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 5

*PYSVMREXIHTSP]QIVRIX[SVOWYWMRKYVIXLERIFEWIH

crosslinOMRK

ƌŽƐƐůŝŶŬŝŶŐŽĨƉŽůĂƌŇƵŽƌŝŶĂƚĞĚƉŽůLJŵĞƌƐ͕ƐƵĐŚĂƐƉŽůLJ;ǀŝŶLJůŝĚĞŶĞŇƵŽƌŝĚĞͿ;Ws&ͿĂŶĚŝƚƐ ĐŽƉŽůLJŵĞƌƐ͕ĂƌĞƌĞĐĞŝǀŝŶŐĐŽŶƐŝĚĞƌĂďůĞƌĞƐĞĂƌĐŚĂƩĞŶƟŽŶĨŽƌĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJƐƚŽƌĂŐĞ ĂƉƉůŝĐĂƟŽŶƐĚƵĞƚŽƚŚĞŝƌŚŝŐŚƉŽůĂƌŝnjĂƟŽŶĂŶĚůĂƌŐĞďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚ͘EŽǁĂĚĂLJƐ͕ ŵĞƚŚŽĚƐƚŽĐŚĞŵŝĐĂůůLJĐƌŽƐƐůŝŶŬWs&ͲďĂƐĞĚŵĂƚĞƌŝĂůƐƚŽĂĐŚŝĞǀĞŚŝŐŚĞƌĞŶĞƌŐLJĚĞŶƐŝƟĞƐ ǁŝƚŚŝŶĐƌĞĂƐĞĚĞĸĐŝĞŶĐŝĞƐĂƌĞůŝŵŝƚĞĚĂŶĚŽŌĞŶƌĞƋƵŝƌĞĞdžƚĞƌŶĂůƉƌŽĐĞƐƐŝŶŐĞƋƵŝƉŵĞŶƚ͘ To overcome this problem, we demonstrate a new approach by introducing vinyl alcohol ;sͿƵŶŝƚƐŝŶƚŚĞWs&ďĂĐŬďŽŶĞƚŚĂƚĐĂŶĞĂƐŝůLJďĞĐƌŽƐƐůŝŶŬĞĚƵƐŝŶŐƵƌĞƚŚĂŶĞĐŚĞŵŝƐƚƌLJ͘ By increasing the degree of crosslinker, a change from ferroelectric to double hysteresis ůŽŽƉĂŶĚůŝŶĞĂƌĚŝĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌŝƐŽďƐĞƌǀĞĚ͘/ŶĂĚĚŝƟŽŶ͕ƚŚĞďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚĂŶĚ ƌĞůŝĂďŝůŝƚLJŽĨƚŚĞŶĞƚǁŽƌŬƐĂƌĞƐŝŐŶŝĮĐĂŶƚůLJŝŶĐƌĞĂƐĞĚĂŌĞƌĐƌŽƐƐůŝŶŬŝŶŐ͕ǁŚŝĐŚŝƐƌĞŇĞĐƚĞĚ ŝŶƚŚĞůĂƌŐĞƌƐƚŽƌĞĚĂŶĚĚŝƐĐŚĂƌŐĞĚĞŶĞƌŐLJĚĞŶƐŝƟĞƐ͘^ŝŶĐĞƚŚĞĐƌŽƐƐůŝŶŬĞĚƐĂŵƉůĞƐƐŚŽǁ ƐůŝŵŵĞƌƉŽůĂƌŝnjĂƟŽŶ͕ŚŝŐŚĞƌĐŚĂƌŐĞͲĚŝƐĐŚĂƌŐĞĞĸĐŝĞŶĐŝĞƐĂƌĞŽďƐĞƌǀĞĚ͘dŚĞƌĞĨŽƌĞ͕ƚŚŝƐ ǁŽƌŬĚĞŵŽŶƐƚƌĂƚĞƐĂƐŝŵƉůĞƐŽůƵƟŽŶƉƌŽĐĞƐƐŝŶŐŵĞƚŚŽĚĂŶĚƐƚƌĂŝŐŚƞŽƌǁĂƌĚƵƌĞƚŚĂŶĞ ĐŚĞŵŝƐƚƌLJ ƚŽ ĐƌŽƐƐůŝŶŬ W;s&-co-sͿ͕ ƐŚŽǁŝŶŐ ŚŝŐŚ ƉŽƚĞŶƟĂů ĨŽƌ ƚŚĞ ƉƌĞƉĂƌĂƟŽŶ ŽĨ ĚŝĞůĞĐƚƌŝĐŵĂƚĞƌŝĂůƐǁŝƚŚŚŝŐŚĞŶĞƌŐLJĚĞŶƐŝƚLJĂŶĚŝŵƉƌŽǀĞĚĞĸĐŝĞŶĐŝĞƐ͕ǁŚŝůĞƉƌŽǀŝĚŝŶŐ ƵƐĞĨƵůŝŶƐŝŐŚƚƐŝŶƚŚĞĐƌLJƐƚĂůůŝnjĂƟŽŶďĞŚĂǀŝŽƌĨŽƌĮŶĞƚƵŶŝŶŐƚŚĞWs&ĐƌLJƐƚĂůƐĨŽƌĨƵƌƚŚĞƌ ĚĞǀĞůŽƉŵĞŶƚŝŶƚŚŝƐĮĞůĚ͘

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: 88PDF page: 88PDF page: 88PDF page: 88

88

Introduction

ZĞŶĞǁĂďůĞĞŶĞƌŐLJƉŽǁĞƌĐŽŶǀĞƌƚĞƌƐ͕ĞůĞĐƚƌŝĐǀĞŚŝĐůĞƐĂŶĚƉƵůƐĞĚƉŽǁĞƌĂƉƉůŝĐĂƟŽŶƐĂƌĞ ŽŶůLJĂĨĞǁŽĨŵĂŶLJĞdžĂŵƉůĞƐƚŚĂƚƌĞƋƵŝƌĞƚŚĞŝŵƉůĞŵĞŶƚĂƟŽŶŽĨƉŽůLJŵĞƌĮůŵƐĚŝĞůĞĐƚƌŝĐƐ with high energy output and low dielectric loss.ϭʹϰ_{/ŶƉĂƌƟĐƵůĂƌ͕ƚŚĞŝƌƐĞůĨͲŚĞĂůŝŶŐĐĂƉĂĐŝƚLJ}

ĂŶĚƐƚĂďůĞĐĂƉĂĐŝƚĂŶĐĞŽǀĞƌůŽŶŐƟŵĞƉĞƌŝŽĚƐ͕ǁŚŝůĞďĞŝŶŐĞĂƐŝůLJƉƌŽĐĞƐƐĂďůĞĂŶĚĐŚĞĂƉ͕ ŽīĞƌƉŽůLJŵĞƌƐŵĂũŽƌĂĚǀĂŶƚĂŐĞƐŽǀĞƌ͕ĨŽƌĞdžĂŵƉůĞ͕ĐĞƌĂŵŝĐƐ͘ϱʹϳ_{dŚĞĐƵƌƌĞŶƚƐƚĂƚĞͲŽĨͲ}

ƚŚĞͲĂƌƚŵĂƚĞƌŝĂů͕ďŝĂdžŝĂůůLJŽƌŝĞŶƚĞĚƉŽůLJƉƌŽƉLJůĞŶĞ͕ƐŚŽǁƐƵůƚƌĂůŽǁĚŝĞůĞĐƚƌŝĐůŽƐƐ͕ĞǀĞŶ ĂƚŚŝŐŚĞůĞĐƚƌŝĐĮĞůĚƐ͘,ŽǁĞǀĞƌ͕ƚŚĞƐƚŽƌĞĚĂŶĚƌĞůĞĂƐĞĚĞŶĞƌŐLJĚĞŶƐŝƚLJ;ΕϮ:ĐŵͲϯ _at

ϰϬϬDsŵͲϭ_{ͿŽĨƚŚŝƐŵĂƚĞƌŝĂůĂƌĞůŝŵŝƚĞĚĚƵĞƚŽƚŚĞůŽǁĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚ͘}8,9 _{For linear}

dielectrics, the dielectric constant (ɸͿĂŶĚƚŚĞďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚŽĨƚŚĞŵĂƚĞƌŝĂůĂƌĞ ŬĞLJĨĂĐƚŽƌƐĚĞƚĞƌŵŝŶŝŶŐƚŚĞĚĞǀŝĐĞƉĞƌĨŽƌŵĂŶĐĞ͕ĂƐĚŝƐƉůĂLJĞĚŝŶƋƵĂƟŽŶϱ͘ϭ͕ǁŚĞƌĞŝŶ ɸ₀ŝƐƚŚĞƉĞƌŵŝƫǀŝƚLJŝŶĨƌĞĞƐƉĂĐĞ͕ĂŶĚE ŝƐƚŚĞĂƉƉůŝĞĚĞůĞĐƚƌŝĐĮĞůĚ͘ϰ  ;ϱ͘ϭͿ dŚĞƌĞĨŽƌĞ͕ĚƵĞƚŽŝƚƐŚŝŐŚĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚ;ΕϭϬͿĂŶĚĚŝĞůĞĐƚƌŝĐďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚ ;ΕϲϬϬDsŵͲϭ_{Ϳ͕ƐĞŵŝͲĐƌLJƐƚĂůůŝŶĞƉŽůLJ;ǀŝŶLJůŝĚĞŶĞŇƵŽƌŝĚĞͿ;Ws&ͿŝƐŽĨƉĂƌƟĐƵůĂƌŝŶƚĞƌĞƐƚ} ĨŽƌĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJƐƚŽƌĂŐĞĂƉƉůŝĐĂƟŽŶƐ͘ϰ͕ϭϬ͕ϭϭ_{,ŽǁĞǀĞƌ͕ǁŚĞŶĂƉƉůLJŝŶŐĂŚŝŐŚĞůĞĐƚƌŝĐ} ĮĞůĚƚŽWs&͕ƚŚĞĐƌLJƐƚĂůůŝŶĞɲͲƉŚĂƐĞǁŝƚŚĂnjĞƌŽŶĞƚĚŝƉŽůĞŵŽŵĞŶƚƚƌĂŶƐĨŽƌŵƐƚŽ ƚŚĞɴͲƉŚĂƐĞ͕ƌĞƐƵůƟŶŐŝŶůĂƌŐĞĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶƐƚŚĂƚƌĞĚƵĐĞƐŝƚƐĐŚĂƌŐĞͲĚŝƐĐŚĂƌŐĞ ĞĸĐŝĞŶĐLJ͘12 _{Nevertheless, the stored energy density enormously increases due to the}

ŶŽŶůŝŶĞĂƌďĞŚĂǀŝŽƌŽĨƚŚĞƉŽůĂƌŝnjĂƟŽŶĂƐĂĨƵŶĐƟŽŶŽĨƚŚĞĞůĞĐƚƌŝĐĮĞůĚ͘/ŶŽƌĚĞƌƚŽƌĞĚƵĐĞ ƚŚĞĞŶĞƌŐLJůŽƐƐĚƵĞƚŽůĂƌŐĞĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶĨŽƌŵĂƟŽŶ͕ĐŽͲĂŶĚƚĞƌƉŽůLJŵĞƌŝnjĂƟŽŶƐŽĨ s&ǁŝƚŚďƵůŬŝĞƌĐŽŵŽŶŽŵĞƌƐ;e.g.ƚƌŝŇƵŽƌŽĞƚŚLJůĞŶĞ;dƌ&Ϳ͕ŚĞdžĂŇƵŽƌŽƉƌŽƉLJůĞŶĞ;,&WͿ͕ ĐŚůŽƌŽƚƌŝŇƵŽƌŽĞƚŚLJůĞŶĞ;d&ͿĂŶĚĐŚůŽƌŽŇƵŽƌŽĞƚŚLJůĞŶĞ;&ͿͿŚĂǀĞďĞĞŶĞŵƉůŽLJĞĚƚŽ ŝŶƚƌŽĚƵĐĞĚĞĨĞĐƚƐŝŶƚŚĞƉŽůLJŵĞƌďĂĐŬďŽŶĞĂŶĚƚŽŝŶĐƌĞĂƐĞƚŚĞĐƌLJƐƚĂůůĂƫĐĞƐƉĂĐŝŶŐĨŽƌ enhancing the dipole reversibility.ϭϯʹϭϵ_{dŚĞǁĞĂŬ;ŝŶW;s&-ter-dƌ&-ter-&ͿͿĂŶĚƐƚƌŽŶŐ}

;ŝŶW;s&-ter-dƌ&-ter-d&ͿͿƐŽͲĐĂůůĞĚƉŚLJƐŝĐĂůƉŝŶŶŝŶŐƐƉŽƚƐƌĞƐƵůƚŝŶĂŶƟĨĞƌƌŽĞůĞĐƚƌŝĐͲ ůŝŬĞĂŶĚƌĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌ͕ƌĞƐƉĞĐƟǀĞůLJ͕ŝŶĐƌĞĂƐŝŶŐƚŚĞĐŚĂƌŐĞͲĚŝƐĐŚĂƌŐĞ ĞĸĐŝĞŶĐLJǁŚŝůĞƐƟůůŚĂǀŝŶŐĂŚŝŐŚƉŽůĂƌŝnjĂƟŽŶ͘20_{/ŶƚĞƌĞƐƟŶŐůLJ͕ĐŚĞŵŝĐĂůĐƌŽƐƐůŝŶŬŝŶŐ}

via ĞůĞĐƚƌŽŶ ďĞĂŵ ŝƌƌĂĚŝĂƟŽŶ ŽĨ W;s&-co-dƌ&Ϳ Žƌ ŚŽƚ ƉƌĞƐƐŝŶŐ ŽĨ W;s&-co-d&Ϳ ƵƐŝŶŐƉĞƌŽdžŝĚĞƐĂŶĚĐƌŽƐƐůŝŶŬŝŶŐĂŐĞŶƚƐƉƌŽǀĞƚŽďĞǀĂůƵĂďůĞŵĞƚŚŽĚƐƚŽĂĐŚŝĞǀĞƐůŝŵ ƉŽůĂƌŝnjĂƟŽŶŚLJƐƚĞƌĞƐŝƐ͘ϮϭʹϮϯ _{Unfortunately, as a result of chain scission and structural}

ĚĞĨŽƌŵĂƟŽŶƐŶŽŝŶĐƌĞĂƐĞŝŶďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚŽĨƚŚĞŝƌƌĂĚŝĂƚĞĚƉŽůLJŵĞƌŝƐŽďƐĞƌǀĞĚ͕ ǁŚĞƌĞĂƐ ŚŽƚ ƉƌĞƐƐĞĚ ĐƌŽƐƐůŝŶŬĞĚ W;s&-co-d&Ϳ ƐŚŽǁƐ ĂŶ ŝŶĐƌĞĂƐĞ ŝŶ ŝƚƐ ĞůĞĐƚƌŝĐĂů ƐƚƌĞŶŐƚŚ͘,ŽǁĞǀĞƌ͕ŝŶďŽƚŚĐĂƐĞƐĞdžƚĞƌŶĂůƉƌŽĐĞƐƐŝŶŐĞƋƵŝƉŵĞŶƚŝƐƌĞƋƵŝƌĞĚ͕ŵĂŬŝŶŐƚŚĞ ƉƌŽĚƵĐƟŽŶƉƌŽĐĞƐƐƌĂƚŚĞƌĞdžƉĞŶƐŝǀĞ͘dŚĞƌĞĨŽƌĞ͕ŶŽǀĞůƐƚƌĂƚĞŐŝĞƐƚŽƉĞƌĨŽƌŵĐŚĞŵŝĐĂů ĐƌŽƐƐůŝŶŬŝŶŐŽĨŇƵŽƌŝŶĂƚĞĚƉŽůLJŵĞƌƐƵƐŝŶŐŵŝůĚĐƌŽƐƐůŝŶŬŝŶŐĐŽŶĚŝƟŽŶƐĂƌĞĞƐƐĞŶƟĂůĨŽƌ

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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89

5

ƚŚĞĚĞǀĞůŽƉŵĞŶƚŽĨĚŝĞůĞĐƚƌŝĐŵĂƚĞƌŝĂůƐǁŝƚŚŚŝŐŚĐŚĂƌŐĞͲĚŝƐĐŚĂƌŐĞĞĸĐŝĞŶĐŝĞƐĂŶĚůĂƌŐĞ

dielectric breakdown strength.

hƐŝŶŐ ĨƵŶĐƟŽŶĂů ŵŽŶŽŵĞƌƐ ƚŽ ĐŽƉŽůLJŵĞƌŝnjĞ s& ĂůůŽǁƐ ĐŽŶƚƌŽů ŽǀĞƌ ƚŚĞ ƐƉĂƟĂů ĚŝƐƚƌŝďƵƟŽŶŽĨƚŚĞĐŽŵŽŶŽŵĞƌƐŝŶƚŚĞƉŽůLJŵĞƌďĂĐŬďŽŶĞ͕ǁŚŝůĞŚĂǀŝŶŐĞĂƐLJĐƌŽƐƐůŝŶŬĂďůĞ ĨƵŶĐƟŽŶĂůŐƌŽƵƉƐ͘ϮϰʹϮϲ _{In this way, strong changes in the materials color or chain scission}

ĐĂƵƐĞĚďLJĚĞŚLJĚƌŽŇƵŽƌŝŶĂƟŽŶƉƌŽĐĞƐƐĞƐĂŶĚŚŝŐŚŝƌƌĂĚŝĂƟŽŶĚŽƐĞƐ͕ƌĞƐƉĞĐƟǀĞůLJ͕ĂƌĞ ĂǀŽŝĚĞĚƐŚŽǁŝŶŐƚŚĞŶĞĞĚĨŽƌĨĂĐŝůĞĂƉƉƌŽĂĐŚĞƐƚŽĐŚĞŵŝĐĂůůLJĐƌŽƐƐůŝŶŬWs&͘ZĞĐĞŶƚůLJ͕ ǁĞƐŚŽǁĞĚƚŚĂƚs&ĐĂŶďĞĐŽƉŽůLJŵĞƌŝnjĞĚƵƐŝŶŐĐŚĞĂƉǀŝŶLJůĂĐĞƚĂƚĞ;sĐͿŵŽŶŽŵĞƌƐ ĨŽůůŽǁĞĚďLJƚŚĞƐƵĐĐĞƐƐĨƵůŚLJĚƌŽůLJƐŝƐƚŽǀŝŶLJůĂůĐŽŚŽů;sͿLJŝĞůĚŝŶŐĨĞƌƌŽĞůĞĐƚƌŝĐW;s&-co-sͿĐŽƉŽůLJŵĞƌƐ͘27_{/ŶƚŚĞƐĞĐŽƉŽůLJŵĞƌƐ͕ƚŚĞŚLJĚƌŽdžLJůĨƵŶĐƟŽŶĂůŝƟĞƐĂƌĞǁĞůůĚŝƐƚƌŝďƵƚĞĚ} ŽǀĞƌƚŚĞƉŽůLJŵĞƌďĂĐŬďŽŶĞ͕ǁŚŝůĞŽīĞƌŝŶŐĞĂƐLJŽƉƉŽƌƚƵŶŝƟĞƐƚŽƚĂŝůŽƌƚŚĞƉƌŽƉĞƌƟĞƐ͕ e.g. viaĐŚĞŵŝĐĂůĐƌŽƐƐůŝŶŬŝŶŐ͘/ŶƚĞƌĞƐƟŶŐůLJ͕ƚŚĞĚĞŐƌĞĞŽĨĐƌLJƐƚĂůůŝŶŝƚLJŝŶƚŚĞW;s&-co-sͿĐŽƉŽůLJŵĞƌƐŝƐƌĞĚƵĐĞĚĐŽŵƉĂƌĞĚƚŽW;s&-co-dƌ&ͿƌĞƐƵůƟŶŐŝŶĂůŽǁĞƌƌĞŵĂŶĞŶƚ ƉŽůĂƌŝnjĂƟŽŶĂŶĚŝŵƉƌŽǀĞĚĐŚĂƌŐĞͲĚŝƐĐŚĂƌŐĞĞĸĐŝĞŶĐŝĞƐ͘ƐŽƉƉŽƐĞĚƚŽĐŽƉŽůLJŵĞƌŝnjĂƟŽŶƐ ǁŝƚŚĞdžƉĞŶƐŝǀĞŇƵŽƌŝŶĂƚĞĚŵŽŶŽŵĞƌƐŽƌƚŚĞƵƐĞŽĨĞdžƉĞŶƐŝǀĞƉƌŽĐĞƐƐŝŶŐƚĞĐŚŶŝƋƵĞƐ͕ ůĂƌŐĞƐĐĂůĞĂƉƉůŝĐĂƟŽŶƐƌĞƋƵŝƌĞĐŚĞĂƉƌĞƐŽƵƌĐĞƐĂŶĚĨĂĐŝůĞƉƌŽĐĞƐƐŝŶŐŵĞƚŚŽĚƐ͕ŵĂŬŝŶŐ sĐĂƐƉƌĞĐƵƌƐŽƌĂŶĚŝƐŽĐLJĂŶĂƚĞƐĂƐĐƌŽƐƐůŝŶŬŝŶŐĂŐĞŶƚƐĞĐŽŶŽŵŝĐĂůůLJŵŽƌĞĨĞĂƐŝďůĞ͘ dŚĞƌĞĨŽƌĞ͕ ŝŶ ƚŚŝƐ ǁŽƌŬ͕ ǁĞ ƌĞƉŽƌƚ ƚŚĞ ĐƌŽƐƐůŝŶŬŝŶŐ ŽĨ ĞĂƐŝůLJ ƉƌĞƉĂƌĞĚ W;s&-co-sͿ ĐŽƉŽůLJŵĞƌƐƵƐŝŶŐƐŝŵƉůĞƵƌĞƚŚĂŶĞĐŚĞŵŝƐƚƌLJĂŶĚŝŶǀĞƐƟŐĂƚĞŝƚƐŚŝŐŚͲĮĞůĚĞůĞĐƚƌŽĂĐƟǀĞ ƉƌŽƉĞƌƟĞƐ͕ƐŚŽǁŝŶŐŝŶĐƌĞĂƐĞĚĞĸĐŝĞŶĐŝĞƐ͕ĚŝƐĐŚĂƌŐĞĚĞŶĞƌŐLJĚĞŶƐŝƟĞƐĂŶĚĚŝĞůĞĐƚƌŝĐ breakdown strength.

Materials and Methods

Experimental

Materials:WŽůLJ;ǀŝŶLJůŝĚĞŶĞŇƵŽƌŝĚĞ-co-ǀŝŶLJůĂůĐŽŚŽůͿ;W;s&-co-sͿͿ͕ĐŽŶƚĂŝŶŝŶŐϭϱŵŽůй vinyl alcohol, was prepared as previously reported.27_{,ĞdžĂŵĞƚŚLJůĞŶĞĚŝŝƐŽĐLJĂŶĂƚĞ;,D/͕}

d/͕ϵϴйͿĂŶĚĐLJĐůŽƉĞŶƚĂŶŽŶĞǁĞƌĞƵƐĞĚĂƐƌĞĐĞŝǀĞĚ͘ &ŝůŵƉƌĞƉĂƌĂƟŽŶ͗W;s&-co-sͿ;ϰϬŵŐ͕Ϭ͘ϬϰϵŵŵŽůsͿĂŶĚ,D/;Ϭϱ͕ϰ͘ϮŵŐ͕ Ϭ͘ϬϮϱŵŵŽů͖ϭϴ͘ϯŵŐ͕Ϭ͘ϬϰϵŵŵŽů͖ϮϬ͕ϭϲϱ͘ϭŵŐ͕Ϭ͘ϵϴŵŵŽůͿǁĞƌĞĐŽŵďŝŶĞĚŝŶϭ͘ϱ ŵ>ĐLJĐůŽƉĞŶƚĂŶŽŶĞĂŶĚĂůůŽǁĞĚƚŽŵŝdžĂƚϴϬΣĨŽƌϯϬŵŝŶ͘ŌĞƌĐŽŽůŝŶŐĚŽǁŶƚŽƌŽŽŵ ƚĞŵƉĞƌĂƚƵƌĞ͕ƚŚĞƐŽůƵƟŽŶǁĂƐƉĂƐƐĞĚƚŚƌŽƵŐŚĂϬ͘ϰϱђŵWd&ĮůƚĞƌŝŶƚŽĂŶĂůƵŵŝŶƵŵƉĂŶ ;ƆϯŵŵͿ͘WƌŝƐƟŶĞW;s&-co-sͿǁĂƐͲĂŌĞƌĚŝƐƐŽůǀŝŶŐŝŶĐLJĐůŽƉĞŶƚĂŶŽŶĞ;ϰϬŵŐŝŶϭ͘ϱŵ>Ϳ ͲĚŝƌĞĐƚůLJƚƌĂŶƐĨĞƌƌĞĚƚŽĂŶĂůƵŵŝŶƵŵƉĂŶƵƐŝŶŐĂϬ͘ϰϱђŵWd&ĮůƚĞƌ͘dŚĞĂůƵŵŝŶƵŵƉĂŶ ǁĂƐƚƌĂŶƐĨĞƌƌĞĚƚŽĂŚĞĂƟŶŐƉůĂƚĞƐĞƚĂƚϭϯϬΣƚŽŝŶĚƵĐĞĐƌŽƐƐůŝŶŬŝŶŐĂŶĚĞǀĂƉŽƌĂƟŽŶŽĨ ƐŽůǀĞŶƚ͘dŚĞŶĞdžƚĚĂLJ͕ƚŚĞ;ĐƌŽƐƐůŝŶŬĞĚͿƐĂŵƉůĞƐǁĞƌĞŚĞĂƚĞĚƚŽϭϲϬΣƚŽĞƌĂƐĞƚŚĞƌŵĂů ŚŝƐƚŽƌLJĂŶĚƐƵďƐĞƋƵĞŶƚůLJƋƵĞŶĐŚĞĚĂƚƌŽŽŵƚĞŵƉĞƌĂƚƵƌĞ͘^ƵďƐĞƋƵĞŶƚůLJ͕ΕϭϱђŵƚŚŝĐŬ

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: 90PDF page: 90PDF page: 90PDF page: 90

90

ĨƌĞĞͲƐƚĂŶĚŝŶŐĮůŵƐǁĞƌĞŽďƚĂŝŶĞĚviaĂůŝŌͲŽīŵĞƚŚŽĚŝŶǁĂƚĞƌ͘ůůƐĂŵƉůĞƐǁĞƌĞĚƌŝĞĚ ŽǀĞƌŶŝŐŚƚƵŶĚĞƌǀĂĐƵƵŵĂƚϲϬ϶͘

Characterization

Fourier transform infrared spectroscopy (FTIR):dŚĞ&d/ZƐƉĞĐƚƌĂŽĨƚŚĞĐŽƉŽůLJŵĞƌƐǁĞƌĞ ƌĞĐŽƌĚĞĚŽŶĂƌƵŬĞƌsĞƌƚĞdžϳϬƐƉĞĐƚƌŽƉŚŽƚŽŵĞƚĞƌƵƐŝŶŐϯϮƐĐĂŶƐĂƚĂŶŽŵŝŶĂůƌĞƐŽůƵƟŽŶ ŽĨϰĐŵͲϭ_{ƵƐŝŶŐĂĚŝĂŵŽŶĚƐŝŶŐůĞƌĞŇĞĐƟŽŶĂƩĞŶƵĂƚĞĚƚŽƚĂůƌĞŇĞĐƚĂŶĐĞ;dZͿ͘}

ŝīĞƌĞŶƟĂů^ĐĂŶŶŝŶŐĂůŽƌŝŵĞƚƌLJ;^Ϳ͗^ƚŚĞƌŵŽŐƌĂŵƐǁĞƌĞƌĞĐŽƌĚĞĚŽŶĂd /ŶƐƚƌƵŵĞŶƚƐ^YϭϬϬϬ͘dŚĞŚĞĂƟŶŐĂŶĚĐŽŽůŝŶŐƌĂƚĞǁĂƐƐĞƚƚŽďĞϭϬΣŵŝŶͲϭ_.

tŝĚĞͲĂŶŐůĞ yͲƌĂLJ ƐĐĂƩĞƌŝŶŐ ;ty^Ϳ͗ ty^ ŵĞĂƐƵƌĞŵĞŶƚƐ ǁĞƌĞ ƉĞƌĨŽƌŵĞĚ Ăƚ ďĞĂŵůŝŶĞDϮϲĂƚƚŚĞƵƌŽƉĞĂŶ^LJŶĐŚƌŽƚƌŽŶZĂĚŝĂƟŽŶ&ĂĐŝůŝƚLJ;^Z&ͿŝŶ'ƌĞŶŽďůĞ ǁŝƚŚĂǁĂǀĞůĞŶŐƚŚʄсϬ͘ϵϳ͘dŚĞty^ƉĂƩĞƌŶǁĂƐĂĐƋƵŝƌĞĚŽǀĞƌĂƟŵĞŝŶƚĞƌǀĂůŽĨϯϬ ƐĞĐŽŶĚƐƵƐŝŶŐĂWŝůĂƚƵƐϯϬϬ<ĚĞƚĞĐƚŽƌ;ϭϰϳϮпϭϵϱƉŝdžĞůƐŽĨϭϳϮʅŵпϭϳϮʅŵƉůĂĐĞĚĂƚ ĂĚŝƐƚĂŶĐĞŽĨϬ͘Ϯϴŵ͘dŚĞƐĐĂƩĞƌŝŶŐǀĞĐƚŽƌƋŝƐĚĞĮŶĞĚĂƐq сϰʋͬʄ(sin ɽͿǁŝƚŚϮɽďĞŝŶŐ ƚŚĞƐĐĂƩĞƌŝŶŐĂŶŐůĞ͘dŚĞĐƌLJƐƚĂůůŝƚĞƐŝnjĞ͕͕ŝƐĚĞƚĞƌŵŝŶĞĚƵƐŝŶŐƚŚĞ^ĐŚĞƌƌĞƌĞƋƵĂƟŽŶ͕ с<Ϯʋͬq_fwhm͕ǁŝƚŚ<ďĞŝŶŐƚŚĞ^ĐŚĞƌƌĞƌĐŽŶƐƚĂŶƚ;Ϭ͘ϵϰͿ28 _{and q}

fwhm being the full width

ĂƚŚĂůĨͲŵĂdžŝŵƵŵŽĨƚŚĞ;ϭϭϬͬϮϬϬͿ_ɴ peak.

ŝƐƉůĂĐĞŵĞŶƚʹůĞĐƚƌŝĐ&ŝĞůĚ;ͲͿŵĞĂƐƵƌĞŵĞŶƚƐ͗ Ͳ loops were obtained using a ƐƚĂƚĞͲŽĨͲƚŚĞͲĂƌƚĂŝdždd&ϮϬϬϬĨĞƌƌŽĞůĞĐƚƌŝĐƚĞƐƚĞƌǁŚĞƌĞĞůĞĐƚƌŝĐĮĞůĚƐ;ƵƉƚŽϭϬ ŬsͿǁĞƌĞĂƉƉůŝĞĚĂĐƌŽƐƐƚŚĞƉŽůLJŵĞƌĮůŵƐǁŝƚŚĂƚƌŝĂŶŐƵůĂƌǁĂǀĞĨŽƌŵĂƚĂĨƌĞƋƵĞŶĐLJ ŽĨϭϬ,nj͘ƌĞĂŬĚŽǁŶŵĞĂƐƵƌĞŵĞŶƚƐǁĞƌĞƉĞƌĨŽƌŵĞĚďLJŝŶĐƌĞĂƐŝŶŐƚŚĞĞůĞĐƚƌŝĐĮĞůĚ ŝƚĞƌĂƟǀĞůLJĚŽŝŶŐƵŶŝƉŽůĂƌůŽŽƉƐƵŶƟůƚŚĞƐĂŵƉůĞǁĂƐďƌŽŬĞŶ͘ŚƌŽŵŝƵŵ;ϱŶŵͿͬŐŽůĚ ;ϭϬϬŶŵͿĞůĞĐƚƌŽĚĞƐǁŝƚŚĂĚŝĂŵĞƚĞƌŽĨϮŵŵǁĞƌĞĚĞƉŽƐŝƚĞĚŽŶďŽƚŚƐŝĚĞƐŽĨW;s&-co-sͿĐŽƉŽůLJŵĞƌ;ĐƌŽƐƐůŝŶŬĞĚͿĮůŵƐďLJǀĂƉŽƌĚĞƉŽƐŝƟŽŶ͘ŚƌŽŵŝƵŵǁĂƐƵƐĞĚŽŶůLJĂƐ ĂĚŚĞƐŝŽŶůĂLJĞƌ͘^ŝůŝĐŽŶŽŝůǁĂƐƵƐĞĚƚŽƉƌĞǀĞŶƚŇĂƐŚŽǀĞƌƐ͘

Results and Discussion

Ɛ ĚĞŵŽŶƐƚƌĂƚĞĚ ŝŶ ŚĂƉƚĞƌ ϰ͕ W;s&-co-sͿ ĐŽƉŽůLJŵĞƌƐ ǁŝƚŚ ϭϱ ŵŽůй ŽĨ s ǁĞƌĞ synthesized viaĨƌĞĞƌĂĚŝĐĂůĐŽƉŽůLJŵĞƌŝnjĂƟŽŶŽĨs&ĂŶĚsĐ͕ĨŽůůŽǁĞĚďLJŚLJĚƌŽůLJƐŝƐ ŝŶĂĚŝŽdžĂŶĞͬŚLJĚƌŽĐŚůŽƌŝĐĂĐŝĚŵŝdžƚƵƌĞƚŽLJŝĞůĚW;s&-co-sͿ͘27 ^ƵďƐĞƋƵĞŶƚůLJ͕W;s&-co-sͿĂŶĚďŝĨƵŶĐƟŽŶĂůŚĞdžĂŵĞƚŚLJůĞŶĞĚŝŝƐŽĐLJĂŶĂƚĞ;,D/ͿǁĞƌĞĚŝƐƐŽůǀĞĚĂƚϴϬΣ ŝŶĐLJĐůŽƉĞŶƚĂŶŽŶĞƚŽĞŶƐƵƌĞŐŽŽĚŵŝdžŝŶŐĂŶĚƚŽŵŝŶŝŵŝnjĞƚŚĞǁĂƚĞƌĐŽŶƚĞŶƚŝŶƚŚĞ ƐŽůƵƟŽŶ͘29_{ ŌĞƌ ĐĂƐƟŶŐ ĂŶĚ ĞǀĂƉŽƌĂƟŽŶ ŽŶ ĂůƵŵŝŶŝƵŵ Ăƚ ϭϯϬ Σ͕ Ă ƐŝŵƉůĞ ƚŚĞƌŵĂů} ƉƌŽĐĞƐƐ Ăƚ ϭϲϬ Σ ;ĂďŽǀĞ ƚŚĞ ŵĞůƟŶŐ ƚĞŵƉĞƌĂƚƵƌĞ ŽĨ W;s&-co-sͿ ǁĂƐ ƉĞƌĨŽƌŵĞĚ ƚŽ ĐƌĞĂƚĞ ŇƵŽƌŝŶĂƚĞĚ ƉŽůLJŵĞƌ ŶĞƚǁŽƌŬƐ ďLJ ƵƌĞƚŚĂŶĞ ďŽŶĚ ĨŽƌŵĂƟŽŶƐ ;&ŝŐƵƌĞ ϱ͘ϭͿ͘

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: 91PDF page: 91PDF page: 91PDF page: 91

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EŽƚĞǁŽƌƚŚŝůLJ͕ĂŶĂĚĚŝƟŽŶĂůĂĚǀĂŶƚĂŐĞŽĨƵƐŝŶŐƵƌĞƚŚĂŶĞĐŚĞŵŝƐƚƌLJŝƐƚŚĂƚŶŽďLJƉƌŽĚƵĐƚƐ͕ ĂĐƟŶŐĂƐƉůĂƐƟĐŝnjĞƌƐ͕ĂƌĞĨŽƌŵĞĚĚƵƌŝŶŐƚŚĞƐLJŶƚŚĞƟĐƉƌŽĐĞƐƐƚŚĂƚĐĂŶĐĂƵƐĞĚŝĞůĞĐƚƌŝĐ ůŽƐƐĞƐŝŶŚŝŐŚĞůĞĐƚƌŝĐĮĞůĚĂƉƉůŝĐĂƟŽŶƐ͘hƐŝŶŐĂůŝŌͲŽīŵĞƚŚŽĚŝŶǁĂƚĞƌ͕ĨƌĞĞƐƚĂŶĚŝŶŐ ƚƌĂŶƐƉĂƌĞŶƚ ŇĞdžŝďůĞ ĐƌŽƐƐůŝŶŬĞĚ ĮůŵƐ ǁĞƌĞ ŽďƚĂŝŶĞĚ͘ dŚĞ ,D/ ĐŽŶƚĞŶƚ ĚƵƌŝŶŐ ƚŚĞ ĐƌŽƐƐůŝŶŬŝŶŐƉƌŽĐĞĚƵƌĞŝƐǀĂƌŝĞĚĂŶĚƚŚĞĐŚĂƌĂĐƚĞƌŝƐƟĐƐŽĨƚŚĞ;ĐƌŽƐƐůŝŶŬĞĚͿW;s&-co-sͿĐŽƉŽůLJŵĞƌƐƵƐĞĚŝŶƚŚŝƐƐƚƵĚLJĂƌĞƐƵŵŵĂƌŝnjĞĚŝŶdĂďůĞϱ͘ϭ͘hƐŝŶŐϬ͘ϱͲ͕ϭ͘ϬͲ͕ĂŶĚ ϮϬͲĨŽůĚĞdžĐĞƐƐŽĨŝƐŽĐLJĂŶĂƚĞŐƌŽƵƉƐĐŽŵƉĂƌĞĚƚŽƚŚĞŚLJĚƌŽdžLJůŐƌŽƵƉƐŽĨW;s&-co-sͿ ĚƵƌŝŶŐƚŚĞĮůŵĨŽƌŵĂƟŽŶ͕ƚŚĞĐƌŽƐƐůŝŶŬĞĚƐĂŵƉůĞƐĂƌĞĚĞŶŽƚĞĚĂƐϬϱ͕ϭĂŶĚϮϬ͕ ƌĞƐƉĞĐƟǀĞůLJ͘dŽĐŽŶĮƌŵƚŚĞĨŽƌŵĂƟŽŶŽĨƚŚĞŇƵŽƌŝŶĂƚĞĚƉŽůLJŵĞƌŶĞƚǁŽƌŬƐ͕Ϭϱ͕ϭ ĂŶĚϮϬĮůŵƐǁĞƌĞŝŵŵĞƌƐĞĚŝŶĚŝŵĞƚŚLJůĨŽƌŵĂŵŝĚĞ;ǁŚŝĐŚŝƐĂŐŽŽĚƐŽůǀĞŶƚĨŽƌW;s&Ͳ coͲsͿĐŽƉŽůLJŵĞƌƐͿĂŶĚǁĞƌĞĨŽƵŶĚƚŽďĞŝŶƐŽůƵďůĞƉƌŽǀŝŶŐƚŚĞŝƌĐƌŽƐƐůŝŶŬĞĚŶĂƚƵƌĞ͘ &ŽƵƌŝĞƌƚƌĂŶƐĨŽƌŵŝŶĨƌĂƌĞĚ;&d/ZͿƐƉĞĐƚƌĂǁĞƌĞƌĞĐŽƌĚĞĚƚŽŝĚĞŶƟĨLJƚŚĞĐŚĂƌĂĐƚĞƌŝƐƟĐ ďĂŶĚƐĂƐĂƌĞƐƵůƚŽĨŶĞƚǁŽƌŬĨŽƌŵĂƟŽŶ;&ŝŐƵƌĞϱ͘ϮͿ͘&ŽƌƚŚĞĐƌŽƐƐůŝŶŬĞĚƉŽůLJŵĞƌƐ͕ƚŚĞ ĐŚĂƌĂĐƚĞƌŝƐƟĐĂďƐŽƌďĂŶĐĞďĂŶĚƐŽĨƚŚĞƵƌĞƚŚĂŶĞĂƉƉĞĂƌĂƚϭϱϮϱĐŵͲϭ _{and the strong}

Figure 5.1: a) Schematic representation of P(VDF-co-VA) crosslinking. b) Flexible transparent

crosslinked P(VDF-co:% GSTSP]QIVƼPQ[MXLGLVSQMYQKSPHIPIGXVSHIW Table 5.1: 'LEVEGXIVMWXMGWSJXLIƽYSVMREXIHTSP]QIVWYWIHMRXLMWWXYH] Polymer ,D/Ă _ȴ, m;:Ő Ͳϭ_Ϳď _X c͕WAXS;йͿ c _D;ŶŵͿd W;s&-co-sͿ Ͳ Ϯϵ͘ϰ ϯϴ ϭϮ͘ϯ C05 0.5 12.5 ϭϯ ϲ͘ϰ C1 1 ϭϬ͘ϯ ϱ͘ϰ ϲ͘ϭ C20 20 0 0 Ͳ

a_{Ratio isocyanate to hydroxyl groups used in P(VDF-co-VA) crosslinking.} b_{Melting enthalpy obtained}

using DSC. c_{(IKVIISJGV]WXEPPMRMX]GEPGYPEXIHEJXIV;%<7TIEOHIGSRZSPYXMSR}d_{Average crystallite}

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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92 ďĂŶĚƐĐŽƌƌĞƐƉŽŶĚŝŶŐƚŽƚŚĞĐĂƌďŽŶLJůƐƚƌĞƚĐŚŝŶŐĂƌĞǀŝƐŝďůĞĂƚϭϳϬϰĐŵͲϭ_{͘/ŶĂĚĚŝƟŽŶ͕ƚŚĞ} ĂƐLJŵŵĞƚƌŝĐƐƚƌĞƚĐŚŽĨŝƐŽĐLJĂŶĂƚĞŐƌŽƵƉƐ͕ĞdžƉĞĐƚĞĚƚŽďĞĂƚϮϮϳϳĐŵͲϭ_{͕ŝƐĂďƐĞŶƚŝŶĚŝĐĂƟŶŐ} ƚŚĂƚŶŽŐƌĂŌŝŶŐŽĨƚŚĞW;s&-co-sͿĐŽƉŽůLJŵĞƌƐǁŝƚŚ,D/ŽĐĐƵƌƌĞĚ͘ϯϬ_{EŽƚĞ͕ƚŚĂƚ,D/} ŝƐĂůŝƋƵŝĚ;ď͘Ɖ͘ϮϱϱΣͿĂŶĚĞǀĂƉŽƌĂƚĞƉĂƌƚůLJŝŶĐŽŶũƵŶĐƟŽŶǁŝƚŚĐLJĐůŽƉĞŶƚĂŶŽŶĞĚƵƌŝŶŐ ĮůŵĨŽƌŵĂƟŽŶ͘ dŽ ŐĂŝŶ ŝŶƐŝŐŚƚƐ ŝŶ ƚŚĞ ĞīĞĐƚ ŽĨ ĐƌŽƐƐůŝŶŬŝŶŐ ŽŶ ƚŚĞ ĐƌLJƐƚĂůůŝŶŝƚLJ ĂŶĚ ƚŚĞ ƚŚĞƌŵĂů ƉƌŽƉĞƌƟĞƐ͕ĚŝīĞƌĞŶƟĂůƐĐĂŶŶŝŶŐĐĂůŽƌŝŵĞƚƌLJ;^ͿŵĞĂƐƵƌĞŵĞŶƚƐǁĞƌĞĐŽŶĚƵĐƚĞĚƚŽ ƐŚŽǁƚŚĞŵĞůƟŶŐĞŶĚŽƚŚĞƌŵƐĨŽƌƚŚĞĂƐƉƌĞƉĂƌĞĚĮůŵƐĂƐĚĞƉŝĐƚĞĚŝŶ&ŝŐƵƌĞϱ͘ϯ͘,ĞƌĞŝŶ͕ ƚŚĞƉƌŝƐƟŶĞW;s&-co-sͿĐŽƉŽůLJŵĞƌƐŚŽǁƐĂƐŝŶŐůĞŵĞůƟŶŐĞŶĚŽƚŚĞƌŵĂƚϭϮϰΣŚĂǀŝŶŐ ĂŵĞůƟŶŐĞŶƚŚĂůƉLJŽĨϮϵ͘ϰ:ŐͲϭ ͘^ŝŶĐĞƚŚĞŵĞůƟŶŐĞŶƚŚĂůƉLJŽĨϭϬϬйĐƌLJƐƚĂůůŝŶĞW;s&-co-sͿŝƐƵŶŬŶŽǁŶ͕ŽŶůLJƚŚĞƌĞůĂƟǀĞĐŚĂŶŐĞƐŝŶĞŶƚŚĂůƉLJďĞƚǁĞĞŶƚŚĞƐĂŵƉůĞƐƉƌŽǀŝĚĞ ŝŶĨŽƌŵĂƟŽŶĂďŽƵƚƚŚĞĐƌLJƐƚĂůůŝŶŝƚLJ͘ƐĐƌŽƐƐůŝŶŬŝŶŐŽĨWs&ͲďĂƐĞĚĐŽƉŽůLJŵĞƌƐƐƚƌŽŶŐůLJ ƌĞĚƵĐĞƐƚŚĞŵŽďŝůŝƚLJĂŶĚŚĂŵƉĞƌƐƚŚĞĐƌLJƐƚĂůůŝnjĂƟŽŶƉƌŽĐĞƐƐ͕LJŝĞůĚŝŶŐƐŵĂůůĞƌĐƌLJƐƚĂůƐ

Figure 5.2: FTIR spectra of P(VDF-co-:% ''ERH'WLS[MRKXLIYVIXLERIFSRHJSVQEXMSR

EJXIVGVSWWPMROMRKERHXLIGV]WXEPPMRI¼TLEWI

Figure 5.3: DSC thermograms of P(VDF-co:% ''ERH'HIQSRWXVEXMRKXLIMQTEGXSJ

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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ĂŶĚůŽǁĞƌŝŶŐƚŚĞĐƌLJƐƚĂůůŝŶŝƚLJ͕ƚŚĞŵĞůƟŶŐƚĞŵƉĞƌĂƚƵƌĞĨŽƌϬϱĂŶĚϭŝƐƌĞĚƵĐĞĚƚŽϵϭ ΣĂŶĚϴϲΣ͕ƌĞƐƉĞĐƟǀĞůLJ͘/ŶĂĚĚŝƟŽŶ͕ĨŽƌďŽƚŚĐƌŽƐƐůŝŶŬĞĚƐĂŵƉůĞƐ͕ĂƐĞĐŽŶĚŵĞůƟŶŐ ĞŶĚŽƚŚĞƌŵŝƐǀŝƐŝďůĞĂƌŽƵŶĚϱϲΣ͘dŚĞŵĞůƟŶŐĞŶƚŚĂůƉLJĨŽƌϬϱŝƐϭϮ͘ϱ:ŐͲϭ_{, whereas} ƚŚĞĞŶƚŚĂůƉLJŽĨϭŝƐĚĞƚĞƌŵŝŶĞĚƚŽďĞϭϬ͘ϰ:ŐͲϭ_{͘tŚĞŶĂϮϬͲĨŽůĚĞdžĐĞƐƐŽĨŝƐŽĐLJĂŶĂƚĞƚŽ} ŚLJĚƌŽdžLJůŐƌŽƵƉƐǁĂƐƵƐĞĚŶŽĐƌLJƐƚĂůůŝnjĂƟŽŶŽĐĐƵƌƌĞĚĂƐĚĞŵŽŶƐƚƌĂƚĞĚďLJƚŚĞĂďƐĞŶĐĞ ŽĨƚŚĞŵĞůƟŶŐĞŶĚŽƚŚĞƌŵŝŶƚŚĞ^ƉƌŽĮůĞ͘ƐĞdžƉĞĐƚĞĚ͕ŝŶĐƌĞĂƐŝŶŐƚŚĞĂŵŽƵŶƚŽĨ ,D/ĚƵƌŝŶŐƚŚĞĐƌŽƐƐůŝŶŬŝŶŐŽĨW;s&-co-sͿƌĞĚƵĐĞƐƚŚĞĐƌLJƐƚĂůůŝŶŝƚLJŽĨƚŚĞĐƌŽƐƐůŝŶŬĞĚ ƐĂŵƉůĞƐĂƐĚĞŵŽŶƐƚƌĂƚĞĚďLJƚŚĞƉƌŽŐƌĞƐƐŝǀĞůLJƌĞĚƵĐĞĚŵĞůƟŶŐĞŶƚŚĂůƉŝĞƐŽĨW;s&-co-sͿ͕ϬϱĂŶĚϭ͘dŚĞƐĞĐŽŶĚĞŶĚŽƚŚĞƌŵǀŝƐŝďůĞŝŶƚŚĞ^ƉƌŽĮůĞƐŽĨϬϱĂŶĚϭĂƌĞ ƉŽƐƐŝďůLJĐĂƵƐĞĚďLJĂĚĚŝƟŽŶĂůŶƵĐůĞĂƟŽŶƉŽŝŶƚƐŽƌŝŐŝŶĂƟŶŐĨƌŽŵƚŚĞƵƌĞƚŚĂŶĞůŝŶŬĂŐĞƐ ŝŶƚŚĞƉŽůLJŵĞƌďĂĐŬďŽŶĞ͕ĨŽƌŵĂƟŽŶŽĨƚŚŝŶŶĞƌůĂŵĞůůĂĞ͕ŽƌƚŚĞĂƉƉĞĂƌĂŶĐĞŽĨĂƵƌŝĞ ƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞ͘ϯϭ dŚĞ ĐƌLJƐƚĂůůŝŶĞ ƉŚĂƐĞƐ͕ ĐƌLJƐƚĂů ůĂƫĐĞ ƐƉĂĐŝŶŐ͕ ĐƌLJƐƚĂůůŝƚĞ ƐŝnjĞ ĂŶĚ ƚŚĞ ĚĞŐƌĞĞ ŽĨ ĐƌLJƐƚĂůůŝŶŝƚLJ ŽĨ ƚŚĞ W;s&-co-sͿ ĐŽƉŽůLJŵĞƌƐ ǁĞƌĞ ŽďƚĂŝŶĞĚ ĨƌŽŵ ƚŚĞ &d/Z ƐƉĞĐƚƌĂ ;&ŝŐƵƌĞϱ͘ϮͿĂŶĚĚĞĐŽŶǀŽůƵƚĞĚty^ƉƌŽĮůĞƐĂƐĚĞŵŽŶƐƚƌĂƚĞĚŝŶ&ŝŐƵƌĞϱ͘ϰ͘ƐƉƌĞǀŝŽƵƐůLJ ƌĞƉŽƌƚĞĚ͕W;s&-co-sͿĐŽƉŽůLJŵĞƌǁŝƚŚϭϱŵŽůйsĐƌLJƐƚĂůůŝnjĞƐĨƌŽŵƚŚĞŵĞůƚƐŽůĞůLJ ŝŶƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐɴͲƉŚĂƐĞĂƐŝŶĚŝĐĂƚĞĚďLJƚŚĞƉĞĂŬŽĨƚŚĞ;ϭϭϬͬϮϬϬͿƌĞĨƌĂĐƟǀĞƉůĂŶĞ Figure 5.4: (IGSRZSPYXIH;%<7TVSƼPIWSJE 4:(*co:% F 'G 'ERHH '

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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ůŽĐĂƚĞĚĂƚϭϰ͘ϲŶŵͲϭ_{ŝŶƚŚĞty^ƉƌŽĮůĞĂŶĚƚŚĞĐŚĂƌĂĐƚĞƌŝƐƟĐĂďƐŽƌƉƟŽŶďĂŶĚƐĂƚ}

ϱϭϬ͕ϴϰϬ͕ϭϮϳϯĐŵͲϭ_{ŝŶƚŚĞ&d/ZƐƉĞĐƚƌƵŵĂƐƐŽĐŝĂƚĞĚǁŝƚŚƚŚĞĂůůͲƚƌĂŶƐĐŽŶĨŽƌŵĂƟŽŶ͘}ϯϮ

The crystalline crosslinked samples, C05 and C1, show that upon crosslinking the highly ƉŽůĂƌɴͲƉŚĂƐĞŝƐŽďƚĂŝŶĞĚ͘,ĞƌĞŝŶ͕ƚŚĞƐĐĂƩĞƌŝŶŐƉĞĂŬŽĨϬϱŚĂƐƌĞŵĂŝŶĞĚĂƚƚŚĞƐĂŵĞ ƉŽƐŝƟŽŶĂŶĚƚŚĂƚŽĨϭĐŚĂŶŐĞĚƚŽϭϰ͘ϱŶŵͲϭ_{, which indicates that more defects are}

ŝŶƚƌŽĚƵĐĞĚŝŶϭƌĞƐƵůƟŶŐŝŶĂŶĞdžƉĂŶƐŝŽŶŽĨƚŚĞĐƌLJƐƚĂůůĂƫĐĞ͘DŽƌĞŽǀĞƌ͕ƵƐŝŶŐƚŚĞ ^ĐŚĞƌƌĞƌ ĞƋƵĂƟŽŶ͕ ƚŚĞ ĐƌLJƐƚĂůůŝƚĞ ƐŝnjĞƐ ŽĨ ƚŚĞ ĐƌLJƐƚĂůůŝŶĞ ƐĂŵƉůĞƐ ǁĞƌĞ ĚĞƚĞƌŵŝŶĞĚ͘ WƌŝƐƟŶĞW;s&-co-sͿƐŚŽǁƐĂŶĂǀĞƌĂŐĞĐƌLJƐƚĂůůŝƚĞƐŝnjĞďĞŝŶŐϭϮ͘ϯŶŵͲϭ_{, whereas the}

ĐƌLJƐƚĂůůŝƚĞƐŝnjĞƐŽĨƚŚĞĐƌŽƐƐůŝŶŬĞĚĐŽƉŽůLJŵĞƌƐ͕ϬϱĂŶĚϭ͕ǁĞƌĞĚĞƚĞƌŵŝŶĞĚƚŽďĞϲ͘ϱĂŶĚ ϲ͘ϮŶŵͲϭ_{͕ƌĞƐƉĞĐƟǀĞůLJ͘/ŶĂĚĚŝƟŽŶ͕ĂďƐŽƌƉƟŽŶďĂŶĚƐŝŶƚŚĞ&d/ZƐƉĞĐƚƌĂĐŽƌƌĞƐƉŽŶĚŝŶŐ} ƚŽƚŚĞɴͲƉŚĂƐĞĂƉƉĞĂƌĨŽƌϬϱĂŶĚϭĂƐǁĞůů͕ĂůďĞŝƚŝŶůŽǁĞƌŝŶƚĞŶƐŝƚLJŝŶĚŝĐĂƟǀĞĨŽƌƚŚĞ ƌĞĚƵĐĞĚĐƌLJƐƚĂůůŝŶŝƚLJ͘KŶƚŚĞĐŽŶƚƌĂƌLJ͕ĨŽƌϮϬ͕ƚŚĞty^ƉƌŽĮůĞũƵƐƚƐŚŽǁƐĂŶĂŵŽƌƉŚŽƵƐ ŚĂůŽ ĂŶĚ ƚLJƉŝĐĂů ĂďƐŽƌƉƟŽŶ ďĂŶĚƐ ĐŽƌƌĞƐƉŽŶĚŝŶŐ ƚŽ ĐƌLJƐƚĂůůŝŶĞ ƉŚĂƐĞƐ ŽĨ Ws& ĂƌĞ ĂďƐĞŶƚ͘dŚĞĚĞŐƌĞĞŽĨĐƌLJƐƚĂůůŝŶŝƚLJŽĨW;s&-co-sͿ͕Ϭϱ͕ϭĂŶĚϮϬǁĂƐƋƵĂŶƟĮĞĚ ďLJƚŚĞĨƌĂĐƟŽŶŽĨĐƌLJƐƚĂůůŝŶĞƉŚĂƐĞviaƉĞĂŬĚĞĐŽŶǀŽůƵƟŽŶŽĨƚŚĞty^ƉƌŽĮůĞƐĂŶĚ ĚĞƚĞƌŵŝŶĞĚƚŽďĞϯϴ͕ϭϯ͕ϱ͘ϰ͕ĂŶĚϬй͕ƌĞƐƉĞĐƟǀĞůLJ͘dŚŝƐůĂƌŐĞƌĞĚƵĐƟŽŶŝŶĐƌLJƐƚĂůůŝŶŝƚLJ ĨŽƌƚŚĞĐƌŽƐƐůŝŶŬĞĚƐĂŵƉůĞƐĐŽŵƉĂƌĞĚƚŽƉƌŝƐƟŶĞW;s&-co-sͿŝƐĂůƐŽƌĞŇĞĐƚĞĚŝŶƚŚĞ ƌĞĚƵĐƟŽŶŽĨƚŚĞŵĞůƟŶŐĞŶƚŚĂůƉŝĞƐ͘/ŶůŝƚĞƌĂƚƵƌĞ͕ƌĞĚƵĐƟŽŶŽĨƚŚĞŵĞůƟŶŐƚĞŵƉĞƌĂƚƵƌĞ ŽĨWs&ͲďĂƐĞĚĐŽƉŽůLJŵĞƌƐĂŌĞƌĐƌŽƐƐůŝŶŬŝŶŐŝƐŽďƐĞƌǀĞĚŝŶďŽƚŚŝƌƌĂĚŝĂƚĞĚƐĂŵƉůĞƐĂŶĚ ƐĂŵƉůĞƐĐƌŽƐƐůŝŶŬĞĚǁŝƚŚĂŵŝŶĞƐĂŶĚƉĞƌŽdžŝĚĞƐ͘ϮϮ͕ϯϯ_{,ŽǁĞǀĞƌ͕ŝŶŚŽŵŽŐĞŶĞŽƵƐŝƌƌĂĚŝĂƟŽŶ} ŽǀĞƌƚŚĞŇƵŽƌŝŶĂƚĞĚƉŽůLJŵĞƌŽƌŵĂĐƌŽƉŚĂƐĞƐĞƉĂƌĂƟŽŶŽĨĐƌŽƐƐůŝŶŬŝŶŐĂŐĞŶƚƐůĞĂĚƚŽĂ ŶŽŶͲƵŶŝĨŽƌŵĚŝƐƚƌŝďƵƟŽŶŽĨĐƌŽƐƐůŝŶŬƐ͕ƌĞƐƵůƟŶŐŝŶůĂƌŐĞĐƌLJƐƚĂůůŝŶĞĚŽŵĂŝŶƐĂŶĚŵĞůƟŶŐ ƚĞŵƉĞƌĂƚƵƌĞƐƐƟůůĐůŽƐĞƚŽƚŚĞƉƌŝƐƟŶĞĐŽƉŽůLJŵĞƌƐ͘/ŶĐŽŶƚƌĂƐƚ͕ƚŚĞǀŝŶLJůĂůĐŽŚŽůƵŶŝƚƐ ŝŶW;s&-co-sͿĂƌĞŶŝĐĞůLJĚŝƐƚƌŝďƵƚĞĚŽǀĞƌƚŚĞƉŽůLJŵĞƌďĂĐŬďŽŶĞ͕ƌĞƐƵůƟŶŐŝŶƐŵĂůůĞƌ ĐƌLJƐƚĂůůŝŶĞĚŽŵĂŝŶƐĂŶĚƚŚĞƌĞĨŽƌĞůŽǁĞƌŵĞůƟŶŐƚĞŵƉĞƌĂƚƵƌĞƐ͘ dŚĞ ĞůĞĐƚƌŽĂĐƟǀĞ ďĞŚĂǀŝŽƌ ŽĨ Ws&ͲďĂƐĞĚ ƉŽůLJŵĞƌƐ ŝƐ ŵĂŝŶůLJ ĚĞƚĞƌŵŝŶĞĚ ďLJ ŝƚƐ ĐƌLJƐƚĂůůŝŶĞƉŚĂƐĞ͕ĐƌLJƐƚĂůůĂƫĐĞƐƉĂĐŝŶŐ͕ĐƌLJƐƚĂůůŝƚĞƐŝnjĞ͕ƉŽůĂƌŝnjĂďŝůŝƚLJŽĨƚŚĞĚŽŵĂŝŶǁĂůůƐ and crystallinity.ϰ͕ϭϯ_{dŽŝŶǀĞƐƟŐĂƚĞƚŚĞĞůĞĐƚƌŝĐĂůƉƌŽƉĞƌƟĞƐŽĨƚŚĞĐƌŽƐƐůŝŶŬĞĚƉŽůLJŵĞƌƐ͕} ĞůĞĐƚƌŝĐ ĮĞůĚƐ ŝŶ Ă ƚƌŝĂŶŐƵůĂƌ ǁĂǀĞĨŽƌŵ Ăƚ ϭϬ ,nj ǁĞƌĞ ĂƉƉůŝĞĚ͕ ǁŚŝĐŚ ŵĞĂƐƵƌĞƐ ƚŚĞ ƉŽůĂƌŝnjĂƟŽŶĂƐƚŚĞŝŶƚĞŐƌĂůŽĨƚŚĞƌĞƐƵůƟŶŐĐƵƌƌĞŶƚ͘ /Ŷ&ŝŐƵƌĞϱ͘ϱ͕ƚŚĞĚŝƐƉůĂĐĞŵĞŶƚʹĞůĞĐƚƌŝĐĮĞůĚ;ͲͿůŽŽƉƐŽĨƉƌŝƐƟŶĞW;s&-co-sͿ͕ Ϭϱ͕ϭĂŶĚϮϬĂƌĞĚĞƉŝĐƚĞĚƵƉƚŽƐŝŵŝůĂƌĮĞůĚƐ;ϮϬϬDsŵͲϭ_{Ϳ͘dŚĞƉƌŝƐƟŶĞĐŽƉŽůLJŵĞƌ} ƐŚŽǁƐĂĨĞƌƌŽĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌ͕ǁŚĞƌĞĂƐϬϱĂŶĚƚŽĂŐƌĞĂƚĞƌĞdžƚĞŶƚ;ůŽǁĞƌƌĞŵĂŶĞŶƚ ƉŽůĂƌŝnjĂƟŽŶͿϭĚĞŵŽŶƐƚƌĂƚĞĚŽƵďůĞŚLJƐƚĞƌĞƐŝƐůŽŽƉƐ;,>Ϳ͘dŚĞĂŵŽƌƉŚŽƵƐĐƌŽƐƐůŝŶŬĞĚ ĐŽƉŽůLJŵĞƌ͕ ϮϬ͕ ƐŚŽǁƐ ĂŶ ĞdžƉĞĐƚĞĚůLJ ůŝŶĞĂƌ ĚŝĞůĞĐƚƌŝĐ ďĞŚĂǀŝŽƌ ĚƵĞ ƚŚĞ ĂďƐĞŶĐĞ ŽĨ ĞůĞĐƚƌŽĂĐƟǀĞ ĐƌLJƐƚĂůƐ ĂŶĚ ĨĂƐƚ ĚŝƉŽůĂƌ ƌĞůĂdžĂƟŽŶ ƉƌŽĐĞƐƐĞƐ ĐŽŵŵŽŶůLJ ŽďƐĞƌǀĞĚ ŝŶ amorphous dielectrics. &ƌŽŵƚŚĞůŝƚĞƌĂƚƵƌĞ͕ŝƚŝƐǁĞůůƵŶĚĞƌƐƚŽŽĚƚŚĂƚĨĞƌƌŽĞůĞĐƚƌŝĐĐŽƵƉůŝŶŐŝŶƚĞƌĂĐƟŽŶƐ ǁŝƚŚŝŶ ƚŚĞ ĨĞƌƌŽĞůĞĐƚƌŝĐ ĐƌLJƐƚĂů ;ƚLJƉĞ /Ϳ͕ ĂŶĚ ďĞƚǁĞĞŶ ĨĞƌƌŽĞůĞĐƚƌŝĐ ĐƌLJƐƚĂůƐ ĂůŽŶŐ

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: 95PDF page: 95PDF page: 95PDF page: 95

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ƚŚĞĮĞůĚĚŝƌĞĐƟŽŶ;ƚLJƉĞ//ͿĂŶĚƉĞƌƉĞŶĚŝĐƵůĂƌƚŽƚŚĞĞůĞĐƚƌŝĐĮĞůĚ;ƚLJƉĞ///ͿĂůůŝŶĚƵĐĞ ƉŽůĂƌŝnjĂƟŽŶƐƚŚĂƚƌĞƐƵůƚŝŶĨĞƌƌŽĞůĞĐƚƌŝĐŝƚLJ͘ϰ_{,ĞƌĞŝŶ͕ƚLJƉĞ/ŚĂƐƚŚĞďŝŐŐĞƐƚŝŶŇƵĞŶĐĞĂŶĚ} ƚLJƉĞ///ƚŚĞůŽǁĞƐƚƚŽƌĞŶĚĞƌĂĨĞƌƌŽĞůĞĐƚƌŝĐƌĞƐƉŽŶƐĞ͘/ŶĂĚĚŝƟŽŶ͕ĂŚŝŐŚƉŽůĂƌŝnjĂďŝůŝƚLJ (i.e.ĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚͿŽĨƚŚĞĂŵŽƌƉŚŽƵƐŵĂƚƌŝdžŝƐŽĨŐƌĞĂƚƐŝŐŶŝĮĐĂŶĐĞƚŽŵĂŝŶƚĂŝŶ ĨĞƌƌŽĞůĞĐƚƌŝĐŝƚLJ͕ƐŝŶĐĞŝƚďĞƩĞƌĂĐĐŽŵŵŽĚĂƚĞƐƉŽůĂƌŝnjĂƟŽŶƐŝŶĚƵĐĞĚďLJƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐ domains.ϯϰ_{/ŶƉƌŝƐƟŶĞW;s&-co-sͿ͕ƚŚĞŝŶƚƌŽĚƵĐƟŽŶŽĨĚĞĨĞĐƚƐŝŶƚŚĞWs&ďĂĐŬďŽŶĞ} ĂŶĚĂŶŝŶĐƌĞĂƐĞŝŶƚŚĞĐƌLJƐƚĂůůĂƫĐĞƐƉĂĐŝŶŐĞŶƐƵƌĞƐƚŚĞĨŽƌŵĂƟŽŶŽĨƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐ ɴͲƉŚĂƐĞ͘/ŶĂĚĚŝƟŽŶ͕ƚŚĞƌĞůĂƟǀĞůLJůĂƌŐĞĐƌLJƐƚĂůůŝƚĞƐĂŶĚĚĞŐƌĞĞƐŽĨĐƌLJƐƚĂůůŝŶŝƚLJĂůůŽǁ ĂůůĐŽƵƉůŝŶŐŝŶƚĞƌĂĐƟŽŶƐƚŽŚĂƉƉĞŶ͕ůĞĂĚŝŶŐƚŽĨĞƌƌŽĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌ͘/ŶĐŽŶƚƌĂƐƚ͕ǁŚĞŶ ƚŚĞĐƌŽƐƐůŝŶŬĞĚĐŽƉŽůLJŵĞƌƐ;ϬϱĂŶĚϭͿĐƌLJƐƚĂůůŝnjĞŝŶƚŚĞɴͲƉŚĂƐĞ͕ďƵƚƚŚĞĐƌLJƐƚĂůƐĂƌĞ ƐĞƉĂƌĂƚĞĚďLJĐƌŽƐƐůŝŶŬƐ͕ƚŚĞƐŵĂůůĐƌLJƐƚĂůůŝƚĞƐŝnjĞƐĚŝŵŝŶŝƐŚƚLJƉĞ/ŝŶƚĞƌĂĐƟŽŶƐ͘ĞƐŝĚĞƐ ƚŚĂƚƚŚĞĐƌLJƐƚĂůƐĂƌĞƐĞƉĂƌĂƚĞĚďLJĐƌŽƐƐůŝŶŬƐĂŶĚƚŚĂƚƚŚĞƌĞŝƐĂƌĞĚƵĐƟŽŶŝŶĐƌLJƐƚĂůůŝŶŝƚLJ͕ ƚŚĞƉŽůĂƌŝƚLJŽĨƚŚĞĐƌLJƐƚĂůůŝŶĞͲĂŵŽƌƉŚŽƵƐŝŶƚĞƌĨĂĐĞŝƐƌĞĚƵĐĞĚďLJŝŶĐůƵĚŝŶŐĂŶŽŶƉŽůĂƌ ĐƌŽƐƐůŝŶŬŝŶŐĂŐĞŶƚŝŶƚŚĞĂŵŽƌƉŚŽƵƐĚŽŵĂŝŶƐ͕ĚŝŵŝŶŝƐŚŝŶŐƚLJƉĞ//ĂŶĚ///ŝŶƚĞƌĂĐƟŽŶƐ͘ ^ŝŶĐĞ ƚŚĞ ĐŽŵƉĞŶƐĂƟŽŶĂů ƉŽůĂƌŝnjĂƟŽŶ ŝƐ ŝŶƐƵĸĐŝĞŶƚ ƚŽ ŵĂŝŶƚĂŝŶ ĚŝƉŽůĞ ŽƌŝĞŶƚĂƟŽŶ ĂŌĞƌĮĞůĚƌĞŵŽǀĂů͕ĂŶŽŶůŝŶĞĂƌ,>ďĞŚĂǀŝŽƌŝƐŽďƐĞƌǀĞĚ͕ǁŚĞƌĞƚŚĞĐƌLJƐƚĂůůŝŶĞĚŝƉŽůĞƐ

Figure 5.5: Displacement – Electric Field (D-E) loops of pristine P(VDF-co:% ''ERH'

up to 200 MV m-1_{[LIVIMRXLIP-E loops become slimmer upon increasing HMDI content and 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

Processed on: 21-3-2019 PDF page: 96PDF page: 96PDF page: 96PDF page: 96

96 ĂĚŽƉƚĂŐĂŝŶĂƌĂŶĚŽŵŽƌŝĞŶƚĂƟŽŶ͘^ŝŵŝůĂƌůLJ͕ƚŚŝƐĞīĞĐƚŽĨƉŽůĂƌŝnjĂďŝůŝƚLJĂƚƚŚĞŶĂŶŽĐƌLJƐƚĂů ŝŶƚĞƌĨĂĐĞŽŶĞůĞĐƚƌŽĂĐƟǀĞƉƌŽƉĞƌƟĞƐŝƐĂůƐŽŽďƐĞƌǀĞĚŝŶW;s&-co-d&ͿĐŽƉŽůLJŵĞƌƐ ŐƌĂŌĞĚǁŝƚŚůŽǁĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚƉŽůLJƐƚLJƌĞŶĞ;W^ͿĂŶĚŝŶW^ͲbͲW;s&-co-dƌ&ͿͲb-PS triblock copolymers.ϯϰ͕ϯϱ_{/ŶďŽƚŚĐĂƐĞƐ͕ƚŚĞŶĂŶŽƐŝnjĞĚĐƌLJƐƚĂůƐĂůƐŽŚĂǀĞĂŶŝŶƐƵůĂƟŶŐ} ;W^ͿůĂLJĞƌĚĞƐƚĂďŝůŝnjŝŶŐƚŚĞƉŽůĂƌŝnjĂƟŽŶŝŶĚƵĐĞĚďLJƚŚĞĞůĞĐƚƌŝĐĮĞůĚ͕ƌĞƐƵůƟŶŐŝŶ,> behavior and for the block copolymer even linear dielectric behavior, severely reducing ƚŚĞĞīĞĐƚŽĨŵĂĐƌŽƐĐŽƉŝĐƉŽůĂƌŝnjĂƟŽŶ͘/ŶƚĞƌĞƐƟŶŐůLJ͕ƚŚŝƐĐŚĂŶŐĞŝŶĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌ ŽĨƚŚĞĐƌŽƐƐůŝŶŬĞĚƐĂŵƉůĞƐŝƐĐŽŵƉůĞƚĞůLJĚŝīĞƌĞŶƚƚŚĂŶŽďƐĞƌǀĞĚĨŽƌƚŚĞŽƚŚĞƌĐŚĞŵŝĐĂůůLJ crosslinking methods (via ŝƌƌĂĚŝĂƟŽŶ Žƌ ƵƐŝŶŐ ĂŵŝŶĞƐͿ͘ Ɛ ƉƌĞǀŝŽƵƐůLJ ĚŝƐĐƵƐƐĞĚ͕ ƚŚĞ inhomogeneous character of these samples results in normal ferroelectric behavior, since ƚŚĞƵŶĞǀĞŶĚŝƐƚƌŝďƵƟŽŶŽĨĐƌŽƐƐůŝŶŬŝŶŐƐŝƚĞƐĂůůŽǁƐƚŚĞĨŽƌŵĂƟŽŶŽĨůĂƌŐĞĨĞƌƌŽĞůĞĐƚƌŝĐ domains.ϯϯ͕ϯϲ͕ϯϳ EĞǀĞƌƚŚĞůĞƐƐ͕ǁŚĞŶƚŚĞĞůĞĐƚƌŝĐĮĞůĚŝƐŝŶĐƌĞĂƐĞĚƚŽĞdžƚƌĞŵĞůLJŚŝŐŚĮĞůĚƐ;ĂďŽǀĞϮϬϬ DsŵͲϭ_{Ϳ͕ƚŚĞĐƌLJƐƚĂůůŝŶĞĐƌŽƐƐůŝŶŬĞĚƐĂŵƉůĞƐďĞĐŽŵĞĨĞƌƌŽĞůĞĐƚƌŝĐͲůŝŬĞĂƐǁĞůů;&ŝŐƵƌĞϱ͘ϲͿ͘} dŚŝƐŝƐůŝŬĞůLJĐĂƵƐĞĚďLJĂďĞƩĞƌĂůŝŐŶŵĞŶƚĂŶĚŝŶĐƌĞĂƐĞĚƐŝnjĞŽĨĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶƐĂƚ ŚŝŐŚĮĞůĚƐ͕ƐŚŽǁŝŶŐƚŚĂƚĨŽƌŚŝŐŚĮĞůĚĂƉƉůŝĐĂƟŽŶƐ͕ĞǀĞŶƵůƚƌĂĮŶĞɴͲĐƌLJƐƚĂůƐŚĂǀĞƚŽďĞ isolated well (e.g. viaďůŽĐŬĐŽƉŽůLJŵĞƌƐĞůĨͲĂƐƐĞŵďůLJͿ͘ϯϰ͕ϯϴʹϰϯ

ƐĂůƌĞĂĚLJƐŚŽǁŶŝŶƋƵĂƟŽŶϱ͘ϭ͕ƚŚĞĚŝĞůĞĐƚƌŝĐƉĞƌĨŽƌŵĂŶĐĞŝƐůĂƌŐĞůLJĚĞƚĞƌŵŝŶĞĚďLJ ƚŚĞĞůĞĐƚƌŝĐĮĞůĚƚŚĂƚĐĂŶďĞĂƉƉůŝĞĚ͘dŽĚĞŵŽŶƐƚƌĂƚĞƚŚĞŝŶĐƌĞĂƐĞĚĚŝĞůĞĐƚƌŝĐƐƚƌĞŶŐƚŚ ĂŶĚŝŵƉƌŽǀĞĚƌĞůŝĂďŝůŝƚLJŽĨƚŚĞĐƌŽƐƐůŝŶŬĞĚŇƵŽƌŝŶĂƚĞĚŶĞƚǁŽƌŬƐĐŽŵƉĂƌĞĚƚŽƉƌŝƐƟŶĞ W;s&-co-sͿ͕ĂƚǁŽͲƉĂƌĂŵĞƚĞƌtĞŝďƵůůĂŶĂůLJƐŝƐǁĂƐƉĞƌĨŽƌŵĞĚƵƐŝŶŐƋƵĂƟŽŶϱ͘Ϯ͘  ;ϱ͘ϮͿ Figure 5.6: (MWTPEGIQIRXƁ)PIGXVMG*MIPHPSSTWSJE 'ERHF 'EXLMKLIPIGXVMGƼIPHW

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: 97PDF page: 97PDF page: 97PDF page: 97

97

5

,ĞƌĞŝŶ͕F(x)ĚŝƐƉůĂLJƐƚŚĞĐƵŵƵůĂƟǀĞƉƌŽďĂďŝůŝƚLJŽĨĨĂŝůƵƌĞ͕x is the measured breakdown

strength, ɲŝƐƚŚĞďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚĂƚǁŚŝĐŚϲϯ͘ϮйŽĨƚŚĞƐĂŵƉůĞƐŚĂǀĞĨĂŝůĞĚĂŶĚ ɴŝƐƚŚĞƐŚĂƉĞƉĂƌĂŵĞƚĞƌ;ĂŚŝŐŚĞƌǀĂůƵĞĨŽƌɴŵĞĂŶƐĂŚŝŐŚĞƌƌĞůŝĂďŝůŝƚLJͿ͘dŚĞtĞŝďƵůů ƉůŽƚƐŽĨW;s&-co-sͿ͕Ϭϱ͕ϭĂŶĚϮϬ͕ǁŚĞƌĞŝŶF(x)ŝƐƉůŽƩĞĚǀĞƌƐƵƐůŽŐĂƌŝƚŚŵŽĨƚŚĞ ĞůĞĐƚƌŝĐĮĞůĚ͕ĂƌĞĚĞƉŝĐƚĞĚŝŶ&ŝŐƵƌĞϱ͘ϳ͘dŚĞďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚĨŽƌϬϱ͕ϭĂŶĚϮϬĂƌĞ ĚĞƚĞƌŵŝŶĞĚƚŽďĞϱϭϴ͕ϱϬϵĂŶĚϱϱϵDsŵͲϭ_{͕ƌĞƐƉĞĐƟǀĞůLJ͕ǁŚĞƌĞĂƐƉƌŝƐƟŶĞW;s&-co-sͿ} ŚĂƐĂďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚŽĨϯϲϵDsŵͲϭ_{͕ĐůĞĂƌůLJĚĞŵŽŶƐƚƌĂƟŶŐƚŚĞŝŵƉƌŽǀĞĚďƌĞĂŬĚŽǁŶ} ƐƚƌĞŶŐƚŚĂƐĂƌĞƐƵůƚŽĨĐŚĞŵŝĐĂůĐƌŽƐƐůŝŶŬŝŶŐ͘ĚĚŝƟŽŶĂůůLJ͕ƚŚĞƐůŽƉĞ;ɴͿŽĨƚŚĞĐƌŽƐƐůŝŶŬĞĚ ƐĂŵƉůĞƐŝŶƚŚĞtĞŝďƵůůƉůŽƚŝƐŵƵĐŚƐƚĞĞƉĞƌ͕ŝŶĚŝĐĂƟŶŐĂŶĂƌƌŽǁĞƌĚŝƐƚƌŝďƵƟŽŶĂŶĚƚŚƵƐĂŶ ŝŶĐƌĞĂƐĞĚƌĞůŝĂďŝůŝƚLJĐŽŵƉĂƌĞĚƚŽƉƌŝƐƟŶĞW;s&-co-sͿ͘^ŝŵŝůĂƌƚƌĞŶĚƐĂƌĞŽďƐĞƌǀĞĚĨŽƌ W;s&-co-d&ͿǁŚĞŶĐƌŽƐƐůŝŶŬĞĚƵƐŝŶŐƉĞƌŽdžŝĚĞƐĂŶĚƚƌŝĂůůLJůŝƐŽĐLJĂŶƵƌĂƚĞ͘22_{,ĞƌĞŝŶ͕ƚŚĞ}

ƉƌŝƐƟŶĞĐŽƉŽůLJŵĞƌŚĂƐĂĚŝĞůĞĐƚƌŝĐďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚŽĨϯϲϬDsŵͲϭ _{and the crosslinked}

ƐĂŵƉůĞƐŚĂǀĞďĞƚǁĞĞŶϰϱϱĂŶĚϲϭϰDsŵͲϭ_{. The restrained chain mobility caused by}

ĐƌŽƐƐůŝŶŬŝŶŐĂůůŽǁƐĨŽƌƚŚĞĨŽƌŵĂƟŽŶŽĨƚƌĂƉƐ͕ƌĞĚƵĐŝŶŐƚŚĞŶƵŵďĞƌŽĨĐŽŶĚƵĐƟŽŶĐĂƌƌŝĞƌƐ ĂŶĚƚŚƵƐƐƵƉƉƌĞƐƐŝŶŐĐŽŶĚƵĐƟǀŝƚLJ͘22_{DŽƌĞŽǀĞƌ͕ĂƌĞĚƵĐƟŽŶŝŶĨĞƌƌŽĞůĞĐƚƌŝĐůŽƐƐĞƐůĞĂĚŝŶŐ} ƚŽďĞƩĞƌŚĞĂƚƌĞŵŽǀĂůĂůƐŽŝŶĐƌĞĂƐĞƐƚŚĞůŝĨĞƟŵĞŽĨƚŚĞĐĂƉĂĐŝƚŽƌƐ͕ũƵƐƚĂƐĂŶŝŶĐƌĞĂƐĞ ŝŶƚŚĞŵĞĐŚĂŶŝĐĂůƉƌŽƉĞƌƟĞƐ͘ϮϮ͕ϰϰ͕ϰϱ dŚĞƐƚŽƌĞĚĂŶĚƌĞůĞĂƐĞĚĞŶĞƌŐLJĚĞŶƐŝƟĞƐĐĂůĐƵůĂƚĞĚĨƌŽŵƚŚĞƵŶŝƉŽůĂƌĚŝƐƉůĂĐĞŵĞŶƚ ʹĞůĞĐƚƌŝĐĮĞůĚůŽŽƉƐĂƌĞďĞŶĐŚŵĂƌŬǀĂůƵĞƐĨŽƌĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJƐƚŽƌĂŐĞĚĞǀŝĐĞƐ͘/Ŷ &ŝŐƵƌĞϱ͘ϴ͕ǁĞĚĞƉŝĐƚƚŚĞƐƚŽƌĞĚĂŶĚƌĞůĞĂƐĞĚĞŶĞƌŐLJĚĞŶƐŝƚLJǀĞƌƐƵƐƚŚĞĞůĞĐƚƌŝĐĮĞůĚ͘Ɛ ĞdžƉĞĐƚĞĚ͕ƌĞĚƵĐŝŶŐƚŚĞĐƌLJƐƚĂůůŝŶŝƚLJĚƵĞƚŽĐƌŽƐƐůŝŶŬŝŶŐůĞĂĚƐƚŽůĞƐƐĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJ ƐƚŽƌĞĚŝŶƐŝĚĞƚŚĞŵĂƚĞƌŝĂůƐĂƚƐŝŵŝůĂƌĞůĞĐƚƌŝĐĮĞůĚƐ͘&ŽƌĞdžĂŵƉůĞ͕ĂƚϮϬϬDsŵͲϭ_{, due to} ƚŚĞŶŽŶůŝŶĞĂƌƌĞůĂƟŽŶŽĨƉŽůĂƌŝnjĂƟŽŶǁŝƚŚŝŶĐƌĞĂƐŝŶŐĞůĞĐƚƌŝĐĮĞůĚ͕ĨĞƌƌŽĞůĞĐƚƌŝĐW;s&-co-sͿƐŚŽǁƐĂŶĞĂƌůLJϰͲĨŽůĚŚŝŐŚĞƌƐƚŽƌĞĚĞŶĞƌŐLJĚĞŶƐŝƚLJ;ϳ͘ϳ:ĐŵͲϯ_{ͿƚŚĂŶůŝŶĞĂƌĚŝĞůĞĐƚƌŝĐ} Figure 5.7: ;IMFYPPEREP]WMWSJFVIEOHS[RWXVIRKXLWSJ4:(*co:% ''ERH'

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: 98PDF page: 98PDF page: 98PDF page: 98

98 ϮϬ;ϭ͘ϴ:ĐŵͲϯ_{Ϳ͕ǁŚĞƌĞĂƐϬϱĂŶĚϭĚĞŵŽŶƐƚƌĂƚĞƉŽůĂƌŝnjĂƟŽŶǀĂůƵĞƐŽĨϲ͘ϭĂŶĚϰ͘ϲ:} cmͲϯ_{͕ƌĞƐƉĞĐƟǀĞůLJ͘,ŽǁĞǀĞƌ͕ĚƵĞƚŽƚŚĞůĂƌŐĞŝŵƉƌŽǀĞŵĞŶƚŝŶďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚ͕ƚŚĞ} ŵĂdžŝŵƵŵĞŶĞƌŐLJĚĞŶƐŝƚLJĚŝƐĐŚĂƌŐĞĚĨƌŽŵƚŚĞĐƌŽƐƐůŝŶŬĞĚĐĂƉĂĐŝƚŽƌƐŝƐŝŶĐƌĞĂƐĞĚϮͲϮ͘ϱ ƟŵĞƐĐŽŵƉĂƌĞĚƚŽƚŚĞƉƌŝƐƟŶĞĐŽƉŽůLJŵĞƌ͘ /ŶƚĞƌĞƐƟŶŐůLJ͕ƚŚĞƌĞůĞĂƐĞĚĞŶĞƌŐLJĚĞŶƐŝƟĞƐŽĨƉƌŝƐƟŶĞW;s&-co-sͿĂƌĞƌĞůĂƟǀĞůLJ ŚŝŐŚĨŽƌĂŶĨĞƌƌŽĞůĞĐƚƌŝĐƉŽůLJŵĞƌ͕ůŝŬĞůLJĐĂƵƐĞĚďLJĂƐƚƌŽŶŐƉŚLJƐŝĐĂůƉŝŶŶŝŶŐĞīĞĐƚŽĨ sƵŶŝƚƐŝŶƚŚĞƉŽůLJŵĞƌďĂĐŬďŽŶĞĂƐŽƉƉŽƐĞĚƚŽǁĞĂŬƉŚLJƐŝĐĂůƉŝŶŶŝŶŐŽĨdƌ&ƵŶŝƚƐŝŶ W;s&-co-dƌ&ͿĐŽƉŽůLJŵĞƌƐ͕ĞŶŚĂŶĐŝŶŐƚŚĞĚŝƉŽůĞƌĞǀĞƌƐŝďŝůŝƚLJ͘ϭϯ_{,ŽǁĞǀĞƌ͕ƚŚĞƌĞůĞĂƐĞĚ} ĞŶĞƌŐLJĚĞŶƐŝƟĞƐŽĨϬϱĂŶĚϭĂƌĞƌĞůĂƟǀĞůLJĐůŽƐĞƚŽƉƌŝƐƟŶĞW;s&-co-sͿĚƵĞƚŽƐŵĂůů ĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶƐŝnjĞ͕ŵŝŶŝŵŝnjŝŶŐĐŽƵƉůŝŶŐŝŶƚĞƌĂĐƟŽŶƐ͕ǁŚŝĐŚůĞĂĚƐƚŽůŽǁƌĞŵĂŶĞŶƚ ƉŽůĂƌŝnjĂƟŽŶƐ͘dŚŝƐĂůƐŽƌĞƐƵůƚƐŝŶĐůĞĂƌůLJŝŶĐƌĞĂƐĞĚĞĸĐŝĞŶĐŝĞƐŽĨƚŚĞĐƌŽƐƐůŝŶŬĞĚƐĂŵƉůĞƐ ĂƚůŽǁĞůĞĐƚƌŝĐĮĞůĚ;ďĞůŽǁϮϬϬDsŵͲϭ_{ͿĂƐĚĞƉŝĐƚĞĚŝŶ&ŝŐƵƌĞϱ͘ϵ͘ƚŚŝŐŚĞƌĞůĞĐƚƌŝĐĮĞůĚƐ͕} ĂďŽǀĞϮϬϬDsŵͲϭ_{͕ƚŚĞĞůĞĐƚƌŝĐĞĸĐŝĞŶĐŝĞƐŽĨϬϱĂŶĚϭĂƌĞƌĞĚƵĐĞĚĚƵĞƚŽĂůŝŐŶŵĞŶƚ} ŽĨĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶƐ͘/ŶĐŽŶƚƌĂƐƚ͕ĂŵŽƌƉŚŽƵƐϮϬĚŝƐƉůĂLJƐŚŝŐŚĞĸĐŝĞŶĐŝĞƐĂďŽǀĞ ϳϬйƵŶƟůϰϬϬDsŵͲϭ_{͕ǁŚŝůĞƐƟůůŚĂǀŝŶŐĚŝƐĐŚĂƌŐĞĚĞŶĞƌŐLJĚĞŶƐŝƟĞƐĨĂƌĂďŽǀĞƐƚĂƚĞͲŽĨͲ} ƚŚĞͲĂƌƚďŝĂdžŝĂůůLJŽƌŝĞŶƚĞĚƉŽůLJƉƌŽƉLJůĞŶĞ͘

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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Conclusions

ŶŽǀĞůŵĞƚŚŽĚƚŽĐŚĞŵŝĐĂůůLJĐƌŽƐƐůŝŶŬŇƵŽƌŝŶĂƚĞĚƉŽůLJŵĞƌƐǁĂƐĚĞŵŽŶƐƚƌĂƚĞĚƉƌŽǀŝĚŝŶŐ ŵĞĂŶƐƚŽƚƵŶĞƚŚĞĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌ͘LJĞŵƉůŽLJŝŶŐƐŝŵƉůĞƵƌĞƚŚĂŶĞĐŚĞŵŝƐƚƌLJƚŽ ĐƌŽƐƐůŝŶŬW;s&-co-sͿĐŽƉŽůLJŵĞƌƐ͕ƚŚĞĚĞŐƌĞĞŽĨĐƌŽƐƐůŝŶŬŝŶŐŝƐǀĂƌŝĞĚďLJĐŚĂŶŐŝŶŐƚŚĞ ĂŵŽƵŶƚŽĨĐƌŽƐƐůŝŶŬŝŶŐĂŐĞŶƚ;,D/Ϳ͘ŌĞƌĐƌŽƐƐůŝŶŬŝŶŐ͕ƚŚĞĐƌLJƐƚĂůůŝŶĞƐĂŵƉůĞƐ͕Ϭϱ ĂŶĚϭƐŚŽǁƚŚĞŚŝŐŚůLJƉŽůĂƌɴͲƉŚĂƐĞŝŶŝƚƐĂůůͲƚƌĂŶƐĐŽŶĨŽƌŵĂƟŽŶ͘dŚĞƉŽůĂƌŝnjĂƟŽŶ hysteresis curves become slimmer as a result of crosslinking. C05 and C1 show double ŚLJƐƚĞƌĞƐŝƐůŽŽƉƐǁŚĞƌĞůŽŽƉƐŽĨϭĚŝƐƉůĂLJĂůŽǁĞƌƌĞŵĂŶĞŶƚĂŶĚŵĂdžŝŵƵŵƉŽůĂƌŝnjĂƟŽŶ ĚƵĞ ƚŽ Ă ƐƚƌŽŶŐĞƌ ƌĞĚƵĐƟŽŶ ŝŶ ĐƌLJƐƚĂůůŝŶŝƚLJ ĂŶĚ ŚĂǀŝŶŐ ĂŶ ŝŶĐƌĞĂƐĞĚ ĐƌLJƐƚĂů ůĂƫĐĞ spacing, enhancing the dipole reversibility. The absence of crystallites in C20 leads ƚŽĂůŝŶĞĂƌƌĞƐƉŽŶƐĞŽĨƉŽůĂƌŝnjĂƟŽŶǁŚĞŶƚŚĞĞůĞĐƚƌŝĐĮĞůĚŝƐŝŶĐƌĞĂƐĞĚ͘/ŶĂĚĚŝƟŽŶ͕ ĐŚĞŵŝĐĂůĐƌŽƐƐůŝŶŬŝŶŐŽĨW;s&-co-sͿĐŽƉŽůLJŵĞƌƐŝŶĐƌĞĂƐĞƐƚŚĞďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚ ĂŶĚƌĞůŝĂďŝůŝƚLJĚƌĂƐƟĐĂůůLJ͕ůĞĂĚŝŶŐƚŽŚŝŐŚĞƌƐƚŽƌĞĚĂŶĚĚŝƐĐŚĂƌŐĞĚĞŶĞƌŐLJĚĞŶƐŝƟĞƐǁŚŝůĞ ŚĂǀŝŶŐŝŶĐƌĞĂƐĞĚĞĸĐŝĞŶĐŝĞƐĐŽŵƉĂƌĞĚƚŽƉƌŝƐƟŶĞĨĞƌƌŽĞůĞĐƚƌŝĐW;s&-co-sͿ͘dŚĞƌĞĨŽƌĞ͕ ĐƌŽƐƐůŝŶŬĞĚW;s&-co-sͿĐŽƉŽůLJŵĞƌƐŽďƚĂŝŶĞĚvia simple urethane chemistry, provide ĂŶŽǀĞůĂƉƉƌŽĂĐŚƚŽƌĞŶĚĞƌŵĂƚĞƌŝĂůƐĨŽƌĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJƐƚŽƌĂŐĞĂƉƉůŝĐĂƟŽŶ͕ǁŚĞƌĞŝŶ ŶŽ ĞdžƚĞƌŶĂů ƉƌŽĐĞƐƐŝŶŐ ŵĞƚŚŽĚƐ ĂƌĞ ƌĞƋƵŝƌĞĚ͕ ǁŚŝůĞ ŽƵƚƉĞƌĨŽƌŵŝŶŐ ƐƚĂƚĞͲŽĨͲƚŚĞͲĂƌƚ ŵĂƚĞƌŝĂůƐƐƵĐŚĂƐďŝĂdžŝĂůůLJŽƌŝĞŶƚĞĚƉŽůLJƉƌŽƉLJůĞŶĞ͘

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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References

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;ϯͿ dĞŽĚŽƌĞƐĐƵ͕Z͖͘>ŝƐĞƌƌĞ͕D͖͘ZŽĚƌşŐƵĞnj͕W͘Grid Converters for Photovoltaic and Wind Power Systems͖tŝůĞLJͲůĂĐŬǁĞůů͕ϮϬϭϬ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϬϮͬϵϳϴϬϰϳϬϲϲϳϬϱϳ͘ĐŚϵ͘

;ϰͿ ŚƵ͕ >͖͘ tĂŶŐ͕ Y͘ EŽǀĞů &ĞƌƌŽĞůĞĐƚƌŝĐ WŽůLJŵĞƌƐ ĨŽƌ ,ŝŐŚ ŶĞƌŐLJ ĞŶƐŝƚLJ ĂŶĚ >Žǁ >ŽƐƐ Dielectrics. Macromolecules ϮϬϭϮ, 45;ϳͿ͕ϮϵϯϳʹϮϵϱϰ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬŵĂϮϬϮϰϬϱϳ͘ ;ϱͿ ĂĞƌ͕ ͖͘ ŚƵ͕ >͘ ϱϬƚŚ ŶŶŝǀĞƌƐĂƌLJ WĞƌƐƉĞĐƟǀĞ͗ ŝĞůĞĐƚƌŝĐ WŚĞŶŽŵĞŶĂ ŝŶ WŽůLJŵĞƌƐ ĂŶĚ

Multilayered Dielectric Films. Macromolecules ϮϬϭϳ, 50 ;ϲͿ͕ ϮϮϯϵʹϮϮϱϲ͘ ŚƚƚƉƐ͗ͬͬĚŽŝ͘ ŽƌŐͬϭϬ͘ϭϬϮϭͬĂĐƐ͘ŵĂĐƌŽŵŽů͘ϲďϬϮϲϲϵ͘ ;ϲͿ ^ĂƌũĞĂŶƚ͕t͘ĂƉĂĐŝƚŽƌƐ͘/dƌĂŶƐĂĐƟŽŶƐŽŶůĞĐƚƌŝĐĂů/ŶƐƵůĂƟŽŶ ϭϵϵϬ, 25;ϱͿ͕ϴϲϭʹϵϮϮ͘ ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϭϬϵͬϭϰ͘ϱϵϴϲϲ͘ ;ϳͿ ^ĂƌũĞĂŶƚ͕t͘:͖͘ŝƌŶŚĞůĚ͕:͖͘DĂĐŽƵŐĂůů͕&͘t͘ĂƉĂĐŝƚŽƌƐ͘/dƌĂŶƐĂĐƟŽŶƐŽŶWůĂƐŵĂ^ĐŝĞŶĐĞ ϭϵϵϴ, 26;ϱͿ͕ϭϯϲϴʹϭϯϵϮ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϭϬϵͬϮϳ͘ϳϯϲϬϮϬ͘ ;ϴͿ ,Ž͕ :͖͘ :Žǁ͕ Z͘ ŚĂƌĂĐƚĞƌŝnjĂƟŽŶ ŽĨ ,ŝŐŚ dĞŵƉĞƌĂƚƵƌĞ WŽůLJŵĞƌ dŚŝŶ &ŝůŵƐ ĨŽƌ WŽǁĞƌ ŽŶĚŝƟŽŶŝŶŐĂƉĂĐŝƚŽƌƐ͕Z>ͲdZͲϰϴϴϬ͖͘ƌŵLJZĞƐĞĂƌĐŚ>ĂďŽƌĂƚŽƌLJ͗ĚĞůƉŚŝ͕D͕ϮϬϬϵ. ;ϵͿ 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 ŵĂĐƉ͘ϮϬϭϳϬϬϲϮϭ͘

;ϭϬͿ >ŽǀŝŶŐĞƌ͕͘:͘&ĞƌƌŽĞůĞĐƚƌŝĐWŽůLJŵĞƌƐ͘Science ϭϵϴϯ, 220;ϰϲϬϮͿ͕ϭϭϭϱʹϭϭϮϭ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ ŽƌŐͬϭϬ͘ϭϭϮϲͬƐĐŝĞŶĐĞ͘ϮϮϬ͘ϰϲϬϮ͘ϭϭϭϱ͘

;ϭϭͿ ^ŽƵůĞƐƚŝŶ͕ d͖͘ >ĂĚŵŝƌĂů͕ s͖͘ ŽƐ ^ĂŶƚŽƐ͕ &͘ ͖͘ ŵĠĚƵƌŝ͕ ͘ sŝŶLJůŝĚĞŶĞ &ůƵŽƌŝĚĞͲ ĂŶĚ dƌŝŇƵŽƌŽĞƚŚLJůĞŶĞͲŽŶƚĂŝŶŝŶŐ&ůƵŽƌŝŶĂƚĞĚůĞĐƚƌŽĂĐƟǀĞŽƉŽůLJŵĞƌƐ͘,ŽǁŽĞƐŚĞŵŝƐƚƌLJ /ŵƉĂĐƚWƌŽƉĞƌƟĞƐ͍Progress in Polymer Science ϮϬϭϳ, 72͕ϭϲʹϲϬ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϭϲͬũ͘ ƉƌŽŐƉŽůLJŵƐĐŝ͘ϮϬϭϳ͘Ϭϰ͘ϬϬϰ͘

;ϭϮͿ >ŝ͕:͖͘DĞŶŐ͕Y͖͘>ŝ͕t͖͘ŚĂŶŐ͕͘/ŶŇƵĞŶĐĞŽĨƌLJƐƚĂůůŝŶĞWƌŽƉĞƌƟĞƐŽŶƚŚĞŝĞůĞĐƚƌŝĐĂŶĚ ŶĞƌŐLJ^ƚŽƌĂŐĞWƌŽƉĞƌƟĞƐŽĨWŽůLJ;sŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞͿ͘Journal of Applied Polymer Science

ϮϬϭϭ, 122;ϯͿ͕ϭϲϱϵʹϭϲϲϴ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϬϮͬĂƉƉ͘ϯϰϬϮϬ͘

;ϭϯͿ zĂŶŐ͕>͖͘>ŝ͕y͖͘ůůĂŚLJĂƌŽǀ͕͖͘dĂLJůŽƌ͕W͘>͖͘ŚĂŶŐ͕Y͘D͖͘ŚƵ͕>͘EŽǀĞůWŽůLJŵĞƌ&ĞƌƌŽĞůĞĐƚƌŝĐ ĞŚĂǀŝŽƌǀŝĂƌLJƐƚĂů/ƐŽŵŽƌƉŚŝƐŵĂŶĚƚŚĞEĂŶŽĐŽŶĮŶĞŵĞŶƚīĞĐƚ͘Polymer ϮϬϭϯ, 54;ϳͿ͕ ϭϳϬϵʹϭϳϮϴ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϭϲͬũ͘ƉŽůLJŵĞƌ͘ϮϬϭϯ͘Ϭϭ͘Ϭϯϱ͘

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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;ϭϰͿ ^ŽƵůĞƐƟŶ͕d͖͘>ĂĚŵŝƌĂů͕s͖͘>ĂŶŶƵnjĞů͕d͖͘ŽŵŝŶŐƵĞƐŽƐ^ĂŶƚŽƐ͕&͖͘ŵĞĚƵƌŝ͕͘/ŵƉŽƌƚĂŶĐĞ ŽĨDŝĐƌŽƐƚƌƵĐƚƵƌĞŽŶƚƌŽůĨŽƌĞƐŝŐŶŝŶŐEĞǁůĞĐƚƌŽĂĐƟǀĞdĞƌƉŽůLJŵĞƌƐĂƐĞĚŽŶsŝŶLJůŝĚĞŶĞ &ůƵŽƌŝĚĞ ĂŶĚ dƌŝŇƵŽƌŽĞƚŚLJůĞŶĞ͘ Macromolecules ϮϬϭϱ, 48 ;ϮϭͿ͕ ϳϴϲϭʹϳϴϳϭ͘ ŚƩƉƐ͗ͬͬĚŽŝ͘ ŽƌŐͬϭϬ͘ϭϬϮϭͬĂĐƐ͘ŵĂĐƌŽŵŽů͘ϱďϬϭϵϲϰ͘ ;ϭϱͿ ^ŽƵůĞƐƟŶ͕d͖͘DĂƌĐĞůŝŶŽŽƐ^ĂŶƚŽƐ&ŝůŚŽ͕W͖͘>ĂĚŵŝƌĂů͕s͖͘dŽƚĠĞ͕͖͘^ŝůůLJ͕'͖͘>ĂŶŶƵnjĞů͕d͖͘ ŽŵŝŶŐƵĞƐŽƐ^ĂŶƚŽƐ͕&͖͘ŵĞĚƵƌŝ͕͘/ŶŇƵĞŶĐĞŽĨdƌĂŶƐͲϭ͕ϯ͕ϯ͕ϯͲdĞƚƌĂŇƵŽƌŽƉƌŽƉĞŶĞŽŶƚŚĞ ^ƚƌƵĐƚƵƌĞʹWƌŽƉĞƌƟĞƐZĞůĂƟŽŶƐŚŝƉŽĨs&ͲĂŶĚdƌ&ͲĂƐĞĚdĞƌƉŽůLJŵĞƌƐ͘Macromolecules ϮϬϭϳ, 50;ϮͿ͕ϱϬϯʹϱϭϰ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬĂĐƐ͘ŵĂĐƌŽŵŽů͘ϲďϬϮϬϭϬ͘ ;ϭϲͿ ^ŽƵůĞƐƟŶ͕d͖͘>ĂĚŵŝƌĂů͕s͖͘>ĂŶŶƵnjĞů͕d͖͘^ĂŶƚŽƐ͕&͖͘͘͘ŵĠĚƵƌŝ͕͘ŝīĞƌĞŶĐĞƐŝŶůĞĐƚƌŽĂĐƟǀĞ dĞƌƉŽůLJŵĞƌƐĂƐĞĚŽŶs&͕dƌ&ĂŶĚϮ͕ϯ͕ϯ͕ϯͲdĞƚƌĂŇƵŽƌŽƉƌŽƉĞŶĞWƌĞƉĂƌĞĚďLJĂƚĐŚ^ŽůƵƟŽŶ ĂŶĚ^ĞŵŝͲŽŶƟŶƵŽƵƐƋƵĞŽƵƐ^ƵƐƉĞŶƐŝŽŶWŽůLJŵĞƌŝnjĂƟŽŶƐ͘Polym. Chem. ϮϬϭϳ, 8;ϰͿ͕ϳϯϱʹ ϳϰϳ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϯϵͬϲWzϬϭϴϳϰ͘ ;ϭϳͿ ĂƌŐĂŝŶ͕&͖͘^ŽƵůĞƐƟŶ͕d͖͘ŽŵŝŶŐƵĞƐŽƐ^ĂŶƚŽƐ͕&͖͘>ĂĚŵŝƌĂů͕s͖͘ŵĠĚƵƌŝ͕͖͘dĞŶĐĠͲ'ŝƌĂƵůƚ͕ ^͘^ĞŵŝĐƌLJƐƚĂůůŝŶĞKƌŐĂŶŝnjĂƟŽŶŽĨs&ͲĂŶĚdƌ&ͲĂƐĞĚůĞĐƚƌŽĂĐƟǀĞdĞƌƉŽůLJŵĞƌƐ͗/ŵƉĂĐƚŽĨ ƚŚĞdƌĂŶƐͲϭ͕ϯ͕ϯ͕ϯͲdĞƚƌĂŇƵŽƌŽƉƌŽƉĞŶĞdĞƌŵŽŶŽŵĞƌ͘Macromolecules ϮϬϭϳ, 50;ϴͿ͕ϯϯϭϯʹϯϯϮϮ͘ ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬĂĐƐ͘ŵĂĐƌŽŵŽů͘ϳďϬϬϬϱϭ͘ ;ϭϴͿ >ŝ͕z͖͘^ŽƵůĞƐƟŶ͕d͖͘>ĂĚŵŝƌĂů͕s͖͘ŵĞĚƵƌŝ͕͖͘>ĂŶŶƵnjĞů͕d͖͘ŽŵŝŶŐƵĞƐŽƐ^ĂŶƚŽƐ͕&͖͘>ŝ͕͘ͲD͖͘ ŚŽŶŐ͕'͘Ͳ:͖͘ŚƵ͕>͘^ƚƌĞƚĐŚŝŶŐͲ/ŶĚƵĐĞĚZĞůĂdžŽƌ&ĞƌƌŽĞůĞĐƚƌŝĐĞŚĂǀŝŽƌŝŶĂWŽůLJ;sŝŶLJůŝĚĞŶĞ &ůƵŽƌŝĚĞͲŽͲdƌŝĨůƵŽƌŽĞƚŚLJůĞŶĞͲŽͲ,ĞdžĂĨůƵŽƌŽƉƌŽƉLJůĞŶĞͿ ZĂŶĚŽŵ dĞƌƉŽůLJŵĞƌ͘ Macromolecules ϮϬϭϳ, 50;ϭϵͿ͕ϳϲϰϲʹϳϲϱϲ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬĂĐƐ͘ŵĂĐƌŽŵŽů͘ϳďϬϭϮϬϱ͘ ;ϭϵͿ ^ŽƵůĞƐƟŶ͕ d͖͘ &ŝůŚŽ͕ W͘ D͘ ͘ ^͖͘ >ĂĚŵŝƌĂů͕ s͖͘ >ĂŶŶƵnjĞů͕ d͖͘ ^ĂŶƚŽƐ͕ &͘ ͘ ͖͘ ŵĠĚƵƌŝ͕ ͘ &ĞƌƌŽĞůĞĐƚƌŝĐ&ůƵŽƌŝŶĂƚĞĚŽƉŽůLJŵĞƌƐǁŝƚŚ/ŵƉƌŽǀĞĚĚŚĞƐŝŽŶWƌŽƉĞƌƟĞƐ͘Polym. Chem. ϮϬϭϳ, 8;ϲͿ͕ϭϬϭϳʹϭϬϮϳ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϯϵͬϲWzϬϮϬϲϯ͘ ;ϮϬͿ ŚƵ͕>͘džƉůŽƌŝŶŐ^ƚƌĂƚĞŐŝĞƐĨŽƌ,ŝŐŚŝĞůĞĐƚƌŝĐŽŶƐƚĂŶƚĂŶĚ>Žǁ>ŽƐƐWŽůLJŵĞƌŝĞůĞĐƚƌŝĐƐ͘ :͘WŚLJƐ͘ŚĞŵ͘>ĞƩ͘ ϮϬϭϰ, 5;ϮϭͿ͕ϯϲϳϳʹϯϲϴϳ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬũnjϱϬϭϴϯϭƋ͘ ;ϮϭͿ ŚĂŶŐ͕Y͘D͖͘ŚĂƌƟ͕s͖͘ŚĂŽ͕y͘'ŝĂŶƚůĞĐƚƌŽƐƚƌŝĐƟŽŶĂŶĚZĞůĂdžŽƌ&ĞƌƌŽĞůĞĐƚƌŝĐĞŚĂǀŝŽƌ ŝŶůĞĐƚƌŽŶͲ/ƌƌĂĚŝĂƚĞĚWŽůLJ;sŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞͲdƌŝŇƵŽƌŽĞƚŚLJůĞŶĞͿŽƉŽůLJŵĞƌ͘Science ϭϵϵϴ, 280;ϱϯϳϮͿ͕ϮϭϬϭʹϮϭϬϰ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϭϮϲͬƐĐŝĞŶĐĞ͘ϮϴϬ͘ϱϯϳϮ͘ϮϭϬϭ͘ ;ϮϮͿ <ŚĂŶĐŚĂŝƟƚ͕W͖͘,ĂŶ͕<͖͘'ĂĚŝŶƐŬŝ͕D͘Z͖͘>ŝ͕Y͖͘tĂŶŐ͕Y͘&ĞƌƌŽĞůĞĐƚƌŝĐWŽůLJŵĞƌEĞƚǁŽƌŬƐ ǁŝƚŚ,ŝŐŚŶĞƌŐLJĞŶƐŝƚLJĂŶĚ/ŵƉƌŽǀĞĚŝƐĐŚĂƌŐĞĚĸĐŝĞŶĐLJĨŽƌŝĞůĞĐƚƌŝĐŶĞƌŐLJ^ƚŽƌĂŐĞ͘ EĂƚƵƌĞŽŵŵƵŶŝĐĂƟŽŶƐ ϮϬϭϯ, 4͕Ϯϴϰϱ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϯϴͬŶĐŽŵŵƐϯϴϰϱ͘ ;ϮϯͿ dĂŐƵĞƚ͕ ͖͘ ŵĞĚƵƌŝ͕ ͖͘ ŽƵƚĞǀŝŶ͕ ͘ ƌŽƐƐůŝŶŬŝŶŐ ŽĨ sŝŶLJůŝĚĞŶĞ &ůƵŽƌŝĚĞͲŽŶƚĂŝŶŝŶŐ Fluoropolymers. In Crosslinking in Materials Science͖ĚǀĂŶĐĞƐŝŶWŽůLJŵĞƌ^ĐŝĞŶĐĞ͖^ƉƌŝŶŐĞƌ ĞƌůŝŶ,ĞŝĚĞůďĞƌŐ͗ĞƌůŝŶ͕,ĞŝĚĞůďĞƌŐ͕ϮϬϬϱ͖ƉƉϭϮϳʹϮϭϭ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϬϳͬďϭϯϲϮϰϱ͘

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: 102PDF page: 102PDF page: 102PDF page: 102

102 ;ϮϰͿ tĞŚďŝ͕D͖͘ĂŶĞƌũĞĞ͕^͖͘DĞŚĚŝ͕͖͘ůĂĂĞĚĚŝŶĞ͕͖͘,ĂĐŚĞŵ͕͖͘ŵĞĚƵƌŝ͕͘sŝŶLJůŝĚĞŶĞ &ůƵŽƌŝĚĞͲĂƐĞĚWŽůLJŵĞƌEĞƚǁŽƌŬǀŝĂƌŽƐƐͲ>ŝŶŬŝŶŐŽĨWĞŶĚĂŶƚdƌŝĞƚŚŽdžLJƐŝůĂŶĞ&ƵŶĐƟŽŶĂůŝƚLJ ĨŽƌWŽƚĞŶƟĂůƉƉůŝĐĂƟŽŶƐŝŶŽĂƟŶŐƐ͘Macromolecules ϮϬϭϳ, 50;ϮϯͿ͕ϵϯϮϵʹϵϯϯϵ͘ŚƩƉƐ͗ͬͬ ĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬĂĐƐ͘ŵĂĐƌŽŵŽů͘ϳďϬϮϭϯϴ͘ ;ϮϱͿ ĂŶĞƌũĞĞ͕^͖͘tĞŚďŝ͕D͖͘DĂŶƐĞƌŝ͕͖͘DĞŚĚŝ͕͖͘ůĂĂĞĚĚŝŶĞ͕͖͘,ĂĐŚĞŵ͕͖͘ŵĞĚƵƌŝ͕͘ WŽůLJ;sŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞͿŽŶƚĂŝŶŝŶŐWŚŽƐƉŚŽŶŝĐĐŝĚĂƐŶƟĐŽƌƌŽƐŝŽŶŽĂƟŶŐĨŽƌ^ƚĞĞů͘ACS Appl. Mater. Interfaces ϮϬϭϳ, 9;ϳͿ͕ϲϰϯϯʹϲϰϰϯ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬĂĐƐĂŵŝ͘ϲďϭϱϰϬϴ͘ ;ϮϲͿ DĞĞƌĞďŽĞƌ͕E͘>͖͘dĞƌnjŝđ͕/͖͘^ƚĞĞŐ͕W͘ǀĂŶĚĞƌ͖WŽƌƚĂůĞ͕'͖͘>ŽŽƐ͕<͘WŚLJƐŝĐĂůWŝŶŶŝŶŐĂŶĚ

ŚĞŵŝĐĂů ƌŽƐƐůŝŶŬŝŶŐͲ/ŶĚƵĐĞĚ ZĞůĂdžŽƌ &ĞƌƌŽĞůĞĐƚƌŝĐ ĞŚĂǀŝŽƌ ŝŶ W;s&ͲdĞƌͲdƌ&ͲdĞƌͲsͿ Terpolymers. J. Mater. Chem. A ϮϬϭϵ, 7;ϲͿ͕ϮϳϵϱʹϮϴϬϯ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϯϵͬϴdϭϭϱϯϰ&͘ ;ϮϳͿ DĞĞƌĞďŽĞƌ͕E͘>͕͘dĞƌnjŝđ͕/͖͘^ƚĞĞŐ͕W͘ǀĂŶĚĞƌ͖ĐƵĂƵƚůĂ͕D͖sŽĞƚ͕s͘^͖͘͘>ŽŽƐ͕<͘ůĞĐƚƌŽĂĐƟǀĞ

ĞŚĂǀŝŽƌŽŶĞŵĂŶĚŝŶW;s&ͲŽͲsͿŽƉŽůLJŵĞƌƐ͘Materials Today Energy ϮϬϭϵ. 11͕ϴϯͲϴϴ ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϭϲͬũ͘ŵƚĞŶĞƌ͘ϮϬϭϴ͘ϭϬ͘Ϭϭϵ

;ϮϴͿ 'ƵĂŶ͕ &͖͘ tĂŶŐ͕ :͖͘ WĂŶ͕ :͖͘ tĂŶŐ͕ Y͖͘ ŚƵ͕ >͘ īĞĐƚƐ ŽĨ WŽůLJŵŽƌƉŚŝƐŵ ĂŶĚ ƌLJƐƚĂůůŝƚĞ ^ŝnjĞ ŽŶ ŝƉŽůĞ ZĞŽƌŝĞŶƚĂƟŽŶ ŝŶ WŽůLJ;sŝŶLJůŝĚĞŶĞ &ůƵŽƌŝĚĞͿ ĂŶĚ /ƚƐ ZĂŶĚŽŵ ŽƉŽůLJŵĞƌƐ͘ Macromolecules ϮϬϭϬ, 43;ϭϲͿ͕ϲϳϯϵʹϲϳϰϴ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬŵĂϭϬϭϬϲϮũ͘

;ϮϵͿ ĞŚƐĂƌŝ͕,͘^͖͘DŝĐŚĞůƐ͕:͘:͖͘ƐĂĚŝ͕<͘WƌŽĐĞƐƐŝŶŐŽĨ&ĞƌƌŽĞůĞĐƚƌŝĐWŽůLJŵĞƌƐĨŽƌDŝĐƌŽĞůĞĐƚƌŽŶŝĐƐ͗ &ƌŽŵDŽƌƉŚŽůŽŐŝĐĂůŶĂůLJƐŝƐƚŽ&ƵŶĐƟŽŶĂůĞǀŝĐĞƐ͘J. Mater. Chem. C ϮϬϭϳ, 5;ϰϬͿ͕ϭϬϰϵϬʹ ϭϬϰϵϳ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϯϵͬϳdϬϭϰϵϱ͘ ;ϯϬͿ <ƌƵŵŽǀĂ͕D͖͘>ſƉĞnj͕͖͘ĞŶĂǀĞŶƚĞ͕Z͖͘DŝũĂŶŐŽƐ͕͖͘WĞƌĞŹĂ͕:͘D͘īĞĐƚŽĨƌŽƐƐůŝŶŬŝŶŐ ŽŶƚŚĞDĞĐŚĂŶŝĐĂůĂŶĚdŚĞƌŵĂůWƌŽƉĞƌƟĞƐŽĨWŽůLJ;sŝŶLJůůĐŽŚŽůͿ͘Polymer ϮϬϬϬ, 41;ϮϲͿ͕ ϵϮϲϱʹϵϮϳϮ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϭϲͬ^ϬϬϯϮͲϯϴϲϭ;ϬϬͿϬϬϮϴϳͲϭ͘ ;ϯϭͿ ,ƵĂŶŐ͕z͖͘yƵ͕:͘Ͳ͖͘^ŽƵůĞƐƟŶ͕d͖͘ŽƐ^ĂŶƚŽƐ͕&͖͘͘>ŝ͕Z͖͘&ƵŬƵƚŽ͕D͖͘>Ğŝ͕:͖͘ŚŽŶŐ͕'͘Ͳ:͖͘>ŝ͕ ͘ͲD͖͘>ŝ͕z͖͘ĞƚĂů͘ĂŶZĞůĂdžŽƌ&ĞƌƌŽĞůĞĐƚƌŝĐĞŚĂǀŝŽƌĞZĞĂůŝnjĞĚĨŽƌWŽůLJ;sŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞͲ ŽͲŚůŽƌŽƚƌŝŇƵŽƌŽĞƚŚLJůĞŶĞͿ΀W;s&ʹd&Ϳ΁ZĂŶĚŽŵŽƉŽůLJŵĞƌƐďLJ/ŶĐůƵƐŝŽŶŽĨd&hŶŝƚƐ ŝŶWs&ƌLJƐƚĂůƐ͍Macromolecules ϮϬϭϴ, 51;ϭϰͿ͕ϱϰϲϬʹϱϰϳϮ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬĂĐƐ͘ macromol.8b01155. ;ϯϮͿ DĂƌƟŶƐ͕ W͖͘ >ŽƉĞƐ͕ ͘ ͖͘ >ĂŶĐĞƌŽƐͲDĞŶĚĞnj͕ ^͘ ůĞĐƚƌŽĂĐƟǀĞ WŚĂƐĞƐ ŽĨ WŽůLJ;sŝŶLJůŝĚĞŶĞ &ůƵŽƌŝĚĞͿ͗ĞƚĞƌŵŝŶĂƟŽŶ͕WƌŽĐĞƐƐŝŶŐĂŶĚƉƉůŝĐĂƟŽŶƐ͘Progress in Polymer Science ϮϬϭϰ, 39;ϰͿ͕ϲϴϯʹϳϬϲ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϭϲͬũ͘ƉƌŽŐƉŽůLJŵƐĐŝ͘ϮϬϭϯ͘Ϭϳ͘ϬϬϲ͘

;ϯϯͿ dĂŶ͕^͖͘,Ƶ͕y͖͘ŝŶŐ͕^͖͘ŚĂŶŐ͕͖͘>ŝ͕,͖͘zĂŶŐ͕>͘^ŝŐŶŝĮĐĂŶƚůLJ/ŵƉƌŽǀŝŶŐŝĞůĞĐƚƌŝĐĂŶĚŶĞƌŐLJ ^ƚŽƌĂŐĞWƌŽƉĞƌƟĞƐǀŝĂhŶŝĂdžŝĂůůLJ^ƚƌĞƚĐŚŝŶŐƌŽƐƐůŝŶŬĞĚW;s&ͲŽͲdƌ&Ϳ&ŝůŵƐ͘J. Mater. Chem. A ϮϬϭϯ, 1;ϯϱͿ͕ϭϬϯϱϯʹϭϬϯϲϭ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϯϵͬϯdϭϭϰϴϰ,͘

;ϯϰͿ dĞƌnjŝĐ͕/͖͘DĞĞƌĞďŽĞƌ͕E͘>͖͘ĐƵĂƵƚůĂ͕D͖͘WŽƌƚĂůĞ͕'͖͘>ŽŽƐ͕<͘ůĞĐƚƌŽĂĐƟǀĞDĂƚĞƌŝĂůƐǁŝƚŚ dƵŶĂďůĞZĞƐƉŽŶƐĞĂƐĞĚŽŶůŽĐŬŽƉŽůLJŵĞƌ^ĞůĨͲƐƐĞŵďůLJ͘EĂƚƵƌĞŽŵŵƵŶŝĐĂƟŽŶƐ ϮϬϭϵ, 10;ϭͿ͕ϲϬϭ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϯϴͬƐϰϭϰϲϳͲϬϭϵͲϬϴϰϯϲͲϮ͘

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: 103PDF page: 103PDF page: 103PDF page: 103

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;ϯϱͿ 'ƵĂŶ͕ &͖͘ zĂŶŐ͕ >͖͘ tĂŶŐ͕ :͖͘ 'ƵĂŶ͕ ͖͘ ,ĂŶ͕ <͖͘ tĂŶŐ͕ Y͖͘ ŚƵ͕ >͘ ŽŶĮŶĞĚ &ĞƌƌŽĞůĞĐƚƌŝĐ WƌŽƉĞƌƟĞƐŝŶWŽůLJ;sŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞͲŽͲŚůŽƌŽƚƌŝŇƵŽƌŽĞƚŚLJůĞŶĞͿͲ'ƌĂŌͲWŽůLJƐƚLJƌĞŶĞ'ƌĂŌ ŽƉŽůLJŵĞƌƐĨŽƌůĞĐƚƌŝĐŶĞƌŐLJ^ƚŽƌĂŐĞƉƉůŝĐĂƟŽŶƐ͘ĚǀĂŶĐĞĚ&ƵŶĐƟŽŶĂůDĂƚĞƌŝĂůƐ ϮϬϭϭ, 21;ϭϲͿ͕ϯϭϳϲʹϯϭϴϴ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϬϮͬĂĚĨŵ͘ϮϬϭϬϬϮϬϭϱ͘

;ϯϲͿ ^ŚŝŶ͕z͘:͖͘<ĂŶŐ͕^͘:͖͘:ƵŶŐ͕,͘:͖͘WĂƌŬ͕z͘:͖͘ĂĞ͕/͖͘ŚŽŝ͕͘,͖͘WĂƌŬ͕͘ŚĞŵŝĐĂůůLJƌŽƐƐͲ >ŝŶŬĞĚdŚŝŶWŽůLJ;sŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞͲŽͲdƌŝŇƵŽƌŽĞƚŚLJůĞŶĞͿ&ŝůŵƐĨŽƌEŽŶǀŽůĂƟůĞ&ĞƌƌŽĞůĞĐƚƌŝĐ Polymer Memory. ACS Appl. Mater. Interfaces ϮϬϭϭ, 3;ϮͿ͕ϱϴϮʹϱϴϵ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬ ĂŵϭϬϭϭϲϱϳ͘

;ϯϳͿ ^ŚŝŶ͕z͘:͖͘<ŝŵ͕Z͘,͖͘:ƵŶŐ͕,͘:͖͘<ĂŶŐ͕^͘:͖͘WĂƌŬ͕z͘:͖͘ĂĞ͕/͖͘WĂƌŬ͕͘ŽŵƉƌĞƐƐŝŽŶŽĨ ƌŽƐƐͲ>ŝŶŬĞĚWŽůLJ;sŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞͲŽͲdƌŝŇƵŽƌŽƚŚLJůĞŶĞͿ&ŝůŵƐĨŽƌ&ĂĐŝůĞ&ĞƌƌŽĞůĞĐƚƌŝĐ WŽůĂƌŝnjĂƟŽŶ͘ACS Appl. Mater. Interfaces ϮϬϭϭ, 3;ϭϮͿ͕ϰϳϯϲʹϰϳϰϯ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬ am201202w. ;ϯϴͿ DĞĞƌĞďŽĞƌ͕E͘>͖͘dĞƌnjŝđ͕/͖͘^ĂŝĚŝ͕^͖͘,ĞƌŵŝĚĂDĞƌŝŶŽ͕͖͘>ŽŽƐ͕<͘EĂŶŽĐŽŶĮŶĞŵĞŶƚͲ/ŶĚƵĐĞĚ ɴͲWŚĂƐĞ&ŽƌŵĂƟŽŶ/ŶƐŝĚĞWŽůLJ;sŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞͿͲĂƐĞĚůŽĐŬŽƉŽůLJŵĞƌƐ͘ACS Macro >ĞƩ͘ ϮϬϭϴ͕ϴϲϯʹϴϲϳ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϮϭͬĂĐƐŵĂĐƌŽůĞƩ͘ϴďϬϬϰϭϴ͘ ;ϯϵͿ dĞƌnjŝđ͕/͖͘DĞĞƌĞďŽĞƌ͕E͘>͖͘>ŽŽƐ͕<͘ƵůŝĐŬŚĞŵŝƐƚƌLJ͗sĞƌƐĂƟůĞƉƉƌŽĂĐŚƚŽǁĂƌĚƐ Ws&ͲĂƐĞĚůŽĐŬŽƉŽůLJŵĞƌƐ͘Polymer Chemistry ϮϬϭϴ. ;ϰϬͿ sŽĞƚ͕s͘^͖͘͘ƌŝŶŬĞ͕'͘ƚĞŶ͖>ŽŽƐ͕<͘tĞůůͲĞĮŶĞĚŽƉŽůLJŵĞƌƐĂƐĞĚŽŶWŽůLJ;sŝŶLJůŝĚĞŶĞ &ůƵŽƌŝĚĞͿ͗&ƌŽŵWƌĞƉĂƌĂƟŽŶĂŶĚWŚĂƐĞ^ĞƉĂƌĂƟŽŶƚŽƉƉůŝĐĂƟŽŶ͘Journal of Polymer Science Part A: Polymer Chemistry ϮϬϭϰ, 52;ϮϬͿ͕ϮϴϲϭʹϮϴϳϳ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϬϮͬƉŽůĂ͘ϮϳϯϰϬ͘ ;ϰϭͿ sŽĞƚ͕s͘^͖͘͘dŝĐŚĞůĂĂƌ͕D͖͘dĂŶĂƐĞ͕^͖͘DŝƩĞůŵĞŝũĞƌͲ,ĂnjĞůĞŐĞƌ͕D͖͘͘ƌŝŶŬĞ͕'͘ƚĞŶ͖>ŽŽƐ͕

<͘WŽůLJ;sŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞͿͬEŝĐŬĞůEĂŶŽĐŽŵƉŽƐŝƚĞƐĨƌŽŵ^ĞŵŝĐƌLJƐƚĂůůŝŶĞůŽĐŬŽƉŽůLJŵĞƌ Precursors. Nanoscale ϮϬϭϮ, 5;ϭͿ͕ϭϴϰʹϭϵϮ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϯϵͬϮEZϯϮϵϵϬ͘ ;ϰϮͿ sŽĞƚ͕s͘^͖͘͘ŬĞŶƐƚĞŝŶ͕'͘K͘Z͘͘ǀĂŶ͖DĞĞƌĞďŽĞƌ͕E͘>͖͘,ŽĨŵĂŶ͕͘,͖͘ƌŝŶŬĞ͕'͘ƚĞŶ͖ >ŽŽƐ͕ <͘ ŽƵďůĞͲƌLJƐƚĂůůŝŶĞ W>>ͲďͲWs&ͲďͲW>> dƌŝďůŽĐŬ ŽƉŽůLJŵĞƌƐ͗ WƌĞƉĂƌĂƟŽŶ ĂŶĚ ƌLJƐƚĂůůŝnjĂƟŽŶ͘Polym. Chem. ϮϬϭϰ, 5;ϳͿ͕ϮϮϭϵʹϮϮϯϬ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϯϵͬϯWzϬϭϱϲϬ͘ ;ϰϯͿ sŽĞƚ͕s͘^͖͘͘,ĞƌŵŝĚĂͲDĞƌŝŶŽ͕͖͘ƌŝŶŬĞ͕'͘ƚĞŶ͖>ŽŽƐ͕<͘ůŽĐŬŽƉŽůLJŵĞƌZŽƵƚĞƚŽǁĂƌĚƐ WŽůLJ;sŝŶLJůŝĚĞŶĞ&ůƵŽƌŝĚĞͿͬWŽůLJ;DĞƚŚĂĐƌLJůŝĐĐŝĚͿͬEŝĐŬĞůEĂŶŽĐŽŵƉŽƐŝƚĞƐ͘RSC Adv. ϮϬϭϯ, 3 ;ϮϭͿ͕ϳϵϯϴʹϳϵϰϲ͘ŚƩƉƐ͗ͬͬĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϯϵͬϯZϰϬϯϲϱ͘ ;ϰϰͿ dĂŶ͕ ^͖͘ >ŝ͕ :͖͘ 'ĂŽ͕ '͖͘ >ŝ͕ ,͖͘ ŚĂŶŐ͕ ͘ ^LJŶƚŚĞƐŝƐ ŽĨ &ůƵŽƌŽƉŽůLJŵĞƌ ŽŶƚĂŝŶŝŶŐ dƵŶĂďůĞ hŶƐĂƚƵƌĂƟŽŶďLJĂŽŶƚƌŽůůĞĚĞŚLJĚƌŽĐŚůŽƌŝŶĂƟŽŶŽĨW;s&ͲŽͲd&ͿĂŶĚ/ƚƐƵƌŝŶŐĨŽƌ ,ŝŐŚWĞƌĨŽƌŵĂŶĐĞZƵďďĞƌƉƉůŝĐĂƟŽŶƐ͘J. Mater. Chem. ϮϬϭϮ, 22;ϯϱͿ͕ϭϴϰϵϲʹϭϴϱϬϰ͘ŚƩƉƐ͗ͬͬ ĚŽŝ͘ŽƌŐͬϭϬ͘ϭϬϯϵͬϮ:Dϯϯϭϯϯ<͘ ;ϰϱͿ ůLJƚŚĞ͕d͖͘ůŽŽƌ͕͘ůĞĐƚƌŝĐĂůWƌŽƉĞƌƟĞƐŽĨWŽůLJŵĞƌƐ͕ϮŶĚĞĚ͖͘ĂŵďƌŝĚŐĞhŶŝǀĞƌƐŝƚLJWƌĞƐƐ͗ EĞǁzŽƌŬ͕ϮϬϬϴ͘