝŐŚƉŽůĂƌŝnjĂƟŽŶƐ͘5,7,8 _{Due to its high degree of crystallinity and crystalline phases} ďĞŶĞĮĐŝĂůĨŽƌĞŶĞƌŐLJƐƚŽƌĂŐĞĂƉƉůŝĐĂƟŽŶƐ͕ŝƚǁĂƐĚĞĐŝĚĞĚƚŽĐƌŽƐƐůŝŶŬW;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ -ter-s_0.10ͿƵƐŝŶŐŚĞdžĂŵĞƚŚLJůĞŶĞĚŝŝƐŽĐLJĂŶĂƚĞ;,D/ͿǁŝƚŚϬ͘ϭͲ͕Ϭ͘ϮϱͲĂŶĚϬ͘ϱͲĨŽůĚĞdžĐĞƐƐ ŽĨŝƐŽĐLJĂŶĂƚĞƚŽŚLJĚƌŽdžLJůŐƌŽƵƉƐ͘dŚĞĐƌŽƐƐůŝŶŬĞĚŇƵŽƌŝŶĂƚĞĚŶĞƚǁŽƌŬƐĂƌĞĚĞƐŝŐŶĂƚĞĚ ĂĐĐŽƌĚŝŶŐƚŽƚŚĞŝƌŝƐŽĐLJĂŶĂƚĞĞdžĐĞƐƐƵƐĞĚ͕ŶĂŵĞůLJW;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10ͿͲϬ͘ϭdž͕ W;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10ͿͲϬ͘ϮϱdžĂŶĚW;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10ͿͲϬ͘ϱdž͘

Ɛ ĞdžƉĞĐƚĞĚ͕ ƚŚĞ ĐƌŽƐƐůŝŶŬĞĚ ŇƵŽƌŽƉŽůLJŵĞƌƐ ĂƌĞ ŝŶƐŽůƵďůĞ ŝŶ ĐŽŵŵŽŶ ŽƌŐĂŶŝĐ ƐŽůǀĞŶƚƐ͕ ƐƵĐŚ ĂƐ ĚŝŵĞƚŚLJůĨŽƌŵĂŵŝĚĞ ;D&Ϳ͕ ƉƌŽǀŝŶŐ ŝƚƐ ĐƌŽƐƐůŝŶŬĞĚ ŶĂƚƵƌĞ ;D& ŝƐ ĂŐŽŽĚƐŽůǀĞŶƚĨŽƌW;s&-ter-dƌ&-ter-sͿƚĞƌƉŽůLJŵĞƌƐͿ͘/ŶĂĚĚŝƟŽŶ͕ƚŚĞ&d/ZƐƉĞĐƚƌĂ͕ ƐŚŽǁŶŝŶ&ŝŐƵƌĞϲ͘ϱĂ͕ĚĞŵŽŶƐƚƌĂƚĞƚŚĞĨŽƌŵĂƟŽŶŽĨƵƌĞƚŚĂŶĞďŽŶĚƐĂƐŝŶĚŝĐĂƚĞĚďLJƚŚĞ ĂƉƉĞĂƌĂŶĐĞŽĨƚŚĞĐĂƌďĂŵĂƚĞĂďƐŽƌƉƟŽŶďĂŶĚĂƚϭϱϮϱĐŵͲϭ _{and the carbonyl stretching} ĂƚϭϳϬϰĐŵͲϭ_{͘DŽƌĞŽǀĞƌ͕ŶŽŐƌĂŌŝŶŐŽĨƚŚĞW;s&}

Ϭ͘ϱϯ-ter-dƌ&Ϭ͘ϯϳ-ter-s0.10ͿƚĞƌƉŽůLJŵĞƌƐ occurred, which is demonstrated by the absence of the asymmetric stretch of isocyanate ŐƌŽƵƉƐĞdžƉĞĐƚĞĚƚŽďĞĂƚĂƌŽƵŶĚϮϮϳϳĐŵͲϭ_.ϯϴ dŚĞ ĐƌLJƐƚĂůůŝŶĞ ƉŚĂƐĞƐ ŽĨ ƚŚĞ ĐƌŽƐƐůŝŶŬĞĚ ƚĞƌƉŽůLJŵĞƌƐ ǁĞƌĞ ĂŶĂůLJnjĞĚ ƵƐŝŶŐ &d/Z ƐƉĞĐƚƌŽƐĐŽƉLJ ĂŶĚ ty^ ĂƐ ĚĞŵŽŶƐƚƌĂƚĞĚ ŝŶ &ŝŐƵƌĞ ϲ͘ϱ͘ /ŶĚĞĞĚ͕ ƚŚĞ ĐƌLJƐƚĂůůŝnjĂƟŽŶ ďĞŚĂǀŝŽƌŝƐĚƌĂƐƟĐĂůůLJĐŚĂŶŐĞĚƵƉŽŶĐƌŽƐƐůŝŶŬŝŶŐ͘dŚĞĐƌLJƐƚĂůůŝŶŝƚLJŽĨĐƌŽƐƐůŝŶŬĞĚW;s&_Ϭ͘ϱϯ -ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10ͿƚĞƌƉŽůLJŵĞƌƐƌĞĚƵĐĞƐǁŝƚŚŝŶĐƌĞĂƐŝŶŐƵƐĞŽĨĐƌŽƐƐůŝŶŬŝŶŐĂŐĞŶƚĂƐ ƐŚŽǁŶŝŶdĂďůĞϲ͘ϭ͘EĞǀĞƌƚŚĞůĞƐƐ͕ƉĞĂŬĚĞĐŽŶǀŽůƵƟŽŶŽĨƚŚĞty^ƉƌŽĮůĞƐƌĞǀĞĂůƐƚŚĂƚ ƚŚĞĨƌĂĐƟŽŶŽĨƉĂƌĂĞůĞĐƚƌŝĐƉŚĂƐĞŝŶƚŚĞĐƌŽƐƐůŝŶŬĞĚƐĂŵƉůĞƐƉƌŽŐƌĞƐƐŝǀĞůLJŝŶĐƌĞĂƐĞƐǁŚĞŶ ƚŚĞĂŵŽƵŶƚŽĨĐƌŽƐƐůŝŶŬŝŶŐĂŐĞŶƚŝƐŝŶĐƌĞĂƐĞĚ͘dŚŝƐŝƐƐƵƉƉŽƌƚĞĚďLJĂŶĂůLJƐŝƐŽĨƚŚĞ&d/Z ƐƉĞĐƚƌĂ͕ǁŚĞƌĞƚŚĞĂďƐŽƌƉƟŽŶďĂŶĚĂƚϱϬϲĐŵͲϭ_{ĐŽƌƌĞƐƉŽŶĚŝŶŐƚŽƚŚĞddd'ĐŽŶĨŽƌŵĂƟŽŶ} becomes more pronounced, while the bands showing the T_ŵхϰĐŽŶĨŽƌŵĂƟŽŶƐƌĞĚƵĐĞŝŶ intensity. Moreover, crosslinking reduces the crystallite size of the paraelectric crystals ŝŶƚŚĞƚĞƌƉŽůLJŵĞƌƐĨƌŽŵϯϰ͘ϵŶŵĨŽƌƉƌŝƐƟŶĞW;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10ͿƚŽũƵƐƚϭϱ͘Ϭ ŶŵĨŽƌW;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10ͿĐƌŽƐƐůŝŶŬĞĚǁŝƚŚϬ͘ϱͲĨŽůĚĞdžĐĞƐƐŽĨ,D/͘ƵĞƚŽ ƚŚĞǁĞůůͲĚŝƐƚƌŝďƵƚĞĚĐƌŽƐƐůŝŶŬŝŶŐƐŝƚĞƐŝŶƚŚĞŇƵŽƌŝŶĂƚĞĚŶĞƚǁŽƌŬƐ͕ŽŶůLJƐŵĂůůĚŝƐŽƌĚĞƌĞĚ ƉĂƌĂĞůĞĐƚƌŝĐĐƌLJƐƚĂůƐĂƌĞĨŽƌŵĞĚ͕ƐĞƉĂƌĂƚĞĚďLJĐŚĞŵŝĐĂůĐƌŽƐƐůŝŶŬƐ͘dŚŝƐƌĞĚƵĐƟŽŶŝŶ the average disordered paraelectric crystallite size is well evidenced by the increase of

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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Figure 6.5: (a) FTIR spectra of the crosslinked P(VDF_0.53-ter-TrFE_0.37-ter-VA_0.10) terpolymers. (b) ;%<7TVSƼPISJ4:(*0.53-ter-TrFE0.37-ter-VA0.10)-0.1x. (c) Schematic representation of the crosslinked

XIVTSP]QIVWH ;%<7TVSƼPISJ4:(*_0.53-ter-TrFE_0.37-ter-VA_0.10)-0.25x. (e) D-E loop of P(VDF_0.53

-ter-TrFE0.37-ter-VA0.10 ERHXLIGVSWWPMROIHXIVTSP]QIVWJ ;%<7TVSƼPISJ4:(*0.53-ter-TrFE0.37

-ter-VA_0.10)-0.5x.

Table 6.1: Crystallization characteristics of the polymers used in this study.

Polymer Xc Ă_{;йͿ F} p ď _F f c _&t,D p ;ŶŵͲϭ_Ϳd &t,Df ;ŶŵͲϭ_Ϳe dp;ŶŵͿ f _d f;ŶŵͿ Ő W;s&_Ϭ͘ϱϯͲdƌ&_Ϭ͘ϯϳͲs_0.10Ϳ ϲϯ Ϭ͘ϯϬ 0.70 0.18 Ϭ͘ϯϱ ϯϰ͘ϵ 18.0 W;s&Ϭ͘ϱϯͲdƌ&Ϭ͘ϯϳͲs0.10ͿͲϬ͘ϭdž ϯϴ Ϭ͘ϯϳ Ϭ͘ϲϯ Ϭ͘ϯϰ Ϭ͘ϯϱ 18.5 18.0 W;s&Ϭ͘ϱϯͲdƌ&Ϭ͘ϯϳͲs0.10ͿͲϬ͘Ϯϱdž ϯϰ Ϭ͘ϰϭ 0.59 Ϭ͘ϰϬ Ϭ͘ϯϱ 15.7 18.0 W;s&_Ϭ͘ϱϯͲdƌ&_Ϭ͘ϯϳͲs_0.10ͿͲϬ͘ϱdž Ϯϲ Ϭ͘ϰϴ 0.52 Ϭ͘ϰϮ Ϭ͘ϯϱ 15.0 18.0

a_{(IKVIISJGV]WXEPPMRMX]GEPGYPEXIHJVSQXLI;%<7TVSƼPIW}b_{Fraction of paraelectric phase.} c_Fraction

of ferroelectric phase.d_{Full width half maximum of the} d_{paraelectric and} e_{ferroelectric phase.}

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: 118PDF page: 118PDF page: 118PDF page: 118

118 ƚŚĞƉĞĂŬǁŝĚƚŚǁŝƚŚŝŶĐƌĞĂƐŝŶŐĐƌŽƐƐůŝŶŬŝŶŐĂƐĚĞƚĞƌŵŝŶĞĚĨƌŽŵty^;dĂďůĞͿ͘/ŶƚŚĞ ůŝƚĞƌĂƚƵƌĞ͕ĂƐŝŵŝůĂƌĐƌLJƐƚĂůƐŝnjĞƌĞĚƵĐƟŽŶŝƐĂůƐŽŽďƐĞƌǀĞĚŝŶĐƌŽƐƐůŝŶŬŝŶŐŽĨW;s&-co-d&Ϳ͕ǁŚŝůĞŽƚŚĞƌĐƌŽƐƐůŝŶŬŝŶŐŵĞƚŚŽĚƐ͕ƐƵĐŚĂƐĞůĞĐƚƌŽďĞĂŵŝƌƌĂĚŝĂƟŽŶ͕ŽīĞƌƉŽŽƌ ĐŽŶƚƌŽůŽǀĞƌƚŚĞĐƌŽƐƐůŝŶŬŝŶŐƐŝƚĞ͕ƌĞƐƵůƟŶŐŝŶĂůĂƌŐĞĚŝƐƚƌŝďƵƟŽŶŽĨĐƌLJƐƚĂůůŝƚĞƐŝnjĞƐ͘Ϯϰ͕ϰϵ dŽĐŽŵƉĂƌĞƚŚĞĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌŽĨƚŚĞ;ĐƌŽƐƐůŝŶŬĞĚͿƚĞƌƉŽůLJŵĞƌƐ͕ĚŝƐƉůĂĐĞŵĞŶƚͲ ĞůĞĐƚƌŝĐĮĞůĚ;ͲͿŵĞĂƐƵƌĞŵĞŶƚƐǁĞƌĞƉĞƌĨŽƌŵĞĚďLJĂƉƉůLJŝŶŐĂŶĞůĞĐƚƌŝĐĮĞůĚƵƉƚŽϮϱϬ DsŵͲϭ_{ŝŶĂƚƌŝĂŶŐƵůĂƌǁĂǀĞĨŽƌŵĂƚĂĨƌĞƋƵĞŶĐLJŽĨϭϬ,nj͕ŵĞĂƐƵƌŝŶŐƚŚĞƉŽůĂƌŝnjĂƟŽŶĂƐ} ƚŚĞŝŶƚĞŐƌĂůŽĨƚŚĞƌĞƐƵůƟŶŐĐƵƌƌĞŶƚ͘ƚůŽǁĞƌĞůĞĐƚƌŝĐĮĞůĚƐ;фϴϬDsŵͲϭ_{Ϳ͕ƚŚĞ;ĐƌŽƐƐůŝŶŬĞĚͿ} ƚĞƌƉŽůLJŵĞƌƐƐŚŽǁůŝŶĞĂƌĚŝĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌ͘ŽŶƐĞƋƵĞŶƚůLJ͕ďLJĐĂůĐƵůĂƟŶŐƚŚĞƐƚŽƌĞĚ ĞŶĞƌŐLJ ĚĞŶƐŝƚLJ ĂŶĚ ƵƐŝŶŐ ĚǀĂŶĐĞĚ ĞůĞĐƚƌŽŶŝĐ ĚĞǀŝĐĞƐ ĂŶĚ ĐŝƌĐƵŝƚƐ͕ ƉƵůƐĞĚ ƉŽǁĞƌ ƚĞĐŚŶŽůŽŐŝĞƐĂŶĚĞůĞĐƚƌŝĐǀĞŚŝĐůĞƐĂƌĞĂŵŽŶŐŽƚŚĞƌƐĂƉƉůŝĐĂƟŽŶƐƚŚĂƚŶĞĞĚŚŝŐŚĞŶĞƌŐLJ ĚĞŶƐŝƚLJĚŝĞůĞĐƚƌŝĐƐĨŽƌĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJƐƚŽƌĂŐĞ͘ϭʹϯ_{EŽǁĂĚĂLJƐ͕ďLJƐĞůĞĐƟŶŐƉŽůLJŵĞƌƐ} ĂƐƚŚĞŵĂƚĞƌŝĂůŽĨĐŚŽŝĐĞ͕ŵĂŝŶƌĞƋƵŝƌĞŵĞŶƚƐƐƵĐŚĂƐůŝŐŚƚǁĞŝŐŚƚŶĂƚƵƌĞ͕ůŽǁĐŽƐƚ͕ĞĂƐĞ ŽĨƉƌŽĐĞƐƐŝŶŐ͕ƐĞůĨͲŚĞĂůŝŶŐĐĂƉĂďŝůŝƚLJĂŶĚŚŝŐŚďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚƐĂƌĞĞĂƐŝůLJĨƵůĮůůĞĚ͘ Unfortunately, inherent to commercially available high breakdown strength polymers ĂƌĞůŽǁĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚƐ͕ƐƵƉƉƌĞƐƐŝŶŐƚŚĞŵĂdžŝŵƵŵĞŶĞƌŐLJĚĞŶƐŝƟĞƐƚŽďĞƐƚŽƌĞĚ ŝŶƐŝĚĞƚŚĞĚŝĞůĞĐƚƌŝĐƐ͘&ŽƌŝŶƐƚĂŶĐĞ͕ƐƚĂƚĞͲŽĨͲƚŚĞͲĂƌƚKWWƐŚŽǁƐĂŶĞŶĞƌŐLJĚĞŶƐŝƚLJŽĨũƵƐƚ Εϰ:ĐŵͲϯ_{ĂƚĂŶĞůĞĐƚƌŝĐĮĞůĚŽĨϲϬϬDsŵ}Ͳϭ_{. Therefore, to improve the energy storage in} ĚŝĞůĞĐƚƌŝĐƐ͕ƚŚĞLJƌĞƋƵŝƌĞďŽƚŚĂŚŝŐŚĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚ;ɸͿĂŶĚŚŝŐŚďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚ͕ since the stored energy density (UͿŝƐƉƌŽƉŽƌƟŽŶĂůƚŽƚŚĞĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚĂŶĚƚŚĞ ĞůĞĐƚƌŝĐĮĞůĚ;EͿƐƋƵĂƌĞĚĂƐĚŝƐƉůĂLJĞĚŝŶƋƵĂƟŽŶϲ͘ϭ͕ƚŚĞĂƉƉĂƌĞŶƚĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚ can be derived.50,51_{/ƚŝƐĨŽƵŶĚƚŚĂƚW;s&}

0.78-ter-dƌ&0.17-ter-s0.05ͿĂŶĚW;s&Ϭ͘ϱϯ-ter-dƌ&Ϭ͘ϯϳ

-ter-s_0.10ͿƐŚŽǁĂŶĂƉƉĂƌĞŶƚĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚ;ɸ_appͿŽĨϮϬĂŶĚϰϱ͕ƌĞƐƉĞĐƟǀĞůLJ͕ǁŚŝůĞŝƚŝƐ progressively reducing for the crosslinked samples due to the lower degree of crystallinity ;dĂďůĞϲ͘ϭͿ͘ƚŚŝŐŚĞƌĞůĞĐƚƌŝĐĮĞůĚƐ;ϮϱϬDsŵͲϭ_{Ϳ͕ƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐĚŝƉŽůĞƐĂůŝŐŶŝŶW;s&}

0.78

-ter-dƌ&_0.17-ter-s_0.05ͿůĞĂĚŝŶŐƚŽĂƉŽůĂƌŝnjĂƟŽŶŽĨϳ͘ϭϯђĐŵͲϮ_{ĂŶĚĂƌĞŵĂŶĞŶƚƉŽůĂƌŝnjĂƟŽŶ} ŽĨϯ͘ϭϬђĐŵͲϮ_{;&ŝŐƵƌĞϲ͘ϲĂͿ͘dŚĞƌĞůĂƟǀĞůLJůŽǁƌĞŵĂŶĞŶƚƉŽůĂƌŝnjĂƟŽŶŽĨW;s&}

0.78 -ter-dƌ&_0.17-ter-s_0.05ͿĐŽŵƉĂƌĞĚƚŽĨĞƌƌŽĞůĞĐƚƌŝĐW;s&ͲĐŽͲdƌ&ͿĐŽƉŽůLJŵĞƌƐĐĂŶďĞĂƐĐƌŝďĞĚ ƚŽƚŚĞĨŽƌŵĂƟŽŶŽĨƉŚLJƐŝĐĂůƉŝŶŶŝŶŐƐƉŽƚƐĞŶŚĂŶĐŝŶŐƚŚĞĚŝƉŽůĞƌĞǀĞƌƐŝďŝůŝƚLJ͘5,8,28 _{In Figure} ϲ͘ϲď͕ƚŚĞͲůŽŽƉƐŽĨW;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10ͿĂŶĚƚŚĞŇƵŽƌŝŶĂƚĞĚŶĞƚǁŽƌŬƐĂƌĞ ĚĞƉŝĐƚĞĚĂƚƐŝŵŝůĂƌĞůĞĐƚƌŝĐĮĞůĚƐ͘,ĞƌĞ͕ƌĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌŝƐŽďƐĞƌǀĞĚŝŶĂůů ƐĂŵƉůĞƐ͘ƵĞƚŽsƉŝŶŶŝŶŐƐƉŽƚƐŝŶƚŚĞŶĂŶŽĐƌLJƐƚĂůƐĂŶĚƚŚĞŵŝdžƚƵƌĞŽĨĚŝƐŽƌĚĞƌĞĚ ƉĂƌĂĞůĞĐƚƌŝĐĂŶĚĨĞƌƌŽĞůĞĐƚƌŝĐƉŚĂƐĞƐ͕W;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10ͿĚĞŵŽŶƐƚƌĂƚĞƐĂůŽǁ ƌĞŵĂŶĞŶƚƉŽůĂƌŝnjĂƟŽŶŽĨϭ͘ϬϭђĐŵͲϮ_{ĂŶĚĂŵĂdžŝŵƵŵƉŽůĂƌŝnjĂƟŽŶŽĨϱ͘ϱϮђĐŵ}ͲϮ _{at 250} DsŵͲϭ_{͘dŚŝƐƌĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌƐŚŽǁƐŐƌĞĂƚƐŝŵŝůĂƌŝƚLJǁŝƚŚƌĞƐƵůƚƐŽďƚĂŝŶĞĚĨŽƌ} ŽƚŚĞƌƌĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐƚĞƌƉŽůLJŵĞƌƐ͘ϱ͕ϴ͕ϮϬ͕ϯϵ

&ŽƌĞdžĂŵƉůĞ͕ĐŽŵƉĂƌĂďůĞƚŽW;s&-ter-dƌ&-ter-&Ϳ͕W;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10ͿĚĞŵŽŶƐƚƌĂƚĞƐĂĐŚĂƌŐĞͲĚŝƐĐŚĂƌŐĞĞĸĐŝĞŶĐLJŽĨ ϲϱйĂƚϭϱϬDsŵͲϭ_.52_{hŶĨŽƌƚƵŶĂƚĞůLJ͕ĐƵƌƌĞŶƚůLJĂǀĂŝůĂďůĞƌĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐƚĞƌƉŽůLJŵĞƌƐ} ƐƵīĞƌĨƌŽŵůĂƌŐĞĨĞƌƌŽĞůĞĐƚƌŝĐůŽƐƐĞƐĂƚŚŝŐŚĞƌĮĞůĚƐ͘dŽŵŝƟŐĂƚĞƚŚĞƐĞĐŽŶĐĞƌŶƐĂŶĚƚŽ

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: 119PDF page: 119PDF page: 119PDF page: 119

119

6

ĐŽŶƐĞƋƵĞŶƚůLJĞŶŚĂŶĐĞƚŚĞĐŚĂƌŐĞͲĚŝƐĐŚĂƌŐĞĞĸĐŝĞŶĐŝĞƐ͕ǁŚŝůĞŵĂŝŶƚĂŝŶŝŶŐƚŚĞůĂƌŐĞ ĚŝƐĐŚĂƌŐĞĞŶĞƌŐLJĚĞŶƐŝƟĞƐ͕ĨĞƌƌŽĞůĞĐƚƌŝĐĐƌLJƐƚĂůƐĂƌĞƌĞƋƵŝƌĞĚƚŽďĞǁĞůůŝƐŽůĂƚĞĚ͘5,15 _The ĐƌŽƐƐůŝŶŬŝŶŐŵĞƚŚŽĚŽĨƌĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐƉŽůLJŵĞƌƐŝŶƚƌŽĚƵĐĞĚŝŶƚŚŝƐǁŽƌŬĂƉƉĞĂƌƐ ƚŽďĞǀĞƌLJƉƌŽŵŝƐŝŶŐ͘ǀĞŶƚŚŽƵŐŚƚŚĞƌĞĚƵĐƟŽŶŝŶĐƌLJƐƚĂůůŝŶŝƚLJĂŶĚŝŶĐƌĞĂƐĞŝŶƚŚĞ ĂŵŽƵŶƚŽĨĐƌLJƐƚĂůƐŝŶƚŚĞĚŝƐŽƌĚĞƌĞĚƉĂƌĂĞůĞĐƚƌŝĐƉŚĂƐĞůŽǁĞƌƚŚĞŵĂdžŝŵƵŵƉŽůĂƌŝnjĂƟŽŶ ŽĨƚŚĞĐƌŽƐƐůŝŶŬĞĚŇƵŽƌŝŶĂƚĞĚƚĞƌƉŽůLJŵĞƌƐ͕ƚŚĞƌĞŵĂŶĞŶƚƉŽůĂƌŝnjĂƟŽŶŝƐĂůƐŽƌĞĚƵĐĞĚ ƐŝŐŶŝĮĐĂŶƚůLJĚƵĞƚŽďĞƩĞƌŝƐŽůĂƟŽŶŽĨĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶƐďLJĐŚĞŵŝĐĂůĐƌŽƐƐůŝŶŬŝŶŐ͘5 ƐƐƵĐŚ͕ƚŚĞW;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10ͿͲϬ͘ϱdžƐŚŽǁƐĂŵĂdžŝŵƵŵƉŽůĂƌŝnjĂƟŽŶŽĨϯ͘ϰϱ ђĐŵͲϮ_{ĂŶĚĂƌĞŵĂŶĞŶƚƉŽůĂƌŝnjĂƟŽŶĂƐůŽǁĂƐϬ͘ϭϱђĐŵ}ͲϮ_{ĂƚϮϲϬDsŵ}Ͳϭ_{͕ƌĞƐƉĞĐƟǀĞůLJ} ;&ŝŐƵƌĞϲ͘ϲĂŶĚdĂďůĞϲ͘ϮͿ͘dŚŝƐůĞĂĚƐƚŽŝŶĐƌĞĂƐĞĚĐŚĂƌŐĞͲĚŝƐĐŚĂƌŐĞĞĸĐŝĞŶĐŝĞƐĂƐĐůĞĂƌůLJ ǀŝƐƵĂůŝnjĞĚŝŶ&ŝŐƵƌĞϲ͘ϳ͘&ŽƌĞdžĂŵƉůĞ͕ĂƚϭϱϬDsŵͲϭ_͕W;s&

Ϭ͘ϱϯ-ter-dƌ&Ϭ͘ϯϳ-ter-s0.10ͿƐŚŽǁƐ ĂŶĞĸĐŝĞŶĐLJŽĨϲϯй͕ǁŚŝůĞƚŚŝƐŝŶĐƌĞĂƐĞĚƚŽϴϮйĨŽƌW;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10ͿͲ Ϭ͘Ϯϱdž͕ǁŚŝůĞďŽƚŚŚĂǀĞĂĚŝƐĐŚĂƌŐĞĞŶĞƌŐLJĚĞŶƐŝƚLJŽĨϮ:ĐŵͲϯ_{. Because these materials} ƐŚŽǁŐƌĞĂƚƉƌŽŵŝƐĞĨŽƌĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJƐƚŽƌĂŐĞĂƉƉůŝĐĂƟŽŶƐ͕ĨƵƚƵƌĞǁŽƌŬƐŚŽƵůĚďĞ ĚĞǀŽƚĞĚƚŽĞdžƉůŽƌŝŶŐƚŚĞĨƵůůƉŽƚĞŶƟĂůŽĨW;s&-ter-dƌ&-ter-sͿƚĞƌƉŽůLJŵĞƌƐ͕ŝŶĐůƵĚŝŶŐ ŽƉƟŵŝnjĂƟŽŶŽĨƚŚĞĐŽŵƉŽƐŝƟŽŶŽĨƚŚĞƚĞƌƉŽůLJŵĞƌƐ͕ĐŚŽŝĐĞŽĨĐƌŽƐƐůŝŶŬŝŶŐĂŐĞŶƚĂŶĚƚŽ ŐĂŝŶďĞƩĞƌŝŶƐŝŐŚƚƐŝŶƚŽƚŚĞŚŝŐŚĮůĞĚĚŝĞůĞĐƚƌŝĐůŽƐƐĂŶĚĨĂŝůƵƌĞŵĞĐŚĂŶŝƐŵƐ͘

Figure 6.6: D-E loops of (a) P(VDF_0.78-ter-TrFE_0.17-ter-VA_0.05) and (b) P(VDF_0.53-ter-TrFE_0.37-ter-VA_0.10) and the crosslinked samples.

dĂďůĞ ϲ͘Ϯ͗ DĂdžŝŵƵŵ ĂŶĚ ƌĞŵĂŶĞŶƚ ƉŽůĂƌŝnjĂƟŽŶ ŽĨ ƚŚĞ ;ĐƌŽƐƐůŝŶŬĞĚͿ W;s&ͲterͲdƌ&ͲterͲsͿ terpolymers used. Polymer P_ŵĂdž;ђĐŵͲϮ_{Ϳ P} ƌĞŵ;ђĐŵ ͲϮ_{Ϳ &ŝĞůĚ;Dsŵ}Ͳϭ_{Ϳ ɸ} ĂƉƉ W;s&_0.78Ͳdƌ&_0.17Ͳs_0.05Ϳ ϳ͘ϭϯ ϯ͘ϭϬ 250 20.0 W;s&Ϭ͘ϱϯͲdƌ&Ϭ͘ϯϳͲs0.10Ϳ 5.52 1.01 250 ϰϱ͘ϯ W;s&Ϭ͘ϱϯͲdƌ&Ϭ͘ϯϳͲs0.10ͿͲϬ͘ϭdž ϰ͘ϱϰ Ϭ͘ϯϳ ϮϲϬ ϯϬ͘ϲ W;s&_Ϭ͘ϱϯͲdƌ&_Ϭ͘ϯϳͲs_0.10ͿͲϬ͘Ϯϱdž ϰ͘Ϭϱ 0.25 ϮϲϬ 20.7 W;s&_Ϭ͘ϱϯͲdƌ&_Ϭ͘ϯϳͲs_0.10ͿͲϬ͘ϱdž ϯ͘ϰϱ 0.15 ϮϲϬ ϭϲ͘ϰ

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: 120PDF page: 120PDF page: 120PDF page: 120

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Conclusions

/ŶƚŚŝƐĐŚĂƉƚĞƌ͕ƚŚĞƐLJŶƚŚĞƐŝƐĂŶĚĐƌŽƐƐůŝŶŬŝŶŐŽĨĂŶŽǀĞůĐůĂƐƐŽĨW;s&-ter-dƌ&-ter-sͿƚĞƌƉŽůLJŵĞƌƐǁĞƌĞĚĞŵŽŶƐƚƌĂƚĞĚ͘dŚĞŝŶƚƌŽĚƵĐƟŽŶŽĨsƵŶŝƚƐŝŶƚŚĞƚĞƌƉŽůLJŵĞƌ ďĂĐŬďŽŶĞĚƌĂƐƟĐĂůůLJĐŚĂŶŐĞĚŝƚƐĐƌLJƐƚĂůůŝnjĂƟŽŶďĞŚĂǀŝŽƌĂŶĚůĞĂĚƐƚŽĂƌĞĚƵĐƟŽŶŽĨ ƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞĐŽŵƉĂƌĞĚƚŽW;s&-co-dƌ&ͿĐŽƉŽůLJŵĞƌĂŶĂůŽŐƵĞƐ͘ dŚĞW;s&_0.78-ter-dƌ&_0.17-ter-s_0.05ͿƚĞƌƉŽůLJŵĞƌŚĂǀŝŶŐĂƌĞůĂƟǀĞůLJůŽǁĐŽŶƚĞŶƚŽĨdƌ& ĂŶĚsĐƌLJƐƚĂůůŝnjĞƐŝŶƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐƉŚĂƐĞĂŶĚĚĞŵŽŶƐƚƌĂƚĞƐĨĞƌƌŽĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌ͘ /Ŷ ĐŽŶƚƌĂƐƚ͕ ƉƌŝƐƟŶĞ W;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10Ϳ ĐƌLJƐƚĂůůŝnjĞƐ ŝŶ Ă ŵŝdžƚƵƌĞ ŽĨ ƚŚĞ ĨĞƌƌŽĞůĞĐƚƌŝĐ ĂŶĚ ƉĂƌĂĞůĞĐƚƌŝĐ ƉŚĂƐĞƐ ƌĞƐƵůƟŶŐ ŝŶ ŶĂƌƌŽǁ ŚLJƐƚĞƌĞƐŝƐ ďĞŚĂǀŝŽƌ ǁŝƚŚ Ă ŵĂdžŝŵƵŵĂŶĚƌĞŵĂŶĞŶƚƉŽůĂƌŝnjĂƟŽŶŽĨϱ͘ϱϮђĐŵͲϮ_{ĂŶĚϭ͘ϬϭђĐŵ}ͲϮ_{͕ƌĞƐƉĞĐƟǀĞůLJ͘} /Ŷ ĂĚĚŝƟŽŶ͕ ĐŚĞŵŝĐĂůůLJ ĐƌŽƐƐůŝŶŬŝŶŐ ŽĨ W;s&_Ϭ͘ϱϯ-ter-dƌ&_Ϭ͘ϯϳ-ter-s_0.10Ϳ ƚĞƌƉŽůLJŵĞƌƐ ƵƐŝŶŐƵƌĞƚŚĂŶĞĐŚĞŵŝƐƚƌLJƉƌŽŵŽƚĞƐƚŚĞĐƌLJƐƚĂůůŝnjĂƟŽŶŝŶƚŚĞƉĂƌĂĞůĞĐƚƌŝĐƉŚĂƐĞĂŶĚ ƚŚĞĨŽƌŵĂƟŽŶŽĨƐŵĂůůŶĂŶŽĐƌLJƐƚĂůƐŐŝǀŝŶŐƵůƚƌĂƐůŝŵŚLJƐƚĞƌĞƐŝƐůŽŽƉƐǁŝƚŚƌĞŵĂŶĞŶƚ ƉŽůĂƌŝnjĂƟŽŶƐĂƐůŽǁĂƐϬ͘ϭϱђĐŵͲϮ_{͘dŚĞůŽǁƌĞŵĂŶĞŶƚƉŽůĂƌŝnjĂƟŽŶůĞĂĚƐƚŽŝŶĐƌĞĂƐĞĚ} ĞĸĐŝĞŶĐŝĞƐĨŽƌƚŚĞƚĞƌƉŽůLJŵĞƌƐĚƵĞƚŽĂƌĞĚƵĐƟŽŶŽĨĨĞƌƌŽĞůĞĐƚƌŝĐůŽƐƐ͕ǁŚŝůĞŵĂŝŶƚĂŝŶŝŶŐ ƐŝŵŝůĂƌĚŝƐĐŚĂƌŐĞĚĞŶĞƌŐLJĚĞŶƐŝƟĞƐ͘^ŝŶĐĞĐƌŽƐƐůŝŶŬŝŶŐƌĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐƚĞƌƉŽůLJŵĞƌƐ ƐŚŽǁŐƌĞĂƚƉƌŽŵŝƐĞĨŽƌĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJƐƚŽƌĂŐĞĂƉƉůŝĐĂƟŽŶƐ͕ĞƐƉĞĐŝĂůůLJĚƵĞƚŽƚŚĞůĂƌŐĞ ŝŶĐƌĞĂƐĞŝŶĞĸĐŝĞŶĐŝĞƐ͕ĨƵƚƵƌĞǁŽƌŬƐŚŽƵůĚďĞĚĞǀŽƚĞĚƚŽĞdžƉůŽƌŝŶŐƚŚĞĨƵůůƉŽƚĞŶƟĂůŽĨ W;s&-ter-dƌ&-ter-sͿƚĞƌƉŽůLJŵĞƌƐ͕ŝŶĐůƵĚŝŶŐŽƉƟŵŝnjĂƟŽŶŽĨƚŚĞĐŽŵƉŽƐŝƟŽŶĂŶĚŐĂŝŶ insights in the dielectric loss and failure mechanisms.

Figure 6.7: 8LIHMWGLEVKIHIRIVK]HIRWMXMIWERHGLEVKIHMWGLEVKIIƾGMIRGMIWSJ4:(*_0.53

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: 121PDF page: 121PDF page: 121PDF page: 121

121

6

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