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Understanding the Composition--structure--property Relationships and Enhancing the Electromechanical Responses in Ferroelectric Polymers

Author : Zhubing Han
Publisher :
Page : 0 pages
File Size : 34,39 MB
Release : 2023
Category :
ISBN :

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Poly(vinylidene fluoride) (PVDF)-based ferroelectric polymers enable a wide range of advanced applications with new functionalities and structure designs due to their high electroactivity, intrinsic flexibility and biocompatibility. One unique feature of these polymers is that their dielectric, ferroelectric and electromechanical properties can be modulated by varying their chemical composition and the processing conditions. Despite the progress over the last decades, a more comprehensive understanding on the composition--structure--property relationships in PVDF-based ferroelectric polymers is still needed to achieve rational design of new materials with enhanced performance. The scope of this dissertation aims to understand the influence of monomer defects on the structures and ferroelectric properties of PVDF-based terpolymers, and to enhance their electromechanical performance enabled by the rational design of new polymer structures and compositions. After a general background introduction, the dissertation starts with two chapters discussing the effect of two different comonomers as chain defects on the structures and ferroelectric properties of the corresponding terpolymers. Chapter 2 reveals that the incorporation of bulky 2-chloro-1,1-difluoroethylene (CDFE) can gradually convert the ferroelectric P(VDF-TrFE) (TrFE: trifluoroethylene) into a relaxor ferroelectric terpolymer as confirmed by the dielectric and structural characterizations. The CDFE comonomer serves as an effective chain defect to destabilize the ferroelectric domain by introducing the gauche conformation. The P(VDF-TrFE-CDFE) with 3.8 mol% CDFE exhibits typically relaxor ferroelectric behaviors such as strong frequency-dependence of dielectric properties, broad and diffuse ferroelectric phase transition, and weak remanent polarization. Chapter 3 systematically investigates the effect of another comonomer defect, vinyl fluoride (VF), which has a smaller size than VDF. It is found that VF plays an opposite role compared with the bulky chlorinated comonomers. Increasing molar content of VF leads to an increase in the Curie temperature and the coercive field of the terpolymers. Structural characterizations and simulations evidences confirm that the all-trans conformation remain energetically more favored than the gauche conformation regardless of the VF content. The results stress the vital role of comonomer structure and size in modulating the structures and properties of the ferroelectric polymers. The next two chapters focus on improving the electromechanical performance of the PVDF-based polymers. In Chapter 4, a series P(VDF-TrFE-CTFE) (CTFE: chlorotrifluoroethylene) with systematic composition variations have been synthesized. Structural characterizations show that the terpolymers with 1.7 to 5.0 mol% CTFE exhibit a mixture and competition of the normal ferroelectric and relaxor ferroelectric phases as a result of the incorporation of CTFE. Specifically, a maximum longitudinal piezoelectric coefficient (d33) of -55.4 pm/V has been observed in P(VDF-TrFE-CTFE) 64.5/33.1/2.4 mol%, corresponding to an 85% improvement compared with the commercial benchmark P(VDF-TrFE) 65/35 mol%. This strategy can potentially be expanded to other polymer systems to improve the piezoelectric response. Chapter 5 aims to enhance the low-electric-field electrostrictive strain in relaxor ferroelectric polymers. The small electrostrain of current relaxor ferroelectric P(VDF-TrFE-CFE) (CFE: 1-chloro-1-fluoroethylene) and P(VDF-TrFE-CTFE) terpolymers at low electric field impedes their usefulness in actuating devices. In situ structural characterizations under the electric field reveal that the electrostrictive strain originates from the field-induced phase transition in P(VDF-TrFE-CFE) and the lattice compression in P(VDF-TrFE-CTFE). Inspired by the distinct functions of CFE and CTFE, a series of P(VDF-TrFE-CFE-CTFE) tetrapolymers have been synthesized, which exhibit significant enhancement of electrostrictive strain at both low and high electric fields due to the synergistic effect of CFE and CTFE. These results provide new insight into the origin of electrostriction in the relaxor ferroelectric polymers, and the tetrapolymers in this study can potentially be used to prototype soft actuators. It is anticipated that the materials, methodologies and results developed in this dissertation will not only provide new insights and understandings on the structure-property relationship in ferroelectric polymers, but also stimulate future work to further enhance the performance in these materials in order to meet the material requirement for practical applications.

PVDF-Based Ferroelectric Polymers

Author :
Publisher : de Gruyter
Page : 500 pages
File Size : 13,81 MB
Release : 2017-05-23
Category :
ISBN : 9783110560015

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The book begins by introducing signals and systems, and then discusses Time-Domain analysis and Frequency-Domain analysis for Continuous-Time systems. It also covers Z-transform, state-space analysis and system synthesis. The author provides abundant examples and exercises to facilitate learning, preparing students for subsequent courses on circuit analysis and communication theory.

Ferroelectric Polymers

Author : E. Fukada
Publisher : CRC Press
Page : 136 pages
File Size : 23,1 MB
Release : 1989
Category : Science
ISBN : 9780677258805

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This volume contains four papers commencing with an introduction to early studies in piezoelectricity, pyroelectricity and ferroelectricity in polymers. Other topics discussed include - ferroelectric properties of fluoride copolymers; structural phase transition in ferroelectric fluorine polymers; and pressure effect on phase transition in ferroelectric polymers .

Ferroelectric Polymers

Author : Hari Singh Nalwa
Publisher : CRC Press
Page : 913 pages
File Size : 39,10 MB
Release : 1995-06-20
Category : Science
ISBN : 1482295458

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This work covers the chemistry and physics of polymeric materials and their uses in the fields of electronics, photonics, and biomedical engineering. It discusses the relationship between polymeric supermolecular structures and ferroelectric, piezoelectric and pyroelectric properties.

New Properties and Applications of Polyvinylidene-Based Ferroelectric Polymer

Author : J.L. Wang
Publisher :
Page : pages
File Size : 44,10 MB
Release : 2015
Category : Technology
ISBN :

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There are different kinds of novel properties and applications of polyvinylidene difluoride (PVDF)-based ferroelectric polymer films. Several issues associated with the structure, properties, and applications of PVDF-based ferroelectric polymer films are discussed. The main achievements of the research include high electric tunability of relaxor ferroelectric Langmuir-Blodgett (LB) terpolymer films, the creep process of the domain switching in poly(vinylidene fluoride-trifluoroethylene) ferroelectric thin films, transition from relaxor to ferroelectric-like phase in poly(vinylidene fluoride-trifluoroethylene -chlorofluoroethylene) terpolymer ultrathin films, abnormal polarization switching of relaxor terpolymer films at low temperatures, huge electrocaloric effect in LB ferroelectric polymer thin films, self-polarization in ultrathin LB polymer films, enhanced dielectric and ferroelectric properties in artificial polymer multilayers, and transition of polarization switching from extrinsic to intrinsic in ultrathin PVDF homopolymer films.

Ferroelectric Materials

Author : Aimé Peláiz-Barranco
Publisher : BoD – Books on Demand
Page : 258 pages
File Size : 48,87 MB
Release : 2015-07-29
Category : Technology & Engineering
ISBN : 9535121472

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Ferroelectric materials receive great attention from the scientific international community because of the interesting phenomena they exhibit and their multiple applications such as transducers, capacitors, pyroelectric sensors, sonars, random access memories, etc. The demand for ferroelectric materials for technological applications enforced the in-depth research, in addition to the improvement of processing and characterization techniques. This book contains nine chapters and offers the results of several researches covering fabrication, properties, theoretical topics, and phenomena at the nanoscale.

Organic Ferroelectric Materials and Applications

Author : Kamal Asadi
Publisher : Woodhead Publishing
Page : 642 pages
File Size : 12,93 MB
Release : 2021-10-27
Category : Technology & Engineering
ISBN : 0128215526

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Organic Ferroelectric Materials and Applications aims to bring an up-to date account of the field with discussion of recent findings. This book presents an interdisciplinary resource for scientists from both academia and industry on the science and applications of molecular organic piezo- and ferroelectric materials. The book addresses the fundamental science of ferroelectric polymers, molecular crystals, supramolecular networks, and other key and emerging organic materials systems. It touches on important processing and characterization methods and provides an overview of current and emerging applications of organic piezoelectrics and ferroelectrics for electronics, sensors, energy harvesting, and biomedical technologies. Organic Ferroelectric Materials and Applications will be of special interest to those in academia or industry working in materials science, engineering, chemistry, and physics. Provides an overview of key physical properties of the emerging piezoelectric and ferroelectric molecular and supramolecular systems Discusses best practices of processing, patterning, and characterization methods and techniques Addresses current and emerging applications for electronics, materials development, sensors, energy harvesting, and biomedical technologies

Development of the Piezoelectric Properties of Poly(vinylidene Fluoride) Based Ferroelectrics and Ferroelectrets Using Fillers and Mechanical Stretching

Author : Nusrat Jahan
Publisher :
Page : 156 pages
File Size : 19,16 MB
Release : 2018
Category :
ISBN :

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Piezoelectric polymers are very useful in various electromechanical applications because of their strong piezoelectric response, flexibility, lightweight and formability. In addition to ferroelectric ceramics, ferroelectric polymers (such as PVDF) and ferroelectrets are also popular as a new group of piezoelectrics. Ferroelectrics based on b-PVDF are interesting due to the ease of preparation with usable piezoelectric response in addition to the above mentioned advantages of polymers. Incorporating nanofillers (e.g. ceramic filler-BaTiO3, PZT, carbon nanotube, clay, ferrite nanoparticles etc.) into PVDF is one of the facile ways to produce b phase in PVDF often followed by mechanical stretching. While fillers nucleate b phase in the PVDF matrix, subsequent mechanical stretching helps in aligning the dipoles to some extent. Therefore, the aim of the first part of this study is to prepare ferroelectric b-PVDF films by incorporating a hybrid filler (micro-CaCO3+ nanoclay) followed by mechanical stretching. While nanoclay is one of the most widely used cost-effective fillers capable of nucleating b-PVDF, synergistic improvement in b phase formation as well as in mechanical, electrical and piezoelectric properties of hybrid composites have been reported in this part of the study. Additionally, the influence of subsequent mechanical stretching e.g. draw ratio, R (final length/initial length), has also been investigated. FTIR and XRD are employed to determine the b phase content in both stretched and unstretched samples. While the tensile properties show a gradual decrease, dielectric constant increased gradually with increasing CaCO3 content in the hybrid filler. The maximum piezoelectric d33 coefficient of 30 pC/N is obtained for stretched hybrid composite films. Ferroelectrets, on the other hand, are another type of functional polymer films with heterogeneous cellular structure and internal quasi-permanent dipole moments. The piezoelectricity in ferroelectrets originates from the change in dipole moments under an applied mechanical stress. Over the past few decades, cellular polypropylene (PP) films have been the most popular and widely investigated ferroelectrets and are already in commercial applications. While the piezoelectric d33 coefficient of PP ferroelectrets could exhibit up to 1000 pC/N or more, their working temperature is quite low, not higher than 60 °C. Recently developed fluoropolymer i.e. polytetrafluoroethylene (PTFE) and fluoroethylene propylene (FEP) based ferroelectrets exhibit strong piezoelectric response and excellent thermal stability. However, processing these fluoropolymer ferroelectrets using commercially viable manufacturing technique such as cast film extrusion poses few challenges because of their very high melt viscosity, high manufacturing temperature, degradation tendency and low tensile elongation. Therefore, in this part of the study, a new thermally stable ferroelectret has been investigated using commercial processing technique with strong piezoelectric response. Cast extrusion of the polymer/filler mixture followed by mechanical stretching is one of the promising techniques for preparing a cellular polymer. Micron scale fillers are usually employed for creating voids from interfacial delamination under applied stress. Polyvinylidene fluoride (PVDF) is a fluoropolymer which is easily melt-processable than other fluoropolymers and showing excellent physical, chemical and electrical properties. An "extrusion-stretching-inflation" process has been followed to prepare a cellular structure in PVDF films. Solid PVDF/hybrid filler (micro-CaCO3 + nanoclay) films were extruded and subsequently stretched to create the initial cellular structure inside the films. While CaCO3 acts as void nucleation centers, nanoclay increases the stretchability of the highly CaCO3 filled PVDF films. Gas diffusion expansion (GDE) or controlled inflation is preformed to adjust the voids dimensions to lens-shaped voids leading to lower elastic moduli and stronger piezoelectricity. Obviously, the gas permeation characteristics in polar polymers is different than non-polar polymers because of their different type of polymer/gas interaction and the final piezoelectric properties of the ferroelectrets strongly depend on the cellular morphology such as void size, shape and distribution. Therefore, two different inflation gases i.e. neutral N2 and polar CO2 are used with various inflation strategies. Combination of pressure, temperature and their way of application (direct or step-wise) is examined for various times to optimize the inflation level. The inflated films are then subjected to corona charging at room temperature to create the dipoles inside the voids. Finally, PVDF ferroelectrets show piezoelectric d33 coefficient as high as 251 pC/N with N2 inflation and 327 pC/N for CO2 treatment. As expected, PVDF ferroelectrets exhibit better thermal stability than PP, PETP, COP and PEN and as high as Teflon. Samples charged at room temperature have their working temperature up to 120 °C