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

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

applications

Meereboer, Niels Laurens

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

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Publication date: 2019

Link to publication in University of Groningen/UMCG research database

Citation for published version (APA):

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 1

PVDF for energy storage applications

/Ŷ ƚŚŝƐ ĮƌƐƚ ĐŚĂƉƚĞƌ͕ ƚŚĞ ƌŽůĞ ŽĨ ƉŽůLJŵĞƌ Įůŵ ĐĂƉĂĐŝƚŽƌƐ ŝŶ ĞůĞĐƚƌŽŶŝĐ ĐŝƌĐƵŝƚƐ ĂŶĚ ĂƉƉůŝĐĂƟŽŶƐŝƐĞůƵĐŝĚĂƚĞĚ͘DĂŝŶůLJĚƵĞƚŽƚŚĞŝƌƵŶŝƋƵĞƚƌĂĚĞͲŽīďĞƚǁĞĞŶŚŝŐŚĞŶĞƌŐLJ ĚĞŶƐŝƚLJ͕ĨĂƐƚĚŝƐĐŚĂƌŐĞƌĂƚĞƐĂŶĚĂďŝůŝƚLJƚŽǁŝƚŚƐƚĂŶĚŚŝŐŚǀŽůƚĂŐĞƐ͕ƚŚĞLJĂƌĞƵƟůŝnjĞĚ ŝŶƉƵůƐĞĚƉŽǁĞƌĂƉƉůŝĐĂƟŽŶƐĂŶĚĂƐƉŽǁĞƌĐŽŶǀĞƌƚĞƌƐ͘,ŽǁĞǀĞƌ͕ƚŚĞĐƵƌƌĞŶƚƐƚĂƚĞͲŽĨͲ ƚŚĞͲĂƌƚŵĂƚĞƌŝĂůƐƐŚŽǁƌĞůĂƟǀĞůLJƉŽŽƌĞŶĞƌŐLJĚĞŶƐŝƟĞƐ͘dŽĞŶŚĂŶĐĞƚŚĞƉƌŽƉĞƌƟĞƐĨŽƌ dielectric materials, large improvements are possible when polymers with high dielectric constant and high breakdown strengths are used. In this respect, poly(vinylidene ŇƵŽƌŝĚĞͿ;Ws&ͿĂƉƉĞĂƌƐƚŽďĞĂŶŝĚĞĂůĐĂŶĚŝĚĂƚĞ͘,ŽǁĞǀĞƌ͕ĂŶŝƌƌĞǀĞƌƐŝďůĞĐƌLJƐƚĂůůŝŶĞ ƉŚĂƐĞ ƚƌĂŶƐĨŽƌŵĂƟŽŶ Ăƚ ŚŝŐŚ ĮĞůĚƐ͕ ƌĞƐƵůƟŶŐ ŝŶ ůĂƌŐĞ ĨĞƌƌŽĞůĞĐƚƌŝĐ ůŽƐƐĞƐ͕ ůŝŵŝƚƐ ŝƚƐ ĂƉƉůŝĐĂďŝůŝƚLJ͘LJŚĂǀŝŶŐĂĐĂƌĞĨƵůůŽŽŬĂƚƚŚĞŵĞĐŚĂŶŝƐŵŽĨĨĞƌƌŽĞůĞĐƚƌŝĐŝƚLJŝŶWs&͕ŝƚ ŝƐƌĞǀĞĂůĞĚƚŚĂƚƚŚĞŚŝŐŚůLJƉŽůĂƌĨĞƌƌŽĞůĞĐƚƌŝĐɴͲƉŚĂƐĞĐĂŶďĞďĞŶĞĮĐŝĂůĨŽƌĚŝĞůĞĐƚƌŝĐ ĞŶĞƌŐLJƐƚŽƌĂŐĞ͘dŽĚŽƚŚŝƐ͕ůĂƌŐĞĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶĐŽƵƉůŝŶŐŝŶƚĞƌĂĐƟŽŶƐŝŶWs& ƐŚŽƵůĚďĞƉƌĞǀĞŶƚĞĚĂŶĚŝƐŽůĂƟŽŶŽĨƚŚĞĐƌLJƐƚĂůƐďLJĂŶŽŶƉŽůĂƌŝŶƚĞƌĨĂĐĞŝƐĚĞƐŝƌĂďůĞƚŽ enhance its crystalline dipole reversibility. Therefore, polymer topologies, assessable ďLJĞĂƐLJƐLJŶƚŚĞƟĐĂƉƉƌŽĂĐŚĞƐ͕ƚŽŝƐŽůĂƚĞĨĞƌƌŽĞůĞĐƚƌŝĐĐƌLJƐƚĂůƐĂŶĚƚŽŵŝŶŝŵŝnjĞĐŽƵƉůŝŶŐ ŝŶƚĞƌĂĐƟŽŶƐ ďĞƚǁĞĞŶ ĨĞƌƌŽĞůĞĐƚƌŝĐ ĚŽŵĂŝŶƐ͕ ĂƌĞ ďƌŝĞŇLJ ĚŝƐĐƵƐƐĞĚ͕ ƐƵĐŚ ĂƐ ĐŽͲ ĂŶĚ ƚĞƌƉŽůLJŵĞƌŝnjĂƟŽŶƐ͕ŐƌĂŌĐŽƉŽůLJŵĞƌƐ͕ĐƌŽƐƐůŝŶŬŝŶŐŽĨŇƵŽƌŝŶĂƚĞĚƉŽůLJŵĞƌƐ͕ŵƵůƟůĂLJĞƌŝŶŐ ŽĨƉŽůLJŵĞƌƐĂŶĚďůŽĐŬĐŽƉŽůLJŵĞƌƐĞůĨͲĂƐƐĞŵďůLJ͘

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Energy Storage

dĞĐŚŶŽůŽŐŝĞƐ ƌĞŐĂƌĚŝŶŐ ĞŶĞƌŐLJ ƉƌŽĚƵĐƟŽŶ͕ ƐƚŽƌĂŐĞ ĂŶĚ ĐŽŶƐƵŵƉƟŽŶ ŚĂǀĞ Ă ƐƚƌŽŶŐ impact on the modern world.1 Nevertheless, running out of fossil fuels and an ever

ŝŶĐƌĞĂƐŝŶŐǁŽƌůĚ͛ƐĞŶĞƌŐLJĐŽŶƐƵŵƉƟŽŶƌĞƋƵŝƌĞƚŚĞĚĞǀĞůŽƉŵĞŶƚŽĨƚŚĞƐĞƚĞĐŚŶŽůŽŐŝĞƐ in a sustainable way.2dŽŵĞĞƚƚŚĞĨƵƚƵƌĞŐůŽďĂůĞŶĞƌŐLJĚĞŵĂŶĚƐ͕ĂůƚĞƌŶĂƟǀĞĞŶĞƌŐLJ ƐŽƵƌĐĞƐ͕ƐƵĐŚĂƐŚLJĚƌŽĞůĞĐƚƌŝĐŝƚLJ͕ďŝŽŵĂƐƐ͕ƐŽůĂƌ͕ǁŝŶĚ͕ǁĂǀĞ͕ƟĚĂů͕ĞƚĐ͘ĂƌĞĐƵƌƌĞŶƚůLJ ĞdžƚĞŶƐŝǀĞůLJŝŶǀĞƐƟŐĂƚĞĚĨŽƌŚĂǀŝŶŐĂďƌŝŐŚƚĨƵƚƵƌĞ͘ϯ͕ϰ EŽǁĂĚĂLJƐ͕ƐƚŽƌĂŐĞŽĨĞŶĞƌŐLJŝƐƉŽƐƐŝďůĞŝŶďĂƩĞƌŝĞƐ͕ƌĞĚŽdžͲŇŽǁďĂƩĞƌŝĞƐ͕ĨƵĞůĐĞůůƐ͕ ĞůĞĐƚƌŽĐŚĞŵŝĐĂůĐĂƉĂĐŝƚŽƌƐ͕ĂŶĚĐĂƉĂĐŝƚŽƌƐ͕ĂůůŵĂŬŝŶŐƵŶŝƋƵĞƚƌĂĚĞͲŽīƐďĞƚǁĞĞŶŚŝŐŚ energy density, high discharge rate, and the ability to withstand high voltages (Figure ϭ͘ϭͿ͘1/ŶƚŚŝƐƌĞƐƉĞĐƚ͕ďĂƩĞƌŝĞƐ͕ĨƵĞůĐĞůůĂŶĚĞůĞĐƚƌŽĐŚĞŵŝĐĂůĐĂƉĂĐŝƚŽƌƐĂƌĞŵĂŝŶůLJƵƐĞĚ

in electrochemical energy storage and conversions, while capacitors deal with direct ĞůĞĐƚƌŝĐĂůĞŶĞƌŐLJĂƉƉůŝĐĂƟŽŶƐ͘

In electrochemical energy storage devices, energy transfer takes place at the ĞůĞĐƚƌŽĚĞͲĞůĞĐƚƌŽůLJƚĞŝŶƚĞƌĨĂĐĞ͕ǁŚŝůĞŝŶĐĂƉĂĐŝƚŽƌƐ͕ĐŚĂƌŐĞƐƌĞƐŝĚĞĂƚƚŚĞĚŝĞůĞĐƚƌŝĐͲ ĞůĞĐƚƌŽĚĞŝŶƚĞƌĨĂĐĞ͕ĞŶũŽLJŝŶŐŵĂũŽƌĂĚǀĂŶƚĂŐĞƐƐƵĐŚĂƐŇĞdžŝďŝůŝƚLJĂŶĚŽƌĚĞƌŽĨŵĂŐŶŝƚƵĚĞ ĨĂƐƚĞƌĚŝƐĐŚĂƌŐĞƌĂƚĞƐ͕ǁŚŝĐŚŵĂŬĞƐƚŚĞŵŝŶĚŝƐƉĞŶƐĂďůĞĨŽƌĂďƌŽĂĚƌĂŶŐĞŽĨĂƉƉůŝĐĂƟŽŶƐ (e.g.ƉŽǁĞƌŝŶǀĞƌƚĞƌƐ͕ƉƵůƐĞĚƉŽǁĞƌĚĞǀŝĐĞƐ͕ĞƚĐ͘Ϳ͘ϭ͕ϯ͕ϱʹϳ For instance, in the internal circuit

ŽĨĐĂƌƐ͕ďƵƐĐĂƉĂĐŝƚŽƌƐŝŶƉŽǁĞƌŝŶǀĞƌƚĞƌƐĂƌĞŽƉĞƌĂƟŶŐƚŽƐǁŝƚĐŚĚŝƌĞĐƚƚŽĂůƚĞƌŶĂƟŶŐ ĐƵƌƌĞŶƚĂŶĚǀŝĐĞǀĞƌƐĂ͕ĂƐŬŝŶŐĨŽƌĚĞŵĂŶĚƐƐƵĐŚĂƐŚŝŐŚĞĸĐŝĞŶĐLJ͕ŚŝŐŚĞŶĞƌŐLJĚĞŶƐŝƚLJ ĂŶĚƌĞůŝĂďŝůŝƚLJ͘KŶƚŚĞŽƚŚĞƌŚĂŶĚ͕ƉƵůƐĞĚƉŽǁĞƌĚĞǀŝĐĞƐ͕ůŝŬĞƌĂĚĂƌƐ͕ĚĞĮďƌŝůůĂƚŽƌƐ͕ĂŶĚ ŚŝŐŚĞŶĞƌŐLJůĂƐĞƌƐ͕ƌĞƋƵŝƌĞůĂƌŐĞĚŝƐĐŚĂƌŐĞĞŶĞƌŐLJĚĞŶƐŝƟĞƐŝŶŵŝĐƌŽƐĞĐŽŶĚƐ͘8

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hŶĨŽƌƚƵŶĂƚĞůLJ͕ ƚŚĞ ƐƚĂƚĞͲŽĨͲƚŚĞͲĂƌƚ ďŝĂdžŝĂůůLJ ŽƌŝĞŶƚĞĚ ƉŽůLJƉƌŽƉLJůĞŶĞ ;KWWͿ Įůŵ ĐĂƉĂĐŝƚŽƌƐŚĂǀĞƌĞůĂƟǀĞůLJůŽǁĞŶĞƌŐLJĚĞŶƐŝƟĞƐĂŶĚĂƚŚŝŐŚĞƌƚĞŵƉĞƌĂƚƵƌĞƐƐĞǀĞƌĞĞŶĞƌŐLJ loss takes place.9ƐĚŝƐƉůĂLJĞĚŝŶdĂďůĞ 1.1, even though its remarkably high dielectric

ĐŽŶƐƚĂŶƚĂŶĚďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚ͕ƉŽůLJ;ǀŝŶLJůŝĚĞŶĞŇƵŽƌŝĚĞͿ;Ws&Ϳ͕ƐŚŽǁƐůŽǁĞƌĞŶĞƌŐLJ ĚĞŶƐŝƟĞƐĐŽŵƉĂƌĞĚƚŽ͕ĨŽƌĞdžĂŵƉůĞ͕KWW͘9dŚĞƌĞĨŽƌĞ͕ĚƵĞƚŽŝƚƐŚŝŐŚƉŽƚĞŶƟĂů͕ƚŚŝƐ

ĚŝƐƐĞƌƚĂƟŽŶǁŝůůĨŽĐƵƐŽŶƚƵŶŝŶŐWs&ƚŽƵƟůŝnjĞŝƚĨŽƌĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJƐƚŽƌĂŐĞŵĂƚĞƌŝĂůƐ͘ ƵƚĮƌƐƚ͕ƚŽŐĂŝŶĂďĞƩĞƌƵŶĚĞƌƐƚĂŶĚŝŶŐŽĨŚŽǁWs&ĐĂŶďĞƵƐĞĚĂƐĂĚŝĞůĞĐƚƌŝĐŵĂƚĞƌŝĂů͕ ƚŚĞďĂƐŝĐĨƵŶĚĂŵĞŶƚĂůƐŽĨĐĂƉĂĐŝƚŽƌƐĂƌĞĚŝƐĐƵƐƐĞĚŝŶƚŚĞŶĞdžƚƐĞĐƟŽŶ͘

Fundamentals in dielectric capacitors

EĞdžƚƚŽǁŝĚĞͲďĂŶĚŐĂƉĐĞƌĂŵŝĐƐ͕ƉŽůLJŵĞƌƐĂƌĞƚŚĞŵĂŝŶŵĂƚĞƌŝĂůŽĨĐŚŽŝĐĞƚŽĨƵŶĐƟŽŶĂƐ ĚŝĞůĞĐƚƌŝĐƐŝŶĐĂƉĂĐŝƚŽƌƐŽǁŝŶŐƚŽƚŚĞŝƌƐƵƉĞƌŝŽƌďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚƐ͕ŇĞdžŝďŝůŝƚLJĂŶĚĞĂƐĞ ŽĨƉƌŽĐĞƐƐŝŶŐ͘/ŶƉĂƌƟĐƵůĂƌ͕ŝŶƐŽůŝĚƉŽůLJŵĞƌƐǁŝƚŚĐŚĞŵŝĐĂůůLJƐĂƚƵƌĂƚĞĚƐƚƌƵĐƚƵƌĞƐ͕ƚŚĞ ĞůĞĐƚƌŽŶƐĂƌĞƟŐŚƚůLJďŽƵŶĚŝŶƚŚĞʍͲďŽŶĚƐďĞƚǁĞĞŶŵĂŝŶůLJĐĂƌďŽŶĂƚŽŵƐ͘dŚŝƐƉƌĞǀĞŶƚƐ ĨƌĞĞĞůĞĐƚƌŽŶƐƚŽĐĂƌƌLJĞůĞĐƚƌŝĐĂůĐƵƌƌĞŶƚ͕ǁŚŝĐŚŵĂŬĞƐƉŽůLJŵĞƌƐĂŶĞdžĐĞůůĞŶƚĐŚŽŝĐĞƚŽ ĨƵŶĐƟŽŶĂƐŝŶƐƵůĂƚŽƌŝŶĐĂƉĂĐŝƚŽƌƐ͘ϭϰ dŚĞŵĂŝŶĐŽŶĮŐƵƌĂƟŽŶŽĨĂĐĂƉĂĐŝƚŽƌ͕i.e.ĂƉĂƌĂůůĞůͲƉůĂƚĞĐĂƉĂĐŝƚŽƌ͕ŝƐĐŽŶƐƚƌƵĐƚĞĚ ŽƵƚŽĨƚǁŽƉůĂƚĞƐƐĞƉĂƌĂƚĞĚďLJĂŶŝŶƐƵůĂƟŶŐŵĞĚŝƵŵ;ĚŝĞůĞĐƚƌŝĐŵĂƚĞƌŝĂůͿǁŝƚŚĚŝƐƚĂŶĐĞ d;&ŝŐƵƌĞϭ͘ϮͿ͘/Ŷ&ŝŐƵƌĞϭ͘ϮĂ͕ƚŚĞĞůĞĐƚƌŝĐĮĞůĚ;EͿƉƌŽĚƵĐĞĚŽǀĞƌƚŚĞƌĞŐŝŽŶ;ǀĂĐƵƵŵͿ between the plates at a certain voltage (VͿǁŝůůďĞƵŶŝĨŽƌŵĂŶĚǁŝůůŚĂǀĞĂŵĂŐŶŝƚƵĚĞŽĨ

Polymer ŝĞůĞĐƚƌŝĐ ĐŽŶƐƚĂŶƚ;Ăƚϭ Ŭ,njͿ DĂdžŝŵƵŵ dĞŵƉĞƌĂƚƵƌĞ ;ΣͿ ƌĞĂŬĚŽǁŶ ^ƚƌĞŶŐƚŚ;Ds mͲϭͿ ŶĞƌŐLJĞŶƐŝƚLJ ;:ĐŵͲϯͿ BOPP10 2.2 105 720 5 WŽůLJĞƐƚĞƌ;WdͿ11 ϯ͘ϯ 125 570 ϭͲϭ͘ϱ WŽůLJĐĂƌďŽŶĂƚĞ;WͿ11 2.8 125 528 Ϭ͘ϱͲϭ WŽůLJƉŚĞŶLJůĞŶĞͲƐƵůĮĚĞ11 ϯ 200 550 ϭͲϭ͘ϱ WŽůLJŝŵŝĚĞ;W/Ϳ12 ϯ͘ϰ 250 ϯϬϬ ϭͲϭ͘ϱ Ws&11 12 125 590 Ϯ͘ϰ ƌŽŵĂƟĐƉŽůLJƵƌĞĂϭϯ ϰ͘Ϯ 200 800 12

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ĞĐĂƵƐĞƚŚĞĞůĞĐƚƌŝĐĮĞůĚĂƉƉůŝĞĚŝƐƵŶŝĚŝƌĞĐƟŽŶĂů͕ŽƵůŽŵďƐůĂǁĚŝĐƚĂƚĞƐƚŚĂƚƚŚĞ charges +Q and -QƉĞƌƵŶŝƚĂƌĞĂƐƚŽƌĞĚŽŶƚŚĞƉůĂƚĞƐĂƌĞĚŝƌĞĐƚůLJƉƌŽƉŽƌƟŽŶĂůƚŽƚŚĞ ŵĂŐŶŝƚƵĚĞŽĨƚŚĞĮĞůĚ͕ŝ͘Ğ͘

The constant ɸ0ŝƐƚŚĞƉĞƌŵŝƫǀŝƚLJŽĨĨƌĞĞƐƉĂĐĞĂŶĚŚĂƐĂǀĂůƵĞŽĨϴ͘ϴϱdžϭϬͲϭϮ FmͲϭ.

This leads to the capacitance C0͕ƚŚĞƌĂƟŽŽĨĐŚĂƌŐĞƐƚŽƌĞĚƉĞƌƵŶŝƚĞůĞĐƚƌŽĚĞĂƌĞĂƚŽ the applied voltage, i.e.

If we now consider that a dielectric material is placed between the parallel plates ;&ŝŐƵƌĞϭ͘ϮďͿ͕ŝƚďĞĐŽŵĞƐŽďǀŝŽƵƐƚŚĂƚƚŚŝƐŵĂƚĞƌŝĂůǁŝůůƌĞƐƉŽŶĚƚŽƚŚĞĂƉƉůŝĞĚĞůĞĐƚƌŝĐ ĮĞůĚďLJƌĞĚŝƐƚƌŝďƵƟŶŐŝƚƐĞůĞĐƚƌŽŶƐĂŶĚƉƌŽƚŽŶƐƚŽĂĐĞƌƚĂŝŶĞdžƚĞŶƚ͕ǁŚĞƌĞŶĞŐĂƟǀĞ ĐŚĂƌŐĞƐĂƌĞĂƩƌĂĐƚĞĚƚŽƚŚĞƉŽƐŝƟǀĞĞůĞĐƚƌŽĚĞĂŶĚǀŝĐĞǀĞƌƐĂ͘dŚŝƐŝƐďĞƩĞƌŬŶŽǁŶ ĂƐƉŽůĂƌŝnjĂƟŽŶ;PͿŽĨƚŚĞŵĂƚĞƌŝĂů͘/ŶŝƐŽƚƌŽƉŝĐŵĂƚĞƌŝĂůƐ͕ĂŶƵŶŝĨŽƌŵĮĞůĚŝŶƚŚĞƉůĂƚĞ ĐĂƉĂĐŝƚŽƌǁŝůůůĞĂĚƚŽƚŚĞŝŶĚƵĐƟŽŶŽĨƐŵĂůůĚŝƉŽůĞŵŽŵĞŶƚƐPdvŝŶƚŚĞĚŝƌĞĐƟŽŶŽĨƚŚĞ ĮĞůĚŝŶĞĂĐŚǀŽůƵŵĞĚv͘dŚĞƌĞĨŽƌĞ͕ƚŚĞƉŽůĂƌŝnjĂƟŽŶŝƐĚĞĮŶĞĚĂƐĂǀĞĐƚŽƌƵŶŝƚƐŚŽǁŝŶŐ ƚŚĞĚŝƌĞĐƟŽŶĂŶĚŵĂŐŶŝƚƵĚĞŽĨƚŚĞĞůĞĐƚƌŝĐŵŽŵĞŶƚƉĞƌƵŶŝƚǀŽůƵŵĞĂƐƌĞƐƉŽŶƐĞƚŽĂŶ ĞdžƚĞƌŶĂůĞůĞĐƚƌŝĐĮĞůĚ;&ŝŐƵƌĞϭ͘ϯͿ͘ƐƐƵĐŚ͕ĞĂĐŚǀŽůƵŵĞĞůĞŵĞŶƚŽĨĂƉŽůĂƌŝnjĞĚŵĂƚĞƌŝĂů behaves electrically as it consists of charges -q and +q that are separated by a distance

dŝŶƚŚĞĮĞůĚĚŝƌĞĐƟŽŶ͕ǁŚŝĐŚĚĞĮŶĞƐƚŚĞĚŝƉŽůĞŵŽŵĞŶƚQd = Pdv͘ŶĂůŽŐŽƵƐƚŽƚŚĞ

ŚĞĂĚͲƚŽͲƚĂŝůĂĚĚŝƟŽŶŽĨŵĂŐŶĞƚƐ͕ƚŚĞĚŝƉŽůĞƐĐŽŵďŝŶĞƚŽŐŝǀĞĐŚĂƌŐĞƐнPĂŶĚͲP per unit

Figure 1.2: A parallel-plate capacitor showing the charges with (a) a vacuum and (b) a dielectric material between the plates.

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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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ƐƵƌĨĂĐĞĂƌĞĂŶĞdžƚƚŽƚŚĞĞůĞĐƚƌŽĚĞƐ͘dŚĞƌĞƐƵůƚĂŶƚŽĨƚŚĞƐĞƉŽůĂƌŝnjĂƟŽŶƐĚĞƌŝǀĞĚĨƌŽŵ the dielectric material means that more charge can be stored on the electrodes of the ĐĂƉĂĐŝƚŽƌĨŽƌƚŚĞƐĂŵĞĞůĞĐƚƌŝĐĮĞůĚ͕ůĞĂĚŝŶŐƚŽĂŶŝŶĐƌĞĂƐĞŝŶƚŚĞĐĂƉĂĐŝƚĂŶĐĞĐŽŵƉĂƌĞĚ ƚŽĂǀĂĐƵƵŵ͘dŚĞƌĂƟŽŽĨƚŚĞŝŶĐƌĞĂƐĞĚĐĂƉĂĐŝƚĂŶĐĞƚŽƚŚĞǀĂĐƵƵŵĐĂƉĂĐŝƚĂŶĐĞŝƐŐŝǀĞŶďLJ ĚĞƉĞŶĚŝŶŐŽĨƚŚĞƉŽůĂƌŝnjĂďŝůŝƚLJŽĨƚŚĞŵĂƚĞƌŝĂů͘dŚŝƐƌĂƟŽŝƐďĞƩĞƌŬŶŽǁŶĂƐƚŚĞ dielectric constant. ŶŽƚŚĞƌƋƵĂŶƟƚLJŽŌĞŶƐĞĞŶŝŶůŝƚĞƌĂƚƵƌĞŝƐƚŚĞĞůĞĐƚƌŝĐĚŝƐƉůĂĐĞŵĞŶƚD͘LJƐƵďƐƟƚƵƟŶŐ Q for ɸoE gives ŝŶĂŐĞŶĞƌĂůǀĞĐƚŽƌŶŽƚĂƟŽŶ͘ZĞĂƌƌĂŶŐŝŶŐƚŚŝƐĞƋƵĂƟŽŶůĞĂĚƐƚŽƚŚĞĨƵŶĚĂŵĞŶƚĂů ĞůĞĐƚƌŝĐĮĞůĚĞƋƵĂƟŽŶƚŚĂƚĂƉƉůŝĞƐƚŽĞǀĞƌLJŵĂƚĞƌŝĂůŝŶĂŶŝƐŽƚƌŽƉŝĐŵĞĚŝƵŵ͘ Figure 1.3: 1SPIGYPIW[MXLETIVQERIRXHMTSPIQSQIRX[MXL E RSI\XIVREPƼIPHERH F ERI\XIVREP ƼIPHETTPMIH

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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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)RIVK]HIRWMX]ERHLMKLƼIPHHMWGLEVKIMRHMIPIGXVMGW

dŚĞĚŝƐƉůĂĐĞŵĞŶƚŝƐĂůƐŽƵƐĞĚŝŶĚĞƚĞƌŵŝŶŝŶŐƚŚĞƐƚŽƌĞĚĂŶĚƌĞůĞĂƐĞĚĞŶĞƌŐLJĚĞŶƐŝƟĞƐ ĂŶĚƚŚĞĐŽƌƌĞƐƉŽŶĚŝŶŐĐŚĂƌŐĞͲĚŝƐĐŚĂƌŐĞĞĸĐŝĞŶĐŝĞƐ͘ϭϰLJƵƐŝŶŐƚŚĞĨŽůůŽǁŝŶŐĞƋƵĂƟŽŶ

the energy density UeŝƐĐĂůĐƵůĂƚĞĚ͘^ŝŵƉůŝĨLJŝŶŐƚŚŝƐĞƋƵĂƟŽŶĨŽƌůŝŶĞĂƌĚŝĞůĞĐƚƌŝĐƐŐŝǀĞƐ

which shows that the energy density scales linearly with the dielectric constant ĂŶĚƋƵĂĚƌĂƟĐĂůůLJǁŝƚŚƚŚĞĞůĞĐƚƌŝĐĮĞůĚ͕ŝŶĚŝĐĂƟŶŐƚŚĞŝŵƉŽƌƚĂŶĐĞŽĨŚŝŐŚďƌĞĂŬĚŽǁŶ ƐƚƌĞŶŐƚŚŵĂƚĞƌŝĂůƐĨŽƌĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJƐƚŽƌĂŐĞ͘

To address losses accompanied with high electric field caused by electronic ĐŽŶĚƵĐƟŽŶ͕ŝŶĐůƵĚŝŶŐďŽƚŚĞůĞĐƚƌŽĚĞͲůŝŵŝƚĞĚ;e.g.&ŽǁůĞƌоEŽƌĚŚĞŝŵĂŶĚĚŝƌĞĐƚƚƵŶŶĞůŝŶŐ͕ ^ĐŚŽƩŬLJĞŵŝƐƐŝŽŶ͕ĂŶĚƚŚĞƌŵŝŽŶŝĐĮĞůĚĞŵŝƐƐŝŽŶͿĂŶĚďƵůŬͲůŝŵŝƚĞĚ;e.g.͕WŽŽůĞо&ƌĞŶŬĞů ĞŵŝƐƐŝŽŶ͕ĞůĞĐƚƌŽŶŚŽƉƉŝŶŐ͕KŚŵŝĐĐŽŶĚƵĐƟŽŶ͕ĂŶĚƐƉĂĐĞͲĐŚĂƌŐĞͲůŝŵŝƚĞĚĐŽŶĚƵĐƟŽŶͿ͕ ĂƌĞƋƵĂŶƟƚĂƟǀĞůLJĐŽŵƉĂƌĞĚďLJĐĂůĐƵůĂƟŶŐŝƚƐĞĸĐŝĞŶĐLJ

where Udischarged and Ustored are the discharged and stored energy densities, ƌĞƐƉĞĐƟǀĞůLJ͘15ƐĐůĂƌŝĮĞĚŝŶ&ŝŐƵƌĞϭ͘ϰ͕ƚŚĞƐƚŽƌĞĚĞŶĞƌŐLJĚĞŶƐŝƚLJŝƐƚŚĞƐƵŵŽĨƚŚĞ

discharged and unreleased energy density.

Figure 1.4: 7GLIQEXMGTSPEVM^EXMSRƁIPIGXVMGƼIPHPSSTWLS[MRKXLIHMWGLEVKIHERHYRVIPIEWIH energy densities.

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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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Breakdown strength

hŶĨŽƌƚƵŶĂƚĞůLJ͕ƚŚĞĞůĞĐƚƌŝĐĮĞůĚƚŚĂƚĐĂŶďĞĂƉƉůŝĞĚƚŽƉŽůLJŵĞƌƐŝƐůŝŵŝƚĞĚ͕ĂƐŚŝŐŚůLJƉŽůĂƌ polymers usually have lower breakdown strengths.ϭϰ,ŽǁĞǀĞƌ͕ƚŚĞĚĞƚĞƌŵŝŶĂƟŽŶŽĨƚŚĞ

ŝŶƚƌŝŶƐŝĐĚŝĞůĞĐƚƌŝĐƐƚƌĞŶŐƚŚŽĨƉŽůLJŵĞƌƐƌĞŵĂŝŶƐĞůƵƐŝǀĞĚƵĞƚŽĂƐƚĂƟƐƟĐĂůǀĂƌŝĂƟŽŶ ŽĨƚŚĞĐŽŵƉŽƐŝƟŽŶŝŶĞĂĐŚƐĂŵƉůĞĂŶĚƚŚĞĞdžƚĞƌŶĂůŝŶŇƵĞŶĐĞƐƐƵĐŚĂƐƚŚĞƉŚLJƐŝĐĂů state and purity of the electrodes. This leads to a variety of possible dielectric failure ŵĞĐŚĂŶŝƐŵƐ͕ŝŶĐůƵĚŝŶŐĞůĞĐƚƌŽŶŝĐďƌĞĂŬĚŽǁŶ;ĞůĞĐƚƌŽŶƐĞŶƚĞƌŝŶŐƚŚĞĐŽŶĚƵĐƟŽŶďĂŶĚͿ͕ ĞůĞĐƚƌŽŵĞĐŚĂŶŝĐĂůďƌĞĂŬĚŽǁŶ;ĐŽŵƉƌĞƐƐŝǀĞĨŽƌĐĞƐĞdžĞƌƟŶŐŽŶƚŚĞŵĂƚĞƌŝĂůͿĂŶĚƚŚĞƌŵĂů ďƌĞĂŬĚŽǁŶ;ŚĞĂƚďƵŝůƚƵƉĚƵĞƚŽƌĞůĂdžĂƟŽŶƉƌŽĐĞƐƐĞƐĞŶŚĂŶĐŝŶŐĐŽŶĚƵĐƟŽŶͿ͘dŚĞƌĞĨŽƌĞ͕ ƚŽĚĞƐĐƌŝďĞƚŚĞďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚŽĨĂŵĂƚĞƌŝĂů͕ĂtĞŝďƵůůĨĂŝůƵƌĞƉƌŽďĂďŝůŝƚLJĨƵŶĐƟŽŶ analysis is commonly used.ϭϰ͕ϭϱ

,ĞƌĞŝƐF(x)ƚŚĞĐƵŵƵůĂƟǀĞƉƌŽďĂďŝůŝƚLJŽĨĨĂŝůƵƌĞĂŶĚEŝƐƚŚĞĂƉƉůŝĞĚĞůĞĐƚƌŝĐĮĞůĚ͘LJ ƌĞǁƌŝƟŶŐƚŚŝƐĞƋƵĂƟŽŶƚŽ ďĞƩĞƌŝŶƐŝŐŚƚƐŝŶƚŚĞŵĞĂŶŝŶŐɲĂŶĚɴĐĂŶďĞŽďƚĂŝŶĞĚ͘ƐƐƵĐŚ͕ɴŝƐƚŚĞƐůŽƉĞŽĨƚŚĞ ƐƚƌĂŝŐŚƚůŝŶĞŽďƚĂŝŶĞĚŝŶƚŚĞĚŽƵďůĞůŽŐĂƌŝƚŚŵŝĐƉůŽƚĂŶĚƐŚŽǁƐƚŚĞƐĐĂƩĞƌ;ƌĞůŝĂďŝůŝƚLJͿ ŽĨƚŚĞƐĂŵƉůĞ͘dŚĞǀĂůƵĞɲŝƐĞƋƵĂůƚŽƚŚĞĮĞůĚĂƚƚŚĞŝŶƚĞƌĐĞƉƚǁŝƚŚƚŚĞdžͲĂdžŝƐ͘/ŶŽƚŚĞƌ ǁŽƌĚƐ͕ɲŝƐǁŚĞƌĞͲůŶ;ϭͲF(x)ͿсϬŽƌǁŚĞƌĞ&;džͿсϭͲϭͬĞсϬ͘ϲϯϮ;ϲϯйͿ͘dŚƵƐ͕ƚŚĞďƌĞĂŬĚŽǁŶ ƐƚƌĞŶŐƚŚĐĂůĐƵůĂƚĞĚƵƐŝŶŐĂĐƵŵƵůĂƟǀĞtĞŝďƵůůĨĂŝůƵƌĞĂŶĂůLJƐŝƐŐŝǀĞƐĂŶĞůĞĐƚƌŝĐĮĞůĚ ĂƐďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚ;ɲͿĂƚƚŚĞƉŽŝŶƚǁŚĞƌĞϲϯйŽĨƚŚĞƐĂŵƉůĞƐŚĂǀĞƐƵƌǀŝǀĞĚĂŶĚĂ ƌĞůŝĂďŝůŝƚLJƉĂƌĂŵĞƚĞƌɴ͘

Polarization types in polymers

ĞƐŝĚĞƐ ƵŶĚĞƌƐƚĂŶĚŝŶŐ ƚŚĞ ƉŚLJƐŝĐƐ ďĞŚŝŶĚ ĐĂƉĂĐŝƚŽƌƐ ĂŶĚ ŚŽǁ ǁĞ ĐĂŶ ƋƵĂŶƟĨLJ ƚŚĞ ĚĞǀŝĐĞ ƉĞƌĨŽƌŵĂŶĐĞ͕ Ă ĐůŽƐĞ ůŽŽŬ Ăƚ ƚŚĞ ƉŽůĂƌŝnjĂďŝůŝƚLJ ŽĨ ŵŽůĞĐƵůĞƐ ŝƐ ƌĞƋƵŝƌĞĚ ĨŽƌ ĮŶĚŝŶŐŵĞƚŚŽĚƐƚŽŝŵƉƌŽǀĞƉŽůLJŵĞƌĚŝĞůĞĐƚƌŝĐƐ͘ϲ͕ϭϰdŚĞƌĞĂƌĞĮǀĞƚLJƉĞƐŽĨƉŽůĂƌŝnjĂƟŽŶƐ ŽĐĐƵƌƌŝŶŐ ŝŶ ƉŽůLJŵĞƌƐ͕ ŶĂŵĞůLJ ĞůĞĐƚƌŽŶŝĐ͕ ĂƚŽŵŝĐ͕ ŽƌŝĞŶƚĂƟŽŶĂů ;ĚŝƉŽůĂƌͿ͕ ŝŽŶŝĐ ĂŶĚ ŝŶƚĞƌĨĂĐŝĂůƉŽůĂƌŝnjĂƟŽŶ͘ĂĐŚƚLJƉĞŚĂƐĂĐŽŶƚƌŝďƵƟŽŶƚŽƚŚĞƚŽƚĂůƉŽůĂƌŝnjĂƟŽŶ͕ǁŚŝĐŚ ĂƌĞĂĐĐŽŵƉĂŶŝĞĚǁŝƚŚĚŝĞůĞĐƚƌŝĐůŽƐƐĞƐĂƚĂĐĞƌƚĂŝŶĨƌĞƋƵĞŶĐLJ͘/ŶƚŚŝƐƌĞƐƉĞĐƚ͕ŝĚĞĂůůLJ͕ ĐĂƉĂĐŝƚŽƌƐ ĂƌĞ ŽƉĞƌĂƟŶŐ ŝŶ ƚŚĞ ƉŽǁĞƌ ĂŶĚ ƌĂĚŝŽ ĨƌĞƋƵĞŶĐŝĞƐ͕ ǁŚŝůĞ ŚĂǀŝŶŐ ůĂƌŐĞ ƉŽůĂƌŝnjĂƟŽŶƐ͘dŚĞƌĞĨŽƌĞ͕ĞůĞĐƚƌŽŶŝĐĂŶĚĂƚŽŵŝĐƉŽůĂƌŝnjĂƟŽŶƐĐĂŶďĞƵƟůŝnjĞĚĨŽƌĞŶĞƌŐLJ

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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: 14PDF page: 14PDF page: 14PDF page: 14

14 ƐƚŽƌĂŐĞ͕ ƐŝŶĐĞ ƚŚĞŝƌ ƌĞůĂdžĂƟŽŶƐ ĂƌĞ ĨŽƵŶĚ ŝŶ ƚŚĞ ŽƉƟĐĂů ĂŶĚ ŝŶĨƌĂƌĞĚ ĨƌĞƋƵĞŶĐŝĞƐ͘ ,ŽǁĞǀĞƌ͕ĂŶĞůĞĐƚƌŝĐĮĞůĚǁŝůůŽŶůLJĐĂƵƐĞĂƐŵĂůůĚŝƐƉůĂĐĞŵĞŶƚŽĨĂƚŽŵƐĂƌŽƵŶĚĂƉŽƐŝƟǀĞ ŶƵĐůĞƵƐĚƵĞƚŚĞƐŵĂůůĚŝƐƚĂŶĐĞ;ϭ ͿĂŶĚƐƚƌŽŶŐĐŽƵůŽŵďŝĐŝŶƚĞƌĂĐƟŽŶďĞƚǁĞĞŶŶƵĐůĞŝ ĂŶĚĞůĞĐƚƌŽŶƐ;ĐĂƵƐŝŶŐĂƐĞǀĞƌĂůŽƌĚĞƌŽĨŵĂŐŶŝƚƵĚĞŚŝŐŚĞƌůŽĐĂůĞůĞĐƚƌŝĐĮĞůĚͿ͕ůŝŵŝƟŶŐ ƚŚĞŝƌƌŽŽŵĨŽƌůĂƌŐĞŝŵƉƌŽǀĞŵĞŶƚƐŝŶƉŽůĂƌŝnjĂƟŽŶ͘ϲ͕ϭϰ ƚ ƚŚĞ ŽƚŚĞƌ ĞŶĚ ŽĨ ƚŚĞ ĨƌĞƋƵĞŶĐLJ ƐƉĞĐƚƌƵŵ͕ ϭϬͲϵ Ͳ ϭϬ ,nj͕ ŝŶƚĞƌĨĂĐŝĂů ĂŶĚ ŝŽŶŝĐ ƌĞůĂdžĂƟŽŶƉƌŽĐĞƐƐĞƐĂƌĞĂĐĐŽŵƉĂŶŝĞĚǁŝƚŚůĂƌŐĞƉŽůĂƌŝnjĂƟŽŶƐ͘hŶĨŽƌƚƵŶĂƚĞůLJ͕ĂƐĂďŽǀĞͲ ŵĞŶƟŽŶĞĚ͕ƚŚĞƐĞƌĞůĂdžĂƟŽŶƉƌŽĐĞƐƐĞƐĂƌĞǁĂLJƚŽŽƐůŽǁƚŽďĞƵƐĞĨƵůĨŽƌĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJ ƐƚŽƌĂŐĞĂƉƉůŝĐĂƟŽŶƐ͘,ĂǀŝŶŐĂŶŝŶƚĞƌŵĞĚŝĂƚĞƉŽůĂƌŝnjĂďŝůŝƚLJ͕ĚŝƉŽůĞƐŝŶƉŽůLJŵĞƌƐƌĞůĂdž ŶŽƌŵĂůůLJŝŶĂƌĞŐŝŽŶďĞƚǁĞĞŶϭ,njĂŶĚϭϬϬD,nj͕ŵƵĐŚĐůŽƐĞƌƚŽƚŚĞƉŽǁĞƌĂŶĚƌĂĚŝŽ ĨƌĞƋƵĞŶĐLJ͘dŚĞƌĞĨŽƌĞ͕ƌĞƐĞĂƌĐŚĞīŽƌƚƐŵĂŝŶůLJĨŽĐƵƐŽŶƚĂŝůŽƌŝŶŐƚŚĞĚŝƉŽůĂƌƉŽůĂƌŝnjĂƟŽŶ͘

Dipolar polymers containing permanent dipoles for dielectric materials may be subdivided in two main groups, i.e. polar amorphous and polar crystalline polymers. ƐůŝƐƚĞĚŝŶdĂďůĞϭ͘ϭ͕ƉŽůĂƌĂŵŽƌƉŚŽƵƐƉŽůLJŵĞƌƐƐƵĐŚĂƐW/ĂŶĚWdŚĂǀĞĂƌĞůĂƟǀĞůLJ ůŽǁĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚĂŶĚƐŚŽǁĂůŝŶĞĂƌƌĞƐƉŽŶƐĞƚŽƚŚĞĂƉƉůŝĞĚĞůĞĐƚƌŝĐĮĞůĚƌĞƐƵůƟŶŐ ŝŶ ƐŵĂůů ĞŶĞƌŐLJ ĚĞŶƐŝƟĞƐ͘ KŶ ƚŚĞ ĐŽŶƚƌĂƌLJ͕ ƉŽůĂƌ ĐƌLJƐƚĂůůŝŶĞ ƉŽůLJŵĞƌƐ͕ ůŝŬĞ Ws&͕ ĚĞŵŽŶƐƚƌĂƚĞ ŶŽŶͲůŝŶĞĂƌ ďĞŚĂǀŝŽƌ ǁŚĞŶ ĂŶ ĞůĞĐƚƌŝĐ ĮĞůĚ ŝƐ ĂƉƉůŝĞĚ͕ ůĞĂĚŝŶŐ ƚŽ ůĂƌŐĞ ƉŽůĂƌŝnjĂƟŽŶƐĚƵĞƚŽŽƌŝĞŶƚĂƟŽŶŽĨƚŚĞĐƌLJƐƚĂůůŝŶĞ;ĂŶĚŝŶĂƐŵĂůůĞƌĞdžƚĞŶƚĂŵŽƌƉŚŽƵƐͿ ĚŝƉŽůĞƐ͘hŶĨŽƌƚƵŶĂƚĞůLJ͕ƚŚĞĐƌLJƐƚĂůůŝŶĞĚŝƉŽůĞŽƌŝĞŶƚĂƟŽŶŝƐƌĞŵĂŶĞŶƚǁŚĞŶƚŚĞĮĞůĚŝƐ ƌĞŵŽǀĞĚ͕ƐƟůůůĞĂĚŝŶŐƚŽůŽǁĚŝƐĐŚĂƌŐĞĚĞŶĞƌŐLJĚĞŶƐŝƟĞƐ;&ŝŐƵƌĞϭ͘ϱĚͿ͘EĞǀĞƌƚŚĞůĞƐƐ͕ ŝĨƚŚĞ;ĐƌLJƐƚĂůůŝŶĞͿĚŝƉŽůĞƌĞǀĞƌƐŝďŝůŝƚLJŝŶWs&ĐĂŶďĞĞŶŚĂŶĐĞĚ͕ŵƵĐŚŚŝŐŚĞƌĞŶĞƌŐLJ ĚĞŶƐŝƟĞƐǁŝůůďĞŽďƚĂŝŶĞĚĂƐǁŝůůďĞĞůƵĐŝĚĂƚĞĚŝŶƚŚĞŶĞdžƚƐĞĐƟŽŶƐ͘ Figure 1.5:7GLIQEXMGVITVIWIRXEXMSRSJXLI()PSSTWHIQSRWXVEXMRKMR E EPMRIEVHMIPIGXVMG F  HSYFPIL]WXIVIWMWFILEZMSV G WMRKPIL]WXIVIWMW VIPE\SVJIVVSIPIGXVMG FILEZMSVERH H JIVVSIPIGXVMG FILEZMSV8LIHMWGLEVKIHERHYRVIPIEWIHIRIVK]HIRWMXMIWEVIMRHMGEXIHMRPMKLXERHHEVOIVFPYI VIWTIGXMZIP]-REHHMXMSRXLIGLEVEGXIVMWXMGVIQERIRXTSPEVM^EXMSRERHGSIVGMZIƼIPHEVIWLS[RJSV a ferroelectric material.

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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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15

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PVDF Ws&ďĞůŽŶŐƐƚŽƚŚĞƐŽͲĐĂůůĞĚĐůĂƐƐŽĨŇƵŽƌŝŶĂƚĞĚƉŽůLJŵĞƌƐ͘ƵĞƚŽƚŚĞƐŵĂůůƌĂĚŝƵƐŽĨ ƚŚĞŇƵŽƌŝŶĞĂƚŽŵ;ϭ͘ϯϮ ͿĂŶĚƚŚĞƐƚƌŽŶŐͲ&ďŽŶĚ;ϰϴϱŬ:ŵŽůͲϭͿ͕ƚŚĞƐĞƉŽůLJŵĞƌƐŚĂǀĞ ŽƵƚƐƚĂŶĚŝŶŐƉƌŽƉĞƌƟĞƐƌĂŶŐŝŶŐĨƌŽŵŚŝŐŚĐŚĞŵŝĐĂů͕ƚŚĞƌŵĂůĂŶĚǁĞĂƚŚĞƌƌĞƐŝƐƚĂŶĐĞ ƚŽŝŶĞƌƚŶĞƐƐƚŽƐŽůǀĞŶƚƐ͕ůŝŬĞŚLJĚƌŽĐĂƌďŽŶƐĂŶĚĂĐŝĚƐƉůƵƐůŽǁŇĂŵŵĂďŝůŝƚLJ͕ƌĞĨƌĂĐƟǀĞ ŝŶĚĞdžĂŶĚŵŽŝƐƚƵƌĞĂďƐŽƌƉƟŽŶ͘ϭϲDŽƌĞŽǀĞƌ͕ĞdžĐĞůůĞŶƚĞůĞĐƚƌŽĐŚĞŵŝĐĂůƐƚĂďŝůŝƚLJĂŶĚĂ ůĂƌŐĞƌĂŶŐĞŽĨĂĐĐĞƐƐŝďůĞĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚƐ;ĨƌŽŵϮ͘ϭƚŽϱϬͿƐŚŽƵůĚďĞŚŝŐŚůŝŐŚƚĞĚŝŶ ƚŚĞĐŽŶƚĞdžƚŽĨƚŚŝƐĚŝƐƐĞƌƚĂƟŽŶĂƐǁĞůů͘17 dŚŝƐŚĂƐůĞĚƚŽƚŚĞŝƌŝŵƉůĞŵĞŶƚĂƟŽŶŝŶĂǁŝĚĞͲƌĂŶŐĞŽĨŵŽĚĞƌŶĚĂLJĂƉƉůŝĐĂƟŽŶƐ͕ƐƵĐŚ ĂƐĐŽĂƟŶŐƐ͕ƉĞƚƌŽĐŚĞŵŝĐĂůƐ͕ĂŶĚĂƵƚŽŵŽƟǀĞŝŶĚƵƐƚƌŝĞƐ͕ŵĞŵďƌĂŶĞƐ͕ŵŝĐƌŽĞůĞĐƚƌŽŶŝĐƐ͕ and many more.ϭϲĞƐƉŝƚĞƚŚĞŚŝŐŚĐŽƐƚŝŶƚŚĞƉƌŽĚƵĐƟŽŶƉƌŽĐĞƐƐŽĨƚŚĞŵĂŝŶůLJŐĂƐĞŽƵƐ

ŵŽŶŽŵĞƌƐ͕ƵŶĐŽŶǀĞŶƟŽŶĂůƉŽůLJŵĞƌŝnjĂƟŽŶƉƌŽĐĞĚƵƌĞƐ͕ĂŶĚƐŵĂůůƉƌŽĚƵĐƟŽŶƐĐĂůĞ͕ƚŚĞ ĚĞŵĂŶĚĨŽƌƚŚĞƐĞƉŽůLJŵĞƌƐĂŶĚŝƚƐŝŶŇƵĞŶĐĞŽŶƚŚĞŵĂƌŬĞƚĂƌĞĞǀĞƌŝŶĐƌĞĂƐŝŶŐ͘ϭϲ,ĂǀŝŶŐ ĂɸсϭϮĂŶĚĂĚŝĞůĞĐƚƌŝĐďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚŽĨΕϲϬϬDsŵͲϭ͕Ws&ĂƩƌĂĐƚƐƐƉĞĐŝĮĐ ĂƩĞŶƟŽŶĨŽƌĞůĞĐƚƌŽŶŝĐĂƉƉůŝĐĂƟŽŶƐ͘/ŶƚĞƌĞƐƟŶŐůLJ͕ƚŚŝƐŝƐĂƩƌŝďƵƚĞĚƚŽŝƚƐĐƌLJƐƚĂůůŝŶĞ ƉŚĂƐĞƐ͘DŽƐƚƉŽůLJŵĞƌƐƌĞƋƵŝƌĞƌĞŐƵůĂƌŝƚLJĂŶĚůŝŵŝƚĞĚĚĞŐƌĞĞƐŽĨďƌĂŶĐŚŝŶŐŝŶŽƌĚĞƌ to crystallize.18&ŽƌĞdžĂŵƉůĞ͕ĂĐŽŶĚĞŶƐĂƟŽŶƉŽůLJŵĞƌ͕ůŝŬĞELJůŽŶ͕ŶĞĞĚƐŝƚƐ ƐĞƋƵĞŶĐĞ͕ ǁŚĞƌĞĂƐ ůĂƌŐĞ ĚĞŐƌĞĞƐ ŽĨ ďƌĂŶĐŚŝŶŐ ƉƌĞǀĞŶƚ ĐƌLJƐƚĂůůŝnjĂƟŽŶ ƉƌŽĐĞƐƐĞƐ ŝŶ ƉŽůLJĞƚŚLJůĞŶĞ͘/ŶĂĚĚŝƟŽŶ͕ĨŽƌƚŚĞĐƌLJƐƚĂůůŝnjĂƟŽŶŝŶǀŝŶLJůͲďĂƐĞĚƉŽůLJŵĞƌƐ͕ƐƚĞƌĞŽƌĞŐƵůĂƌŝƚLJ ŝƐĂŶŝŵƉŽƌƚĂŶƚŝƐƐƵĞ͘ƐƐƵĐŚ͕ƉŽůLJƉƌŽƉLJůĞŶĞŽŶůLJƚĞŶĚƐƚŽĐƌLJƐƚĂůůŝnjĞǁŚĞŶŝƚĐŽŶƚĂŝŶƐĂ ŚŝŐŚĚĞŐƌĞĞŽĨƐLJŶĚŝŽͲŽƌŝƐŽƚĂĐƟĐŝƚLJ͘KŶƚŚĞĐŽŶƚƌĂƌLJ͕Ws&ŝƐĞdžƚƌĞŵĞůLJĐƌLJƐƚĂůůŝŶĞĂŶĚ ƌĞĂĐŚŝŶŐůĂƌŐĞĚĞŐƌĞĞƐŽĨĐƌLJƐƚĂůůŝŶŝƚLJ;ƵƉƚŽϳϬйͿ͘/ƚĂůůŽǁƐƐŵĂůůĚĞŐƌĞĞƐŽĨďƌĂŶĐŚĞƐĂŶĚ ĚĞĨĞĐƚƐ͕ƐƵĐŚĂƐŵŽŶŽŵĞƌŝŶǀĞƌƐŝŽŶƐ͕ďĂƌĞůLJŚĂŵƉĞƌŝŶŐƚŚĞĐƌLJƐƚĂůůŝnjĂƟŽŶƉƌŽĐĞƐƐ͘YƵŝƚĞ ƌĂƌĞĨŽƌƐLJŶƚŚĞƟĐƉŽůLJŵĞƌƐ͕Ws&ĐƌLJƐƚĂůůŝnjĞƐŝŶŵĂŝŶůLJƚŚƌĞĞĐƌLJƐƚĂůƉŽůLJŵŽƌƉŚƐ͕i.e. the ɲͲ͕ɴͲ͕ĂŶĚɶͲƉŚĂƐĞ͕ĚŝƌĞĐƚůLJƌĞůĂƚĞĚƚŽƚŚĞ;ƐŵĂůůͿĚŝīĞƌĞŶĐĞƐŝŶƌĂĚŝŝŽĨƚŚĞŚLJĚƌŽŐĞŶ ;ϭ͘ϮϬ ͿĂŶĚŇƵŽƌŝŶĞĂƚŽŵƐ͘ϭϲ dŚĞ ĐƌLJƐƚĂůůŝŶĞ ƐƚƌƵĐƚƵƌĞƐ ŽĨ Ws& ĂƌĞ ŽĨ ƉĂƌƚŝĐƵůĂƌ ŝŶƚĞƌĞƐƚ ĨŽƌ ĞůĞĐƚƌŽŶŝĐƐ ĂƉƉůŝĐĂƟŽŶƐ͕ƐŝŶĐĞƚŚĞLJƌĞƐƵůƚŝŶŝƚƐŚŝŐŚƉŽůĂƌŝnjĂďŝůŝƚLJ͘ŵŽŶŐƚŚĞĐƌLJƐƚĂůůŝŶĞƉŚĂƐĞƐ͕ ƚŚĞɲͲƉŚĂƐĞŝƐŬŝŶĞƟĐĂůůLJƚŚĞƌĞƐƵůƚŽĨƚŚĞŵŽƐƚĨĂǀŽƌĂďůĞĐƌLJƐƚĂůůŝnjĂƟŽŶƉƌŽĐĞƐƐ͘,ĞƌĞŝŶ͕ ƚŚĞĐŽŶƐƟƚƵĞŶƚŵŽŶŽŵĞƌƐĂĚŽƉƚĂŶŽŶͲƉŽůĂƌƚƌĂŶƐͲŐĂƵĐŚĞĐŽŶĨŽƌŵĂƟŽŶ;TGTG’Ϳ͕ǁŚĞƌĞ ƚŚĞŚLJĚƌŽŐĞŶĂŶĚŇƵŽƌŝŶĞĂƚŽŵƐĂůƚĞƌŶĂƚĞŽŶďŽƚŚƐŝĚĞŽĨƚŚĞƉŽůLJŵĞƌďĂĐŬďŽŶĞ͘19 In the ĐƌLJƐƚĂůůŝŶĞƵŶŝƚĐĞůů;ůĂƫĐĞƉĂƌĂŵĞƚĞƌƐ͗ĂсϬ͘ϰϵϲŶŵ͕ďсϬ͘ϵϲϰŶŵ͕ĐсϬ͘ϰϲϮŶŵͿ͕ƚŚĞ ĐŚĂŝŶƐƉĂĐŬĂŶƟƉĂƌĂůůĞů͕ůĞĂĚŝŶŐƚŽĂŶĞƚĚŝƉŽůĞŵŽŵĞŶƚŽĨϬ͘20tŚĞŶWs&ĐƌLJƐƚĂůůŝnjĞƐ ŝŶƚŚĞƚŚĞƌŵŽĚLJŶĂŵŝĐĂůůLJŵŽƐƚƐƚĂďůĞĂŶĚ͕ĂĚĚŝƟŽŶĂůůLJ͕ŵŽƐƚƉŽůĂƌƉŚĂƐĞ͕ƚŚĞɴͲƉŚĂƐĞ͕ ƚŚĞƉŽůLJŵĞƌĐŚĂŝŶƐŽƌŐĂŶŝnjĞƚŚĞŵƐĞůǀĞƐŝŶƉůĂŶĂƌĂůůͲƚƌĂŶƐĐŽŶĨŽƌŵĂƟŽŶƐ;ddddͿŚĂǀŝŶŐ ĐƌLJƐƚĂůůŝŶĞůĂƫĐĞƉĂƌĂŵĞƚĞƌƐŽĨĂсϬ͘ϴϱϴŶŵ͕ďсϬ͘ϰϵϭŶŵ͕ĂŶĚĐсϬ͘ϮϱϲŶŵ͘dŚŝƐŚŝŐŚůLJ ƉŽůĂƌɴͲƉŚĂƐĞŚĂƐƚŚĞůĂƌŐĞƐƚŶĞƚĚŝƉŽůĞŵŽŵĞŶƚŽĨϮ͘ϭƉĞƌŵŽŶŽŵĞƌŝĐƵŶŝƚĐŽŵƉĂƌĞĚ ƚŽƚŚĞŽƚŚĞƌĐƌLJƐƚĂůůŝŶĞƉŚĂƐĞƐ͘dŚĞůĂƫĐĞƉĂƌĂŵĞƚĞƌƐŽĨƚŚĞɶͲƉŚĂƐĞĂƌĞƐůŝŐŚƚůLJŚŝŐŚĞƌ

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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: 16PDF page: 16PDF page: 16PDF page: 16

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ƚŚĂŶĨŽƌƚŚĞɴͲƉŚĂƐĞĂŶĚĂƌĞĚĞƚĞƌŵŝŶĞĚƚŽďĞĂсϬ͘ϴϲϲŶŵ͕ďсϬ͘ϰϵϯŶŵ͕ĂŶĚĐсϬ͘Ϯϱϴ Ŷŵ͕ǁŚĞƌĞŝŶƚŚĞĐŚĂŝŶƐŚĂǀĞĂĚŽƉƚĞĚĂddd'ĐŽŶĨŽƌŵĂƟŽŶ͘,ĞƌĞŝŶ͕ƚŚĞĐŚĂŝŶƐŽƌŝĞŶƚ ƉĂƌĂůůĞůƚŽĞĂĐŚŽƚŚĞƌŝŶƚŚĞĐƌLJƐƚĂůůĂƫĐĞƌĞƐƵůƟŶŐŝŶĂŶĞƚĚŝƉŽůĞŵŽŵĞŶƚŽĨϭ͘Ϯ per monomeric unit.20dŚĞƉĞƌŵĂŶĞŶƚĚŝƉŽůĞƐŝŶƚŚĞɴͲĂŶĚɶͲƉŚĂƐĞŐŝǀĞƌŝƐĞƚŽWs&͛Ɛ

ǁĞůůͲŬŶŽǁŶƉŝĞnjŽĞůĞĐƚƌŝĐŝƚLJ͕ĮƌƐƚĚŝƐĐŽǀĞƌĞĚďLJ<ĂǁĂŝŝŶϭϵϲϵ͕ĂŶĚĂŌĞƌůŽŶŐĚĞďĂƚĞŝŶ ůŝƚĞƌĂƚƵƌĞ͕ĂůƐŽŚĞůĚƌĞƐƉŽŶƐŝďůĞĨŽƌƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐƉƌŽƉĞƌƟĞƐ͘21,22 In fact, we should ĐĞůĞďƌĂƚĞƚŚĞϱϬLJĞĂƌĂŶŶŝǀĞƌƐĂƌLJŽĨĞůĞĐƚƌŽĂĐƟǀĞƉƌŽƉĞƌƟĞƐƌĞĐŽŐŶŝnjĞĚŝŶWs&ĂƚƚŚĞ ƟŵĞŽĨƚŚŝƐWŚĚĞĨĞŶƐĞ͘ &ĞƌƌŽĞůĞĐƚƌŝĐƐĂƌĞŵĂƚĞƌŝĂůƐƚŚĂƚŚĂǀĞĂƐƉŽŶƚĂŶĞŽƵƐƉŽůĂƌŝnjĂƟŽŶƚŚĂƚĐĂŶďĞƌĞǀĞƌƐĞĚ ďLJƚŚĞĂƉƉůŝĐĂƟŽŶŽĨĂŶĞůĞĐƚƌŝĐĮĞůĚ͘/Ŷ&ŝŐƵƌĞϭ͘ϱ͕ƚŚĞĚŝƐƟŶĐƚĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌƐ ŽĨ ŵĂƚĞƌŝĂůƐ ŝŶ ƌĞƐƉŽŶƐĞ ƚŽ ĂŶ ĞůĞĐƚƌŝĐ ĮĞůĚ ĂƌĞ ƐŚŽǁŶ͘ /Ŷ ĨĞƌƌŽĞůĞĐƚƌŝĐƐ͕ ŝŵƉŽƌƚĂŶƚ ƉĂƌĂŵĞƚĞƌƐ ĂƌĞ ƚŚĞ ĐŽĞƌĐŝǀĞ ĮĞůĚ ĂŶĚ ƌĞŵĂŶĞŶƚ ƉŽůĂƌŝnjĂƟŽŶ ĂƐ ŝŶĚŝĐĂƚĞĚ ŝŶ &ŝŐƵƌĞ ϭ͘ϱĚ͘dŚĞĐŽĞƌĐŝǀĞĮĞůĚ;EcͿĐŽƌƌĞƐƉŽŶĚƐƚŽƚŚĞĞůĞĐƚƌŝĐĮĞůĚǁŚĞƌĞĂĐŚĂŶŐĞŽĨƚŚĞ ŶĞƚƉŽůĂƌŝnjĂƟŽŶĨƌŽŵƉŽƐŝƟǀĞƚŽŶĞŐĂƟǀĞŽƌǀŝĐĞǀĞƌƐĂŽĐĐƵƌƐ͘/ŶĐƌĞĂƐŝŶŐƚŚĞĞůĞĐƚƌŝĐ ĮĞůĚĨƵƌƚŚĞƌǁŝůůĮŶĂůůLJůĞĂĚƚŽƐĂƚƵƌĂƟŽŶŽĨƚŚĞĐƌLJƐƚĂůůŝŶĞĚŝƉŽůĞƐ͕ŐŝǀŝŶŐĂƐĂƚƵƌĂƟŽŶ ƉŽůĂƌŝnjĂƟŽŶ͘ŌĞƌƌĞŵŽǀĂůŽĨƚŚĞĞůĞĐƚƌŝĐĮĞůĚ͕ƚŚĞĚŝƉŽůĞƐǁŝůůƌĞŵĂŝŶƉĂƌƚůLJŽƌŝĞŶƚĞĚ͕ ďĞƩĞƌŬŶŽǁŶĂƐƚŚĞƌĞŵĂŶĞŶƚƉŽůĂƌŝnjĂƟŽŶ;PrͿ͘dŚŝƐůĂƌŐĞƌĞŵĂŶĞŶƚƉŽůĂƌŝnjĂƟŽŶƐŝŶ ĨĞƌƌŽĞůĞĐƚƌŝĐŵĂƚĞƌŝĂůƐŝƐƚŚĞŵĂŝŶƌĞĂƐŽŶǁŚLJWs&ŝƐŚŝŐŚůLJƵŶƐƵŝƚĂďůĞĨŽƌĚŝĞůĞĐƚƌŝĐ ĂƉƉůŝĐĂƟŽŶƐ͘ KĨ ĐŽƵƌƐĞ͕ ƚŚĞ ƋƵĞƐƟŽŶ ŝĨ ɲͲƉŚĂƐĞ Ws& ĐĂŶ ďĞ ƵƐĞĚ ĨŽƌ ĚŝĞůĞĐƚƌŝĐƐ ŝŵŵĞĚŝĂƚĞůLJĂƌŝƐĞƐ͘hŶĨŽƌƚƵŶĂƚĞůLJ͕ĞůĞĐƚƌŝĐĮĞůĚŝŶĚƵĐĞĚĐƌLJƐƚĂůůŝŶĞƉŚĂƐĞƚƌĂŶƐĨŽƌŵĂƟŽŶƐ ƌĞƐƵůƚĂůƌĞĂĚLJĂƚƌĞůĂƟǀĞůŽǁĮĞůĚƐ;ϭϬϬͲϭϱϬDsŵͲϭͿŝŶĂŶŝƌƌĞǀĞƌƐŝďůĞɲͲƚŽɶͲƉŚĂƐĞ ƚƌĂŶƐĨŽƌŵĂƟŽŶĂŶĚĂƚŚŝŐŚĮĞůĚ;ϱϬϬDsŵͲϭͿŝŶƚŚĞĨŽƌŵĂƟŽŶƚŚĞƚŚĞƌŵŽĚLJŶĂŵŝĐĂůůLJ ĨĂǀŽƌĂďůĞĨĞƌƌŽĞůĞĐƚƌŝĐɴͲƉŚĂƐĞ͕ƌĞŶĚĞƌŝŶŐĂĨĞƌƌŽĞůĞĐƚƌŝĐƉŽůLJŵĞƌ͘ϮϮ͕Ϯϯ /ĚĞĂůůLJ͕ĨŽƌĐĂƉĂĐŝƟǀĞĞŶĞƌŐLJƐƚŽƌĂŐĞ͕Ws&ĚŝƐƉůĂLJƐƐŝŶŐůĞ;ƌĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐͿ or double hysteresis loop behavior due to the strongly reduced energy losses, while ŵĂŝŶƚĂŝŶŝŶŐĂůĂƌŐĞƉŽůĂƌŝnjĂƟŽŶ͕ĂƐŝƐĚĞƉŝĐƚĞĚŝŶ&ŝŐƵƌĞϭ͘ϱďĂŶĚϭ͘ϱĐ͘ϲ To obtain this,

ĂƚŚŽƌŽƵŐŚƵŶĚĞƌƐƚĂŶĚŝŶŐŽĨĨĞƌƌŽĞůĞĐƚƌŝĐŝƚLJŝŶWs&ŝƐĚĞƐŝƌĞĚ͘ƐĚĞŵŽŶƐƚƌĂƚĞĚŝŶ &ŝŐƵƌĞϭ͘ϲ͕ƚŚĞƉŽůĂƌŝnjĂƟŽŶŵĞĐŚĂŶŝƐŵŝŶWs&ŝƐĞdžƉůĂŝŶĞĚƵƐŝŶŐĂƐĞƌŝĂůĐĂƉĂĐŝƚŽƌ model.ϳ͕ϭϰ/ŶŚĞƌĞ͕ĂWs&ĐƌLJƐƚĂůŝŶĂŶĂŵŽƌƉŚŽƵƐŵĂƚƌŝdžŝƐƐĂŶĚǁŝĐŚĞĚďĞƚǁĞĞŶƚǁŽ ƉĂƌĂůůĞůƉůĂƚĞƐĂŶĚĂŶĞůĞĐƚƌŝĐĮĞůĚŝƐĂƉƉůŝĞĚ͘ƵĞƚŽƚŚĞĚŝīĞƌĞŶĐĞƐŝŶƉŽůĂƌŝnjĂďŝůŝƚLJ ŽĨƚŚĞĂŵŽƌƉŚŽƵƐĂŶĚĐƌLJƐƚĂůůŝŶĞĚŽŵĂŝŶƐ͕ƚŚĞŝŶƚĞƌŶĂůĞůĞĐƚƌŝĐĮĞůĚƐŝŶƚŚĞŵĂƚĞƌŝĂů ǀĂƌLJďĞƚǁĞĞŶƚŚĞĂŵŽƌƉŚŽƵƐĂŶĚĐƌLJƐƚĂůůŝŶĞĚŽŵĂŝŶƐ͘dŚĞƌĞĨŽƌĞ͕ĂŌĞƌĂůŝŐŶŵĞŶƚŽĨ ĐƌLJƐƚĂůůŝŶĞĚŝƉŽůĞƐ͕ĂůŽĐĂůĚĞƉŽůĂƌŝnjĂƟŽŶĞůĞĐƚƌŝĐĮĞůĚǁŝůůŝŶĚƵĐĞƉŽůĂƌŝnjĂƟŽŶƐ;PinͿĂƚ ƚŚĞĐƌLJƐƚĂůůŝŶĞͲĂŵŽƌƉŚŽƵƐŝŶƚĞƌĨĂĐĞĂĐĐŽƌĚŝŶŐƚŽƚŚĞĨŽůůŽǁŝŶŐƌĞůĂƟŽŶ dŚĞŝŶĚƵĐĞĚƉŽůĂƌŝnjĂƟŽŶĂƚƚŚĞĐƌLJƐƚĂůůŝŶĞͲĂŵŽƌƉŚŽƵƐŝŶƚĞƌĨĂĐĞǁŝůůŝŶƚƵƌŶŐŝǀĞĂŶ ĞŶŚĂŶĐĞĚƉŽůĂƌŝnjĂƟŽŶŽĨĂŵŽƌƉŚŽƵƐĚŝƉŽůĞƐŶĞĂƌƚŚĞŝŶƚĞƌĨĂĐĞ͘dŚŝƐŝƐƚŚĞƐŽͲĐĂůůĞĚ

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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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ĐŽŵƉĞŶƐĂƟŽŶĂůƉŽůĂƌŝnjĂƟŽŶ;PcompͿ ĂŶĚŝƚƐƋƵĂŶƟƚLJŝƐĚĞƚĞƌŵŝŶĞĚďLJƚŚƌĞĞĨĂĐƚŽƌƐ͕i.e. the dipole density of the amorphous region (N0,amͿ͕ƚŚĞƉŽůĂƌŝnjĂďŝůŝƚLJŽĨƚŚĞĚŝƉŽůĞƐ;ɲamͿ ĂŶĚƚŚĞůŽĐĂůĞůĞĐƚƌŝĐĮĞůĚŝŶƚŚĞĂŵŽƌƉŚŽƵƐƉŚĂƐĞ;EL,amͿ͘

Ɛ ƐƵĐŚ͕ Pcomp does not necessarily match Pin͘ Ɛ ƐŚŽǁŶ ƉƌĞǀŝŽƵƐůLJ͕ ƚŚĞ ůŽĐĂů ƉŽůĂƌŝnjĂƟŽŶĮĞůĚ;EpolarͿŝƐŝŵƉŽƐĞĚĨƌŽŵĐŚĂƌŐĞƐŽŶƚŚĞĞůĞĐƚƌŽĚĞƐĂŶĚĐĂŶďĞĚĞĮŶĞĚĂƐ

where Q is the charge density between two parallel plates in a vacuum.

Since it can be assumed that dipoles nearby the ferroelectric crystal are randomly ŽƌŝĞŶƚĞĚ;ůĂƌŐĞƚŚĞƌŵĂůŇƵĐƚƵĂƟŽŶĚƵĞƚŽĂůŽǁŐůĂƐƐƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞ;Tg͕;ͲϰϬΣͿ ůĞĂĚƐƚŽĨĂƐƚƌĞůĂdžĂƟŽŶƐĂŶĚƚŚƵƐƌĂŶĚŽŵŽƌŝĞŶƚĂƟŽŶƐͿ͕ƚŚĞŵĂŝŶƚǁŽƐŽƵƌĐĞƐĚĞƚĞƌŵŝŶŝŶŐ ĚŝƉŽůĞƌĞǀĞƌƐŝďŝůŝƚLJĂƌĞƚŚĞůŽĐĂůĂŶĚĚĞƉŽůĂƌŝnjĂƟŽŶĮĞůĚ͘ϳ͕ϭϰdŚĞĐŽŵƉĞƟƟŽŶďĞƚǁĞĞŶE

polar

and EdepolarƌĞƐƵůƚƐŝŶĚŝƐƟŶĐƚĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌĂŶĚŝƐĞdžƉůĂŝŶĞĚĂƐĨŽůůŽǁƐ͘tŚĞŶ Figure 1.6: A PVDF crystal embedded in an amorphous matrix in between two metal plates when an IPIGXVMGƼIPHMWETTPMIH(MTSPIEPMKRQIRXEJXIVETTP]MRKERIPIGXVMGƼIPHPIEHWXSEPSGEPHITSPEVM^EXMSR ƼIPH Edepolar) inducing polarization (Pin) at the interface allowing additional amorphous dipoles to become polarized at the interface (Pcomp).

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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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ĂƉƉůLJŝŶŐĂŶĞůĞĐƚƌŝĐĮĞůĚĂďŽǀĞƚŚĞĐŽĞƌĐŝǀĞĮĞůĚQ+Pcomp > Pin͕ƌĞƐƵůƟŶŐŝŶEpolar > Edepolar. If ƚŚĞĞůĞĐƚƌŝĐĮĞůĚŝƐƌĞŵŽǀĞĚƚǁŽƉŚĞŶŽŵĞŶĂĐĂŶŚĂƉƉĞŶ͘^ŝŶĐĞďŽƚŚEpolar and Edepolar get ůŽǁĞƌ͕ƚŚĞĚŝƉŽůĞƐďĞĐŽŵĞůĞƐƐƐƚĂďůĞĂŶĚŵĂLJƐǁŝƚĐŚďĂĐŬƚŽƚŚĞŽƉƉŽƐŝƚĞĚŝƌĞĐƟŽŶ͘/Ĩ ƚŚŝƐŚĂƉƉĞŶƐ͕ƚŚĞŵĂƚĞƌŝĂůƐǁŝůůŚĂǀĞĂŶĞĂƌϬƌĞŵĂŶĞŶƚƉŽůĂƌŝnjĂƟŽŶĂŶĚĐĂŶďĞƌĞĨĞƌƌĞĚ ƚŽĂƐĂŶƟͲĨĞƌƌŽĞůĞĐƚƌŝĐ͘/ŶĐŽŶƚƌĂƐƚ͕ĨŽƌWs&ŝŶƚŚĞɴͲƉŚĂƐĞ͕Epolar is always higher than EdepolarĞǀĞŶǁŚĞŶƚŚĞĞůĞĐƚƌŝĐĮĞůĚŝƐĐŽŵƉůĞƚĞůLJƌĞŵŽǀĞĚ͕ŐŝǀŝŶŐĨĞƌƌŽĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌ͘ Therefore, reducing the polarizability of the region surrounding the ferroelectric crystal ĂƉƉĞĂƌƐĂƐĂŶĞīĞĐƟǀĞĂƉƉƌŽĂĐŚƚŽĞŶŚĂŶĐĞƚŚĞĚŝƉŽůĞƌĞǀĞƌƐŝďŝůŝƚLJ͘

EĞdžƚƚŽƚŚĞƉŽůĂƌŝnjĂďŝůŝƚLJŽĨƚŚĞĐƌLJƐƚĂůůŝŶĞĂŵŽƌƉŚŽƵƐŝŶƚĞƌĨĂĐĞ͕ĐŽƵƉůŝŶŐŝŶƚĞƌĂĐƟŽŶƐ ŝŶĚƵĐŝŶŐ ƉŽůĂƌŝnjĂƟŽŶƐ ;PcompͿalso play an important role in ferroelectric behavior.ϲ͕ϳ

/Ŷ&ŝŐƵƌĞϭ͘ϳ͕ĚŝƐƟŶĐƚĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶƐĂƌĞƐŚŽǁŶŝŶĐůƵĚŝŶŐƚŚĞŝƌƚŚƌĞĞĐŽƵƉůŝŶŐ ŝŶƚĞƌĂĐƟŽŶƐ͘/ŶƚLJƉĞ/ŝŶƚĞƌĂĐƟŽŶƐ͕ĐŽƵƉůŝŶŐǁŝƚŚŝŶƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐĐƌLJƐƚĂůƐŝƐƌĞĂůŝnjĞĚ͘ ŽƵƉůŝŶŐŝŶďĞƚǁĞĞŶƐĞƉĂƌĂƚĞĚĨĞƌƌŽĞůĞĐƚƌŝĐĐƌLJƐƚĂůƐďƵƚĂůŽŶŐƚŚĞĮĞůĚĚŝƌĞĐƟŽŶŚĂƉƉĞŶ ŝŶƚLJƉĞ//ŝŶƚĞƌĂĐƟŽŶƐ͘7&ŝŶĂůůLJ͕ƚLJƉĞ///ŝŶƚĞƌĂĐƟŽŶƐĂƌĞŝŶƚĞƌĚŽŵĂŝŶƉĞƌƉĞŶĚŝĐƵůĂƌƚŽ

Figure 1.7: 'V]WXEPPMRIHSQEMRWIQFIHHIHMREREQSVTLSYWQEXVM\[LIRERIPIGXVMGƼIPHMWETTPMIH showing the distinct coupling interactions.

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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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1

ƚŚĞĞůĞĐƚƌŝĐĮĞůĚ͘ŶĂůŽŐŽƵƐƚŽƚŚĞPcomp derived for the amorphous domain in the serial capacitor model, Pcomp can also be described for type I coupling as

Since the polarizability of the crystalline domains are higher than for the amorphous ƌĞŐŝŽŶ͕ƚLJƉĞ/ŝŶƚĞƌĂĐƟŽŶƐĂƌĞƐƚƌŽŶŐĞƌƚŚĂŶƚLJƉĞ//͘/ŶĂĚĚŝƟŽŶ͕ĚƵĞƚŽĂŶŝƐŽƚƌŽƉLJŽĨ ƚŚĞĐŽƵƉůŝŶŐŝŶƚĞƌĂĐƟŽŶƐ͕ƚLJƉĞ///ŝŶƚĞƌĂĐƟŽŶƐĂƌĞŵƵĐŚǁĞĂŬĞƌƚŚĂŶƚLJƉĞ//͘dŚĞƌĞĨŽƌĞ͕ ďĞƐŝĚĞƐƌĞĚƵĐŝŶŐƚŚĞƉŽůĂƌŝnjĂďŝůŝƚLJŽĨƚŚĞĐƌLJƐƚĂůůŝŶĞͲĂŵŽƌƉŚŽƵƐŝŶƚĞƌĨĂĐĞ͕ŝƐŽůĂƟŶŐƐŵĂůů ɴͲƉŚĂƐĞĐƌLJƐƚĂůƐŝƐĂƐĞĐŽŶĚĂƉƉĞĂůŝŶŐƐƚƌĂƚĞŐLJƚŽƌĞĚƵĐĞĨĞƌƌŽĞůĞĐƚƌŝĐŝƚLJŝŶWs&͘ Strategies &ƌŽŵƚŚĞĚŝƐĐƵƐƐŝŽŶĂďŽƵƚĨĞƌƌŽĞůĞĐƚƌŝĐŝƚLJŝŶWs&͕ŝƚŝƐƵŶĚĞƌƐƚŽŽĚƚŚĂƚWs&ĐƌLJƐƚĂůƐ ĂƌĞƌĞƋƵŝƌĞĚƚŽďĞƐŵĂůů͕ǁĞůůͲŝƐŽůĂƚĞĚ͕ĂŶĚƚŽŚĂǀĞĂůŽǁƉŽůĂƌŝnjĂďŝůŝƚLJŽĨƚŚĞĐƌLJƐƚĂůůŝŶĞͲ ĂŵŽƌƉŚŽƵƐ ŝŶƚĞƌĨĂĐĞ ĨŽƌ ŽďƚĂŝŶŝŶŐ Ws&ͲďĂƐĞĚ ŵĂƚĞƌŝĂůƐ ƐƵŝƚĂďůĞ ĚŝĞůĞĐƚƌŝĐ ĞŶĞƌŐLJ ƐƚŽƌĂŐĞ͘dŽĂĐŚŝĞǀĞƚŚŝƐ͕ĐŚĂŶŐŝŶŐƚŚĞƉŽůLJŵĞƌƚŽƉŽůŽŐLJŝƐĂƐƚƌĂŝŐŚƞŽƌǁĂƌĚƐƚƌĂƚĞŐLJ͘/Ŷ ƚŚĞůŝƚĞƌĂƚƵƌĞ͕ĐŚĞŵŝĐĂůĂƉƉƌŽĂĐŚĞƐƚŽĞŶŚĂŶĐĞĚŝƉŽůĞƌĞǀĞƌƐŝďŝůŝƚLJŝŶWs&ĨŽƌĐŚĂŶŐŝŶŐ ŝƚƐ ĞůĞĐƚƌŽĂĐƟǀĞ ďĞŚĂǀŝŽƌ ŝŶĐůƵĚĞ ĐŽͲ ĂŶĚ ƚĞƌƉŽůLJŵĞƌŝnjĂƟŽŶ ǁŝƚŚ ŽƚŚĞƌ ŇƵŽƌŝŶĂƚĞĚ ŵŽŶŽŵĞƌƐ͕ŐƌĂŌĐŽƉŽůLJŵĞƌŝnjĂƟŽŶƐ͕ĐŚĞŵŝĐĂůĐƌŽƐƐůŝŶŬƐ͕ŵƵůƟůĂLJĞƌŝŶŐǁŝƚŚŝŶƐƵůĂƟŶŐ ƉŽůLJŵĞƌƐ͕ĂŶĚƚŚĞŶĂŶŽĐŽŶĮŶĞŵĞŶƚƵƐŝŶŐďůŽĐŬĐŽƉŽůLJŵĞƌƐ͘/ŶƚŚĞĨŽůůŽǁŝŶŐƐĞĐƟŽŶ͕ ƚŚĞLJĂƌĞďƌŝĞŇLJĂĚĚƌĞƐƐĞĚ͘

Co- and terpolymerizations

sŝŶLJůŵŽŶŽŵĞƌƐĂƌĞŽƌŐĂŶŝnjĞĚŝŶƚǁŽĐůĂƐƐĞƐ͕i.e. ŵŽƌĞĂĐƟǀĂƚĞĚŵŽŶŽŵĞƌƐ;DDͿƐĂŶĚ ůĞƐƐĂĐƟǀĂƚĞĚŵŽŶŽŵĞƌƐ;>DƐͿ͘Ϯϰ/ŶDD͕ƚŚĞĚŽƵďůĞďŽŶĚŝƐĐŽŶũƵŐĂƚĞĚŝŶĂŶĂƌŽŵĂƟĐ ƐLJƐƚĞŵŽƌǁŝƚŚĂŶĂĐƌLJůĂƚĞ͕ǁŚŝůĞŝŶ>DƐĂŶĞůĞĐƚƌŽŶůŽŶĞƉĂŝƌĨƌŽŵĂŶŝƚƌŽŐĞŶŽƌŽdžLJŐĞŶ ĂƚŽŵŝƐŶĞdžƚƚŽƚŚĞĚŽƵďůĞďŽŶĚ͘dŚĞƚǁŽŇƵŽƌŝŶĞĂƚŽŵƐĂĚũĂĐĞŶƚƚŽƚŚĞĚŽƵďůĞďŽŶĚ ŵĂŬĞs&Ă>D͕ůĞĂĚŝŶŐƚŽĐŽƉŽůLJŵĞƌŝnjĂƟŽŶƐŽĨs&ǁŝƚŚŵŽƐƚůLJŽƚŚĞƌŇƵŽƌŝŶĂƚĞĚ ĂůŬĞŶĞƐ͕ǁŚĞƌĞĂƐĐŽƉŽůLJŵĞƌŝnjĂƟŽŶǁŝƚŚDDƐĂƌĞŶŽƚĨĞĂƐŝďůĞ͘ϭϲEĞdžƚƚŽƚŚĞŵŽƌĞ ďƵůŬLJŇƵŽƌŝŶĂƚĞĚŵŽŶŽŵĞƌĂƐŚĞdžĂŇƵŽƌŽƉƌŽƉLJůĞŶĞ;,&WͿĂŶĚďƌŽŵŽƚƌŝŇƵŽƌŽĞƚŚLJůĞŶĞ ;d&Ϳ͕ƌĞůĂƟǀĞůLJƐŵĂůůŝŶƐŝnjĞ͕ƚƌŝŇƵŽƌŽĞƚŚLJůĞŶĞ;dƌ&Ϳ͕ĐŚůŽƌŽƚƌŝŇƵŽƌŽĞƚŚLJůĞŶĞ;d&Ϳ͕ ĐŚůŽƌŽŇƵŽƌŽĞƚŚLJůĞŶĞ;&ͿĐŽŵŽŶŽŵĞƌƐĂƌĞǁŝĚĞůLJĞdžƉůŽƌĞĚŝŶĐŽƉŽůLJŵĞƌŝnjĂƟŽŶǁŝƚŚ s&ĨŽƌĚŝĞůĞĐƚƌŝĐĂƉƉůŝĐĂƟŽŶƐ͘17 /ŶƚĞƌĞƐƟŶŐůLJ͕ŝŶW;s&ͲcoͲdƌ&ͿĐŽƉŽůLJŵĞƌƐĐŽĐƌLJƐƚĂůůŝnjĂƟŽŶŽĐĐƵƌƐĂŶĚǁŚĞŶŚĂǀŝŶŐ ĂŵŽůĂƌĐŽŶƚĞŶƚŽĨs&ďĞƚǁĞĞŶϱϬͲϴϬй͕ƚŚĞĐŽƉŽůLJŵĞƌƐĂƌĞĨĞƌƌŽĞůĞĐƚƌŝĐƌĞŐĂƌĚůĞƐƐ ŽĨƚŚĞŝƌƉƌŽĐĞƐƐŝŶŐĐŽŶĚŝƟŽŶƐ͘25dŚĞƐůŝŐŚƚůLJŝŶĐƌĞĂƐĞĚƐŝnjĞŽĨdƌ&ŵŽŶŽŵĞƌƐĚƵĞƚŽĂŶ

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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: 20PDF page: 20PDF page: 20PDF page: 20

20 ĂĚĚŝƟŽŶĂůŇƵŽƌŝŶĞĂƚŽŵůĞĂĚƐƚŽĂŶŝŶĐƌĞĂƐĞŝŶƚŚĞĐƌLJƐƚĂůůĂƫĐĞƐƉĂĐŝŶŐ͕ĂůůŽǁŝŶŐĐŚĂŝŶƐ ƚŽĂĚŽƉƚƚŚĞĂůůͲƚƌĂŶƐĐŽŶĨŽƌŵĂƟŽŶŵŽƌĞĞĂƐŝůLJ͘Ϯϲ/ŶĂĚĚŝƟŽŶ͕ƚŚĞLJŚĂǀĞĂĨĞƌƌŽĞůĞĐƚƌŝĐͲ ƚŽͲƉĂƌĂĞůĞĐƚƌŝĐƉŚĂƐĞƚƌĂŶƐŝƟŽŶ;ƵƌŝĞƚƌĂŶƐŝƟŽŶͿƵƉŽŶŚĞĂƟŶŐ;ĂŶĚǀŝĐĞǀĞƌƐĂǁŚĞŶ ĐŽŽůĞĚĨƌŽŵƚŚĞŵĞůƚͿƚŚĂƚĚĞĐƌĞĂƐĞƐŝŶƚĞŵƉĞƌĂƚƵƌĞǁŝƚŚŝŶĐƌĞĂƐŝŶŐdƌ&ĐŽŶƚĞŶƚ͕ǁŚŝůĞ ĂƵƌŝĞƚƌĂŶƐŝƟŽŶŝƐŶŽƚƐĞĞŶŝŶWs&ŚŽŵŽƉŽůLJŵĞƌƐ͘27 dŚŝƐ ƵƌŝĞ ƚƌĂŶƐŝƟŽŶ ŝƐ ŚŝŐŚůLJ ŝŶƚĞƌĞƐƟŶŐ͕ ŶŽƚ ŽŶůLJ ĨŽƌ ĐĂƉĂĐŝƟǀĞ ĞŶĞƌŐLJ ƐƚŽƌĂŐĞ ĂƉƉůŝĐĂƟŽŶƐ͕ďƵƚĂůƐŽĨŽƌĞůĞĐƚƌŽĐĂůŽƌŝĐĐŽŽůŝŶŐĚĞǀŝĐĞƐ͘17tŚĞŶĂŶĞůĞĐƚƌŝĐĮĞůĚŝƐĂƉƉůŝĞĚ͕ ůĂƌŐĞŝŶĐƌĞĂƐĞƐŝŶĚŝƉŽůĂƌŽƌĚĞƌŝŶŐ;ƵƉƚŽɸсϱϬͿĂƌŽƵŶĚƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶĂůůŽǁĞŶƚƌŽƉŝĐ ĞŶĞƌŐLJƚŽďĞĐĂƉƚƵƌĞĚĨƌŽŵƚŚĞƐƵƌƌŽƵŶĚŝŶŐƌĞƐƵůƟŶŐŝŶĂŶĞŶŽƌŵŽƵƐĞůĞĐƚƌŽĐĂůŽƌŝĐ ĞīĞĐƚ͘28EĞǀĞƌƚŚĞůĞƐƐ͕ƵƐŝŶŐdƌ&ĂƐĐŽŵŽŶŽŵĞƌ͕ƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞŽŶůLJ ĚƌŽƉƐƚŽΕϲϬΣ͕ǁŚĞƌĞĂŶĞĂƌƌŽŽŵƚĞŵƉĞƌĂƚƵƌĞƵƌŝĞƚƌĂŶƐŝƟŽŶŝƐĚĞƐŝƌĂďůĞ͘27,28 If ƚŚĞŵŽůĂƌĐŽŶƚĞŶƚŽĨdƌ&ŝƐĞdžĐĞĞĚŝŶŐϱϬйĂĐŚĂŶŐĞŝŶĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌ͕ĨƌŽŵ ĨĞƌƌŽĞůĞĐƚƌŝĐƚŽƌĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐ͕ŝƐŽďƐĞƌǀĞĚ͘ZĞĐĞŶƚƐƚƵĚŝĞƐďLJƚŚĞtĂŶŐŐƌŽƵƉŚĂǀĞ ŚŝŐŚůŝŐŚƚĞĚƚŚĞƌŽůĞŽĨĐŚĂŝŶƚĂĐƟĐŝƚLJ͘ƚĂƌŽƵŶĚϱϬŵŽůйdƌ&͕ĂŶĂĚĚŝƟŽŶĂůĐƌLJƐƚĂůůŝŶĞ ƉŚĂƐĞĂƉƉĞĂƌƐĐĂƵƐĞĚďLJĂŶŝŶĐƌĞĂƐĞĚĂŵŽƵŶƚŽĨŝƐŽƚĂĐƟĐĐŽŶĨŽƌŵĂƟŽŶŽĨŵŽŶŽŵĞƌƐ ĞŶĞƌŐĞƟĐĂůůLJĨĂǀŽƌŝŶŐĂϯͬϭŚĞůŝĐĂůĨŽƌŵĂƟŽŶĂƐŽƉƉŽƐĞĚƚŽƚŚĞĂůůͲƚƌĂŶƐĐŽŶĨŽƌŵĂƟŽŶ͘29 ŽƉŽůLJŵĞƌŝnjĂƟŽŶƐŽĨs&ǁŝƚŚŽƚŚĞƌŇƵŽƌŝŶĂƚĞĚŵŽŶŽŵĞƌƐĂůůƌĞƐƵůƚŝŶĞdžĐůƵƐŝŽŶŽĨ ƚŚĞĐŽŵŽŶŽŵĞƌĨƌŽŵƚŚĞĐƌLJƐƚĂůůĂƫĐĞƐŝŶĐĞƚŚĞŵŽŶŽŵĞƌƐĂƉƉĞĂƌƚŽďĞƚŽŽďƵůŬLJ͘Ϯϲ ,ŽǁĞǀĞƌ͕ŝƚďƌĞĂŬƐƵƉďŝŐĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶƐĂƐĚŝƐĐƵƐƐĞĚƉƌĞǀŝŽƵƐůLJ͘7/ŶƚĞƌĞƐƟŶŐůLJ͕ ƵŶŝĂdžŝĂůůLJ ƐƚƌĞƚĐŚĞĚ ;ĐƌLJƐƚĂůůŝŶĞ ĚŝƉŽůĞƐ ǁŝůů ŽƌŝĞŶƚ ŝŶ ƚŚŝƐ ŵĂŶŶĞƌͿ W;s&Ͳco-d&Ϳ ĐŽƉŽůLJŵĞƌƐƐŚŽǁƐƚĂďŝůŝnjĂƟŽŶŽĨƚŚĞɶͲƉŚĂƐĞ͕ǁŚŝĐŚŝƐĚŝīĞƌĞŶƚƚŚĂŶW;s&ͲcoͲd& ĂŶĚ W;s&ͲcoͲ,&WͿ ĐŽƉŽůLJŵĞƌƐ ƚŚĂƚ ƌĞůLJ ƵŶĂǀĂŝůŝŶŐůLJ ŽŶ ƌĞǀĞƌƐŝďůĞ ɲͲ ƚŽ ɴͲƉŚĂƐĞ ƚƌĂŶƐĨŽƌŵĂƟŽŶƐ͘ϯϬ͕ϯϭ dŚĞƌĞĨŽƌĞ͕ ƐƵƌƉƌŝƐŝŶŐůLJ͕ W;s&ͲcoͲd&Ϳ ĐŽƉŽůLJŵĞƌƐ ƐŚŽǁ ŚŝŐŚ ĚŝƐĐŚĂƌŐĞĞŶĞƌŐLJĚĞŶƐŝƟĞƐĂƚĞdžƚƌĞŵĞĮĞůĚƐ;ϮϬ͘ϴ:ĐŵͲϯĂƚϳϭϲDsŵͲϭͿ͘ϯϬ dŚĞŝŶĐŽƌƉŽƌĂƟŽŶŽĨĂƚŚŝƌĚŵŽŶŽŵĞƌůĞĂĚƐƚŽĂŶŝŶƚƌŝŐƵŝŶŐďĞŚĂǀŝŽƌ͘ƐĞdžƉůĂŝŶĞĚŝŶ ƚŚĞƉƌĞǀŝŽƵƐƉĂƌĂŐƌĂƉŚŵŽŶŽŵĞƌƐŽƚŚĞƌƚŚĂŶdƌ&ĂƌĞĞdžĐůƵĚĞĚĨƌŽŵƚŚĞWs&ĐƌLJƐƚĂůƐ͘ ,ŽǁĞǀĞƌ͕ǁŚĞŶĂƚĞƌƉŽůLJŵĞƌŝƐƐLJŶƚŚĞƐŝnjĞĚǁŝƚŚs&ĂŶĚdƌ&͕ďƵůŬŝĞƌĐŽŵŽŶŽŵĞƌƐƐƵĐŚ ĂƐ&ĂŶĚd&ĐĂŶďĞŝŶĐůƵĚĞĚŝŶƚŚĞĐƌLJƐƚĂůƐ͘ϯϮƉƉĂƌĞŶƚůLJ͕ƚŚŝƐŐƌĂĚŝĞŶƚŽĨŵŽŶŽŵĞƌ ƐŝnjĞƐĂůůŽǁƚŚĞŵƚŽĐŽĐƌLJƐƚĂůůŝnjĞ͘KŶƚŚĞĐŽŶƚƌĂƌLJ͕d&͕ŵŽŶŽŵĞƌƐďĞĂƌŝŶŐĂͲ&ϯ group, ŽƌŚĂǀŝŶŐĂƐŝĚĞĐŚĂŝŶĂƌĞĞdžĐůƵĚĞĚĨƌŽŵƚŚĞĐƌLJƐƚĂůƐǁŚĞŶŵĞůƚĐƌLJƐƚĂůůŝnjĞĚ͕ǁŚŝůĞ͕ ŝŶƚĞƌĞƐƟŶŐůLJ͕ƵŶŝĂdžŝĂůůLJƐƚƌĞƚĐŚŝŶŐĂůůŽǁƐ,&WƚŽďĞŝŶĐůƵĚĞĚ͘ϯϯdŚĞĐŽĐƌLJƐƚĂůůŝnjĂƟŽŶ͕

indeed, leads to a further increase in the distance between the chains, lowering the ƌŽƚĂƟŽŶĂůďĂƌƌŝĞƌƐ͕ǁŚĞŶĂŶĞůĞĐƚƌŝĐĮĞůĚŝƐĂƉƉůŝĞĚ͘ϮϰŽŶƐĞƋƵĞŶƚůLJ͕W;s&ͲterͲdƌ&ͲterͲ &ͿĂŶĚW;s&ͲterͲdƌ&ͲterͲd&ͿƚĞƌƉŽůLJŵĞƌƐĂƌĞĚĞŵŽŶƐƚƌĂƟŶŐĐŽŵƉůĞƚĞůLJĚŝīĞƌĞŶƚ ďĞŚĂǀŝŽƌƚŚĂŶWs&ĂŶĚW;s&ͲcoͲdƌ&Ϳ͘&ŽƌW;s&ͲterͲdƌ&ͲterͲ&Ϳ͕ĚŽƵďůĞŚLJƐƚĞƌĞƐŝƐ ůŽŽƉďĞŚĂǀŝŽƌŝƐŽďƐĞƌǀĞĚ͕ǁŚŝůĞW;s&ͲterͲdƌ&ͲterͲd&ͿƐŚŽǁƐƌĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐ behavior.ϲ/ŶďŽƚŚĐĂƐĞƐ͕ƚŚĞĐƌLJƐƚĂůůĂƫĐĞŝƐĞdžƉĂŶĚĞĚďLJƉŝŶŶŝŶŐƚŚĞƉŽůLJŵĞƌǁŝƚŚ ďƵůŬŝĞƌĐŽŶƐƟƚƵĞŶƚƐ͕LJĞƚƚŚĞƌĞŝƐĂĚŝīĞƌĞŶĐĞŝŶĚŝƉŽůĞŵŽŵĞŶƚďĞƚǁĞĞŶƚŚĞŵŽŶŽŵĞƌƐ͘ dŚĞĚŝƉŽůĞŵŽŵĞŶƚƐŽĨs&͕dƌ&͕&ĂŶĚd&ĂƌĞϮ͘ϭ͕ϭ͘ϰ͕ϭ͘ϴĂŶĚϬ͘ϲϰ͕ƌĞƐƉĞĐƟǀĞůLJ͘ϲ

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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: 21PDF page: 21PDF page: 21PDF page: 21

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1

ƐǁĞŬŶŽǁ͕ƚŚĞƌĞƐƉŽŶƐĞƚŽĂŶĞdžƚĞƌŶĂůĮĞůĚŝƐŚŝŐŚĞƌǁŚĞŶƚŚĞŵŽůĞĐƵůĞƐĂƌĞŵŽƌĞ ƉŽůĂƌ͘dŚĞƌĞĨŽƌĞ͕ĚƵĞƚŽƚŚĞƌĞůĂƟǀĞůLJŚŝŐŚĚŝƉŽůĞŵŽŵĞŶƚŽĨ&͕ƚŚĞƌĞŝƐĂŚŝŐŚPcomp ƉƌĞǀĞŶƟŶŐĚŝƉŽůĞƐƚŽƐǁŝƚĐŚŝŵŵĞĚŝĂƚĞůLJĂƚŚŝŐŚĮĞůĚƐ͕ǁŚŝůĞĂƚůŽǁĞƌĮĞůĚƐQ+Pcomp < Pin, leading to Epolar < Edepolar͘/ŶW;s&ͲterͲdƌ&ͲterͲd&ͿƚĞƌƉŽůLJŵĞƌƐĂƐƚƌŽŶŐĞƌƉŝŶŶŝŶŐ ĞīĞĐƚĚĞƐƚĂďŝůŝnjĞƐƚŚĞŽƌŝĞŶƚĞĚĚŝƉŽůĞƐĂůƌĞĂĚLJĂƚŚŝŐŚĮĞůĚƐ͕ŝŵŵĞĚŝĂƚĞůLJŵŝƐĂůŝŐŶŝŶŐƚŚĞ ĚŝƉŽůĞƐǁŚĞŶƚŚĞĮĞůĚŝƐƌĞĚƵĐĞĚ͕ƌĞƐƵůƟŶŐŝŶƌĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌ͘ůƚŚŽƵŐŚ͕ ƚĞƌƉŽůLJŵĞƌƐŽĨs&͕dƌ&ĂŶĚĂƚŚŝƌĚŇƵŽƌŝŶĂƚĞĚĐŽŵŽŶŽŵĞƌƐŚŽǁƵŶŝƋƵĞƉƌŽƉĞƌƟĞƐ͕ ŝŶĚƵƐƚƌŝĂůĂƉƉůŝĐĂƟŽŶƐĂƌĞƐƟůůĨĂƌŽīĚƵĞƚŽƚŚĞŚŝŐŚĐŽƐƚŽĨŵŽŶŽŵĞƌƐLJŶƚŚĞƐŝƐ͘ϭϲƐ ƐƵĐŚ͕ƚŚĞƐĞƚĞƌƉŽůLJŵĞƌƐƐƟůůĐŽƐƚŽǀĞƌΨϭϬ͕ϬϬϬŬŐͲϭĂŶĚĂůƚĞƌŶĂƟǀĞĐŚĞĂƉĞƌƐƚƌĂƚĞŐŝĞƐ ĂƌĞƌĞƋƵŝƌĞĚ͘5

PVDF-based graft copolymers

'ƌĂŌŝŶŐWs&ǁŝƚŚƐŚŽƌƚƐŝĚĞĐŚĂŝŶƐŝƐĂŶŽƚŚĞƌŵĞƚŚŽĚƚŽƚƵŶĞŝƚƐĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌ ĂŶĚŚĂƐĂƩƌĂĐƚĞĚŵŽĚĞƐƚƌĞƐĞĂƌĐŚĂƩĞŶƟŽŶ͘ϯϰdŚĞůĂĐŬŽĨƌĞĂĐƟǀŝƚLJŽĨƚŚĞƐƚƌŽŶŐͲ& ďŽŶĚƐůŝŵŝƚƐƚŚĞĂǀĂŝůĂďŝůŝƚLJŽĨƚĞĐŚŶŝƋƵĞƐƚŽĐŽŶƚƌŽůůĂďůLJŐƌĂŌWs&͘dŚĞƌĞĨŽƌĞ͕ĐŽͲ ĂŶĚƚĞƌƉŽůLJŵĞƌƐĐŽŶƚĂŝŶŝŶŐĂĐŚůŽƌŝŶĞŐƌŽƵƉŚĂǀĞďĞĞŶĞdžƉůŽƌĞĚ͘ŽŶƐĞƋƵĞŶƚůLJ͕ĂƚŽŵ ƚƌĂŶƐĨĞƌƌĂĚŝĐĂůƉŽůLJŵĞƌŝnjĂƟŽŶƐ;dZWͿŽĨƉŽůLJƐƚLJƌĞŶĞ;W^Ϳ͕ƉŽůLJ;ŵĞƚŚLJůŵĞƚŚĂĐƌLJůĂƚĞͿ ;WDDͿĂŶĚƉŽůLJ;ĞƚŚLJůŵĞƚŚĂĐƌLJůĂƚĞͿ;WDͿŚĂǀĞďĞĞŶĞŵƉůŽLJĞĚ͕ŐŝǀŝŶŐW;s&ͲterͲ dƌ&ͲterͲd&ͿͲgͲW^͕W;s&ͲterͲdƌ&ͲterͲd&ͿͲgͲWDDĂŶĚW;s&ͲterͲdƌ&ͲterͲd&ͿͲgͲ WDŐƌĂŌĐŽƉŽůLJŵĞƌƐ͘ϯϱʹϯϴEŽƚĞǁŽƌƚŚŝůLJ͕ůŽǁŵŽůĞĐƵůĂƌW^ŐƌĂŌƐĚŽŶŽƚƉŚĂƐĞƐĞƉĂƌĂƚĞ͕ ďƵƚůĞĂĚƚŽĚĞŶƐŝƚLJŇƵĐƚƵĂƟŽŶŝŶƚŚĞĂŵŽƌƉŚŽƵƐƉŚĂƐĞ͘ϯϱĞƐŝĚĞƐƚŚĞŐƌĂŌƐďĞŝŶŐůŽǁ ŵŽůĞĐƵůĂƌǁĞŝŐŚƚ͕ŵŝƐĐŝďŝůŝƚLJŽĨWs&ǁŝƚŚĂĐƌLJůĂƚĞƐŝƐǁĞůůŬŶŽǁŶĚƵĞƚŽŶƵŵĞƌŽƵƐ ƐƚƵĚŝĞƐŽĨWs&ͬWDDďůĞŶĚƐ͘LJŝŶƚƌŽĚƵĐŝŶŐW^ŐƌĂŌƐŝŶƚŚĞĐŽƉŽůLJŵĞƌƐ͕ŝƚŝƐƉŽƐƚƵůĂƚĞĚ ďLJŚƵĂŶĚĐŽǁŽƌŬĞƌƐƚŚĂƚƚŚĞLJŝƐŽůĂƚĞƚŚĞWs&ĐƌLJƐƚĂůƐ͘/ŶƚŚŝƐǁĂLJ͕ƚŚĞƉŽůĂƌŝnjĂďŝůŝƚLJ (PcompͿŽĨƚŚĞĐƌLJƐƚĂůůŝŶĞͲĂŵŽƌƉŚŽƵƐŝŶƚĞƌĨĂĐĞŝƐƌĞĚƵĐĞĚ͕ƐŝŶĐĞƚŚĞƉŽůĂƌŝnjĂďŝůŝƚLJŽĨƚŚĞ amorphous phase is lower. Indeed, this again results in double hysteresis loop behavior. hŶĨŽƌƚƵŶĂƚĞůLJ͕ƵƐŝŶŐdZWƚŽŐƌĂŌWs&ͲďĂƐĞĚĐŽƉŽůLJŵĞƌƐ͕ĐĂƌĞƐŚŽƵůĚĂůǁĂLJƐďĞƚĂŬĞŶ ƚŽƌĞŵŽǀĞĐŽƉƉĞƌŝŽŶƐƚŽŵŝƟŐĂƚĞŝŽŶŝĐůŽƐƐĞƐĂŶĚƌĞŵŽǀĞŝƚƐƌĞĂĐƟǀĞďĂƐŝĐůŝŐĂŶĚƚŽ ƉƌĞǀĞŶƚĚĞŚLJĚƌŽŇƵŽƌŝŶĂƟŽŶ͘ϯϲ͕ϯϵ 'VSWWPMROMRKƽYSVMREXIHTSP]QIVW ^ŝŵŝůĂƌƚŽŐƌĂŌĐŽƉŽůLJŵĞƌƐ͕ĨƵŶĐƟŽŶĂůŐƌŽƵƉƐĂƌĞƌĞƋƵŝƌĞĚĨŽƌĐƌŽƐƐůŝŶŬŝŶŐŇƵŽƌŝŶĂƚĞĚ ƉŽůLJŵĞƌƐ͘,ŽǁĞǀĞƌ͕ƐŝŶĐĞĐŽŶƚƌŽůŝƐŽŶůLJƌĞƋƵŝƌĞĚƚŽǁĂƌĚƐƚŚĞůŽĐĂƟŽŶĂŶĚƚŚĞĚĞŐƌĞĞ of crosslinking, a wider spectrum of a chemistries become available. Crosslinking via ĞůĞĐƚƌŽŶďĞĂŵŝƌƌĂĚŝĂƟŽŶŚĂƐďĞĞŶƉĞƌĨŽƌŵĞĚŽŶW;s&ͲcoͲdƌ&ͿĐŽƉŽůLJŵĞƌƐĐŽŶƚĂŝŶŝŶŐ

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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: 22PDF page: 22PDF page: 22PDF page: 22

22 ϱϬŵŽůйdƌ&͕ƐŚŽǁŝŶŐƚŚĂƚĐƌŽƐƐůŝŶŬĞĚĐŽƉŽůLJŵĞƌĐŚĂŶŐĞƐĨƌŽŵĨĞƌƌŽĞůĞĐƚƌŝĐƚŽƌĞůĂdžŽƌ ĨĞƌƌŽĞůĞĐƚƌŝĐ ǁŝƚŚ ƐƚƌŽŶŐ ĞůĞĐƚƌŽƐƚƌŝĐƟŽŶ͘ϰϬ ,ŽǁĞǀĞƌ͕ ĐƌŽƐƐůŝŶŬŝŶŐ ƵƐŝŶŐ ŚŝŐŚ ĚŽƐĞ ŝƌƌĂĚŝĂƟŽŶĚƌĂƐƟĐĂůůLJŝŵƉĂŝƌƐƚŚĞŵĞĐŚĂŶŝĐĂůƉƌŽƉĞƌƟĞƐ͕ƌĞƐƵůƟŶŐŝŶďƌŝƩůĞĮůŵƐ͘ ƚǁŽͲƐƚĞƉĐƌŽƐƐůŝŶŬŝŶŐŵĞĐŚĂŶŝƐŵŝƐƉĞƌĨŽƌŵĞĚƵƐŝŶŐƚĞůĞĐŚĞůŝĐďŝƐĂŵŝŶĞƐ͘ϰϭ͕ϰϮ First, ĂĚĞŚLJĚƌŽŇƵŽƌŝŶĂƟŽŶƌĞĂĐƟŽŶůĞĂĚƐƚŽƚŚĞĨŽƌŵĂƟŽŶŽĨŝŶƚĞƌŶĂůĚŽƵďůĞďŽŶĚƐ͕ǁŚŝĐŚ ŝƐĨŽůůŽǁĞĚďLJĂDŝĐŚĂĞůĂĚĚŝƟŽŶƚŽŐŝǀĞƚŚĞĐƌŽƐƐůŝŶŬƐ͘ĂƐŝĐĂůůLJ͕ĂůůĞdžĂŵƉůĞƐŝŶƚŚĞ ůŝƚĞƌĂƚƵƌĞƐŚŽǁƌĞƚĞŶƟŽŶŽĨƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐƉƌŽƉĞƌƟĞƐ͕ƉƌŽďĂďůLJĚƵĞƚŽĂŶŽŶƵŶŝĨŽƌŵ ĚŝƐƚƌŝďƵƟŽŶŽĨĐƌŽƐƐůŝŶŬŝŶŐĂŐĞŶƚ͕ĂůůŽǁŝŶŐůĂƌŐĞĨĞƌƌŽĞůĞĐƚƌŝĐĚŽŵĂŝŶƐƚŽďĞĨŽƌŵĞĚ͘ϰϭ͕ϰϮ dŚĞƌŵĂů ĐƌŽƐƐůŝŶŬŝŶŐ ĂĐƟǀĂƚĞĚ ďLJ ƉĞƌĞƐƚĞƌ ŝŶŝƟĂƚŽƌƐ ŚĂƐ ďĞĞŶ ƵƐĞĚ ƚŽ ĐƌŽƐƐůŝŶŬ W;s&ͲcoͲd&Ϳ͘ϯϭ͕ϰϯ /Ŷ ƚŚŝƐ ĐĂƐĞ͕ ƚŚĞ ĐŽƉŽůLJŵĞƌŝnjĂƟŽŶ ĂůůŽǁƐ Ă ƌĂŶĚŽŵ ĚŝƐƚƌŝďƵƟŽŶ

of crosslinking sites over the polymer backbone, leading to high energy density and ŝŵƉƌŽǀĞĚĚŝƐĐŚĂƌŐĞĞĸĐŝĞŶĐŝĞƐ͘/ŶĂĚĚŝƟŽŶ͕ĐƌŽƐƐůŝŶŬŝŶŐƌĞƐƵůƚƐŝŶŚŝŐŚĞƌƌĞůŝĂďŝůŝƟĞƐĂŶĚ ďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚƐĐŽŶĨĞƌƌĞĚďLJƚŚĞŝŶĐƌĞĂƐĞŝŶŵĞĐŚĂŶŝĐĂůƉƌŽƉĞƌƟĞƐ͘ϯϭ WŚŽƚŽĐŚĞŵŝĐĂůƐƚƌĂƚĞŐŝĞƐďLJĐŽƉŽůLJŵĞƌŝnjŝŶŐs&ǁŝƚŚĂĐƌLJůĂƚĞĐŽŶƚĂŝŶŝŶŐŵŽŶŽŵĞƌƐ ĂƌĞ ĂůƐŽ ĞŵƉůŽLJĞĚ͕ ďƵƚ ŶŽ ƐƚƵĚŝĞƐ ŽŶ ƚŚĞ ĞůĞĐƚƌŽĂĐƟǀĞ ƉƌŽƉĞƌƟĞƐ ĂƌĞ ĂǀĂŝůĂďůĞ͘17 ,ŽǁĞǀĞƌ͕ĨƌŽŵƚŚĞƉƌĞǀŝŽƵƐůLJĚĞƐĐƌŝďĞĚŵĞƚŚŽĚƐ͕ǁĞĐĂŶĐŽŶĐůƵĚĞƚŚĂƚĐŽŶƚƌŽůŽǀĞƌ ƚŚĞĚŝƐƚƌŝďƵƟŽŶŽĨĐƌŽƐƐůŝŶŬƐŝƐĞƐƐĞŶƟĂůĨŽƌŽďƚĂŝŶŝŶŐŚŝŐŚĞŶĞƌŐLJĚĞŶƐŝƚLJĚŝĞůĞĐƚƌŝĐƐǁŝƚŚ ŐŽŽĚĐŚĂƌŐĞͲĚŝƐĐŚĂƌŐĞĞĸĐŝĞŶĐLJ͘ŚĞŵŝĐĂůĐƌŽƐƐůŝŶŬƐŚĂǀĞƚŚĞĂĚĚŝƟŽŶĂůĂĚǀĂŶƚĂŐĞƚŚĂƚ the breakdown strength and reliability of the dielectric material increases, while high ĚŽƐĞŝƌƌĂĚŝĂƟŽŶĚĞƚĞƌŝŽƌĂƚĞƐƚŚĞŵĂƚĞƌŝĂůƐƉƌŽƉĞƌƟĞƐ͘

1YPXMPE]IVMRKSJƽYSVMREXIHTSP]QIVW

EĂŶŽůĂLJĞƌĐŽĞdžƚƌƵƐŝŽŶŽĨŝŶĚĞƉĞŶĚĞŶƚůLJƐLJŶƚŚĞƐŝnjĞĚƉŽůLJŵĞƌƐŝƐĂŶŽƚŚĞƌĞůĞŐĂŶƚŵĞƚŚŽĚ ƚŽŐĂŝŶŝŵƉƌŽǀĞĚĚŝĞůĞĐƚƌŝĐƉƌŽƉĞƌƟĞƐ͘5 In this manner, a high breakdown strength, high

TgƉŽůLJŵĞƌĐĂŶĞĂƐŝůLJďĞůĂŵŝŶĂƚĞĚǁŝƚŚŚŝŐŚĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚŇƵŽƌŝŶĂƚĞĚƉŽůLJŵĞƌƐ͕ ĐƌĞĂƟŶŐŽŶĞͲĚŝŵĞŶƐŝŽŶĂůŶĂŶŽĐŽŶĮŶĞŵĞŶƚŝŶƚŚĞĞůĞĐƚƌŝĐĮĞůĚĚŝƌĞĐƟŽŶ͘ĞĐĂƵƐĞŚŝŐŚ ŵŽůĞĐƵůĂƌǁĞŝŐŚƚWs&ŝƐƉŽůLJŵĞƌŝnjĞĚviaĞŵƵůƐŝŽŶŽƌƐƵƐƉĞŶƐŝŽŶƉŽůLJŵĞƌŝnjĂƟŽŶƐ͕ŝƚ ŝƐĨŽƵŶĚƚŚĂƚǁŚĞŶWs&ŝƐŵƵůƟůĂLJĞƌĞĚǁŝƚŚƉŽůLJĐĂƌďŽŶĂƚĞ͕ƚŚŝŶŶĂŶŽůĂLJĞƌƐŵŝƟŐĂƚĞ dielectric losses caused by ionic surfactants.ϰϰ ,ŽǁĞǀĞƌ͕ ŶŽŶƵŶŝĨŽƌŵ ĞůĞĐƚƌŝĐ ĮĞůĚ

ĚŝƐƚƌŝďƵƟŽŶĚƵĞƚŽĚŝīĞƌĞŶƚĚŝĞůĞĐƚƌŝĐĐŽŶƐƚĂŶƚƐŽĨWs&;ɸсϭϮͿĂŶĚW;ɸсϯͿ͕ƉƌĞǀĞŶƚ ĚŝƉŽůĞƐƚŽƐǁŝƚĐŚƌĞƐƵůƟŶŐŝŶƌĞůĂƟǀĞůLJůŽǁƉŽůĂƌŝnjĂƟŽŶƐ͘ϰϱ͕ϰϲ/ŶƚĞƌĞƐƟŶŐůLJ͕ƐƵƌĨĂĐƚĂŶƚ ŝŽŶƐŝŶůĂŵŝŶĂƚĞĚƉŽůLJƐƵůĨŽŶĞ;W^&ͿĂŶĚWs&ĂƌĞůŽĐŬĞĚŝŶƚŚĞW^&ĂŌĞƌƉŽůŝŶŐĂŶĚ ĂƌĞƐƚĂďůĞƵƉƚŽϭϮϬΣ͘ŽŶƐĞƋƵĞŶƚůLJ͕ƚŚĞŶĂƌƌŽǁŚLJƐƚĞƌĞƐŝƐůŽŽƉƐŽďƚĂŝŶĞĚĂŶĚŚŝŐŚ ƚŚĞƌŵĂůƐƚĂďŝůŝƚLJŽīĞƌŚŝŐŚƉŽƚĞŶƟĂůŝŶƚŚĞĂƵƚŽŵŽƟǀĞŝŶĚƵƐƚƌLJ͘ϰϳĚĚŝƟŽŶĂůůLJ͕ĞŶŚĂŶĐĞĚ ďƌĞĂŬĚŽǁŶƐƚƌĞŶŐƚŚƐĂŶĚůŽǁĞƌĐŽŶĚƵĐƟŽŶĂƌĞĨŽƵŶĚǁŚĞŶƚŚĞƚŚŝĐŬŶĞƐƐŽĨƚŚĞƐĞůĂLJĞƌƐ ŝƐхϭϬϬŶŵĚƵĞƚŽŚŝŐŚĞƌŝŶƚĞƌĨĂĐŝĂůƉŽůĂƌŝnjĂƟŽŶůĞĂĚŝŶŐƚŽĐŚĂƌŐĞƚƌĂƉƐĨŽƌĞůĞĐƚƌŽŶƐ

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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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ŝŶũĞĐƚĞĚĨƌŽŵƚŚĞĞůĞĐƚƌŽĚĞƐ͘ϰϴZĞƐĞĂƌĐŚŝŶƚŚŝƐĮĞůĚŝƐŽŶŐŽŝŶŐƚŽŵĂdžŝŵŝnjĞƚŚĞĚŝƐĐŚĂƌŐĞ

energy density via ĐƌLJƐƚĂůŽƌŝĞŶƚĂƟŽŶĂŶĚĂůƚĞƌŶĂƟǀĞŵƵůƟůĂLJĞƌĐŽŵƉŽƐŝƟŽŶƐ͘5

Block copolymers ĂƉĂĐŝƟǀĞĞŶĞƌŐLJƐƚŽƌĂŐĞƵƐŝŶŐďůŽĐŬĐŽƉŽůLJŵĞƌƐŝƐƵŶƟůŶŽǁƵŶĞdžƉůŽƌĞĚĚƵĞƚŽƚŚĞ ůŝŵŝƚĞĚ ĂǀĂŝůĂďŝůŝƚLJ ŽĨ ƐLJŶƚŚĞƟĐ ŵĞƚŚŽĚƐ ĨŽƌ ƐLJŶƚŚĞƐŝnjŝŶŐ Ws& ďůŽĐŬ ĐŽƉŽůLJŵĞƌƐ ŝŶ ĂĐŽŶƚƌŽůůĞĚĨĂƐŚŝŽŶ͕ǁŚŝůĞŚĂǀŝŶŐŵĞĐŚĂŶŝĐĂůƉƌŽƉĞƌƟĞƐƐƵŝƚĂďůĞĨŽƌђŵƚŚŝĐŬĨƌĞĞͲ ƐƚĂŶĚŝŶŐĮůŵĨŽƌŵĂƟŽŶ͘EĞǀĞƌƚŚĞůĞƐƐ͕ƚŚĞƌŝĐŚƉŚĂƐĞďĞŚĂǀŝŽƌŽĨďůŽĐŬĐŽƉŽůLJŵĞƌƐ ĚƵĞƚŽĐŽŶƚƌŽůŽǀĞƌƚŚĞůĞŶŐƚŚƌĂƟŽƐ͕ŵŽůĞĐƵůĂƌǁĞŝŐŚƚ͕ĂŶĚƉŚLJƐŝĐĂůĐŚĂƌĂĐƚĞƌŝƐƟĐƐ ŽĨƚŚĞďůŽĐŬƐŽīĞƌĂǁŝĚĞƉŽƚĞŶƟĂůƚŽŐĂŝŶŝŵƉƌŽǀĞĚĚŝĞůĞĐƚƌŝĐƉƌŽƉĞƌƟĞƐ͘ŵŽŶŐƚŚĞ ĂǀĂŝůĂďůĞŵĞƚŚŽĚƐƚŽƐLJŶƚŚĞƐŝnjĞďůŽĐŬĐŽƉŽůLJŵĞƌƐ͕dZWĨƌŽŵWs&ƚĞůŽŵĞƌƐƌĞƐƵůƚƐ ŝŶ ďŝŵŽĚĂů ĚŝƐƚƌŝďƵƟŽŶ͕ ĐŽƉƉĞƌ ŝŵƉƵƌŝƟĞƐ ĂŶĚ ŝŶ ƵŶĚĞƐŝƌĞĚ ŐƌĂŌ ĐŽƉŽůLJŵĞƌƐ ĂŌĞƌ ĚĞŚLJĚƌŽŇƵŽƌŝŶĂƟŽŶƉƌŽĐĞƐƐĞƐ͘ϰϵ͕ϱϬ  ƐĞĐŽŶĚ ŵĞƚŚŽĚ ƚŽ ƐLJŶƚŚĞƐŝnjĞ Ws& ďůŽĐŬ ĐŽƉŽůLJŵĞƌƐ ŝƐ ƵƐŝŶŐ ƌĞǀĞƌƐŝďůĞ ĚĞĂĐƟǀĂƟŽŶƌĂĚŝĐĂůƉŽůLJŵĞƌŝnjĂƟŽŶƚĞĐŚŶŝƋƵĞƐ͕ƐƵĐŚĂƐƌĞǀĞƌƐŝďůĞĂĚĚŝƟŽŶͲĨƌĂŐŵĞŶƚĂƟŽŶ ĐŚĂŝŶͲƚƌĂŶƐĨĞƌ ;Z&dͿ Žƌ ŝŽĚŝŶĞ ĐŚĂŝŶ ƚƌĂŶƐĨĞƌ ;/dWͿ ƉŽůLJŵĞƌŝnjĂƟŽŶ ƚĞĐŚŶŝƋƵĞƐ͘ϱϭʹϱϯ hŶĨŽƌƚƵŶĂƚĞůLJ͕ĂĐĐƵŵƵůĂƟŽŶŽĨĚĞĂĚͲĐŚĂŝŶĞŶĚƐďLJŝŶǀĞƌƐĞŵŽŶŽŵĞƌĂĚĚŝƟŽŶƐƉƌĞǀĞŶƚƐ ŐŽŽĚ ƐĞƋƵĞŶƟĂů ŵŽŶŽŵĞƌ ƉƌŽƉĂŐĂƟŽŶ͘ EĞǀĞƌƚŚĞůĞƐƐ͕ ǀŝŶLJů ĂĐĞƚĂƚĞ ;sĐͿ ĐĂŶ ďĞ ƌĞŝŶŝƟĂƚĞĚĨƌŽŵWs&Ͳ,2· radical chain ends, albeit at a slower rate.ϱϰ

dĞůĞĐŚĞůŝĐĐŚůŽƌŝŶĞͲĨƵŶĐƟŽŶĂůŝnjĞĚWs&ŵĂĐƌŽŵŽůĞĐƵůĞƐĐĂŶďĞĞĂƐŝůLJƉƌĞƉĂƌĞĚƵƐŝŶŐ ĂďŝĨƵŶĐƟŽŶĂůŝnjĞĚĐŚůŽƌŝŶĞďĞŶnjŽLJůƉĞƌŽdžŝĚĞŝŶŝƟĂƚŽƌ͘ϱϱ͕ϱϲ,ĞƌĞŝŶ͕ŚŝŐŚĞŶĚŐƌŽƵƉĮĚĞůŝƚLJ ŝƐĂĐŚŝĞǀĞĚĨƌŽŵǁŚĞƌĞdZWĂŶĚĐůŝĐŬĐŚĞŵŝƐƚƌLJĂƌĞĨƵƌƚŚĞƌĞdžƉůŽƌĞĚďLJŽƵƌƌĞƐĞĂƌĐŚ ŐƌŽƵƉƚŽLJŝĞůĚďůŽĐŬĐŽƉŽůLJŵĞƌƐ͕ƐŚŽǁŝŶŐƚŚĞǀĞƌƐĂƟůŝƚLJŽĨƚŚŝƐĂƉƉƌŽĂĐŚ͘ϯϰ͕ϱϳʹϲϬ The most ŝŶƚĞƌĞƐƟŶŐĨĞĂƚƵƌĞŽĨƵƐŝŶŐĐůŝĐŬĐŚĞŵŝƐƚƌLJŝƐƚŚĂƚĂůƐŽƉŽůLJŵĞƌƐĐŽŶƐŝƐƟŶŐŽƵƚŽĨDDƐ ďĞĐŽŵĞĂǀĂŝůĂďůĞĂƐƐĞĐŽŶĚďůŽĐŬ͕ǁŚŝĐŚĂƌĞŽŌĞŶŚŝŐŚTgƉŽůLJŵĞƌƐ͕ůŝŬĞW^͕ƉŽůLJ;ϮͲǀŝŶLJů ƉLJƌŝĚŝŶĞͿ;WϮsWͿĂŶĚWDD͘ϲϬ/ŶƚŚŝƐǁĂLJ͕ƐŵĂůůWs&ĐƌLJƐƚĂůƐĐĂŶďĞŽďƚĂŝŶĞĚŝŶŽŶĞ͕ ƚǁŽĂŶĚƚŚƌĞĞŶĂŶŽĐŽŶĮŶĞĚĚŝŵĞŶƐŝŽŶƐĚĞƉĞŶĚŝŶŐŽŶƚŚĞďůŽĐŬƌĂƟŽƐ͘dŚĞƌĞĨŽƌĞ͕ĐůŝĐŬ ĐŚĞŵŝƐƚƌLJŝƐƵŶƟůŶŽǁƚŚĞďĞƐƚWs&ďůŽĐŬĐŽƉŽůLJŵĞƌĂƉƉƌŽĂĐŚƚŽŐĂŝŶĐŽŶƚƌŽůŽǀĞƌŝƚƐ ƉŚĂƐĞďĞŚĂǀŝŽƌĂŶĚƚŽƉƌŽǀŝĚĞĨƵŶĚĂŵĞŶƚĂůŝŶƐŝŐŚƚƐŝŶŶĂŶŽƐƚƌƵĐƚƵƌĞĚĐƌLJƐƚĂůůŝnjĂƟŽŶŽĨ Ws&ŝŶƌĞůĂƟŽŶƚŽƚŚĞ;ƉƌŽďĂďůLJĞŶŚĂŶĐĞĚͿĚŝĞůĞĐƚƌŝĐƉƌŽƉĞƌƟĞƐ͘

In conclusion, a wide variety of chain architectures are available in order to enhance Ws&͛ƐĚŝĞůĞĐƚƌŝĐƉƌŽƉĞƌƟĞƐ͘dŚĞůĂƌŐĞĨĞƌƌŽĞůĞĐƚƌŝĐŚLJƐƚĞƌĞƐŝƐŝƐƐƵƉƉƌĞƐƐĞĚŽƌĐŚĂŶŐĞĚ ďLJƉŚLJƐŝĐĂůƉŝŶŶŝŶŐĂŶĚŝƐŽůĂƟŶŐĐƌLJƐƚĂůƐvia ĐŽƉŽůLJŵĞƌŝnjĂƟŽŶ͕ŐƌĂŌŝŶŐ͕ĐƌŽƐƐůŝŶŬƐŽƌ ƚŚĞ ĨŽƌŵĂƟŽŶ ŽĨ ŶĂŶŽƐƚƌƵĐƚƵƌĞƐ͘ <ĞLJ ƉŽŝŶƚƐ ĨŽƌ ĨƵƚƵƌĞ ĚĞǀĞůŽƉŵĞŶƚƐ ĂƌĞ ĞdžƉůŽƌŝŶŐ ƚŚĞƉŽƐƐŝďŝůŝƟĞƐƚŽƉŝŶĂŶĚŝƐŽůĂƚĞĐƌLJƐƚĂůƐŝŶWs&ŝŶĂĐŚĞĂƉŵĂŶŶĞƌ͕ǁŚŝůĞŽĨĐŽƵƌƐĞ maintaining a high dielectric constant and preferably increased breakdown strengths.

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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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Scope of the thesis

ƐŵĂŶLJŝŶǀĞƐƟŐĂƟŽŶƐŝŶƚƵŶŝŶŐƚŚĞĞůĞĐƚƌŝĐĂůƌĞƐƉŽŶƐĞŽĨWs&ĂƌĞŽŶŐŽŝŶŐ͕ďůŽĐŬ ĐŽƉŽůLJŵĞƌƐƚƵĚŝĞƐĂƌĞůĂŐŐŝŶŐďĞŚŝŶĚ͘dŚĞƌĞĨŽƌĞ͕ĂƐĂĮƌƐƚƐƚĞƉ͕ŶĂŶŽĐŽŶĮŵĞŶƚƐƚƵĚŝĞƐ ŽŶƚŚĞĐƌLJƐƚĂůůŝnjĂƟŽŶƉƌŽĐĞƐƐĞƐŽĨWs&ͲďĂƐĞĚ;ĐŽͿƉŽůLJŵĞƌƐĂƌĞĞůƵĐŝĚĂƚĞĚŝŶŚĂƉƚĞƌ ϮĂŶĚϯƵƐŝŶŐĂďůŽĐŬĐŽƉŽůLJŵĞƌĂƉƉƌŽĂĐŚ͘/ŶŚĂƉƚĞƌϮ͕Ws&ďůŽĐŬĐŽƉŽůLJŵĞƌƐĂƌĞ ĚĞƐŝŐŶĞĚƚŽƐĞůĨͲĂƐƐĞŵďůĞŝŶĚŝƐƟŶĐƚŵŽƌƉŚŽůŽŐŝĞƐ͕ŝŶĐůƵĚŝŶŐůĂŵĞůůĂĞĂŶĚƐƉŚĞƌĞƐ͘ ,ĞƌĞŝŶ͕ ƚŚĞ ĐƌLJƐƚĂůůŝnjĂƟŽŶ ŵĞĐŚĂŶŝƐŵ ƐǁŝƚĐŚĞĚ ĨƌŽŵ ŚĞƚĞƌŽŐĞŶĞŽƵƐ ŶƵĐůĞĂƟŽŶ ĨŽƌ ůĂŵĞůůĂĞƚŽŚŽŵŽŐĞŶĞŽƵƐŶƵĐůĞĂƟŽŶĨŽƌƐƉŚĞƌĞƐƌĞƐƵůƟŶŐŝŶƚŚĞĨŽƌŵĂƟŽŶŽĨŝƐŽůĂƚĞĚ ɴͲĐƌLJƐƚĂůƐŝŶƚŚĞƐƉŚĞƌŝĐĂůŵŽƌƉŚŽůŽŐLJ͘/ŶƚŚŝƐǁĂLJ͕ĂƐLJŶƚŚĞƟĐŵĞƚŚŽĚŝƐĚĞŵŽŶƐƚƌĂƚĞĚ ĨŽƌŝƐŽůĂƟŶŐWs&ŶĂŶŽĐƌLJƐƚĂůƐŝŶƚŚĞŚŝŐŚůLJƉŽůĂƌɴͲƉŚĂƐĞ͘ /ŶŚĂƉƚĞƌϯ͕ƚŚĞŚŽƌŝnjŽŶŝƐďƌŽĂĚĞŶĞĚƚŽW;s&Ͳco-dƌ&ͿͲďĂƐĞĚďůŽĐŬĐŽƉŽůLJŵĞƌƐĂŶĚ ƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶŝƐŝŶǀĞƐƟŐĂƚĞĚĂƐĨƵŶĐƟŽŶŽĨƚŚĞĚŽŵĂŝŶǁĂůůƉŽůĂƌŝƚLJ͘/ƚŝƐĨŽƵŶĚƚŚĂƚ ƚŚĞƉŽůĂƌĚŽŵĂŝŶǁĂůůƐƌĞƐƵůƚŝŶĂƌĞĚƵĐƟŽŶŽĨƚŚĞƵƌŝĞƚƌĂŶƐŝƟŽŶƚĞŵƉĞƌĂƚƵƌĞ͕ŝŵƉŽƌƚĂŶƚ ŬŶŽǁůĞĚŐĞ ĨŽƌ ĚŝĞůĞĐƚƌŝĐƐ͕ ĞůĞĐƚƌŽĐĂůŽƌŝĐ ĐŽŽůŝŶŐ ĂƉƉůŝĐĂƟŽŶƐ ĂŶĚ ŵŝŶŝĂƚƵƌŝnjĂƟŽŶ ŽĨ organic ferroelectrics. ŚĂƉƚĞƌϰĚĞĂůƐǁŝƚŚĐŽƉŽůLJŵĞƌŝnjĂƟŽŶĂƉƉƌŽĂĐŚĞƐƚŽŝŶƚƌŽĚƵĐĞĨƵŶĐƟŽŶĂůŝƟĞƐŝŶ ƚŚĞWs&ďĂĐŬďŽŶĞ͕ŝŶƐƵĐŚĂǁĂLJƚŚĂƚĞĂƐLJĐŚĞŵŝƐƚƌŝĞƐĐĂŶďĞĞŵƉůŽLJĞĚƚŽƚƵŶĞƚŚĞ ƉƌŽƉĞƌƟĞƐĞǀĞŶĨƵƌƚŚĞƌ͘LJĐŽƉŽůLJŵĞƌŝnjŝŶŐs&ǁŝƚŚsĐĂŶĚƐƵďƐĞƋƵĞŶƚůLJŚLJĚƌŽůLJnjŝŶŐ ƚŚĞ ĂĐĞƚĂƚĞ ƵŶŝƚƐ ƚŽ ǀŝŶLJů ĂůĐŽŚŽů͕ W;s&ͲcoͲsͿ ĐŽƉŽůLJŵĞƌƐ ĂƌĞ ŽďƚĂŝŶĞĚ ŚĂǀŝŶŐ Ă ƐƵƌƉůƵƐŽĨŚLJĚƌŽdžLJĨƵŶĐƟŽŶĂůŝƟĞƐŝŶƚŚĞďĂĐŬďŽŶĞ͘KŶĞŝŵƉŽƌƚĂŶƚƐŝĚĞĂƐƉĞĐƚŝƐƚŚĞůŽǁ ƉƌŝĐĞŽĨƚŚĞƵƐĞĚĐŽŵŽŶŽŵĞƌ͘/ŶƚĞƌĞƐƟŶŐůLJ͕ƚŚĞƐŵĂůůƐŝnjĞĚsƵŶŝƚƐĐŽͲĐƌLJƐƚĂůůŝnjĞǁŝƚŚ s&ƌĞƐƵůƟŶŐŝŶĂĨĞƌƌŽĞůĞĐƚƌŝĐɴͲƉŚĂƐĞĨƌŽŵƚŚĞŵĞůƚ͘ĚĚŝƟŽŶĂůůLJ͕ƚŚĞĨĞƌƌŽĞůĞĐƚƌŝĐ ƉƌŽƉĞƌƟĞƐĂƌĞĐŽŶĮƌŵĞĚƵƐŝŶŐĂƐƚĂƚĞͲŽĨͲƚŚĞͲĂƌƚĨĞƌƌŽĞůĞĐƚƌŝĐůŽŽƉƚĞƐƚĞƌ͘ ŚĞŵŝĐĂůůLJĐƌŽƐƐůŝŶŬĞĚŇƵŽƌŝŶĂƚĞĚŶĞƚǁŽƌŬƐĂƌĞƐŚŽǁŶŝŶŚĂƉƚĞƌϱvia crosslinking W;s&Ͳco-sͿ ĐŽƉŽůLJŵĞƌƐ ƵƐŝŶŐ ĨĂĐŝůĞ ƵƌĞƚŚĂŶĞ ĐŚĞŵŝƐƚƌLJ͘ dŚĞ ŚŝŐŚ ĮĞůĚ ĚŝĞůĞĐƚƌŝĐ ƉƌŽƉĞƌƟĞƐĂƌĞŝŶǀĞƐƟŐĂƚĞĚĨŽƌǀĂƌŝŽƵƐĐŽŶƚĞŶƚƐŽĨĐƌŽƐƐůŝŶŬŝŶŐĂŐĞŶƚ͘ĐůĞĂƌĐŚĂŶŐĞ ŝŶĞůĞĐƚƌŽĂĐƟǀĞďĞŚĂǀŝŽƌŝƐĨŽƵŶĚ͕ĐŚĂŶŐŝŶŐĨƌŽŵĨĞƌƌŽĞůĞĐƚƌŝĐͲĂƐĚŝƐƉůĂLJĞĚŝŶŚĂƉƚĞƌ ϰͲƚŽĚŽƵďůĞŚLJƐƚĞƌĞƐŝƐůŽŽƉƐĂŶĚůŝŶĞĂƌĚŝĞůĞĐƚƌŝĐƐ͘ hƐŝŶŐ ƚŚĞ ƐĂŵĞ ĂƉƉƌŽĂĐŚĞƐ ĂƐ ĚĞƐĐƌŝďĞĚ ŝŶ ŚĂƉƚĞƌ ϰ ĂŶĚ ϱ͕ ƚŚĞ ĞůĞĐƚƌŽĂĐƟǀĞ ƉƌŽƉĞƌƟĞƐŽĨW;s&ͲterͲdƌ&-terͲsͿƚĞƌƉŽůLJŵĞƌƐĂŶĚƚŚĞŝƌĐƌŽƐƐůŝŶŬĞĚĚĞƌŝǀĂƟǀĞƐĂƌĞ ƐŚŽǁŶŝŶŚĂƉƚĞƌϲ͘ĞƉĞŶĚĞŶƚŽŶƚŚĞƚĞƌƉŽůLJŵĞƌĐŽŵƉŽƐŝƟŽŶ͕W;s&ͲterͲdƌ&-terͲsͿ ƐŚŽǁƐƌĞůĂdžŽƌĨĞƌƌŽĞůĞĐƚƌŝĐďĞŚĂǀŝŽƌ͘/ŶĚĞĞĚ͕ĂůƐŽŝŶƚŚŝƐĐĂƐĞ͕ƚŚĞĞůĞĐƚƌŽĂĐƟǀĞƉƌŽƉĞƌƟĞƐ ĐĂŶďĞƚƵŶĞĚďLJĐŚĞŵŝĐĂůĐƌŽƐƐůŝŶŬŝŶŐƵƐŝŶŐƵƌĞƚŚĂŶĞĐŚĞŵŝƐƚƌLJ͘dŚĞĚŝƐƉůĂĐĞŵĞŶƚͲ ĞůĞĐƚƌŝĐĮĞůĚůŽŽƉƐĂŌĞƌĐƌŽƐƐůŝŶŬŝŶŐďĞĐĂŵĞŶĂƌƌŽǁĞƌĐŽŵƉĂƌĞĚƚŽƉƌŝƐƟŶĞW;s&ͲterͲ dƌ&-terͲsͿĚƵĞƚŽĂƌĞĚƵĐƟŽŶŝŶĨĞƌƌŽĞůĞĐƚƌŝĐůŽƐƐĞƐ͕ƌĞƐƵůƟŶŐŝŶŚŝŐŚĞƌĚŝƐĐŚĂƌŐĞĚ ĞŶĞƌŐLJĚĞŶƐŝƟĞƐǁŝƚŚŝŶĐƌĞĂƐĞĚĞĸĐŝĞŶĐŝĞƐ͘

Referenties

GERELATEERDE DOCUMENTEN

Conclusions /Ŷ ĐŽŶĐůƵƐŝŽŶ͕ ƚŚŝƐ ƚŚĞƐŝƐ ƐŚŽǁƐ ĐĂƌĚŝŽŵĞƚĂďŽůŝĐ ƌŝƐŬ ĨĂĐƚŽƌƐ ǁĞƌĞ ŚŝŐŚůLJ ƉƌĞǀĂůĞŶƚ ŝŶ ƚŚŝƐ ŐƌŽƵƉ ŽĨ ƐĞǀĞƌĞůLJ ŽďĞƐĞ ĐŚŝůĚƌĞŶ

( b ) In contrast with the planar conformations of the multilayered lamellar crystals grown from the 0.5 /99.5 blends, a conformationally complex motif of dendritic

/ŶŚŽŽĨĚƐƚƵŬϭůĞƌĞŶǁĞĚĂƚĚĞŚŽŐĞƉŽůĂƌŝƐĂƟĞŝŶɴͲĨĂƐĞŬƌŝƐƚĂůůĞŶŐĞďƌƵŝŬƚŬĂŶ ǁŽƌĚĞŶ ǀŽŽƌ ĚŝƌĞŬƚĞ ĞŶĞƌŐŝĞŽƉƐůĂŐ͘ ĞŶ ǀŽŽƌǁĂĂƌĚĞ

120 Conclusions

The introduction of hydroxyl functional groups in fluorinated co-and terpolymer chains gives easy accessible crosslinking sites for tuning the crystallization

ϭϴϭ 10 dŚĞĮƌƐƚĂŝŵŽĨƚŚŝƐƚŚĞƐŝƐǁĂƐƚŽŝŶǀĞƐƟŐĂƚĞƚŚĞĞīĞĐƚŽĨ/dŝŶƚŚĞƚƌĞĂƚŵĞŶƚŽĨ ĚLJƐŬŝŶĞƟĐ ĐĞƌĞďƌĂů ƉĂůƐLJ ;WͿ͘ dŚĞ ĨŽĐƵƐ ǁĂƐ ƉƌŝŵĂƌŝůLJ

ϱϳ  /Ŷ ǀŝǀŽ ŝƚ ŝƐ ĚŝĸĐƵůƚ ƚŽ ĚĞŵŽŶƐƚƌĂƚĞ ƚŚĞ ƌŽůĞ ŽĨ ĂŶLJ ƐƉĞĐŝĮĐ ďĂĐƚĞƌŝĂů ƐƚƌĂŝŶ ŝŶ ĐŽŵƉŽƐŝƚĞ ĚĞŐƌĂĚĂƟŽŶ͕ ĂƐ ƚŚĞ

dŚĞŐĞŶĞƌĂůĂŝŵŽĨƚŚŝƐƐƚƵĚLJŝƐƚŽĐŽŵƉĂƌĞƚŚĞĞīĞĐƚƐŽĨŝŶƚƌĂͲŽƌĂůǁĞĂƌĂŶĚ ďƌƵƐŚŝŶŐ ŽŶ ƚŚĞ ƐƵƌĨĂĐĞ ƉƌŽƉĞƌƟĞƐ ŽĨ ĚŝƌĞĐƚ ĂŶĚ