Mesoscopic Phenomena in Multifunctional Materials: Synthesis, Characterization, Modeling and Applications

324 Pages·2014·13.745 MB·English

by  Avadh Saxena, Antoni Planes (eds.)

Springer Series in Materials Science 198
Avadh Saxena
Antoni Planes Editors
Mesoscopic
Phenomena in
Multifunctional
Materials
Synthesis, Characterization, Modeling
and Applications
Springer Series in Materials Science
Volume 198
Series editors
Robert Hull, Charlottesville, USA
Chennupati Jagadish, Canberra, Australia
Richard M. Osgood, New York, USA
Jürgen Parisi, Oldenburg, Germany
Shin-ichi Uchida, Tokyo, Japan
Zhiming M. Wang, Chengdu, China
For furthervolumes:
http://www.springer.com/series/856
The Springer Series in Materials Science covers the complete spectrum of mate-
rials physics, including fundamental principles, physical properties, materials
theory and design. Recognizing the increasing importance of materials science in
future device technologies, the book titles in this series reflect the state-of-the-art
in understanding and controlling the structure and properties of all important
classes of materials.
Avadh Saxena Antoni Planes
•
Editors
Mesoscopic Phenomena
in Multifunctional Materials
Synthesis, Characterization, Modeling
and Applications
123
Editors
AvadhSaxena Antoni Planes
Theoretical Division Estructura iConstitutents delaMatèria
Los AlamosNational Laboratory Universitat deBarcelona
Los Alamos Barcelona
USA Catalonia
Spain
ISSN 0933-033X ISSN 2196-2812 (electronic)
ISBN 978-3-642-55374-5 ISBN 978-3-642-55375-2 (eBook)
DOI 10.1007/978-3-642-55375-2
Springer Heidelberg NewYork Dordrecht London
LibraryofCongressControlNumber:2014943128
(cid:2)Springer-VerlagBerlinHeidelberg2014
Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartof
the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation,broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionor
informationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar
methodology now known or hereafter developed. Exempted from this legal reservation are brief
excerpts in connection with reviews or scholarly analysis or material supplied specifically for the
purposeofbeingenteredandexecutedonacomputersystem,forexclusiveusebythepurchaserofthe
work. Duplication of this publication or parts thereof is permitted only under the provisions of
theCopyright Law of the Publisher’s location, in its current version, and permission for use must
always be obtained from Springer. Permissions for use may be obtained through RightsLink at the
CopyrightClearanceCenter.ViolationsareliabletoprosecutionundertherespectiveCopyrightLaw.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexempt
fromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse.
While the advice and information in this book are believed to be true and accurate at the date of
publication,neithertheauthorsnortheeditorsnorthepublishercanacceptanylegalresponsibilityfor
anyerrorsoromissionsthatmaybemade.Thepublishermakesnowarranty,expressorimplied,with
respecttothematerialcontainedherein.
Printedonacid-freepaper
SpringerispartofSpringerScience+BusinessMedia(www.springer.com)
Preface
‘‘Mesoscopic Phenomena in Multifunctional Materials’’ is at the heart of many
current technologies and entails a fundamental need to control various materials
functionalities such as magnetoelectricity and piezo-response at the mesoscale.
Thebookbringsoutthestateoftheartonthepresentunderstandingandpotential
applications of complex multifunctional materials. The main emphasis is on the
multiscalebridgingofpropertiesfromnano-tomacroscopicscalesinthisclassof
(multiferroic and multifunctional) materials with the aim of discovering novel
properties and applications in the context of Materials by Design. The book is
expected to be broadly accessible and caters to graduate students, beginning
researchers as well as experts.
The twelve chapters in the book are partly a review with a broad perspective
and partly original research that delineates open issues in the field. The scope of
thebookisasfollows.‘‘Ahighlydesirablefeatureofmodernmaterialsscienceis
to optimize multiple functionalities in the same single phase material and control
these via cross-response in multiple external fields. Magnetoelastic and multifer-
roic materials are representative examples of this paradigm. Now that the nano-
and continuum length (and time) scales have been understood in great detail, the
next important frontier is to connect these two limiting scales by probing and
modelingthemesoscalephysicsofthesematerials.Seamlessintegrationacrossthe
scales and information flow between different length (and time) scales are key
features. Clearly these concepts can also be extended to composites of materials
with complementary properties.’’
Thefirsttwochaptersprovideadescriptionofnanoscalecharacterizationofand
nanoscale phase transformations in multifunctional materials. Chapter 3 focusses
ontherelevanceofmodellingofmicrostructure,heterogeneitiesanddiscussesthe
importance of using large computational capabilities in designing materials with
desired properties. A special emphasis is placed on information theoretic and
co-design aspects of materials modeling strategies. The thermodynamics of mul-
tiferroic materials is developed in detail in the next chapter including technolog-
ically important multicaloric effects. Examples for prototypical multiferroic
systems are also provided. Chapters 5 and 6 provide an in-depth description of
high resolution imaging techniques for both real-space and k-space imaging of
mesoscopic phenomena, in particular domains, anti-phase boundaries, magnetic
fluxlines andmagneticvorticesinmagneticshape memoryandrelatedmaterials.
v
vi Preface
Some examples of the techniques include energy-filtered transmission electron
microscopy, phase reconstructed Lorentz transmission electron microscopy and
electron holography.
Chapter7isanextensivereviewofcombinatorialandothersynthesisstrategies
fortechnologicallyimportant(e.g.inmagneticrecording,datastorageandmobile
communications) magnetoelectric hexagonal ferrites, in particular single phase
cryogenic as well as room temperature materials. Chapter 8 deals with domain
boundary engineering by functionalizing them, examples being conductive twin
boundaries and chiral twin walls. It also delineates how to achieve high domain
wall densities to optimize functionality. Chapter 9 further emphasizes the physics
offerroic and multiferroic domain walls including their dynamics and octahedral
tilts.Chapters10and11focusontheroleofdisorderinrelaxorferroelectricsand
ferroelastics,respectively,withanemphasisonglassyphenomena:polarglassand
strainglass(as ferroic extensionsofspin glass).Thenotionsofpolarnanoregions
and strain nanodomains are specifically emphasized in this context. Finally, the
last chapter elucidates two important applications of shape memory materials in
power generation and refrigeration technologies based on entropy change during
thetransformationandreversiblechangesintheirphysicalproperties.Therolesof
hysteresis, fatigue, magnetocrystalline anisotropy and combinatorial synthesis are
underscored.
These chapters discuss many open questions and set the stage for future
research in this still evolving field. A close integration of various synthesis,
characterization, modeling, simulation and data-aware strategies (that use tech-
niques from information science, e.g. data mining and machine learning) is
urgently needed to fully harness the potential of multifunctional materials. In
addition to researchers, the book will serve as a valuable resource for graduate
studentsinmaterialsscienceandengineering,condensedmatterphysicsandother
related disciplines.
Los Alamos, USA Avadh Saxena
Barcelona, Spain Antoni Planes
Contents
1 Nanoscale Characterization of Multiferroic Materials . . . . . . . . . 1
Jan Seidel and Ramamoorthy Ramesh
1.1 Scanning Probe Microscopy: Nanoscale Transport
and Electronic Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2 X-Ray Based Techniques: XRD, XAS
and XMCD- and XMLD-PEEM. . . . . . . . . . . . . . . . . . . . . . 8
1.3 Probing Magnetism: Neutron Scattering
and Mössbauer Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . 12
1.4 Optical Methods: Raman Spectroscopy and Second
Harmonic Generation (SHG) . . . . . . . . . . . . . . . . . . . . . . . . 13
1.5 High-Resolution Electron Microscopy and Spectroscopy. . . . . 15
1.6 Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2 Nanoscale Phase Transformations in Functional Materials. . . . . . 23
T. Waitz, W. Schranz and A. Tröster
2.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.1.1 Multifunctional Materials . . . . . . . . . . . . . . . . . . . . 24
2.1.2 Size Effects on Functional Properties . . . . . . . . . . . . 25
2.2 General Aspects of Phase Stability in Nanomaterials . . . . . . . 27
2.3 Critical Temperatures of Nanoscale Ferromagnetic
and Ferroelectric Materials . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.4 First Order Phase Transformations and Ferroelastic
Martensitic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.4.1 Phase Transformations of Nanoscale
Martensitic Materials . . . . . . . . . . . . . . . . . . . . . . . 33
2.4.2 Functional Properties of Nanoscale
Martensitic Materials . . . . . . . . . . . . . . . . . . . . . . . 35
2.4.3 Transition Pathways of First Order Phase
Transformations in Nanostructured Solids . . . . . . . . . 38
2.5 Domains in Ferroic Materials. . . . . . . . . . . . . . . . . . . . . . . . 39
2.5.1 Size Dependent Domain Pattern and Scaling Laws. . . 42
2.5.2 Kinetics of Nanodomains. . . . . . . . . . . . . . . . . . . . . 48
vii
viii Contents
2.6 Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3 Heterogeneities, The Mesoscale and Multifunctional
Materials Codesign: Insights and Challenges. . . . . . . . . . . . . . . . 57
Turab Lookman
3.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.2 Beyond Bloch and Boltzmann . . . . . . . . . . . . . . . . . . . . . . . 58
3.3 The Mesoscale. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.4 Codesign. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3.5 Materials Codesign. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.6 Materials Informatics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3.7 Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
4 Thermodynamics of Multiferroic Materials. . . . . . . . . . . . . . . . . 73
Teresa Castán, Antoni Planes and Avadh Saxena
4.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.2 Basic Field Equations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
4.3 General Thermodynamic Description of Multiferroic
Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
4.3.1 Clausius–Clapeyron Equations. . . . . . . . . . . . . . . . . 83
4.3.2 Multicaloric Effects in Multiferroic Materials . . . . . . 84
4.3.3 Example: The Case of Magnetic Ferrotoroidic
Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
4.4 Landau Models: Examples of Multiferroic Materials. . . . . . . . 90
4.4.1 Example: Magnetoelectric Materials. . . . . . . . . . . . . 92
4.4.2 Example: Magnetic Shape-Memory Materials . . . . . . 96
4.4.3 Example: Ferrotoroidic Materials . . . . . . . . . . . . . . . 100
4.5 Ferroic Tweed and Generalized Glassy States . . . . . . . . . . . . 103
4.6 Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
5 High Resolution Imaging Techniques for Understanding
of Mesoscopic Phenomena. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
Yasukazu Murakami
5.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
5.2 Analysis of Crystallographic Nanostructures . . . . . . . . . . . . . 110
5.2.1 Method of Energy-Filtered TEM . . . . . . . . . . . . . . . 111
5.2.2 Structure Analysis for the Premartensitic State
in Ti Ni Fe Alloy. . . . . . . . . . . . . . . . . . . . . . . . 113
50 48 2
5.2.3 Real Space Observations for the Premartensitic
State. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
5.2.4 Premartensitic Modulation Observed
in Lattice Images . . . . . . . . . . . . . . . . . . . . . . . . . . 118
Contents ix
5.3 Analysis of Magnetic Nanostructures . . . . . . . . . . . . . . . . . . 120
5.3.1 Methods of Magnetic Imaging. . . . . . . . . . . . . . . . . 121
5.3.2 Revealing Magnetic Nanostructures
in CMR Manganites . . . . . . . . . . . . . . . . . . . . . . . . 123
5.3.3 Understanding of Interface Magnetism
in a Heusler Alloy Ni Mn Al Ga . . . . . . . . . . 128
50 25 12.5 12.5
5.4 Concluding Remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
6 Imaging of Domains and Vortices
in Multifunctional Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
Charudatta Phatak and Marc De Graef
6.1 Background. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
6.2 Magnetic Domain Observations in the Transmission
Electron Microscope. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
6.2.1 Classical Lorentz Transmission
Electron Microscopy. . . . . . . . . . . . . . . . . . . . . . . . 139
6.2.2 Quantum Mechanical Description of LTEM . . . . . . . 141
6.2.3 Phase Reconstruction . . . . . . . . . . . . . . . . . . . . . . . 146
6.3 Domain Observations in Ni MnGa Alloys. . . . . . . . . . . . . . . 148
2
6.3.1 Domain Walls in Austenite . . . . . . . . . . . . . . . . . . . 148
6.3.2 Domain Walls in Martensite . . . . . . . . . . . . . . . . . . 151
6.3.3 Vortices in Finely Twinned Martensite . . . . . . . . . . . 153
6.4 Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
7 Multiferroic and Magnetoelectric Hexagonal Ferrites . . . . . . . . . 159
Robert C. Pullar
7.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
7.1.1 Multiferroic and Magnetoelectric Hexaferrites . . . . . . 162
7.2 The Structure of the Hexagonal Ferrites . . . . . . . . . . . . . . . . 163
7.2.1 The S, R and T Blocks. . . . . . . . . . . . . . . . . . . . . . 165
7.2.2 The M Ferrites. . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
7.2.3 The Y Ferrites . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
7.2.4 The Z Ferrites . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
7.2.5 The U Ferrites . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
7.2.6 Electrical Conductivity of Ferrites . . . . . . . . . . . . . . 170
7.3 Formation of Hexagonal Ferrites . . . . . . . . . . . . . . . . . . . . . 171
7.3.1 Formation of the M Ferrites. . . . . . . . . . . . . . . . . . . 173
7.3.2 Formation of Y Ferrite . . . . . . . . . . . . . . . . . . . . . . 175
7.3.3 Formation of Z Ferrite . . . . . . . . . . . . . . . . . . . . . . 175
7.3.4 Formation of U Ferrite . . . . . . . . . . . . . . . . . . . . . . 176