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Nanostructured Ceramics: Characterization and Analysis

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Nanostructured Ceramics
Characterization and Analysis

Debasish Sarkar
CRC Press
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Debasish Sarkar dedicates this book with great sense of gratitude and love to his parents,

Late Chandidas Sarkar and Mrs. Madhuri Sarkar

Contents

Preface ........................................................................................................................................... xiii

Acknowledgment ....................................................................................................................... xvii
Author ........................................................................................................................................... xix

1. Nanoscale Ceramics ...............................................................................................................1

1.1 Introduction ...................................................................................................................1
1.2 Confinement and Functional Change in Nanoscale ................................................2
1.2.1 Density of States .............................................................................................2
1.2.2 Confinement and Band Gap .........................................................................3
1.2.3 Surface Area to Volume ................................................................................6
1.2.4 Surface Atom Density ...................................................................................8
1.2.5 Surface Energy and Dangling Bonds ..........................................................9
1.2.6 Gibbs Free Energy and Critical Radius .................................................... 10
1.2.7 Cohesive Energy .......................................................................................... 11
1.2.8 Lattice Parameters and Strains .................................................................. 13
1.2.9 Frequency ...................................................................................................... 15
1.2.10 Velocity and Motion in Fluid ..................................................................... 16
1.3 Classification of Ceramics .......................................................................................... 17
1.3.1 Traditional Ceramics ................................................................................... 19
1.3.2 Advanced Ceramics..................................................................................... 20
1.4 Rationale of Energy, Environment, and Health Materials ....................................22
1.5 Handling and Ethical Issues ..................................................................................... 23
1.6 Concluding Remarks .................................................................................................. 24
References ............................................................................................................................... 25

2. Material Characterizations ................................................................................................. 27

2.1 Introduction ................................................................................................................. 27
2.2 Thermal Analysis ........................................................................................................ 27
2.2.1 Differential Scanning Calorimetry and TG Patterns ............................. 28
2.2.2 Specific Heat Capacity .................................................................................30
2.2.3 Enthalpy Change ......................................................................................... 31
2.2.4 Kinetics and Activation Energy of Crystallization ................................. 31
2.3 X-Ray Diffraction Analysis ........................................................................................ 33
2.3.1 Indexing and d-Spacing ..............................................................................34
2.3.2 Theoretical Density ..................................................................................... 36
2.3.3 Phase Identification and Quantification ................................................... 38
2.3.4 Crystallite Size and Microstrain ................................................................ 39
2.4 Transmission Electron Microscopic Analysis ......................................................... 41
2.4.1 Indexing of Polycrystal ...............................................................................44
2.4.2 Indexing of Single Crystal ..........................................................................44
2.4.3 Morphology, d-Spacing, and Indexing of WO3 ....................................... 45

vii
viii Contents

2.5 Particle Size and Surface Area .................................................................................. 46

2.5.1 Statistical Analysis of Particle Size.............................................................. 46
2.5.2 Surface Area and Particle Pore Size ............................................................ 48
2.6 Spectroscopy Analysis ............................................................................................... 50
2.6.1 Photoluminescence Spectra .......................................................................... 51
2.6.2 Raman Spectroscopy .....................................................................................54
2.6.3 X-Ray Photoelectron Spectroscopy ............................................................. 55
2.6.4 Ultraviolet Visible and Diffuse Reflection Spectroscopy ......................... 58
2.6.5 Fourier Transformation Infrared ................................................................. 61
2.7 Concluding Remarks ..................................................................................................63
References ...............................................................................................................................63

3. Surface and Suspension Phenomena................................................................................ 67

3.1 Introduction ................................................................................................................. 67
3.2 Surface Wetting ........................................................................................................... 68
3.2.1 Contact Angle and Hysteresis...................................................................... 68
3.2.2 Critical Parameters for Superhydrophobic Surface................................... 71
3.2.3 Critical Parameters for Superhydrophilic Surface .................................... 72
3.2.4 Critical Boundary in Hydrophilic and Hydrophobic Surface ................. 72
3.3 Surface Tension ............................................................................................................ 74
3.3.1 Surface Tension Estimation Protocols ......................................................... 74
3.3.2 Critical Surface Tension ................................................................................ 76
3.3.3 Influence of Foreign Elements in Surface Tension .................................... 76
3.4 Colloidal Suspension .................................................................................................. 79
3.4.1 Electrical Double Layer .................................................................................80
3.4.2 Electrostatic Stabilization ............................................................................. 81
3.4.3 Steric Stabilization ......................................................................................... 82
3.4.4 Electrosteric Stabilization .............................................................................84
3.4.5 Zeta Potential and Isoelectric Point of SiO2 and MgO: Influence
of pH ..................................................................................................... 85
3.4.6 Zeta Potential and Isoelectric Point of ZrO2: Influence of pH
and Particle Size ............................................................................................. 86
3.4.7 Packing Fraction and Sedimentation .......................................................... 86
3.5 Viscosity of Suspension .............................................................................................. 88
3.5.1 Rheology of Suspensions .............................................................................. 89
3.5.2 Particle Size and Volume Fraction on Viscosity ........................................ 90
3.6 Concluding Remarks .................................................................................................. 92
References ............................................................................................................................... 93

4. Photocatalytic Phenomena.................................................................................................. 95
4.1 Introduction ................................................................................................................. 95
4.2 Photocatalyst for Photo-Degradation ....................................................................... 95
4.2.1 Band Gap and Valence Band–Conduction Band Position........................ 96
4.2.2 Electron-Hole Charge Transportation Phenomena................................... 98
4.2.3 Role of Scavenger ......................................................................................... 100
4.2.4 Surface Modifications .................................................................................. 100
4.2.5 Influence of Particle Size ............................................................................. 102
4.3 Photocatalyst for Photo-Electrochemical Cell....................................................... 103
4.3.1 Regenerative Photo-Electrochemical Cell (Solar Cells) .......................... 103
Contents ix

4.3.2Photo-Synthetic Solar Cells ........................................................................ 105

[Link] Electrochemical Photo-Electrolytic Cells .................................. 105
[Link] Electrochemical Photocatalytic Cells ........................................ 106
4.3.3 Semiconductor–Electrolyte Interaction and Band Bending .................. 106
4.3.4 Conventional Materials for Photo-Electrochemical Cells ...................... 107
4.3.5 Output and Governing Parameters for Photo-Electrochemical Cells ...... 107
4.4 Concluding Remarks ................................................................................................ 113
References ............................................................................................................................. 113

5. Magnetics and Piezoelectrics ........................................................................................... 117

5.1 Introduction ............................................................................................................... 117
5.2 Magnetic Phenomena ............................................................................................... 119
5.2.1 Magnetic Moment ........................................................................................ 119
5.2.2 Ferrimagnetic Behavior of Soft and Hard Ferrites ................................. 120
5.2.3 Superparamagnetic Behavior ..................................................................... 121
5.2.4 Magnetization and Hysteresis ................................................................... 123
5.2.5 Magnetocrystalline Anisotropic Constant (K) ........................................ 124
5.2.6 Specific Loss Powers .................................................................................... 125
5.2.7 Magnetoresistance Change ........................................................................ 126
5.2.8 Exchange-Spring Magnet ........................................................................... 127
5.2.9 Particle Size Effect on Magnetic Saturation ............................................. 128
5.3 Piezoelectric Phenomena ......................................................................................... 129
5.3.1 Ferroelectric Behaviors ............................................................................... 130
5.3.2 Dielectric Permittivity and Loss ................................................................ 132
5.3.3 Piezoelectric Constants ............................................................................... 133
5.3.4 Role of Grain Size on Dielectrics and Piezoelectrics .............................. 138
5.4 Concluding Remarks ................................................................................................ 141
References ............................................................................................................................. 142

6. Mechanical Properties ....................................................................................................... 145

6.1 Introduction ............................................................................................................... 145
6.2 Elastic Moduli ............................................................................................................ 145
6.2.1 Single Phase Nanocrystalline Ceramics ................................................... 146
6.2.2 Multi-Phase Nanocrystalline Ceramics .................................................... 148
6.2.3 Relation in Elastic Modulus and Porosity ................................................ 149
6.2.4 Effect of Grain Size and Porosity ............................................................... 150
6.3 Strength ...................................................................................................................... 151
6.3.1 Compressive Strength ................................................................................. 151
6.3.2 Flexural Strength ......................................................................................... 153
6.3.3 Effect of Grain Size on Strength ................................................................ 154
6.3.4 Effect of Porosity on Strength .................................................................... 155
6.4 Weibull Modulus....................................................................................................... 156
6.5 Fracture Toughness................................................................................................... 158
6.5.1 Competitive Single Edge “V” Notch Beam and Indentation
Toughness ..................................................................................................... 159
6.5.2 Effect of Grain Size on Toughness ............................................................. 161
6.6 Hardness .................................................................................................................... 163
6.6.1 Vickers Indentation...................................................................................... 164
6.6.2 Hardness by Penetration Depth ................................................................ 164
x Contents

6.6.3 Effect of Grain Size ...................................................................................... 166

6.6.4 Effect of Load................................................................................................ 167
6.7 Fatigue of Ceramics .................................................................................................. 168
6.8 Superplasticity ........................................................................................................... 169
6.9 Friction and Wear...................................................................................................... 170
6.10 Concluding Remarks ................................................................................................ 172
References ............................................................................................................................. 172

7. Nanostructured Ceramics for Renewable Energy ....................................................... 175

7.1 Introduction ............................................................................................................... 175
7.2 Nanostructured TiO2 for Solar to Electrical Energy, Dye-Sensitized
Solar Cell .................................................................................................................... 176
7.2.1 Background................................................................................................... 176
7.2.2 Importance of Nanostructured TiO2, Anatase ........................................ 177
7.2.3 Materials and Methods ............................................................................... 178
7.2.4 Working Principle of Dye-Sensitized Solar Cell ..................................... 178
7.2.5 Characterization and Analysis .................................................................. 179
7.2.6 Research and Development Scope ............................................................ 181
7.3 Nanostructured WO3/TiO2 for H2 Gas through H2O Splitting,
Tandem Cell ........................................................................................................ 181
7.3.1 Background................................................................................................... 181
7.3.2 Importance of Dual Semiconductors ........................................................ 182
7.3.3 Materials and Methods ............................................................................... 183
7.3.4 Working Principle ........................................................................................ 183
7.3.5 Characterization and Analysis .................................................................. 184
7.3.6 Research and Development Scope ............................................................ 185
7.4 Nanostructured WO3/TiO2 for Solar to Electrical Energy and
Harvesting, Photovoltaically Self-Charging Battery ........................................... 186
7.4.1 Background................................................................................................... 186
7.4.2 Materials and Methods ............................................................................... 187
7.4.3 Working Principle ........................................................................................ 188
7.4.4 Characterization and Analysis .................................................................. 189
7.4.5 Research and Development Scope ............................................................ 190
7.5 Nanostructured ZrO2 for Gaseous Fuel to Electric Energy ................................ 190
7.5.1 Background................................................................................................... 190
7.5.2 Importance of Nanostructured YSZ ......................................................... 191
7.5.3 Materials and Method ................................................................................. 192
7.5.4 Working Principle ........................................................................................ 192
7.5.5 Characterization and Analysis .................................................................. 194
7.5.6 Research and Development Scope ............................................................ 195
7.6 Nanostructured BaTiO3 for Mechanical to Electrical Energy ............................. 195
7.6.1 Background................................................................................................... 195
7.6.2 Importance of Nanostructured BaTiO3..................................................... 196
7.6.3 Materials and Method ................................................................................. 196
7.6.4 Working Principle ........................................................................................ 197
7.6.5 Characterization and Analysis .................................................................. 198
7.6.6 Research and Development Scope ............................................................ 199
7.7 Concluding Remarks ................................................................................................ 199
References ............................................................................................................................. 200
Contents xi

8. Nanostructured Ceramics for Environment ................................................................. 201

8.1 Introduction ............................................................................................................... 201
8.2 Nanostructured WO3 for Electrochromic Smart Glass ........................................ 202
8.2.1 Background................................................................................................... 202
8.2.2 Materials and Method ................................................................................. 203
8.2.3 Working Principle ........................................................................................ 203
8.2.4 Characterization and Analysis .................................................................. 204
8.2.5 Research and Development Scope ............................................................ 206
8.3 Nanostructured WO3-ZnO for Pollutant Dye Degradation ................................ 206
8.3.1 Background................................................................................................... 206
8.3.2 Materials and Method ................................................................................. 207
8.3.3 Working Principle ........................................................................................ 207
8.3.4 Characterization and Analysis .................................................................. 209
8.3.5 Research and Development Scope ............................................................ 211
8.4 Mechanically Induced Waste Water Treatment .................................................... 211
8.4.1 Background................................................................................................... 211
8.4.2 Materials and Method ................................................................................. 213
8.4.3 Working Principle ........................................................................................ 213
8.4.4 Characterization and Analysis .................................................................. 214
8.4.5 Research and Development Scope ............................................................ 215
8.5 Purification of High Salinity Waste Water ............................................................ 216
8.5.1 Background................................................................................................... 216
8.5.2 Materials and Methods ............................................................................... 217
8.5.3 Working Principle ........................................................................................ 217
8.5.4 Characterization and Analysis .................................................................. 218
8.5.5 Research and Development Scope ............................................................ 219
8.6 Self-Cleaning Coating .............................................................................................. 219
8.6.1 Background................................................................................................... 219
8.6.2 Importance of Nanostructured TiO2 for Self-Cleaning .......................... 220
8.6.3 Materials and Methods ............................................................................... 220
8.6.4 Working Principle ........................................................................................ 220
8.6.5 Characterization and Analysis ..................................................................222
8.6.6 Research and Future Scope ........................................................................222
8.7 Concluding Remarks ................................................................................................223
References .............................................................................................................................223

9. Nanostructured Ceramics for Health .............................................................................225

9.1 Introduction ...............................................................................................................225
9.2 Nanostructured ZrO2 for Dental Ceramic Blank.................................................. 226
9.2.1 Background................................................................................................... 226
9.2.2 Advantages of Nanostructured Zirconia ................................................. 227
9.2.3 Materials and Method ................................................................................. 227
9.2.4 Characterization and Analysis .................................................................. 227
9.2.5 Research and Development Scope ............................................................ 229
9.3 Nanostructured Zirconia Toughened Alumina Femoral Ball Head ................. 230
9.3.1 Background................................................................................................... 230
9.3.2 Advantage of Nanostructured Zirconia Toughened Alumina ............. 230
9.3.3 Materials and Method ................................................................................. 231
xii Contents

9.3.4 Characterization and Analysis .................................................................. 231

9.3.5 Research and Development Scope ............................................................ 233
9.4 Nano Hydroxyapatite-Gelatin Porous Bone Scaffold ..........................................234
9.4.1 Background...................................................................................................234
9.4.2 Advantage of Nano Hydroxyapatite in Scaffold ..................................... 235
9.4.3 Materials and Method ................................................................................. 235
9.4.4 Characterization and Analysis .................................................................. 235
9.4.5 Research and Development Scope ............................................................ 237
9.5 Nanostructured ZnO for Cancer Therapy ............................................................ 238
9.5.1 Background................................................................................................... 238
9.5.2 Advantages of Nanostructured Hollow ZnO .......................................... 238
9.5.3 Materials and Method ................................................................................. 239
9.5.4 Working Principle ........................................................................................ 239
9.5.5 Characterization and Analysis .................................................................. 241
9.5.6 Research and Development Scope ............................................................ 242
9.6 Nanoscale Core-Shell Ferrite for Hyperthermia .................................................. 242
9.6.1 Background................................................................................................... 242
9.6.2 Advantages of Core-Shell Nanoparticles ................................................. 243
9.6.3 Materials and Method ................................................................................. 243
9.6.4 Working Principle ........................................................................................ 244
9.6.5 Characterization and Analysis .................................................................. 244
9.6.6 Research and Development Scope ............................................................ 246
9.7 Concluding Remarks ................................................................................................ 246
References ............................................................................................................................. 247

10. Problems and Answers ...................................................................................................... 251

Index ............................................................................................................................................. 263

Preface

My decision to write this book is initiated in order to support UG/PG student and
researchers who are in front of difficulties to interpret in systematic approach and con-
clude the research objective. Now-a-days, the science and engineering has become mul-
tidisciplinary in nature, and the books in the market are either totally for basic science
or complete edition of different classical synthesis, characterizations, and applications of
nanomaterials and nanotechnologies. So this book targets to bring forth the paradigm
either oriented on fundamental aspects or totally hover onto data interpretations of nano-
structured ceramics involved in functional and structural applications.
The book starts with a general overview of ceramics followed by different fundamental
aspects and their judicial use in different horizon of nanostructured ceramic research. In
this context, Chapter 1 deals with the confined growth of nanomaterials and their influence
on fundamental aspects primarily band gap, surface area, surface atom density, surface
energy, dangling bonds, Gibbs free energy, nucleation, cohesive energy, lattice parame-
ters, strains, frequency, and particle velocity are discussed. One can correlate the physi-
cal properties of nanomaterials with help of these phenomenologies. A classic illustration
and future scope in both traditional and advanced ceramics by nanoscale modulation are
highlighted. Nanomaterials handling and ethical issues are enlightening to make aware
of nanoresearch. Eventually, the bird-eye view has been illustrated in the perspective of
case studies like energy, environment, and health issues. Chapter 2 briefs the data analy-
sis and quantification strategy during synthesis of nanoparticles in order to explain the
material properties effectually. Not all, but a cluster of inevitable material characteriza-
tions are being encountered and discussed. After reading this chapter, quantification of the
phase transformation temperature, specific heat capacity, enthalpy, kinetics and activation
energy of crystallization, X-ray and electron diffraction pattern indexing, lattice spacing
and strain, crystallite size, theoretical density, imaging, particle size phenomena, surface
area, and spectroscopic data can be done. The effect of nanoparticle size and processing
conditions are also highlighted and eventually explored the probable research scope in
nanostructured ceramics. Chapter 3 describes the surface and suspension phenomena that
eventually mandate to improve recent nanotechnology evolution for the different sectors
including energy, environmental science, medicine, food, transportation, construction, and
many others. While discussing the use of nanoparticles, practical performance depends
on the concurrence of an optimum solid containing suspension that eventually controls
by surface characteristics of particles. In previous chapters, the discussion focused on the
plausible physical properties revision when particle size is reducing from bulk counter-
part. In this conjecture, the surface of solids and their resultant suspension characteristic
variation with nanoparticles are discussed. The influence of particle size on diverse fea-
tures are analyzed in consideration of recent research data.
Increasing pure water demand and global warming due to exhaustive greenhouse gas
emissions from fossil fuel motivates to concentrate on the utilization of abundant solar
energy for pollutant degradation and renewable energy by photocatalyst. Thus, Chapter 4
deals with the basic philosophy on the probable use of ceramic photocatalyst to solving
the serious environmental pollution and energy problems. Fundamental concept on band
gap, selection of band position, electron-hole charge transportation phenomena, role of

xiii
xiv Preface

scavenger, surface modifications, details about regenerative and photosynthetic solar

cells, semiconductor–electrolyte interaction and band bending, output, and governing
parameters are discussed and compared with nanoscale particle size and characterization
parameters.
Ferrimagnetic and ferroelectric material has analogous functional behavior and domi-
nates in recent nanotechnology. Manipulation and modeling of atoms, molecules, and
macromolecular structure design promotes unique and enhanced properties to open up
a new and exciting research field with revolutionary applications not only in electronic
technology, but also in the field of energy sector, environmental science, and medical
diagnosis. Thus, precise properties including magnetic moment, superparamagnetism,
magnetization and hysteresis, magneto crystalline anisotropic, specific loss powers, mag-
neto resistance change, exchange-spring magnet, dielectric permittivity and loss, and
piezoelectric constants are discussed and analyzed their behavioral change with respect
to particle or grain size in Chapter 5.
One-dimensional (1D) confined growth nanofiber experience more strain compared to
equivalent volume of spherical or cuboid nanoparticles, but the same spherical particle is
being consolidated more effectively than other morphologies. In consideration of density,
the compact can be classified into transparent, dense, and porous ceramics that eventu-
ally enables to alter the mechanical properties under stress with respect to grain size and
porosity content. Nanostructured bulk ceramic is competent in high strain rate at elevated
temperature, although degree of deformation depends on grain size and morphology,
and their distribution. In the perspective of structural ceramic research and development,
some fundamental and classical mechanical properties are discussed in Chapter 6.
Chapter 7 discusses about the probable generation of renewable energy and their har-
vesting through solar energy, solid oxide fuel cell, and waste vibrational energy. Recent
research progress has several directions to meet the excessive energy demand without
evolving any toxic pollutant and maintaining the safe world. In this regard, it is easy to
penetrate and solve the targeted goal when critically involve material scientists, instru-
mentation engineers, technocrats, and so on. A couple of ceramic oxides are encountered
to solve this issue, although unlimited scope exists to use nanostructured ceramics in this
perspective. Synthesis protocol, working principle, characterization, and analysis of differ-
ent modules are discussed to facilitate the renewable energy research and development.
Ceramic is an ancient material and serves as natural air conditioner, filter for toxic gases,
and industrial waste water; major concern of global warming. Growing population expo-
nentially using vehicles, civil construction, and industries, and disposes tons of heat, toxic
gases, and chemical compounds either in air or water. In preference, metal catalyst along
with ceramic substrate facilitate gas filtration, however, chemical engineers and material
researchers are effectively solving water pollution with using of abundant solar energy
and waste mechanical energy. Several critical issues including smart glass, water purifica-
tion, and minimization of water usability by nanostructured ceramics are focused in the
perspective of environment research in Chapter 8.
Adult human skeletal system including teeth and bone weight is near to 15% of total
body weight, out of this, 60% inorganic constituent known as hydroxyapatite. Simply, 60 kg
human being carries near to 6  kg ceramics (10 wt%), and thus it is expected to replace
our skeleton by artificial implants made of ceramics. Pollution, diseases, and accident
either deteriorates or fractures the bone/teeth and necessitates both dense bioimplant and
porous scaffold analogous to hard and spongy tissues, respectively. Despite the shaped
nanostructured ceramics, photodynamic and magnetic ceramic nanoparticles are in fore-
front to solve the cancer treatment that also being considered and discussed in Chapter 9.
Preface xv

Chapter 10 deals with the different numerical and basic questions to initiate early stage
of translational research that eventually help to develop real component for society. After
solving and answering these basic questions, it is assumed that students can get interest in
material research and able to analyze independently during development of new class of
nanostructured ceramics. Provided numerical questions can be effectively considered for
15 weeks tutorial class in one semester. The book content can be started as a new course
work, namely, either “Nanostructured Ceramics” or “Nanosciences and Nanotechnology”
for graduate students.
In summary, this book gives a comprehensive account on the solved numerical and
brainstorming unsolved (partial hints) problem to boost up the data interpretation skill,
and one can envisage the correlation between synthesis process and properties in the per-
spective of the new material development. It serves as a concise text to answer the basics
and achieve research goal for academia and industrial research.
Acknowledgment

I would like to convey my heartfelt thanks to family member son Achyut, wife Shubhra,
nieces Diya and Sana, brothers Subhash and Amit and sister Rina for their constant
endorsement and motivation throughout the journey of writing the book. I would like to
thank my students Sarath, Sushree, Sangeeta, Venkat, Akbar, Megha, Barsa, Monali, Satish,
and Sanjaya, for their uninterrupted cooperative actions in manuscript preparation. Their
inquisitiveness for advancement in the field of ceramics has consistently simulated me for
further research and, finally, putting the efforts into this book.
I would like to acknowledge to NIT, Rourkela; Department of Science and Technology
(DST), India; Department of Biotechnology (DBT), India; Board of Research in Nuclear
Sciences (BRNS), India; Korea Research Institute of Science and Standards (KRISS), South
Korea; Tata Steel Ltd., Jamshedpur; and Tata Krosaki Refractories Ltd., Belpahar for their
support.
I would like to thank to all the researchers for their contributions to the scientific society
which are the building blocks of the conceptual knowledge of this book.
Lastly, my sincere apology to those whose names are inadvertently not mentioned.

xvii
Author

Dr. Debasish Sarkar is currently a professor at the Department of Ceramic Engineering,

National Institute of Technology (NIT), Rourkela, Odisha, India. After his undergraduate
in Ceramic Engineering from University of Calcutta in 1996, he completed a [Link] in
Metallurgical and Materials Engineering from Indian Institute of Technology, Kanpur,
followed by a Ph.D in Ceramic Engineering at NIT, Rourkela. In due course of visiting
researcher in Korea Research Institute of Standards and Science (KRISS), South Korea, he
has gained extensive experience in synthesis, characterizations, and fabrication protocols
of nanostructured ceramics. As Principal Investigator, he has managed several research
projects including nanomaterials for functional and structural applications and refractories.
The government of India and industry like Tata Steel Ltd., Tata Krosaki Refractories Ltd.,
etc. sponsored most of the funding.
Debasish is an internationally recognized expert in the academic, industrial, and trans-
lational research in ceramics. Several works are highlighted in “Global Medical Discovery,
Canada,” as well as published as European patent. He has been awarded Materials Research
Society (MRSI) of India Medal Award, 2016, for the work on patient-specific orthopaedic
implants, is a symbol of his outstanding career.
He has cumulative 22 years of experience and published 60 peer-reviewed international
journal papers, 15 papers in conference proceedings, and 2 book chapters in Pan Stanford
Publisher, Singapore and Wiley-VCH Verlag GmbH. He has been a lead inventor in one
Korean patent, one European patent, and one Indian patent, and co-inventor for two
Korean patents. He has published and reviewed in ACS, Blackwell Publishing Inc.,
Electrochemical Society, Elsevier, RSC, Springer, etc. He is holding positions as a member
of different editorial boards and technical committees around the globe.

xix
1
Nanoscale Ceramics

1.1 Introduction
Day to day, magic is gradually becoming logic by the invention of various scientific facts.
As we are moving forward in time, we are coming up with new ideas to explore the oppor-
tunities in science and technology. The one that is growing interest among scientists and
industries for the last few decades is “nanoscience and nanotechnology.” Nanoscience
implies cumulative knowledge together with the physical, chemical, and structural study
of materials of nano (10−9 m) range that is 1–100 nm. However, nanomaterials defend as
interlink in between nanoscience and nanotechnology. Nanotechnology is in the forefront
in the support of various scientific and engineering horizons that invention has made our
life quite easy and portable. For an example, in a tiny place, a vast data storage facilitates
the data processing technology. Not only mammoth growth in the electronics industry, it
is helping to make our life comfortable and user-friendly to a large extent starting from
food to health care, packaging to paints, renewable energy to environmental issues, mis-
siles to security application, and so on. In order to develop reliable and effective products,
one should be aware of synthesis, properties, and effective characterizations in the per-
spective of nanomaterial development. Knowledge on lab scale module fabrication made
of nanostructured material is eventually going to provide the advancement and luxury of
our society.
In consideration of basic electron transfer phenomenon, the material world can be classi-
fied in conductors, semiconductors, and insulators. However, a common platform encom-
passes their existence as metals, ceramics, polymers, or a combination of them. Thus, in
consideration of these three, we can achieve any properties in the recent era, although
their size controls the resultant appearance and properties of products or devices. Apart
from the monolithic single-phase materials, a combination of material results in different
composites including metal matrix composite, polymer matrix composite, ceramic matrix
composite, or any other alteration. Despite two classic groups of materials like metals and
polymers, herein, ceramics are preferentially targeted and discussed, in specific, in the
form of nanostructured ceramics. In the perspective of book content, this section starts
with a correlation with size and physical properties of materials to intellect and justify the
synthesis of nanoscale materials. In the end, details of classification of ceramics are high-
lighted, and their probable use in modern burning issues like energy, environment, and
health treatment is emphasized.

1
2 Nanostructured Ceramics

1.2 Confinement and Functional Change in Nanoscale

Continuous improvement toward device miniaturization demands nanoscale particles
and coatings for advanced applications. Herein, the focus has been emphasized on the
confined growth (0D, 1D, 3D) of nanoparticles and nanostructured bulk ceramics, not
nanocoating (2D) material. In a convention, nanoparticles are studied as a solid form, but
it represents as an intermediate between the gaseous or molecular structure and the bulk
solid state. Consequently, the physical properties of nanoscale materials which consist of
any dimension below 10 nm (cluster of ~25 atoms or molecules!) are different from their
bulk structures. When the particle size is made to be nanoscale, properties such as sur-
face energy, melting point, catalytic, piezoelectric, magnetic, optical, mechanical proper-
ties, and chemical reactivity varies as a function of particle size, but obviously not linear
relationship in all features. At the same time, a definite window size of particles or grains
exhibits best properties, and these aspects have been discussed in subsequent chapters.
As nanoparticles are closer to the size of an atom, consideration of quantum mechan-
ics is come across in order to explain the motion and energy of these particles. In this
nanoscale dimension, gravitational force becomes negligible, simultaneously, the electro-
magnetic force dominates and determines the physical properties. Quantum confinement
describes the availability of electrons in particular space, rather than free to move in bulk
of material, and this allows discrete energy levels to differentiate from bulk materials.
Despite quantum confinement, nanoscale chemistry plays an important role to explain the
properties influenced by bonding and surface characteristics. In the upcoming section, the
reader can concentrate in more detail on the impact of nanoscale size, and why it is differ-
ent from bulk counterpart.

1.2.1 Density of States

Material has free electrons, and their chance of availability within valence band and
conduction band, and this incidence differentiate insulator, semiconductor, and con-
ductor. A selective number of valence electrons very close to the Fermi energy within
kBT (where kB  =  1.38  ×  10−23  J/K, and T  =  absolute temperature) has a probability of
shifting to conduction band at a particular temperature. Thus, free electrons are not
entirely free, as well as not available in any energy state, whereas they must fit into a
specific energy state within the solid. In this context, the Fermi distribution function,
f(E), is a statistical approach that describes the probability of finding a free electron in
energy state of E [1]:

1
f (E) = (1.1)
e ( ( E − E F ) k BT ) + 1

All materials have at least some free electrons, and, hence, this function applies to illus-
trate the properties of insulator, semiconductor, and conductor. It is worthy to mention
that the Fermi energy (EF) is in the middle of the highest occupied band in conductors, or
in another way, the Fermi energy is the band gap for semiconductors and insulators. This
discussion focused in the consideration of a uniform availability of states of electrons in
either the valence or conduction bands. Although, in reality, it is not true. Thus, it is neces-
sary to introduce density of state (DOS) function as Ds(E) for real solids, and this function
Nanoscale Ceramics 3

describes the availability of states for electrons to occupy in different states. This 3D DOS
function represents the number of available electron energy states per unit volume, per
unit energy. It can be applied to bulk 3D materials without any growth direction confine-
ment and is independent of the dimension.

8 2 πm 3/2
Ds ( E ) = E (1.2)
h3

where m is the mass of an electron (9.11  ×  10−31  kg), h is the Planck’s constant
(6.626 × 10−34 m2 kg/s). The electron population depends on the resultant product of the
Fermi function and electron density of states. The number of electrons per unit volume
with energy between E and E + ∆E is given by the multiplication of Equations 1.1 and 1.2:

n(E) ∆E = f (E) D s (E) ∆E (1.3)

Thus, the number of free electrons per unit volume is:

∞

n=
∫ n ( E ) dE
Ec
(1.4)

Figure 1.1a demonstrates the characteristic behavior of conventional Fermi energy func-
tion above T > 0, density of states for 3D bulk, and resultant integral of Equation 1.4 as the
shaded area. It is worthwhile to derive the Equation 1.2 applying the infinite 3D box model
that refers the plausible growth of the particles without any confinement [2]. Figure 1.1b
illustrates the growth pattern of the particles with having confinement (shown by arrows)
in one or multiple directions that results in 2D nanolayer, 1D nanowire, and 0D quantum
dot, respectively. In actual, the Ds varies with respect to dimensional features, and thus it
varies with E1/2, E0, E−1/2, and δ(E) for 3D, 2D, 1D, and 0D, respectively. The characteristic
behavior of density of states of semiconductors with 3, 2, 1, and 0 degrees of freedom for
electron propagation with respect to energy is represented in Figure 1.1c. Systems with 2, 1,
and 0 degrees of freedom are referred to as quantum wells, quantum wires, and quantum
boxes, respectively.
Virtually, high magnetic susceptibility, X-ray radiated emission, outstanding optical
properties, specific heat, electrical properties, and many others depend on the availability
and motion of the electrons. This density of state is most relevant on nanoscale and with
the support of the aforesaid understanding, a later section describes how a small portion
of a bulk solid behaves electronically like an artificial atom, that is the key feature of device
miniaturization and advance nanodevices.

1.2.2 Confinement and Band Gap

In an effort to enhance the functionality, comfortability, and reduce energy consump-
tion, the major effort to concentrate on the development of nanoscale materials is followed
by effective and portable devices. As a result, electronic devices have changed from few
centimeter- to millimeter-sized down to nanometer sized. It was possible because of syn-
thesis of nanoscale materials having atomistic and their tunable properties. In this context,
4 Nanostructured Ceramics

f (E) EF Ds (E) for 3D

1

Density of states
Probability
n(E)
Bulk -3D Quantum well -2D
0.5

0
(a) Energy (eV) (b) Quantum wire -1D Quantum dot -0D

Bulk -3D
Density of states (cm−3 ev−1)

Quantum well -2D

Quantum wire -1D

Quantum dot -0D

(c) Energy (meV)

FIGURE 1.1
(a) Probability of finding a free electron and density of states of 3D with respect to band energy; (b) plausible
growth confinement of nanoscale materials; and (c) an insight view of DOS and electron energy of 0D, 1D, 2D,
and 3D confined nanomaterials.

it is interesting to introduce how a tiny particle either originated from bulk or synthesized
nanoscale size can behave as an atom.
In convention, at T = 0 K, the electron distribution goes from zero energy up to the Fermi
energy for a conductor and thus taking into account of the Equations 1.1 through 1.4, so,
the resultant number of free electrons per unit volume or electron density is:

EF
8 2 πm 3/2 E
n=
h3 ∫ e ( E − E )/k (0) + 1 dE
0
F B
(1.5)

Therefore, electron density at 0 K is:

8 2 πm 3/2  2 3/2 
n=  3 EF  (1.6)
h3

A bulk solid has unlimited and thick energy bands, whereas atom has limited thin and
discrete energy states, that implies the development of atomistic scale tiny particles
Nanoscale Ceramics 5

compared to bulk, may behave electronically like an atom. Rearranging Equation 1.6, the
Fermi energy is dependent on variable “n = number of free electrons per unit volume”
(number of free electrons “N” per unit volume, i.e., D3, D edge length of a cube), and we
can obtain:

N
EF v (1.7)
D3

However, the Fermi energy does not depend on the size of the material, and it is true for
conductor, semiconductor, and insulators as well. In order to discuss the total energy state
and spacing, it can be justified that the total energy states’ span of small volume material
is identical with large volume, but the former has wider spacing between energy states to
cover the cumulative energy state span. Let total free electrons “N” occupied up to EF, and
thus the average span ∆E is:

EF
∆E ≈ (1.8)
N

In consideration of Equations 1.7 and 1.8, we can obtain the average spacing between
energy states is inversely proportional to volume:

1
∆E ≈ (1.9)
D3

In other words, the spacing between energy states gets larger as the volume gets smaller,
and it forms a band in case of the bulk solid. Thus, the average spacing (∆E) has rela-
tion with Fermi energy and consists of total number of valence electrons, Nv (number of
valence electron is same with total free electrons “N” for metal, at T = 0 K within EF), and
can equate as:

4E F
∆E = (1.10)
3N v

When dimension is typically small, it provides fewer number of valence electrons, and,
hence, the spacing between energy state ∆E grows inversely, and thus continuous incre-
ment of ∆E, or reduction in size, restricts the movement of electrons and needs more energy
(temperature) to conduct, so under the condition of ∆E > kBT, metal exhibits nonmetallic
behavior. This feature is very useful to make metal-semiconductor junction to fabricate
different electronic devices [3,4].
Confinement concept implies the band-gap energy increment because of size reduction
[Eg(r)], and thus one metal can behave as semiconductor. In another way, the quantum con-
finement prediction for the band-gap energy increment for ceramic oxides by [5]:

2π2h 2
E g (r) = Eg (bulk ) + (1.11)
D 2µ

where 1/µ = ( 1 m e + 1 m h ).
in which me, mh, μ, and D are the effective mass of electron, effective mass of hole,
reduced mass, and diameter of nanoparticle, respectively. In preference, the quantum
6 Nanostructured Ceramics

4.2

4.0

Band gap (eV) 3.8

3.6

3.4

3.2
De Broglie wavelength ∼15 nm
3.0
0 5 10 15 20 25 30 35 40 45
Average particle size (nm)

FIGURE 1.2
The change in band gap of BaTiO3 with respect to particle size. Band gap becomes constant beyond the De
Broglie wavelength (~15 nm), it varies from material to material. (From Supasai, T. et al., Appl. Surf. Sci., 256,
4462–4467, 2010.)

confinement effect is predominant if particle size is less than the De Broglie wavelength
(DDB = 4πεοεrh2/μe2). The band gap of BaTiO3 approaches to only bulk value when particle
size is beyond DDB = 15 nm, whether a steep change in band gap below this critical limit
is found, as described in Figure 1.2, ‘a similar pattern of Figure 1.3b’. This is attributed to
minimize the particle diameter and their effective mass of electrons and holes, as described
in Equation 1.11.
Apart from the different behavior in nanoscale attribute to energy state spacing, it is
essential to encounter the surface phenomena including the increment of surface area to
volume ratio, surface atom density, and surface energy in order to understand the different
physical properties and adequate applications of nanostructured materials.

1.2.3 Surface Area to Volume

Surface area is nothing but the cumulative area of the exposed surfaces of an object. Theoretical
estimation of perfect cuboid, sphere, rod, and other geometry is easy to calculate, and one can
compare the influence of shape on surface area of identical volume of the different geometries
of same material. In fact, this surface-to-volume ratio for individual shape is different, and
thus there is chance of different degree of activity with other species. Interestingly, this basic
understanding can be established in consideration of smaller fragments of isotropic geom-
etry, say cube, has 24% larger surface area compared to the equal volume of sphere.
Let us consider a piece of cubic particle with having edge dimension of 1 cm and weight
1 gm. Imagine, gradual and uniform fragmentation of the same cube up to several small
cubes which consist of 1 nm (size of two atoms!) inside length and thus results in high
surface area and eventually high surface-to-volume ratio for identical 1 gm of material.
This surface area and their surface-to-volume ratio phenomena can be explained through
simple analysis (Table 1.1) and representative plot, as illustrated in Figure 1.3a.
The logarithm of surface-to-volume ratio increases near to four times compared to the
logarithm of surface area for cubic particles. The resultant surface area of 1 gm, 1 nm cubic
Nanoscale Ceramics 7

TABLE 1.1
Theoretical Calculation of Surface Area of Cubic Particle, and Effect of Particle Size on the Surface
Area and Surface-to-Volume Ratio
Cubic Log Volume of Specific Log Surface/
Particle Edge (Particle Particles Number of Surface Area (Surface Volume
(cm) Size) (cm3) Particles (cm 2 /gm) Area) (S/V) Log (S/V)

1 0 1 1 6 0.78 6 0.78
1 × 10−1 −1 1 × 10−3 1 × 103 6 × 101 1.78 6 × 104 4.78
1 × 10−2 −2 1 × 10−6 1 × 106 6 × 102 2.78 6 × 108 8.78
1 × 10−3 −3 1 × 10−9 1 × 109 6 × 103 3.78 6 × 1012 12.78
1 × 10−4 −4 1 × 10−12 1 × 1012 6 × 104 4.78 6 × 1016 16.78
1 × 10−5 −5 1 × 10−15 1 × 1015 6 × 105 5.78 6 × 1020 20.78
1 × 10−6 −6 1 × 10−18 1 × 1018 6 × 106 6.78 6 × 1024 24.78
1 × 10−7 −7 1 × 10−21 1 × 1021 6 × 107 7.78 6 × 1028 28.78

30 30

25 25

Log (Surface area/volume)

Log (Surface area)

20 20

15 15

10 10

5 5

0 0

0 −2 −4 −6 −8
(a) Log (Particle size)

100 7

6
Log (Number of surface atom)
Log (Number of total atom)

80
Percentage surface atom

60 4

3
40
2
20 1

0
0
−1
0 10 20 30 40 50 60
(b) Particle size (nm)

FIGURE 1.3
A representative plot for (a) surface area and surface/volume ratio, and (b) percentage surface atom and total
atom as a function of particle size. The details calculated data for the plot is tabulated in Table 1.1.
8 Nanostructured Ceramics

particle envisages equivalent a soccer ground (118 × 92 m) area. In this context, one can
understand why chopped potato softens faster than uncut one! Thus, when it comes to
material science, a single parameter that is particle size can have a noticeable impact on
properties of the material.
Fundamental material science defines macro-sized material properties depend upon its
chemical composition and atomic structure. The bulk properties of material are negligibly
associated with the surface atoms, as the number of surface atoms is quite less in compari-
son to that of core atoms. Hence, the properties of the bulk material are not very much
dependent on the surface atoms. Thus, the question is what benefit can be obtained due to
high surface-to-volume ratio? The answer is a dramatic increment in surface atom density
that results in surface energy due to formation of unsaturated bond and exposed atoms.
Section 1.2.4 illustrates how available surface atom density changes in consideration of
simple example of FCC metallic silver particle below 100 nm.

1.2.4 Surface Atom Density

How number of surface atoms enhances with nanoscale and thus surface atom density?
In order to understand this circumstance, a simple FCC metallic Ag has been considered
and calculated the total number and surface atoms with increment of dimension from 1
to 60 nm, thus surface atom density (ρs) defines the ratio of number of surface atoms to
total number of atoms. Let, total number of atoms N, so, Ntotal is being calculated by the
formula [6]:

N total = (1/3) 10p 3 − 15p 2 + 11p − 3  (1.12)

and their number of surface atom

N surf = 10p 2 − 20p + 12  (1.13)

where p  =  number of layers, assume consecutive layers are grown on reconstructed

spherical unit cell, and consider “p” = 1, 2, 3, 4, … 100, respectively. The equation for
total number of atom (Ntotal) is valid for p ≥ 1, however, Nsurf is more feasible when p > 1.
In the same time, the diameter of particle can be calculated by the equation D = (2p − 1)d,
“d” is the distance between the centers of nearest-neighbor atoms and, d = a/(2)1/2, where
a  =  lattice constant. Let, lattice constant for Ag, a  =  4.079  Å. Calculation in each step
provides three pieces of information on total number of atoms, surface atoms of each
individual particle, and percentage surface atom, followed by surface atom density, and
their logarithmic data are plotted with respect to particle diameter in Figure 1.3b.
A clear difference is noticed in between total number of atoms and surface atoms beyond
10 nm particles, whereas below 10 nm size, there is no significant difference that exists.
Indeed, such difference clearly predicts the availability of more number of exposed atoms
in nanoscale that eventually responsible for the change in different properties compared
to bulk. Thus, as we move toward lower dimensions, more entities are present on or near
surface than bulk. In fact, questions are coming to mind, how those surface atoms appear
and their consequences.
In bulk, valence of atoms is satisfied by its coordination number, whether surface
atoms have unsaturated bonds and lower coordination number compared to bulk entity
comprises higher energy, resembles to surface energy, and it would be discussed in
Section 1.2.5.
Nanoscale Ceramics 9

1.2.5 Surface Energy and Dangling Bonds

Nanoscale synthesis protocol follows two basic philosophies: top-down and bottom-up
approach. Nevertheless, bottom-up approach preferentially develops tailor-made shape
and morphology including 0D, 1D, 2D, or 3D nanoscale particles, where synthesis of such
confined growth by top-down approach is limited. Reduction in smaller particle size
facilitates new surfaces or crystal faces that involves high surface defects. In any synthe-
sis process, existence of unsaturated surface atom is common phenomena that result in
unsaturated (green circle) valences, refers to “dangling bond,” and experience an inward
acting force due to underlying atoms.
These surface atoms possess excessive energy as compared to bulk (orange circle)
known as surface energy. This is the (thermodynamically unfavorable) energy of making
“dangling bonds” at the surface, as illustrated in Figure 1.4. This surface energy is always
associated with surface, regardless of the type of bonding whether covalent, ionic, or non-
covalent. Every system wants to get rid of this excess energy or thermodynamically stable
by some means. In general, the surface energy is often denoted as “γ,” that is defined as
the free energy required to create a unit area of new surface of a material; so, γ = (δG/δA),
where G = Gibbs free energy and A = surface area. It implies, more surface energy attrib-
uted for smaller area, that is ‘NANO.’
This surface energy depends on available surface atoms, and thus it is very high pref-
erentially below 10 nm particles (Section 1.2.4). Again, consider the one centimeter cubic
particle, and cut into two equal halves, by ignoring the interactions of neighboring atoms,
the surface energy density or energy per unit area further can be represented as:

1
γ= N b ρs σ (1.14)
2

Surface atom: Unsatisfied vacancies

(Dangling bonds)

Bulk atom: All vacancies satisfied

FIGURE 1.4
A schematic representation of the bulk core atom (orange color) satisfied with coordination number, and unsat-
urated valence atom (green color), refers as dangling bond, responsible for surface energy. High S/V ratio com-
prises more unsaturated bonds; surface energy.
10 Nanostructured Ceramics

where, N b is number of broken bonds by forming new surface, ρs is surface atomic density,
σ is half of bond strength. This surface energy of each crystal plane is different due to pres-
ence of different number of broken bonds. Close-packed plane has the highest coordina-
tion number or closest neighboring atoms that comprise fewest dangling bonds, and thus
broken-bond model estimates the surface energy order for FCC γ(110)  >  γ(100)  >  γ(111),
but BCC γ(111) > γ(100) > γ(110) metals, respectively [7]. However, the surface energy per
unit area may alter this sequence. The crystal plane has different surface energies and
thus thoughtful synthesis parameter can effectively determine the possibility of preferred
plane growth and subsequent performance of nanoscale materials. In convention, a mate-
rial is thermodynamically more stable at its lowest Gibbs free energy, and it controls the
nuclei formation during synthesis of nanoparticles that in time related with surface energy
as well.

1.2.6 Gibbs Free Energy and Critical Radius

High surface-to-volume (S/V) ratio comprehends high surface energy that contributes
maximum Gibbs free energy of nanoparticles. A brief illustration of how Gibbs free energy
and surface energy per unit area result in the critical radius during synthesis of nanoscale
is discussed. Basic thermodynamics describe a new phase that appears either exceeding
the solute solubility limit or reduction in temperature below the phase transformation
point. Herein, this new phase says nanoparticle formation mechanism through wet chemi-
cal method is considered. Let, C is the concentration of solute, and Co is the solubility or
equilibrium concentration. The change in Gibbs free energy per unit volume of the solid
phase, ∆Gv, is dependent on the concentration of solute:

ln(1 + σs )
∆Gv = −k BT (1.15)
v
where, “kB,” Boltzmann constant, “T” process temperature, “σs” supersaturation of the
solution, i.e. (C−Co)/Co and “v” molar volume. Under this condition, no nucleation occurs
if σs = 0, whether a spontaneous and favorable nucleation occurs when C > Co, hence the,
Gibbs free energy per unit volume of the solid phase (∆Gv) is negative. Supersaturate solu-
tion possesses a high Gibbs free energy, thus the overall energy of the system is like to
reduce, that is the driving force to form new phase from the solution. Assuming a spheri-
cal nucleus of solid particle with a radius “r” develops from liquid phase, and this total
change of chemical potential is the summation of volume free energy (∆μv) and interfacial
energy (∆μs). So, overall Gibbs free energy (∆G) is:

4 3
∆G = πr ∆Gv + 4πr 2 γ (1.16)
3

where γ is the surface energy per unit area.

In order to favor the formation of nucleus, the process has to overcome critical
energy (∆G*) barrier, in other way the formation of critical radius (r*). It is only favorable
when d∆G/dr = 0. Under this condition, r* = –2γ/∆Gv; and ∆G* = [16πγ3]/[3(∆Gv)2]; and plot-
ted in Figure 1.5. Thus, with help of Equation 1.15, the

2γv
critical radius ( r ∗) = (1.17)
[k BT ln(1 + σs )]
Nanoscale Ceramics 11

Interfacial energy, 4πr2γ

ΔG∗

ΔG
J/cc r∗
Total energy

Volume free energy, 4/3πr3Gv

FIGURE 1.5
Theoretical representation of change in Gibbs free energy as a function of particle radius.

From Equation 1.17, one can reduce critical radius during synthesis either decrease
the required surface energy per unit area for nanoparticle or increase T and σs. Below
the nucleation of critical radius, ∆G is positive and dissolved back to the parent phase,
nevertheless, beyond critical radius, addition of further atom (r > r*) encompasses growth
followed by Ostwald ripening with time. This philosophy is effective for homogenous
nucleation, however, most often a system follows heterogeneous nucleation at prefer-
ential sites, such as phase boundaries or impurities like dust and requires less energy
than homogenous nucleation. At such preferential sites, the operative surface energy is
lower and results in reducing the free energy barrier and accelerating the rate of reaction.
Surface energy promotes advance nucleation sites because of variation of wetting phenom-
enon, and thus contact angle (θ) determines the ease of nucleation by reducing the energy
needed. A simple relation between ∆Ghete and ∆Ghomo can be expressed as Equation 1.18:

∆Ghete = ∆Ghomo . f (θ) (1.18)

where f(θ) = 1/2 + 3/4 cos θ − 1/4 cos 3θ.

Eventually, the nanoparticle synthesis protocol follows competitive nucleation and
growth process and results in different size distribution that facilitates surface energy
difference of particles and association together to form agglomeration and change the par-
ticle size distribution. With judicious selection of process parameters, one can control the
particle size distribution.

1.2.7 Cohesive Energy

Particle size influences the melting and Debye temperature, and both depend on cohesive
energy. Cohesive energy defines the amount of energy required to make free atoms from
crystal, and thus cohesive energy per mole [kJ/mol] is conventionally lower for nanosolid (Ens)
when number of free surface atoms is relatively high in nanosolids compared to bulk ones.
In consideration of Nsurf and Ntotal, the total cohesive energy (Etotal) is the result of both interior
and surface atoms. Hence, number of interior atoms is (Ntotal − Nsurf), and:

1
ETotal = Eo ( N total − N surf ) + Eo N surf (1.19)
2
12 Nanostructured Ceramics

where Eo is the cohesive energy per atom, so, Equation 1.19 becomes:

 N  (1.20)
Ens = E bs 1 − surf 
 2 N total 

where Ens AEtotal /N total and Ebs = AEo; A = Avogadro number. As cohesive energy and
melting temperature both describe the bond strength and follow the linear relationship,
the melting temperature of nanosolid (Tns) can relate with melting temperature of bulk
solid (T bs) and are represented as [8]:

 N 
Tns = Tbs 1 − surf  (1.21)
 2N total 

Debye temperature (θ) describes the highest temperature achieved due to single mode
of vibration or in another way beyond this temperature, the thermal vibrations are more
important than quantum effect. In consideration of Lindemann criterion on melting for
small particles, a crystal prefers to melt when the root mean square displacement of atoms
in the crystal exceeds a certain fraction of the interatomic distance [9]. Under this situation,
the simple relation between Debye temperature of nanosolid (θns) and Debye temperature
of bulk solid (θbs) can be represented as analogous to Equation 1.21 [10]:
1/2
 N surf  (1.22)
θns = θbs 1 −
 2N total 
Apart from size phenomenon, identical material may have different cohesive energy and
melting temperature because of different shape and morphology. In this context, simple
3D (spherical), 2D (thin film), and 1D (nanowire) morphology have been considered
and highlighted their competitive values, as every size and shape have definite inter-
est of application. Let, “d” is the diameter of the atom, and D is the diameter of spher-
ical solid, then Ntotal is expressed as the volume ratio of nanosolid and atom, and thus
Ntotal = (πD3/6)/(πd3/6). Similarly, total surface area of nanosolid is 4π(D/2)2, and the con-
tribution of each surface atom to surface area of nanosolid is the area of the highest circle
of the atom, π(d/2)2, so, Nsurf = (4πD2/4)/(πd2/4), so the ratio of Nsurf/(2Ntotal) = 2d/D and
the Equations 1.20–122 becomes:

 2d 
Ens = E bs 1 − (1.23)
 D 
 2d 
Tns = Tbs 1 − (1.24)
 D 
1/2
 2d 
θ ns = θ bs 1 −  (1.25)
 D

Confined nanofilm (2D) with thickness (h) and nanowire (1D) with diameter (Ø)
and length = l of same atomic diameter “d” provide the ratio of Nsurf/(2Ntotal) is 2d/3h and
4d/3Ø, respectively. From this information, the cohesive energy, melting temperature,
and  Debye temperature of 2D and 1D nanostructured materials can also be calculated.
Nanoscale Ceramics 13

−2.0

Cohesive energy (×100 kJ/mol)

−2.2

−2.4

−2.6

−2.8

−3.0
0 10 20 30 40 50
Particle size, D (nm)

FIGURE 1.6
Variation of cohesive energy with respect to particle size of Ag. (From Zhu, Y. F. et  al., Appl. Phys. Lett., 95,
083110, 2009.)

In consideration of Ebs  =  −295.9  kJ/mol, the variation of cohesive energy with respect to
particle size of Ag, preferably below 50 nm, is illustrated in Figure 1.6. A dramatic change
is noticed beyond 10 nm and followed consistent plateau when particle size is bigger than
40 nm, this is further well matching for both experimental and theoretical concepts [11].
The aforesaid fundamental concept is also true for ionic bonding, where the surface
atom has lower binding energy than the bulk and contributes lower cohesive energy
per mole.

1.2.8 Lattice Parameters and Strains

Small nanoscale consists of high percentage free surfaces and comprises lattice contraction
induced by high surface-to-volume ratio. In mechanical point of view, hydrostatic pressure
on the surface induced by intrinsic surface stress results in lattice contraction or lattice
strain. Consider a perfect liquid sphere having diameter 2R, that experiences excess pres-
sure ∆P toward inside the sphere because of curvature, and thus Laplace relation depicts:

∆P dV = γdA (1.26)

or

2γ
∆P = (1.27)
R
where dV (V = 4/3πR3) is the volume change corresponding to a change dA (A = 4πR2)
in the area of the droplet, and γ is the surface energy per unit area. In this context, the
nanosolid experience extensive elastic strain (ε), and thus encounters this phenomenon to
understand and evaluate the influence of particle size on the resultant lattice parameters.
The pure metallic nanoparticles experience contraction with decreasing particle size,
however, above critical size limit, the lattice parameters do not vary with particle size [12].
14 Nanostructured Ceramics

Usually, the increment of surface energy of nanoparticles inclines to contract their sizes by
distorting their crystal lattice elastically, although it is very small compared to the entire
particle size. Thus, the cumulative energy (F) variation is the result of both increased surface
energy and increased elastic energy. Taking the equilibrium condition, and minimizing the
total energy at dF/dε, the elastic strain becomes:

1
ε= (1.28)
1 + ( πG/2 γ 0 ) D

where, ε = elastic strain, D = particle diameter, γo = surface energy per unit area at room
temperature, G = shear modulus of material. Interesting to note that the lattice strain
increasing with decreasing particle size, whereas above critical size, say 10 nm, the lattice
parameter of Ag does not contract anymore [13]. In ideal crystal lattice, the parameter
contraction is proportional to the particle diameter, so:

∆a ( 1 − ε ) D − D (1.29)
=
ao D

Elastic contraction results in D − εD and ∆a = aparticle − ao, where aparticle and ao are the lat-
tice parameter of nanoparticle and bulk material, respectively. Considering Equations 1.27
through 1.29:

∆a 1
=− (1.30)
ao 1 + MD

where M = πG/(2γo), and both estimation of G and γo encompass a correlation with percent-
age contraction with respect to particles size, and such behavior for Ag is represented in
Figure 1.7.
The degree of contraction may vary with respect to particle morphology. This aforesaid
relation is valid within a particle range of 1–15  nm of pure metallic spherical nanopar-
ticles that experience more strain compared to metal oxide particles, however, this con-
cept fails to predict the contraction behavior of 1D or 2D morphologies. However, some
particles exhibit dilatation of lattice parameters with smaller particle size because of

−0.5

−1.0
Δa/ao (%)

−1.5

−2.0

−2.5
0 4 8 12 16 18 20 22 24 26 28
Particle size, D (nm)

FIGURE 1.7
Contraction behavior of FCC Ag with respect to nanoscale particle size. An optimum ~10 nm particle size is
noticed in this case. (From Wasserman, H. J. and Vermaak, J. S., Surf. Sci. 22, 164–172, 1970.)
Nanoscale Ceramics 15

pseudomorphism, substitution of oxygen, carbon, and hydrogen atoms [14]. Recent

research shows interesting experimental data and their explanation on ceramic oxide (e.g.,
Ceria, CeO2), emphasizing better insight of this phenomenon. Availability of oxygen atom
and vacancy alter the oxidation state of Ce in between Ce3+(1.034Å) and Ce4+(0.92Å) that
expedite different catalytic properties. In a recent study, both lattice parameter (α) and
elastic strain (ε) of nanocrystalline CeO2 enhances with reduction of particle size (D) dur-
ing synthesis through the wet chemical method [15]. This phenomenon can be explained
in the consideration of crystal structure of CeO2. The pure CeO2 has fluorite structure,
where Ce4+ surrounded by eight O2− ions, but soft chemical reaction facilitates the reduc-
tion to Ce3+ and creates oxygen vacancy that leads to distortion of local symmetry, enhanc-
ing the resultant bond length of Ce – O, and overall lattice parameter, but loss of oxygen
ion in nanoscale (<3 nm) results in high strain. However, extensive experimental data and
theoretical simulation on the effect of particle size and shape on the lattice parameters
and lattice strain for different crystal structures and materials including metal oxides,
perovskites, carbides, and nitrides are expected to explain the strain assisted phenomena
like sintering to cell interaction with nanoparticles.

1.2.9 Frequency
Every motion and position can be predicted exactly by classical mechanics, and this is
an inevitable consequence for larger objects. However, Newton’s revelation is occasion-
ally insufficient when object is very small, preferably nanoscale. This group of material
exhibit some weird and unusual phenomena that are advantageous for the new generation
nanotechnology. The classical mechanics cannot explain their behavior, rather quantum
mechanics can do it. Thus, oscillation is most concerned in consideration of motion of
small-scale objects. An oscillation or vibration follows repetitive motion in time with a
particular frequency that depends on the mass and stiffness of the object. Prior to explain-
ing such phenomena, let us consider a simple ball with having mass “m” is attached to a
spring with spring constant of “k.” This spring follows simple harmonic motion when it
is slightly displaced in the direction of “x” from its equilibrium position, and this force
F = −kx. From Newton’s 2nd law of motion:

 d2x  (1.31)
F = m  2  = − kx
 dt 

So,

d2x k
= −   x = − ω2x (1.32)
dt 2 m

The angular frequency ω(rad/sec) = 2πf = (k/m)1/2  represents sinusoidal behavior of the

previous equation with expression of x = A cos(ωt + ϕ), where A is the amplitude of oscil-
lation, and ϕ is the phase of oscillation. In the same time, the frequency of oscillation ‘f’ is
the inverse of the oscillation period “τ.” Thus:

1
1  k 2
f=   (1.33)
2π  m 
16 Nanostructured Ceramics

The resultant or effective mass is meff = 0.24 m for rectangular beam when beam is sub-
jected to fix in one end. The stiffness further depends on the dimension (length-L and
width-w, thickness-t) and elastic modulus (E), for an example, the stiffness of a rectangular
beam (kbeam) is:

Ewt
k beam (1.34)
4L3

Nevertheless, this frequency is very high for nanoscale objects and enables to detect and
like to store the information rapidly (may be in nanosecond!) in the world of miniaturiza-
tion devices. In order to support this phenomenon, let’s consider a 10 μm long, 0.5 μm width
and 0.2 μm thin Si beam having density (ρ = 2.33 g/cc) and elastic modulus (E = 110 GPa)
is attached in one end, and it enables to switch over within nanoseconds from downward
to upward direction during vertical vibration [16]. Thus, frequency of 1D nanoscale objects
inversely proportional to two important parameters mass and length of the wires, whis-
kers, or tubes, etc.

1.2.10 Velocity and Motion in Fluid

Take a spherical (5  mm diameter) small iron (ρFe  =  7.1  [Link]−3) bearing ball and allow
to fall under gravitational force within a jar of water (viscosity η = 0.89cP), and, hence, it
will slowly fall down under in a particular terminal velocity and direction. Now reduce
the particle size from millimeter to micron and, finally, nanoscale, and what will be the
expected velocity and motion? Importance of such small-scale object is very important
in consideration to design micron size nanorobots for imaging and surgery or make sus-
pended drug-loaded nanoparticles for targeted medication. While discussing this aspect,
it is worth to remember the influence of surface by volume ratio of nanoscale particles
that expose and adsorb more molecules compared to bulk entities. Furthermore, particle
surface roughness and annular space dimension may alter the velocity and motion of the
solid objects during flow in a fluid. Either inertial force or viscous force is the predomi-
nant factor to control the velocity of fluid. In the same fluid, velocity and characteristics
may change due to the presence of foreign particles. The ratio of such forces is known as
Reynold’s number (Re), it is nondimensional quantity and defined by:

inertial force ρvD

Re = = (1.35)
viscous force η

where, ρ = density of the fluid (kg/m3), v = characteristics velocity (m/s), D = characteristics

diameter or dimension of the object (m), η = coefficient of the dynamic viscosity (N.S/m2).
It seems that a different degree of horizontal movement is expected when 2 m long human
swims in water (ρ = 1000 kg/m3, η = 0.89 × 10−3 N s/m2) at the speed of 1 m/s compared
to 2 μm long bacteria at 10 μm/s. A distinct difference Re in the order of 1012 is observed
in two cases that encompass the larger object dominates by inertial momentum, whereas
smaller objects prefer viscous force only. In this context, one can think about to equate the
Reynold’s number by alteration of density, velocity, and viscosity, however, daily activity of
human life at very low Reynold’s number is tough, but nanoscale prefers! In order to esti-
mate the settling velocity of nanoscale object, an interesting force balance among viscous
drag force (Fv), buoyancy of liquid (Fb), and gravitational force (Fg) can be balanced, and it
depicts:
Nanoscale Ceramics 17

Fv + Fb = Fg (1.36)

where Fv  =  6πRvsη; F b  =  ρfVpg; and Fg  =  ρPVpg; in which R  =  radius of particle (D/2),
vs = settling velocity, ρf = fluid density, ρP = particle density, Vp = volume of the particles,
and g = gravitational acceleration. Substituting the parameters and solving the Equation
1.36, the following relation can obtain, where the settling velocity is square proportional
of radius (R) of the particle:

2R 2 ρ f  ρ P 
vs =  − 1 g (1.37)
9 η  ρf 

In consideration of the previous equation, 0.2  μm, Fe3O4 magnetic particle

(density = 5.6 g/cc) experience settling velocity of few micron/sec in water and main-
tain suspension more than a day when crossed 30  cm long columnar passage. The
earlier equation is explicit that the velocity is proportional to the square of the diam-
eter of particles and enhance the retention time to travel that further increases the
probability of the motion across jig jag path, known as Brownian motion. This particle
motion can be represented by Gaussian distribution, where the diffusivity (D’) of par-
ticle is inversely proportional to the particle radius (R), and described as [17]:

kT
D′ = (1.38)
6πηR

k = Boltzmann constant, T = temperature, R = particle radius, η = fluid viscosity. However,

three-dimensional nanoscale particle motion is a complicated issue and need to solve the
differential equations with concern of both diffusive motion and viscosity of the fluid in
describing the particle’s motion. Discussed data and plots imply both metal and ceramics
have several different physical properties when size reduces in bulk, and thus nanomate-
rials are an interesting choice to fabricate components for different horizons. In the per-
spective of book content, however, a brief classification and synopsis on the ceramics are
emphasized in consecutive sections.

1.3 Classification of Ceramics

Materials selection, and understanding their properties, is often a challenging task, and
argument is there to select either metal or ceramic or polymer for structural and functional
applications. Nevertheless, it is indeed that each and every material has different degree
of advantages and disadvantages to target better and extensive performance of a specific
application for prolong duration, some are highlighted in Table 1.2. A brief material clas-
sification along with the influence of nanoscale for both traditional and advanced ceramics
is illustrated in Figure 1.8.
Metals have characteristics like a decent mechanical strength, hardness, high thermal
and electrical conductivity, ductility, etc. These are often prone to corrosion damage, as
the metals react with their environment to re-form those compounds. They have a very
good property to be shiny due to nonlocalized electron clouds on the surface, which reflect
18 Nanostructured Ceramics

TABLE 1.2
Comparative Properties of Metal, Ceramic, and Polymers
Properties Metals Ceramics Polymers

High temperature strength (MPa) Moderate High Very poor

Ease of fabrication Good (ductile) Poor (brittle) Very good (ductile)
Conduction (Thermal or electrical) (W/m.K or S/m) Good conductor Insulator Insulator
Resistance to chemical attack (mm/year) Poor Inert Inert
Dimensional stability (stiffness) (N/m) High High Poor
Density (gm/cc) Very high Low Very low
Lustre (GU) Excellent Poor Poor
Elastic modules (MPa) High Very high Low
Melting point (°C) Moderate High Low
Heat capacity (J/K) High Moderate Low
Hardness (GPa) Moderate High Low
Toughness (MPa) High Moderate Low
Coefficient of thermal expansion (K−1) Moderate Low High
Compressive strength (MPa) Moderate High Low
Tensile strength (MPa) High Moderate Low
Dielectric constant (unit-less) Infinity High Very low
Magnetism (T) High Low–high Very low
Band gap (eV or J) Very low Moderate High
Wear rate (mm3/Nm) Moderate Low High
Coefficient of friction (unit-less) High Low Very low

Metal Ceramic Polymer

Traditional Advanced
ceramics ceramics

Refractories Structural

Whiteware Electronic
Nanostructured
Cement Magnetic
ceramics

Abrasives Optical

Glass Bioinspired

Pure and stoichiometric compositions

Precious processing protocols
Preferential surface controlled properties

FIGURE 1.8
Classification of materials in specific ceramics. Nanostructured ceramics has multivariant scope to develop
both traditional and advanced ceramics, although precious control demands to achieve the desirable properties.
Nanoscale Ceramics 19

back the light rays. To the contrary, the ceramics are generally nonmetallic, inorganic com-
pounds, preferentially oxides, nitrides, and carbides that either exist in nature or are syn-
thetic, preferentially at high pressure and/or temperature [18].
Most of the ceramics have electrical and thermal insulation, high temperature resis-
tance, and corrosion resistant behavior. In comparison to metals, these materials have
lower electrical and thermal conductivity, higher stiffness, good resistance to corrosive
environments, and lower fracture toughness, but exceptional thermal conductivity is
also noticed, for example, some nonoxide ceramics such as SiC [19]. Polymers are gener-
ally organic compounds. This group of material has very large molecular structures,
consisting of unit structures known as monomers. Usually, these are light weighed, low
density materials, and not stable at high temperatures. From a day-to-day activities point
of view, polymers are mostly used materials due to their easy moldability, in turn, can
be formed into complex shapes. Their strength, stiffness, and melting temperatures are
generally much lower than those of metals and ceramics. Their lightweight, low cost, and
ease of forming make them the preferred material for many engineering applications.
Among all materials, prime emphasize is given to ceramics, and this can be further clas-
sified into two types: traditional ceramics and advanced ceramics. High purity and surface
chemistry, precious stoichiometric composition, and processing protocol are more popular to
fabricate the advanced ceramics compared to traditional ceramics, and thus component cost
is relatively higher in the former case. However, recent trends are converging to synchronize
the traditional ceramics through nanoscale materials. Thus, it is worthy to highlight about the
gigantic potentiality of nanostructured ceramic in both traditional and advanced ceramics.

1.3.1 Traditional Ceramics

From ancient age, the use of traditional ceramics in preference clay-based components
and their multimode uses are well known to our society. In advance, the traditional
ceramics including refractories, whitewares, tiles, cement, abrasives, and glasses have
significant interest and regular use for socio-economic benefit. Apart from the use of
conventional raw materials and fabrication protocol, insertion of nanoscale materials is
now a new horizon of research to enhance the performance and user-friendly of such
traditional ceramics.
Literally, refractories are the ceramic materials that can withstand very high temperature,
have high thermo-mechanical strength, and have high corrosion resistance. Several
shaped and unshaped refractories lining are essentially required for the metal and alloys
manufacturing vessel. Despite conventional refractories, high surface area nanoscale carbon
particles facilitate synergetic strengthening effect and reduce the carbon content in shaped
refractories, and, thus, results enhance slag resistance and low carbon pick-up during
manufacturing of steel [20]. Recently, nanobonded refractory castable is also attempted to
develop unshaped refractories through using nanocolloidal silica mullite and alumina [21].
Whitewares are often referred to as the triaxial bodies owing to clay, quartz, and feld-
spar. This broad class of ceramic products is favorably white to off-white in appearance,
but not necessarily white always. Ware is the technical name for a ceramic object that is
sold in commerce. These includes porcelain, sanitary ware, earthenware, stoneware, bone
china, and vitreous tiles. Regardless of the decorative and aesthetic appearance, research-
ers have tried photocatalytic nanotitanium dioxide (TiO2), anatase-coated functional tiles
to make self-cleaning, self-sterilizing, and air purification under irradiation of ultraviolet
sun light [22].
20 Nanostructured Ceramics

Cements are the binding agent generally used for the building and construction pur-
pose, having a composition of calcium silicate, referred as Portland cement. Another
type of cement is also there which can be used at a very high temperature, particularly
used in refractory industries, known as refractory cement, and generally has a compo-
sition of mixture of various calcium aluminates. However, uncontrolled microvoids in
the cement matrix of cementitious material drastically reduce the load-bearing capacity
because of weak interface between aggregates and mortar that induces microcrack ini-
tiation and promote crack propagation. It, therefore, becomes imperative to reduce the
voids in the mortar and promote a better hydration degree of cement. A method that has
been proven to be effective is the use of nanocement particles. The smaller cement par-
ticles result in an effective hydration process and create smaller ettringites and calcium
hydrates [23].
Abrasives are preferentially ceramics that can withstand very high mechanical abrasion
without any wear and tear. These are used to cut, grind, and polish other softer materials
and shape or finish a work-piece through systematic and precious grinding and polishing.
Nanoscale abrasives can reduce the average roughness of surface up to the extent of a few
nanometers. In this aspect, Saint-Gobain develops a wide range of nanoabrasive slurries
that are capable to withstand outstanding polishing speed and excellent surface finish on
a variety of substrates [24].
Glass can be defined as amorphous solid produced by the cooling of molten state of
material, where the cooling rate should be faster compared to the crystallization time of
their atoms. In earlier days, glass was considered as ceramic material, but now-a-days with
the inventions of science, metal and polymer can also be transformed to metallic glass and
amorphous-polymers in a suitable heating profile. Interestingly, nanocrystallized trans-
parent glass provides very high hardness and strength compared to ordinary glass or even
standard crystallized glass results much harder than ordinary glass. High temperature
up to 1800°C and prolonged time of more than a day prefers molecular alignment of the
glass on a nanoscopic scale and results in hardening [25]. Furthermore, the advancements
of nanotechnology applied in the field of glass technology are resulting in smart glasses,
self-cleaning glass, etc.

1.3.2 Advanced Ceramics

From prehistoric time to modern technical era, humans are dependent on ceramics.
This demand is more and more in the recently advanced technological world. With
advancement of technology, the understanding level of composition, structure, prop-
erties, and application of ceramics has been improved in wide horizons. These assists
help to grow their applications in space, automobiles, electronics, renewable energy,
environment, paints, textile, water filtration, food storage, medication, etc. Thus,
advancement of ceramics leads us to a smart life with progressive models in various
interdisciplinary broad groups, like structural ceramics, functional ceramics, and bio
ceramics. In convention, structural ceramics is predominately designed for load bear-
ing application, although ceramic hip prosthesis is an example of structural ceram-
ics as well as bioceramics. So, one successful material has to cover different range of
criteria.
Moreover, functional ferrite particles are being used for cancer treatment and imag-
ing, and thus researchers are encountered as bioceramics as well. However, all structure
Nanoscale Ceramics 21

ceramics like Si3N4  piston, zirconia scissors, alumina cutting tool insert, and so much
more are no longer related to bioceramics. In preference, functional ceramics including
magnetic, dielectric, optical, photocatalytic, mechanoelectrical and more have versatile
applications and enormous potential in recent days. Although, one can debate on this
classification, however, any modern advance ceramics that are not included in tradi-
tional ceramics will get nearer within this class of advanced ceramics. It is commend-
able to mention that current research progress has enough upcoming thrust to convert
the traditional ceramics to advanced mode by the judicious use of nanomaterials and
nanotechnology.
Interestingly, ceramics exhibit extensive range of properties including conductors (In2O3,
SnO2, YSZ, etc.), semiconductors (WO3, ZnO, TiO2, BaTiO3, CoFe2O4, etc.), and insulators
(Al2O3, ZrO2, Ca10(PO3)6(OH)2, etc.) in variation of crystal structure and dimension. In addi-
tion, the composite materials containing nanoceramics have captured attention of many
technologists. By inclusion of nanostructured ceramics in varying volume fractions, the
properties of the composite materials can be tailored well, resulting according to the
desired application fields. In order to develop dense ceramics for advance application, it is
necessary to consider the granulometry and their packing density that eventually reflects
in density and porosity. However, the controlling over microstructure is desired for par-
ticular applications. These materials also cover in order to understand the structural, func-
tional, and biological applications in the perspective of energy, environment, and health
issues (Figure 1.9). Prior to analyzing these burning zones, a brief understanding on the

Nanostructured ceramics:
Case studies
characterization and analysis

Energy
Material Solar energy to electrical energy
characterizations H2 gas by water splitting
Solar energy harvesting
Electrical energy by H2 gas
Mechanical to electrical energy harvesting
Surface and suspension
phenomena
Environment
Sun light protective smart glass
Pollutant dye degradation
Photocatalytic Mechanically induced water treatment
phenomena Purification of high salinity waste water
Self-cleaning coating

Magnetics and Health

piezoelectrics Dental ceramic blank
Femoral head for hip prosthesis
Porous bone scaffold
Cancer therapy
Ferrofludis for hyperthermia
Mechanical properties

FIGURE 1.9
Bird-eye view of the book content in the perspective of characterization and analysis of nanostructured ceramics.
22 Nanostructured Ceramics

different characterizations of nanostuctured ceramics, surface and suspension phenom-

ena, photocatalytic behavior, magnetics, piezoelectrics, and mechanical properties have
been discussed in consecutive sections, followed by case studies that are enlightened to
understand the importance of the subject and future development.

1.4 Rationale of Energy, Environment, and Health Materials

Nanotechnology has become the most demanded arena that is providing us a blessed life-
style for having the potential to improvise renewable energy sources, make pollution free
environment, and advance medication. Energy storage has been greatly enhanced by uti-
lizing nanomaterials as both energy sources and energy storage. Nanomaterials are also
being intensely used for the conventional photovoltaic cells. In the case of silicon crystal
solar cells, an anti-reflecting coating made of nanomaterials is adhered for higher light
yield that ultimately gives a better efficiency. It leads to a path to develop other alternative
solar cells, consists of silicon, copper, selenium, indium, or gallium, and many more with
very high absorption coefficient and flexibility in use. An innovative recent development
in energy application is organic solar cells. It is a two-type, dye-sensitized solar cell con-
sisting of liquid electrolyte and polymer solar cell made of solid electrolyte [26]. In fact, the
latter is more flexible to fabricate for different modes of utility including military tents,
bag packs, and portable electronic devices and so on, but conversion efficiency is less
compared to counterpart dye-sensitized solar cell. Apart from the invention in renewable
energy sources, batteries, super-capacitors, and nanocatalyts are tremendously growing
in energy sectors. The gift of nanotechnology does not end at this. It has also provided
us safe and effective water purification, filtration, and desalination through cheap and
portable systems, which can lead the world into a better future where everyone will have
possibility of their drinking water resources. In this aspect, several nanomaterials are
seeking attention, for example, TiO2, BaTiO3, ZnO, WO3, etc. as effective adsorbents and
nanoscale photocatalyst to remove contaminants from the waste water of textile indus-
tries through several mechanisms. Nanosilver impregnated ceramic filters have already
marketed due to their anti-bacterial and anti-viral action, for example, the nanosilver is
used in infant soaps and many more cosmetic products to avoid anti-bacterial treatment.
Synthetic biomolecules are better known as nanomedicine and have massive opportunity
for unprecedented breakthroughs in medicines to damage monitoring, repairing, con-
struction, and immune human biological systems at molecular level. A different class of
synthetic nanoparticles (using as direct) and nanostructured bulk ceramics (as indirect
application of nanoparticles) may be used as a bridging material within nanoscience and
nanotechnology that eventually resolve different successive applications including drug
delivery, medical imaging, cancer treatment, porous scaffolds, bioimplants, etc. In theo-
retical perspective, bottom-up nanomaterial synthesis resembles a natural phenomenon
and thus controls synthesis, and device fabrication can target more precise and effec-
tive components. Thus, successive synthesis materials and their judicious selection pro-
vide renewable energy, clean environment, and effective medical treatment that in due
course are beneficial to maintain healthy life for ourselves and next generation as well. In
brief, this class of materials research is rationalized in the view of both socio-economic
advantages.
Nanoscale Ceramics 23

1.5 Handling and Ethical Issues

Development of nanoscience and, hence, nanotechnology is like a double-ended sword.
Undoubtedly, it has the capability to enhance the status of human life. At the same time, it
can destroy its origin, if not used wisely. Miniaturized electronics and molecular machines
sound amazing, but it also arises many potential threats to mankind by violation of basic
human rights. Molecular microphones and cameras can peep into our freedom and pri-
vacy. Unregulated use of nanotechnology leads to issues related to health, safety, social,
philosophical, environmental, educational, and other legal issues. Nanoethics is a dis-
cipline which deals with the study of societal and moral implications of advances in
nanotechnology and handling of such enormous advancements without disturbing the
universal balance. It provides a set of guidelines that should be followed while using these
nanomaterials. Issues that nanoethics takes into consideration are broadly classified as:

1. Health and safety issues

2. Societal and philosophical issues
3. Environmental issues
4. Educational issues
5. Other issues (moral and legal etc.)

Thus, proper handling of nanomaterials involves:

• Warning signs at the entrance of labs using nanomaterials

• Labeling of storage containers
• Identification of people who are potentially exposed to nanoparticles and haz-
ardous equipment; provide them adequate medical care regularly and necessary
nanosafety training
• People working with nanoparticles may inhale them or get them on their skin and
that may be carcinogenic or cause dermal issues, and, thus, we need to protect
them from skin disease

Usually, the influence of nanoparticles on human body can be done three ways:

1. Inhalation: Gases and vapors are the most common substances, although inhaled
mists, aerosols, fine dust in preference nanoparticles, nanoobjects, their agglomer-
ates, and aggregates may directly injure the pulmonary epithelium at various lev-
els of the respiratory tract, leading to a wide range of tissue damage and disorders
from tracheitis and bronchiolitis to pulmonary edema. For example, silicosis is a
common disease for industrial workers who are frequently exposed to nanoscale
silica-based particles [27].
2. Dermal exposure: Skin comprising of epidermis and dermis, wherein, hair follicles
and sweat glands provide pathways across these layers and peripheral blood flow-
ing into the dermis. Intact stratum corneum (protective epidermis layer) provides
an effective barrier against viruses, bacteria, and atmospheric toxic components.
Although, this barrier is not absolutely impervious and theoretically very small
24 Nanostructured Ceramics

particles can diffuse across the stratum corneum via cellular and/or intercellu-
lar pathways. The damaged barrier can facilitate permeation of foreign particles
through skin. For example, the subchronic skin exposures to TiO2 (in sun pro-
tection cosmetics) could induce inflammation of the epidermis, leading to effects
such as focal parakeratosis and spongiosis, whereas chronic exposures to TiO2
may accelerate skin aging [28].
3. Ingestion: Use of biomedicine made of polymeric, solid lipid, hydrogels, metal, and
ceramic nanosystems are growing exponentially, as these enhance the treatment
efficacy and reduce the side effects. However, unwanted ingestion of nanoparticles,
overdose, and noncompeting nanomedicine may be the reason of gastrointestinal
diseases that affect any part of the gastrointestinal tract including acute, chronic,
recurrent, functional disorders, or liver damage [29]. Thus, the parameters such as
shape, size, surface chemistry, and geometry of nanoparticles are also important to
encounter in the designing of a nanocarrier.

The handling of nanomaterials and careful utilization is a civic concern during synthesis
of nanomaterials and manufacturing of nanodevices.

1.6 Concluding Remarks

The last two decades continuous advent in spectroscopic and imaging technique provides
us deeper insight on how small object functions in the atomic scale and these up growing
approach allowing quantum level understanding of materials. Combined with advanced
physics and chemistry, scientists have been enabled to develop continuous nanostructured
products consisting of unique properties, often tailored to meet specific applications in
diverse areas such as agriculture, information technology, defense, energy (harvesting,
conversion, and storage), environment, medicine, etc. Despite existence technologies, we
common people consume fresh air, water, food, medicine, energy, wood, and minerals
in our daily lives, as well as cropping food, pumping groundwater, harvesting wood,
mining minerals, and burning fuel exhaust our resource base and produces pollution.
In fact, this trend turns exponentially as population is highly correlated with consump-
tion of energy, domestic water, and medicine, as when diseases increasing day to day in
a polluted atmosphere. Resource use and their impact in environment are critically mea-
sured by the energy consumption. This causes increasing prevalence of chronic diseases
and tissue damages that contribute toward the increase in total healthcare expenditure on
medicine and medical devices. Because of our continuous intervention, either natural energy
resources are decreasing or water getting polluted that gradually asks for more dependency on syn-
thetic medicine, and thus nanotechnology is in upfront to supply low cost renewable energy, protect
environment, and cure critical health disorder by several classes of nanomaterials. Among mate-
rial worlds, nanostructured ceramic oxides encompass astonishing properties and are opening up
attractive horizons for these highlighted and challenging applications. In this context, a
brief discussion and understanding on the different material characterization and their
analysis are highlighted in Chapter 2.
Nanoscale Ceramics 25

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