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Polymer Composites for Electrical Engineering
Polymer Composites for Electrical Engineering
Edited by
Xingyi Huang
Shanghai Key Laboratory of Electrical Insulation and Thermal Aging, Shanghai
Jiao Tong University, Shanghai, China
Toshikatsu Tanaka
Waseda University, Tokyo, Japan
This edition first published 2022
© 2022 John Wiley & Sons Ltd
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or
transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise,
except as permitted by law. Advice on how to obtain permission to reuse material from this title is available
at http://www.wiley.com/go/permissions.
The right of Xingyi Huang and Toshikatsu Tanaka to be identified as the authors of the editorial material
in this work has been asserted in accordance with law.
Registered Offices
John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA
John Wiley & Sons, Ltd., The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, UK
Editorial Office
The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, UK
For details of our global editorial offices, customer services, and more information about Wiley products
visit us at www.wiley.com.
Wiley also publishes its books in a variety of electronic formats and by print-on-demand. Some content
that appears in standard print versions of this book may not be available in other formats.
10 9 8 7 6 5 4 3 2 1
v
Contents
List of Contributors xv
Preface xix
Index 419
xv
List of Contributors
Zhonglei Li En Tang
Key Laboratory of Smart Grid of China-Spain Collaborative Research
Education Ministry, School of Electrical Center for Advanced Materials, School
and Information Engineering, Tianjin of Materials Science and Engineering,
University, Tianjin, China Chongqing Jiaotong University,
Chongqing, China
Wang Liming
Engineering Laboratory of Power Takahiro Umemoto
Equipment Reliability in Complicated Advanced Technology Research and
Coastal Environments, Tsinghua Shenzhen Development Center, Mitsubishi Electric
International Graduate School, Tsinghua Corporation, Amagasaki-shi, Tokyo, Japan
University, Shenzhen, Guangdong, China
Wang Xilin
Suibin Luo
Engineering Laboratory of Power
Shenzhen Institute of Advanced Electronic
Equipment Reliability in Complicated
Materials, Shenzhen Institutes of
Coastal Environments, Tsinghua
Advanced Technology, Chinese Academy
Shenzhen International Graduate
of Sciences, Shenzhen, China
School, Tsinghua University, Shenzhen,
Guangdong, China
Takahiro Mabuchi
Advanced Technology Research and
Jie Yang
Development Center, Mitsubishi Electric
College of Polymer Science and
Corporation, Amagasaki-shi, Tokyo, Japan
Engineering, Sichuan University, State
Key Laboratory of Polymer Materials
Hirotaka Muto
Engineering, Chengdu, Sichuan, P. R. China
Advanced Technology Research and
Development Center, Mitsubishi Electric
Corporation, Amagasaki-shi, Tokyo, Japan Ming-Bo Yang
College of Polymer Science and
Sen Niu Engineering, Sichuan University, State
Key Laboratory of High Performance Key Laboratory of Polymer Materials
Plastics (Jilin University), Ministry of Engineering, Chengdu, Sichuan, P. R. China
Education. College of Chemistry, Jilin
University, Changchun, P. R. China Wei Yang
College of Polymer Science and
Yoitsu Sekiguchi Engineering, Sichuan University, State
Sumitomo Electric Industries, Ltd., Key Laboratory of Polymer Materials
Osaka, Japan Engineering, Chengdu, Sichuan, P. R. China
Preface
As such, this book is well-structured with basics and application to transfer sufficient
coordinated knowledge not only to experts in electrical engineering and material science
but also to university students who intend to work in this field in near future.
We greatly thank all contributors for bringing this wonderful book to the community,
which is the first comprehensive book focusing on the design, fabrication, processing, anal-
ysis, and applications of polymer composites in electrical engineering. Xingyi Huang, one
of the coeditors, would like to thank Shanghai Key Laboratory of Electrical Insulation and
Thermal Aging and National Natural Science Foundation of China for their long-time
support.
1
1
Polymer Composites for Electrical
Energy Storage
Yao Zhou
Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA, USA
1.1 Introduction
Electrical energy storage in dielectric materials that involves the movement and separation of
opposite charges between the two electrodes under the applied electric field is ubiquitous in
electrical engineering. The electrostatic capacitors are widely employed in the power electronic
devices in various applications, including grid-connected wind farm and photovoltaic, hybrid
electric vehicle, medical defibrillator, electric power transmission, etc. [1–4]. Polymer dielec-
trics have been widely adopted in electrostatic capacitors because of their high breakdown
strength, light weight, ease of processing, low cost, and excellent flexibility [5–10]. However,
the relatively low dielectric constant restricts the application of polymer dielectrics because of
the low discharged energy density [11]. To overcome this issue, a polymer composite approach
has been proposed to combine the advantages of polymers and inorganic nanofillers to attain
both high dielectric constant and high breakdown strength, as well as low energy loss [12–14].
Over the past decades, great achievements have been made in developing high perfor-
mance polymer composites for electrical energy storage application. A variety of material
structure designs and processing strategies have been proposed to increase the energy den-
sity of the polymer composites. This chapter provides a comprehensive understanding of
the fundamentals and recent development in the field of polymer composites for electrical
energy storage. The strategies of achieving high electrical energy storage performance such
as controlling the nanofiller dimension and morphology, controlling the nanofiller distri-
bution and orientation, modifying the nanofiller/polymer interface, introducing multiple
nanofillers, and constructing multilayer-structured composites are particularly discussed.
1.2 General Considerations
In general, the stored electrical energy density (Us) in the dielectric materials can be
expressed as
Polymer Composites for Electrical Engineering, First Edition. Edited by Xingyi Huang and Toshikatsu Tanaka.
© 2022 John Wiley & Sons Ltd. Published 2022 by John Wiley & Sons Ltd.
2 1 Polymer Composites for Electrical Energy Storage
Us EdD (1.1)
where E is the applied electric field and D is the electric displacement [15]. To measure the
stored energy density, discharged energy density (Ud), and charge/discharge efficiency (η)
of the dielectrics, the electric displacement (D) is measured as a function of applied electric
field (E) during the charging and discharging processes, which is also called as the D-E
loop. The schematic of typical D-E loop of the dielectric material is shown in Figure 1.1.
The stored energy density can be calculated by integrating the area bounded by the charg-
ing curve, the D-axis, and the horizontal line y = Dmax. Similarly, the discharged energy
density can be calculated by integrating the area bounded by the discharging curve, the
D-axis, and the horizontal line y = Dmax. The energy loss (Ul) during the charge/discharge
circle can be represented by the area bounded by the charging and discharging curves.
Apparently, the stored energy density equals to the discharged energy density plus the
energy loss, that is, Us = Ud + Ul. The charge/discharge efficiency is defined as η = Ud/Us
× 100%. For linear dielectrics, the electric displacement increases linearly with the applied
electric field, i.e. D = ε0εrE, where ε0 is the vacuum dielectric constant (8.85 × 10−12 F/m)
and εr is the relative dielectric constant of the dielectric material [16–18]. As a result, the
stored energy density of linear dielectrics can be simplified as
1 2
Us EdD 0 r EdE 0 rE (1.2)
2
It is suggested from Eqs. (1.1) and (1.2) that the energy density of dielectric materials can
be improved by increasing at least one of the two parameters, i.e. the dielectric constant (εr)
and the electrical breakdown strength (Eb). This is because the dielectric constant deter-
mines the electric displacement, while the electrical breakdown strength determines the
maximum electric field that can be applied on the dielectric material. For polymer dielec-
tric materials, the dielectric constant is relatively lower than their ceramic counter-
parts [19–21], so inorganic nanofillers with high dielectric constant are introduced to
Dmax
Electric displacement D
Ud ng
argi
ch
dis
Ul ng
a rgi
ch
Us = (Ud + Ul)
η = 100% × Ud/Us
Electric field E
improve the dielectric constant of polymer dielectrics. In terms of improving the break-
down strength, highly insulated nanofillers are incorporated into the polymer dielectrics.
For capacitive energy storage in dielectric materials, the stored energy density cannot be
fully discharged at the removal of the applied electric field because of various energy
losses, such as polarization loss, conduction loss, and hysteresis loss [22]. In most cases,
the energy loss would be converted into waste heat, which accelerates the dielectric aging
and even causes thermal runaway of the dielectric materials [23, 24]. Therefore, the
charge/discharge efficiency is another key parameter for dielectric materials. Since the
energy loss is converted into waste heat, which is harmful to the operation of dielectric
materials, it is more meaningful to concurrently improve the energy density and the
charge/discharge efficiency of the dielectric materials, rather than simply increasing the
energy density. In order to increase the charge/discharge efficiency, the energy loss, espe-
cially conduction loss under high electric field, should be suppressed. To achieve the inhi-
bition of conduction loss, some highly insulated nanofillers have been introduced into the
polymer dielectrics.
Simultaneous enhancement of dielectric constant and breakdown strength is highly
desired in the development of high performance polymer composites for electrical energy
storage. However, in most cases, the increase in dielectric constant would result in the
decrease of breakdown strength, which restricts the improvement of the energy density. So
achieving high dielectric constant while maintaining high breakdown strength is still a
great challenge. Because of the large mismatch of the electrical parameters between the
inorganic nanofillers and polymer matrix, the electric field at the nanofiller/polymer inter-
face is greatly enhanced, which results in the reduced breakdown strength. Moreover, the
dispersion of inorganic nanofillers into polymer matrix is always a challenge in the devel-
opment of polymer composites because of the high surface energy of nanofillers and the
different surface physical and chemical properties between the nanofillers and polymer
matrix. As a result, nanofiller aggregation is observed in polymer composites. The aggrega-
tion of nanofillers would introduce numerous defects in the polymer matrix, which would
decrease the electrical breakdown strength and increase the conduction loss. To address
these issues, various strategies have been proposed to develop high performance polymer
composites for electrical energy storage, including controlling the nanofiller dimension
and morphology, controlling the nanofiller distribution and orientation, modifying the
nanofiller/polymer interface, introducing multiple nanofillers, and constructing multilay-
ered composites.
To increase the capacitive energy storage performance of the polymer composites, various
inorganic nanofillers have been used to utilize the interfacial polarization and the high
dielectric constant of the nanofillers, as well as the inhibition of conduction loss and elec-
trical breakdown. Nanofillers with high dielectric constant, such as titanium oxide (TiO2),
barium titanate (BaTiO3, BT), strontium titanate (SrTiO3), barium strontium titanate
(BaxSr1 − xTiO3, BST), lead zirconate titanate (PbZrxTi1 − xO3, PZT), and calcium copper
titanate (CaCu3Ti4O12, CCTO), have been used to improve the dielectric constant and
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machine à vapeur qui distribue l’électricité dans la prison modèle de
Wellington-Gaol.
Enfin, vers onze heures, les couloirs et les fenêtres des cellules
parurent moins lumineux et un silence relatif remplaça le vacarme de
tout à l’heure.
— Allons ! à l’œuvre… me dis-je.
J’atteignis au toucher la petite scie roulée en spirale et
dissimulée dans mon gilet, puis j’ouvris la fenêtre avec précaution.
C’était une sorte de baie cintrée de moyenne ouverture qui
présentait deux barreaux verticaux espacés l’un de l’autre de vingt
centimètres environ.
Comme je suis très mince, il me suffisait d’enlever un seul
barreau.
Je me mis donc au travail.
Les dents imperceptibles de ma scie faisaient merveille. Je les
sentais mordre âprement le fer et c’est à peine si l’on entendait un
léger crissement.
Tout en activant ma besogne, je mesurais de l’œil la hauteur à
laquelle je me trouvais. Rien d’une évasion romanesque du haut
d’un donjon, en effet !… car ma cellule était au premier étage du
bâtiment. N’eussent été le risque de faire une chute sur quelque
obstacle invisible et la crainte du bruit que produirait inévitablement
la rencontre de mes bottines avec le sol, j’aurais pu sauter
simplement sans avoir recours à ma corde.
Le barreau céda enfin.
D’une violente poussée, je l’écartai au dehors pour y glisser ma
modeste corpulence. Cela fait, je revins à mon lit, y pris mon
overcoat, et d’un coup de dent, je pratiquai dans la doublure un tout
petit trou par lequel je pinçai du bout des doigts la corde enroulée à
l’intérieur.
Cette corde extraite de sa cachette, je la triplai, non pour lui
donner plus de force, car elle était, comme je l’ai dit, d’une solidité à
toute épreuve, mais de façon à pouvoir la serrer avec mes mains,
puis j’en fixai une extrémité au barreau demeuré intact.
Tout était prêt…
J’écoutai encore pendant quelques minutes, puis j’endossai mon
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En trois flexions de bras, j’avais atteint le sol où j’atterris sans
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J’éprouvai, je l’avoue, une réelle satisfaction à me sentir à l’air
libre, quelque chose comme la joie du collégien partant en vacances
ou du militaire qui vient d’être libéré.
— Aïe ! je m’étais réjoui trop tôt !
J’étais dehors, sans doute, mais dans la cour… c’est-à-dire
encore entre les murs de la prison.
Il me restait à franchir le pas le plus redoutable : la grande
porte… et le cerbère qui la gardait ne manquerait certainement pas
de s’étonner en me voyant surgir des ténèbres. Il fallait payer
d’audace jusqu’au bout.
Je me dirigeai donc, d’un pas assuré et en faisant sonner le
talon, vers la voûte sous laquelle s’ouvrait la loge du concierge.
Devant moi la lourde porte dressait ses vantaux ferrés et
rébarbatifs.
Au delà c’était la liberté !
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awake !… (Réveillez-vous).
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de véritable angoisse…
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vivement !
Une porte s’entre-bâilla et je vis apparaître à la lueur du falot qui
éclairait la voûte, une figure d’homme mal éveillée enfouie dans une
barbe à la Robinson.
Je ne laissai pas le temps au brave portier d’ouvrir la bouche :
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quelconque à deux places… Monsieur le directeur me suit…
L’homme me regarda en clignant des yeux, comme un hibou
surpris par l’aurore :
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Le portier balbutia, me sembla-t-il, quelques excuses, puis, ne
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dix heures…
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Et d’un swing vigoureusement appliqué, j’envoyai le malheureux
door-keeper rouler sous la voûte.
Inutile de dire que lorsqu’il se releva j’étais déjà loin.
Cette fois j’avais été bien servi par le hasard, puisque je
ressemblais, paraît-il, à un certain M. Nash qui devait être quelque
fonctionnaire important de Wellington-Gaol.
Et, de fait, j’eus plus tard l’occasion de constater qu’entre M.
Nash et moi on pouvait parfaitement se méprendre.
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m’illustrer dans l’affaire de Green-Park.
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wagon de première classe, je roulais vers Broad-West.
XIII
L’ALIBI
. . . . . . . . . . . . . . . . . . . .
Et je signai.
Le chief-inspector lut le papier, le tendit au directeur de la prison,
puis prononça d’une voix grave :
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Il évita aussi de faire allusion à l’affaire de Green-Park.
C’était un homme prudent qui craignait les complications et ne se
compromettait jamais ; il laissait ce soin à ses agents et aux pauvres
détectives.