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Junichi Hojo Editor
Materials
Chemistry
of Ceramics
Materials Chemistry of Ceramics
Junichi Hojo
Editor
Materials Chemistry of
Ceramics
Editor
Junichi Hojo
Faculty of Engineering
Kyushu University
Fukuoka, Japan
ISBN 978-981-13-9934-3 ISBN 978-981-13-9935-0 (eBook)

https://doi.org/10.1007/978-981-13-9935-0
© Springer Nature Singapore Pte Ltd. 2019

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Preface
Inorganic chemistry is based on the understanding of various elements on the Earth,

and the wide variety of functional materials have been created by chemical design
starting from atoms or molecules. They are extensively used as essential and crucial
matters in our life and industry activities and have also contributed to the develop-
ment of new fields of environment, energy, informatics, biomaterials, and so
on. Ceramics are typical inorganic materials. They have made a widespread evolu-
tion by generation of new substances, innovation of new technologies, and precise
design of structure and morphology. The concept of material chemistry is a key for
production and utilization of practical ceramics. This book introduces a comprehen-
sive content from fundament to application on the backbone of inorganic synthetic
chemistry and solid-state chemistry.
Ceramic industries have advanced from traditional ceramic manufactures: pottery
and porcelain, refractory, glass, and cement. They are produced by firing process
using kiln. The raw materials are natural silicate compounds. Silicates are composed
of silica, alumina, alkaline oxide, and alkaline earth oxide and easily mined on the
Earth’s crust. The advantage is the low melting point. Therefore, sintered ceramics
and melted glasses do not require a very high temperature. Meanwhile, new ceramics
have developed using artificial raw materials during the past half-century. Industrial
new ceramics seem to start from electric insulator. Ceramic insulators are superior in
mechanical strength and insulation performance to suspend high-voltage electrical
power lines. New ceramics mean the usage of new substances and compounds.
Oxides are typical ingredients of ceramics, but highly pure oxides are required.
Non-oxides such as nitride, carbide, and boride have high strength and thermal
stability but are naturally not afforded. Various inorganic compounds can be made
by a combination of numerous elements in binary, ternary, and multiple systems,
leading to appearance of a variety of electromagnetic devices. Fine ceramics aim at
new and high function based on material design, that is, homogeneous composition,
fine microstructure, and morphological control such as nanoparticle, nanosheet,
nanofiber, etc. Such a trend of new materials has induced high-pressure and high-
temperature technologies, or new synthetic methods like chemical vapor deposition
v
vi Preface
(CVD), sol-gel technique, etc. As a result, many kinds of ceramics have been
practically applied as high-temperature structural material, mechanical part, cutting
tool, semiconductor, dielectric, magnetic device, optical fiber, artificial bone, and
so on.
Ceramic structures are classified into single crystal, polycrystal, and amorphous
crystal/glass. Single crystal has a regular arrangement of atoms in whole body.
Amorphous crystal and glass have no long-range regular arrangement with random
atomic bonding. Polycrystal is an aggregate of small crystalline grains. Since most of
ceramics are fabricated by sintering of raw powder, they are obtained in polycrys-
talline form. Even by homogeneous processes (CVD, sol-gel), the final products are
mostly polycrystalline. Chemical design means the synthesis from atomic or molec-
ular level through chemical route and the intentional control of microstructure and
morphology toward desirable properties. Thus, we need the basic knowledge in
chemical synthesis, crystal structure, and physical and chemical characteristics of
solids to establish the practical technologies for functional material design. This
book describes the structure and synthesis of ceramics in the anterior half and then
the practical functions of ceramics in the posterior half. The last organic-inorganic
hybrid is a new scope beyond the category of ceramics. It is our great pleasure if all
of the readers understand what ceramics are and how we can use it. Please create the
future ceramics for the next generation.
Fukuoka, Japan Junichi Hojo

November, 2019
Contents
1 Crystal Structures of Inorganic Materials . . . . . . . . . . . . . . . . . . . . 1

Junichi Hojo and Miki Inada
2 Phase Equilibrium and Phase Diagram . . . . . . . . . . . . . . . . . . . . . . 23
Junichi Tatami
3 Solid State Reactions and Sintering . . . . . . . . . . . . . . . . . . . . . . . . . 45
Satoshi Tanaka
4 Powder and Thin Film Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Toshinobu Yogo
5 Chemical Functions of Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
Shu Yin and Tsugio Sato
6 Biological Functions of Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
Masakazu Kawashita
7 Mechanical Properties of Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . 133
Junichi Matsushita
8 Electromagnetic Properties of Ceramics . . . . . . . . . . . . . . . . . . . . . 153
Akira Kishimoto
9 Optical Properties of Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
Krisana Kobwittaya and Takanori Watari
10 Organic-Inorganic Hybrid Materials . . . . . . . . . . . . . . . . . . . . . . . . 213
Yoshiyuki Sugahara
vii
Contributors
Junichi Hojo Faculty of Engineering, Kyushu University, Fukuoka, Japan

Miki Inada Center of Advanced Instrumental Analysis, Kyushu University,
Fukuoka, Japan
Masakazu Kawashita Department of Inorganic Biomaterials, Institute of
Biomaterials and Bioengineering, Tokyo Medical and Dental University, Tokyo,
Japan
Akira Kishimoto Graduate School of Natural Science and Technology, Okayama
University, Okayama, Japan
Krisana Kobwittaya Department of Science and Advanced Technology, Graduate
School of Science and Engineering, Saga University, Saga, Japan
Junichi Matsushita Department of Materials Science, Tokai University, Hiratsuka,
Japan
Tsugio Sato Institute of Multidisciplinary Research for Advanced Materials,
Tohoku University, Sendai, Japan
Yoshiyuki Sugahara Department of Applied Chemistry, School of Advanced
Science and Engineering, Waseda University, Tokyo, Japan
Kagami Memorial Research Institute for Materials Science and Technology, Waseda
University, Tokyo, Japan
Satoshi Tanaka Department of Materials Science and Technology, Nagaoka Uni-
versity of Technology, Nagaoka, Japan
Junichi Tatami Graduate School of Environment and Information Sciences,
Yokohama National University, Yokohama, Japan
Takanori Watari Department of Science and Advanced Technology, Graduate
School of Science and Engineering, Saga University, Saga, Japan
ix
x Contributors
Shu Yin Institute of Multidisciplinary Research for Advanced Materials, Tohoku

University, Sendai, Japan
Toshinobu Yogo Institute of Materials and Systems for Sustainability, Nagoya
University, Nagoya, Japan
Chapter 1
Crystal Structures of Inorganic Materials
Junichi Hojo and Miki Inada
Abstract Ceramics have high hardness and mechanical strength, excellent chemical
and thermal stabilities, and particular electromagnetic and optical properties. Based
on these unique properties, they have been widely used in our life, industry activities,
and various environmental and energy fields. The durability of ceramics is derived
from strong chemical bonding, that is, covalent and ionic bonds, and tight atomic
packing. The electrical properties are dominated by crystal and electronic band
structures and typically classified into insulator, dielectric, semiconductor, and
metallic conductor. Typical covalent crystals are diamond, graphite, and hexagonal
boron nitride (h-BN). Diamond, having 3D carbon network, is extremely hard,
whereas graphite and h-BN are soft due to the hexagonal layer structure. Structural
principle in ionic crystal is the alternate arrangement of cation and anion different in
charge and size. The coordination configuration consisting of centered cation and
surrounding anions is the elemental unit: for example, silica is constructed by SiO4
tetrahedrons and titania by TiO6 octahedrons. Lattice defects, such as vacancy and
interstitial atom, provide a large influence on semiconductor and ionic conductor.
Glass has a random network structure and has been applied in optical fields. Recent
trend is the dimensional control of morphology from zero- to three-order. New
functions of ceramics have been created using nanoparticle, nanofiber, nanosheet,
hybrid, and nanoporous materials.
Keywords Chemical bonding · Crystal · Glass · Defect structure · Dimensional

control
J. Hojo (*)
Faculty of Engineering, Kyushu University, Fukuoka, Japan
e-mail: hojo.junichi.090@gmail.com
M. Inada
Center of Advanced Instrumental Analysis, Kyushu University, Fukuoka, Japan
e-mail: inada.miki.300@m.kyushu-u.ac.jp
© Springer Nature Singapore Pte Ltd. 2019 1

J. Hojo (ed.), Materials Chemistry of Ceramics,
https://doi.org/10.1007/978-981-13-9935-0_1
2 J. Hojo and M. Inada
1.1 Fundamental Structures and Properties of Materials
Materials are generally classified into ceramic, metallic, and organic ones. Organic
materials are comprised mainly of carbon, hydrogen, oxygen, and nitrogen.
Although the number of constituent element is small, there are many organic
compounds owing to the variety of molecular structures based on directional cova-
lent bonding. Plastics are formed by connection of small monomers. The main chain
is strong due to the covalent C-C bond, but hydrogen bonding or van der Waals
bonding between main chains is weak. Therefore, they are soft and flexible, but
inferior in heat resistance. Typical metallic materials are iron, aluminum, copper, etc.
Most of metallic elements belong to transition metals. Metal crystals are constructed
by regular packing of spherical atoms. Metallic bonding is a kind of covalent
bonding in a broad meaning. The heat resistance is high compared to organic
compounds. Since electrons are not localized but extensively shared among atoms,
electrons easily move, causing high electrical and thermal conduction. The displace-
ment of atoms is also easy, causing high ductility. Ceramics are mainly composed of
positive and negative elements in the left and right sides, respectively, of the periodic
table. They are connected by covalent and ionic bonding. Since shared electrons and
electrostatic attraction among atoms cause strong bonding force, they are mechan-
ically rigid and undeformable, and thermally and chemically stable. Furthermore, the
electronic state is wide-ranged owing to the combination of various atoms, leading to
the appearance of versatile electronic materials, such as insulator, dielectrics, semi-
conductor, and so on.
Typical fabrication process and schematic model of microstructure in ceramics
are demonstrated in Fig. 1.1. Most of ceramics are fabricated by powder forming and
subsequent high-temperature sintering, resulting in polycrystalline structure com-
posed of agglomerated crystal grains. There are grain boundaries between grains
with different crystal orientations. If raw powders include metallic impurities,
foreign particles remain as inclusions. If the sintering is not completed, pores remain
Powder Crystal grain Grain boundary
Forming Die pressing

Slip casting
Sintering Pressureless sintering

Hot pressing
Hot isostatic pressing
Machining Cutting
Polishing
Inclusion Pore
Fig. 1.1 Schematic of fabrication process of ceramics and model of sintered texture
1 Crystal Structures of Inorganic Materials 3
in sintered body. Grain boundary, inclusion, and pore seriously affect the mechanical
strength. The total structure of ceramics is classified into texture and transgranular
structure. The texture means the agglomerated-grain structure. The final properties of
ceramics are affected by various factors: grain size, pore size, volume, and so on. The
transgranular structure is involved with atomic bonding and crystal structure. In this
chapter, the crystal structures of ceramics are introduced for better understanding of
the principal properties and functions.
1.2 Crystal Structure of Inorganic Material
1.2.1 Packing Manner of Rigid Spheres
Crystal structures are simply explained from packing manner of rigid spheres.
Figure 1.2 demonstrates fundamental crystal structures. The minimum unit of crystal
is called unit lattice or unit cell. Simple cubic (SC) structure has four atoms in the
corners. Body-centered cubic (BCC) structure includes an additional atom in the
body center. Close packing structures are most stable. As shown in the packing
(c) Cubic closed packing (CCP)

(a) Simple cubic (SC) (b) Body centered cubic (BCC) Face centered cubic (FCC)
: A layer
: B layer
: C layer
(d) Hexagonal closed packing (HCP)
Fig. 1.2 Fundamental crystal structures based on packing of rigid spheres, and closed packing
manner in HCP, ABAB order, and CCP(FCC), ABCABC order
manner of spheres, the stable packing is based on triangular arrangement. When

putting spheres on the first layer (A), they are settled on the concave of three spheres
in underlayer to form the second layer (B). There are two possibilities for the third
layer. When spheres are placed on the same positions of (A), they form hexagonal
close packing (HCP) structure in the ABAB order. It is normally illustrated as
hexagonal column, but the unit cell is rhombohedral column with equivalent a-
and b-axes and c-axis. When the third spheres are placed on the different positions
from (A), the new layer is recognized as (C), forming cubic close packing (CCP)
structure in the ABCABC order. The unit cell is illustrated as face-centered cubic
(FCC) structure placing atoms in the center of cube face. The close packing direction
is in the diagonal of cube.
SC structure is scarcely observed because the open space inside the cube makes it
unstable. Metals have simple crystal structures of BCC, CCP, and HCP because
spherical atoms with the same size are packed. In contrast, ceramics have different
types of complicated crystal structures because constituent atoms are different in size
and charge.
1.2.2 Coordination Configuration
In crystal structures, atoms are surrounded by the other atoms. It is called coordina-
tion configuration which is determined by atomic size and bonding direction. The
variation of coordination configuration with ionic radius and bonding orbital is
explained as in Table 1.1. Typical coordination figures and numbers are triangular
(3), tetrahedral (4), octahedral (6) and cubic (8). The coordination number of
12 means the close packing, but it is not the case in ionic crystals.
Coordination polyhedrons of ionic crystals are illustrated in Fig. 1.3. Ionic bonds
form between positive and negative elements. For instance, MgO is composed of
Mg2+ and O2. Cations and anions are bonded by electrostatic attraction (the
Coulomb’s force). The bonding force depends on distance between ions, but not
on direction. Generally, cations have smaller size than anions. Cations form with
release of electrons from atoms, resulting in the increase of effective nuclear charge.
The outer electrons are strongly attracted by nuclear, causing the shrinkage of
Table 1.1 Variation of coordination configuration with radius ratio of cation to anion and shape of
hybrid orbital of center atom
Cation/anion radius ratio
Coordination number Theoretical Range Configuration Hybrid orbital
3 0.155 0.155–0.225 Triangular sp2
4 0.225 0.225–0.414 Tetrahedral sp3
6 0.414 0.414–0.732 Octahedral d2sp3
8 0.732 0.732–1.000 Cubic
12 1.000 Closed packing
(a) 3-coordination (b) 4-coordination
(c) 6-coordination (d) 8-coordination
Fig. 1.3 Typical coordination configuration in ionic crystals. Small cation is centered and
surrounded by large anions
cations. On the other hand, anions form by addition of extra electrons, which lowers
the effective nuclear charge and causes the expansion of anions. In ionic crystals,
small cations are settled in voids of packing structure of large anions. The coordi-
nation number of anions surrounding cation is determined by the ionic radius ratio.
Large cation can be surrounded by many anions. Therefore, the coordination number
increases with an increase in radius ratio of cation to anion. It is called “Pauling’s
law.” Theoretical ratio means the calculated one when cation just fits the void of
surrounding anions. When the cation-to-anion radius ratio is equal to the theoretical
one or above, the crystal structure is stable. When the cation size is smaller than the
theoretical one, the structure becomes unstable because small cation cannot be
settled in the center of interstice surrounded by anions.
Covalent bonds form by sharing of localized electrons in overlapping of atomic
orbitals, in which the orbital direction determines the coordination configuration.
Generally, it can be explained from hybrid orbitals of centered cation which are
constructed by s, p, and d orbits: sp2 hybrid (3-coordination, triangular), sp3 hybrid
(4-coordination, tetrahedron), and d2sp3 (6-coordination, octahedron). These coor-
dination figures are similar to those in ionic bonding. The compounds constructed by
different elements exhibit both covalent and ionic behaviors. When the coordination
configuration expected from ionic size is the same as in atomic orbital, the crystal
structure is stable. SiO2 is expected to have 4-oxygen coordination from both ionic
size and atomic orbital of silicon. It is hard and thermally stable. ZnO is expected to
have 6-oxygen coordination from ionic size but 4-oxygen coordination from atomic
orbital of zinc. Therefore, ZnO is less stable than SiO2.
1.2.3 Covalent Crystals
Typical covalent material is a carbon family with various crystal structures, includ-
ing diamond, graphite, fullerene, carbon nanotube, and graphene. The crystal struc-
tures and bonding orbitals of diamond and graphite are illustrated in Fig. 1.4.
109 28’
(a) Diamond sp3
free electron
p orbital
120
C
sp2
(b) Graphite
Fig. 1.4 Crystal structures of diamond derived from sp3 hybrid orbital and graphite derived from
sp2 hybrid orbital. There is a free electron in p orbital perpendicular to sp2 hybrid orbital of graphite
Fig. 1.5 Crystal structure empty p orbital pared electrons

of h-BN and electron
configuration in p orbitals
perpendicular to sp2 hybrid
orbitals of boron and
nitrogen
B N
:B :N
Diamond has three-dimensional network structure consisting of carbon tetrahedrons

with 4-coordination. This structure is derived from sp3 hybrid orbital. Graphite has
two-dimensional layer structure consisting of stacked hexagonal planes with
3-coordination. This structure is derived from sp2 hybrid orbitals. Diamond has an
extremely high hardness because all four orbitals covalently bond. Since there is no
free electron, it is an insulator and the single crystal is transparent. Graphite has
strong covalent bonds in the in-plane direction of hexagonal network, but the van der
Waals bonding between planes is so weak that hexagonal planes easily exfoliate.
Since graphite is soft, it has been applied as solid lubricant. One p orbital remains in
the perpendicular direction of sp2 hybrid orbital. One electron exists in this p orbital,
and the unpaired electron works as free electron. Therefore, graphite has high
electrical conductivity due to the easy electron transport along hexagonal planes.
The free electrons absorb light in wide range, and, therefore, graphite looks black.
Boron nitride forms graphite-like hexagonal structure (Fig. 1.5). Boron and
nitrogen atoms are alternately bonded and form BN hexagonal planes through
covalent bonding between sp2 hybrid orbitals of boron and nitrogen. Since the
bonding between planes is weak, the hexagonal boron nitride (h-BN) is soft. The p
orbital in the perpendicular direction of sp2 hybrid orbitals is empty in boron, but has
two electrons with antiparallel spins in nitrogen. Since the pared electrons are stable
and localized, they cannot move. Therefore, h-BN is an insulator. Since light is
scattered without absorption, the powder looks white. The h-BN is called “white
graphite.” Boron nitride can form cubic crystal structure similar to diamond under
high pressure. The cubic boron nitride (c-BN) also has high hardness. Silicon carbide
(SiC) has diamond-like crystal structure, and the hardness is high. The similarity in
crystal structure among carbon, boron nitride, and silicon carbide is easily under-
stood in the periodical table. Boron and nitrogen are placed in the left and right from
carbon, and silicon is placed just under carbon. They can form the similar covalent
bonding using s and p orbitals.
1.2.4 Ionic Crystals
Ionic crystals are formed by alternate arrangement of cation and anion. The crystal
structures are determined by coordination number based on ratio of ionic radius and
chemical composition. Multicomponent ceramics have more complex crystal
structures.
1.2.4.1 Coordination Number and Crystal Structure
When the size of cation is large, the cation can be surrounded by many anions. That
is, the crystal structures with high coordination number become stable. This is
demonstrated for one-to-one compounds as follows.
Zinc blende and wurtzite structures have 4-coordination number. Zinc blende is
the mineral name of β-ZnS. β-SiC belongs to this structure. Zinc blende structure is
illustrated in Fig. 1.6. Anions form CCP structure. Cation is surrounded by 4 anions
in the shape of tetrahedron. The number of 4-coordination position is 8 in the unit
cell. Four cations are placed in half of the 4-coordination positions in the sterically
alternate manner to reduce the repulsion between cations. Coordinate graphic is
convenient to indicate the positions of atoms. In zinc blende structure, anions are
located at the corners and faces of cube. The origin of unit cell is situated at the basal
plane. The positons of origin, half unit, and lattice unit are represented by 0, 1/2, and
1, respectively. Cations are located at 1/4 and 3/4 units from origin. Wurtzite is the
mineral name of α-ZnS. Anions form HCP structure and cations are placed in half of
the 4-coordination positions. This structure is easy to understand as hexagonal
column (Fig. 1.7a). However, the unit cell should be written as rhombohedral
column (Fig. 1.7b). α-SiC, AlN, and ZnO have this structure. AlN has been applied
as insulating substrate and ZnO as semiconductor.
0, 1 1/2 0, 1
1/4 3/4
1/2 1/2
0, 1
3/4 1/4
0, 1 1/2 0, 1
: Cation : Anion : Cation : : Anion
Fig. 1.6 Zinc blende structure and coordinate graphic (projection figure)
Fig 1.7 Wurtzite structure

illustrated in two manners:
hexagonal and
rhombohedral columns
(a) Hexagonal column (b) Rhombohedral column

: Caon : Anion
Fig. 1.8 Crystal structures

of rock salt and CsCl types
(a) Rock salt (b) CsCl

: Cation : Anion
Typical crystal structure with 6-coordination number is rock salt type. Rock salt is
the mineral name of NaCl. The crystal structure is illustrated in Fig. 1.8a. Anions
form CCP structure. Cation is surrounded by 6 anions in the shape of octahedron. All
6-coordination positions are occupied by cations. Cation and anion, respectively,
form FCC structure. However, this structure cannot be assigned to FCC, because the
crystal consists of different ions. The rock salt structure is observed in many metal
compounds, such as halide (LiF, NaCl, KCl, AgCl), oxide (MgO, CaO, MnO, CoO,
NiO), nitride, carbide (TiN, TiC), etc.
CsCl structure has 8-coordination number as seen in Fig. 1.8b. Anions are located
at the corners of simple cube, and the body center is occupied by cation. However,
this structure should not be assigned to BCC. NH4Cl has this structure. Although
atomic radius of nitrogen is small, cation size of NH4+ becomes large. As described
here, the large cation can form high-coordination crystal structures.
1.2.4.2 Various Chemical Compositions
Metal ions have various electric charges. Depending on the electric charge, the
cation-to-anion ratio is changed. It makes the crystal structure complicated. As
one-to-two compound, SiO2 and TiO2 are typically cited. SiO2 is considered as
ionic crystal, but the contribution of covalent bonding is large between silicon and
oxygen. Therefore, the crystal structure is explained based on SiO4 tetrahedron. SiO4
units are shared at the corner of tetrahedron by covalent bonding through oxygen.
The bonding angle at the corner is flexible. Therefore, there are many polymorphic
structures: α and β phases of quartz, tridymite, and cristobalite.
Rutile is one of the crystal structures of TiO2 (Fig. 1.9). Anions form HCP
structure, but it is distorted to form tetragonal unit cell. Cation is placed in the
6-coordination position. This structure is also explained in the connection manner of
: Ti :O
Fig. 1.9 Crystal structure of rutile: unit cell and connection manner of TiO6 octahedrons
TiO6 octahedrons. As seen in Fig. 1.9, TiO6 units are shared at the edge of
octahedron in c-axis direction, and the connected chains are bonded by corner
sharing in a- and b-axes. The other crystal structures of TiO2 are anatase and
brookite. They are also explained in different connection manners of TiO6 octahe-
dron. The connection model of oxygen polyhedron is convenient to explain the
complicated crystal structure. TiO2 has been applied as white pigment,
photocatalyst, semiconductor, dielectric, etc. SnO2 has the rutile structure. It has
been used as transparent semiconductor, gas sensor, and so on.
Corundum is the mineral name of α-Al2O3. Anions form HCP structure. Cations
are placed in 2/3 of the 6-coordination positions. The distribution of cations is not
random, but periodical from A to B layers in HCP structure. The crystal structure of
α-Al2O3 is also explained by the connection model of AlO6 octahedron, in which
AlO6 units are shared at the edge and face of octahedron. The stability of sharing of
oxygen polyhedron decreases in the sequence of corner, edge, and face because the
short distance between cations increases electrostatic repulsion. Therefore, Al2O3
tends to form the other polymorphic structures such as γ-Al2O3 with spinel structure.
Among them, α-Al2O3 is most stable. It has been widely applied as mechanical part,
cutting tool, crucible, sodium vapor lamp, IC substrate, etc., because of the balanced
excellent properties in hardness, heat and chemical resistance, electrical insulation,
heat conduction, and optical transparency.
1.2.4.3 Solid Solution and Complex Compound
ZrO2 has a cubic type of fluorite structure with 8-coordination number. Fluorite is the
mineral name of CaF2. ThO2 and UO2 have this structure. Since the cation size is
large, they can have high-coordination number. ZrO2 has been applied as typical
ceramics material. However, the cubic phase (c-ZrO2) needs to be stabilized by solid
solution. The crystal structure of c-ZrO2 is illustrated as overall view in Fig. 1.10. SC
oxygen lattice and CsCl-type lattice including Zr in 8-oxygen coordination are
alternately arranged. Figure 1.11 shows the unit cell and the coordinate graphic. Zr
forms FCC structure, and SC oxygen cube is placed in the FCC center. c-ZrO2 is a
high-temperature phase. During cooling, it transforms to tetragonal phase at 2370 C
and to monoclinic phase at 1000 C. Transformation to monoclinic phase causes
abnormal large-volume expansion, resulting in collapse of ZrO2 ceramics. Since the
Fig. 1.10 Crystal structure

of c-ZrO2: alternative
arrangement of SC oxygen CsCl-type lattice
lattice and CsCl-type lattice
including Zr at the center : Zr :O
SC oxygen lattice

of c-ZrO2: unit cell and 0, 1 1/2 0, 1
coordinate graphic
1/4, 3/4 1/4, 3/4

1/2 1/2
0, 1
1/4, 3/4 1/4, 3/4

0, 1 1/2 0, 1
: Zr :O : Cation : Anion

of cubic perovskite
(BaTiO3) and displacement
of ions in tetragonal phase Ti
O Ba
(a) Cubic lace (b) Ion displacement in tetragonal
: Ba : Ti :O
ionic radius of Zr4+ (0.082 nm) is smaller than optimal radius (0.102 nm) in
8-oxygen coordination, c-ZrO2 becomes unstable at low temperatures. The c-ZrO2
can be stabilized by substitutional solution of Ca2+ (0.103 nm) and Y3+ (0.096 nm)
having larger ionic radius. This is the “stabilized zirconia.” The substitution of
low-valent cation for Zr4+ forms oxygen vacancies, leading to the application to
oxide ion conductor. Partially stabilized zirconia (PSZ) is produced by reducing
amount of stabilizer. The tetragonal zirconia polycrystal (TZP) has high toughness,
leading to mechanical and structural application.
Complex oxides include different metal ions at the cation site. Typical one is
perovskite represented in ABX3 formula. Perovskite is the mineral name of CaTiO3.
BaTiO3, SrTiO3, PbTiO3, and PbZrO3 have this structure and have been applied as
dielectric and piezoelectric materials. A-site cation is large and B-site cation is small.
The crystal structure of BaTiO3 is explained here. Large Ba2+ cation is coordinated
by 12 oxygens and small Ti4+ cation by 6 oxygens. The structure based on TiO6
octahedron is generally used as seen in Fig. 1.12a. Ba2+ cations are placed at the
corners and TiO6 unit inside the unit cell. The ideal structure is cubic, and the cubic
phase is stable above 120 C. It is distorted around room temperature and changes to
tetragonal phase. The reason is the small size of Ti4+ cation compared to the optimal
size in 6-oxygen coordination. For practical application, the tetragonal phase is
important. As illustrated in Fig. 1.12b, Ti4+ cation somewhat sifts from the center of
O2 coordination. The displacement between centers of plus and minus charges is
aligned in small domain, causing spontaneous polarization. Thus, tetragonal BaTiO3
has been applied as high capacitance condenser because of the ferroelectricity.
Various metal cations can be incorporated in A and B sites of perovskite. Such a
versatile design of solid solution has developed many functions of perovskite
compounds.
Spinel is represented in AB2X4 formula. Spinel is the mineral name of MgAl2O4.
This is main component of refractory brick for steel making, and also used as
transparent ceramics etc. The crystal structure is cubic, and explained like fluorite
structure in alternate arrangement of two types of cubic units including A-site or
B-site. A-site has 4-oxygen coordination and B-site has 6-oxygen coordination.
When A-sites are occupied by A2+ ions and B-sites by B3+ ions, that is, in
(A)[B]2O4, it is called normal spinel, including MgAl2O4, ZnFe2O4, CdFe2O4, etc.
When A-sites are occupied by the half of B3+ ions, and B-sites by A2+ ions and the
half of B3+ ions, that is, in (B)[A,B]O4, it is called inverse spinel, including
MgFe2O4, NiFe2O4, etc. Such a substitution in A and B-sites is possible between
A and B atoms with similar ionic sizes. γ-Fe2O3 (maghemite) is represented as
(Fe)[Fe5/3□1/3]O4, in which there are cation vacancies in B-sites. Magnetic iron oxide
compounds are called ferrites. Generally, spinel ferrites are easy for magnetization
and inversion of magnetic dipole, and, therefore, applied as soft magnetic material in
magnetic recording and high frequency transformer. Fe3O4 (magnetite) has the
mixed valence in the inverse spinel type of (Fe3+)[Fe2+,Fe3+]O4. This is classified
into hard magnetic material and used as permanent magnet.
1.3 Defect Structures in Crystal
Crystal structures are understood on the assumption of perfect ones, in which atoms
are ideally arranged in an orderly manner at lattice points. However, there are lattice
defects in real crystals. This is caused by thermal oscillation of atoms. Unless the
absolute temperature is 0 K, atoms jump out of lattice points with a certain proba-
bility and move to the other positions. Defect structures are thermodynamically
considered to be stable. The Gibb’s free energy increases in the term of enthalpy
due to decrease in the number of atomic bonds, but decreases in the term of entropy
due to the structural diverseness of atomic arrangement, totally leading to the
decrease in free energy by defect formation. There are some kinds of lattice defects.
Point defects form at the lattice points themselves. Extended defects form by three-
dimensional aggregation and rearrangement of point defects: cluster, sheared struc-
ture, and block structure. Dislocation is the line defect by linear arrangement of point
defects, and plays an important role in plastic deformation of metal crystals. Point
defects provide a large influence on atomic diffusion, and electromagnetic and
optical properties of ceramics.
Fig. 1.13 Point defects in M+X crystal. Foreign cation (L2+) and anion (Y2) are included as
impurities
1.3.1 Point Defects
Fundamental point defects in solid crystal are vacancy and interstitial atom. Impurity
atom and associated center are also considered. In many cases, different point defects
coexist in crystal structure. The point defects are summarized as follows:
Vacancy: regular lattice points are empty.
Interstitial atom: some atoms exist between lattice points.
Impurity atom: foreign atoms occupy lattice point or interstitial site.
Associated center: Point defects interact with each other by the Coulombic force.
Point defects form in covalent and ionic crystals. The defect structures are deter-
mined by atomic size and ionic charge balance. Figure 1.13 illustrates the schematic
model of point defects in ionic crystal. These point defects are notated in a peculiar
manner to clarify defect reaction among ions and electrons. The Kröger-Vink
notation is widely used to symbolize point defects as Aab. “A” means atomic symbol.
Vacancy is represented by “V.” The subscript “a” means atomic position on lattice
which is denoted by original atom. Interstitial site is represented by “i.” The
superscript “b” means effective charge, indicating the relative charge based on
original charge of lattice point. It is denoted as plus ( • ), minus ( 0 ), and neutral
( x ). This notation is explained for M+X crystal as below. Vacancies at M and
X-sites are denoted as VM0 and VX•, respectively. This means that vacancies exist at
M and X-sites. The real charge of vacancy should be neutral. Based on the charge of
M+ and X, the effective charge of vacancy negatively sifts by minus one for M-site,
and positively by plus one for X-site. M+ and X at interstitial sites are denoted as
Mi• and Xi0 , respectively. This means that M+ and X exist at i-sites. Since the real
charge of interstitial site is neutral, the effective charges of M+ and X at interstitial
sites are plus one and minus one, respectively. Impurity cation, L2+, substituted for
M+ is denoted as LM•, and impurity anion, Y2 , substituted for X as YX0 . L2+ and
Y2 at interstitial sites are denoted as Li•• and Yi00 , respectively.
1.3.2 The Schottky Defect and the Frenkel One
Typical point defects in ionic crystals are the Schottky type and the Frenkel type as
shown in Fig. 1.14. The Schottky defect consists of the paired vacancies at cation
and anion sites as VM0 -VX• in M+X crystal. They are found in many metal
compounds, such as halides (NaCl, etc.) and oxides (MgO, etc.). The Frenkel defect
consists of the pair of cation vacancy and interstitial cation as VM0 -Mi• or the pair of
anion vacancy and interstitial anion as VX•-Xi0 . CaF2 and UO2 have the Frenkel
defects because the interstitial sites are large. Generally, the ionic radius of cation is
small in ionic crystals, and therefore, the Frenkel defect tends to appear in cation
sublattice. AgBr and AgCl have the Frenkel defects. This is explained as polarizable
Ag ions easily enter interstitial sites. Table 1.2 demonstrates some reaction formulas
for formation of the Schottky defects and the Frenkel ones. The Schottky defect is
written to form from “null.” The Frenkel defect is written to form from neutral atom.
Different defect structures can coexist in some compounds.
Fig. 1.14 The Schottky defect and the Frenkel one in M+X crystal
Table 1.2 Reaction formulas for formation of the Schottky defect and the Frenkel one in halides
and oxides
Compound Defect equilibrium Compound Defect equilibrium
NaCl null ¼ V0Na þ VCl•
MgO null ¼ V00Mg þ VO• •
LiF null ¼ V0Li þ VF• CaO null ¼ V00Ca þ VO• •
CaF2 FFX ¼ VF• þ F0i UO2 OOX ¼ VO• • þ O00i
X
CaCa ¼ V00Ca þ Cai• • UUX ¼ V0000
U þ Ui
••••
null ¼ V00Ca þ 2VF• null ¼ VU þ 2VO• •

0000
BeO null ¼ V00Be þ VO• • AgBr, AgCl X

AgAg ¼ V0Ag þ Agi•
1.3.3 Nonstoichiometric Defects
Compounds of typical elements have definite compositions depending on the ionic

valence. On the contrary, transition metal compounds exhibit a variation of compo-
sition from the integer ratio of cation to anion, because the atomic valence of
transition metal is variable. They are called “nonstoichiometric compound” and
classified into the following four types. Here, “δ” means the deviation from
stoichiometry.
Cation-deficiency type (cation vacancy): Fe1-δO, Co1-δO, Ni1-δO, Cu2-δO
Cation-excess type (interstitial cation): Zn1+δO, Cr2+δO3, Cd1+δO
Anion-deficiency type (anion vacancy): ZrO2-δ, PrO2-δ
Anion-excess type (interstitial anion): UO2+δ
Since the ionic radius of cation is smaller than that of anion, cation-deficiency and
cation-excess types easily form. Fe1-δO has a large amount of cation vacancy as δ
0.15, but the defect amount is ordinarily small as δ < 0.01 in Co1-δO, Ni1-δO, and
Zn1+δO. When the cation size is large, the anion-deficiency and anion-excess types
are found because the lattice space expands. The oxygen vacancies form in ZrO2-δ.
The formation of interstitial anion is rare as in UO2+δ.
The nonstoichiometry in transition metal oxides provides a large influence on the
electronic properties. ZnO works as n-type semiconductor due to cation-excess
defect. According to the Kröger-Vink notation, the equilibrium equation for the
formation of interstitial cation is written as follows:
ZnO ¼ Zni x þ 1=2O2 ð1:1Þ
This equation means that oxygen is removed from stoichiometric ZnO, leaving Zn at
interstitial site, where neutral Zn atom (Znix) is assumed although the formal cation is
Zn2+ on lattice. The neutral Zn atom releases the first electron and then the second
one as follows:
Znix ¼ Zni • þ e0 ð1:2Þ

• •• 0
Zni ¼ Zni þe ð1:3Þ
There are three interstitial defects: Znix, Zni• and Zni••, which depend on temperature
and oxygen partial pressure (Po2). The content of interstitial Zn increases at low
oxygen pressure. The major interstitial defect is suggested by applying the mass
action law to these equilibrium equations. When Znix is major, the content is
proportional to Po21/2. When Zni• is major, the content is proportional to Po21/4.
When Zni•• is major, the content is proportional to Po21/6. According to Eqs. (1.2)
and (1.3), the concentration of electron (n) is determined from the content of
interstitial Zn: n¼[Zni•] or n¼2[Zni••]. Therefore, the electrical conductivity depends
on oxygen partial pressure. Figure 1.15 illustrates the schematic of the dependence
Fig. 1.15 Schematic of dependence of electrical conductivity on oxygen partial pressure and
electron energy band model of ZnO
of electrical conductivity on oxygen partial pressure and electron energy band model
of ZnO. The conductivity is proportional to Po21/4 at low temperature, indicating
that the major defect is Zni•. At higher temperature, the proportionality to Po21/6
indicates the major defect of Zni••. Znix and Zni• form shallow impurity level and
deep one, respectively, within the bandgap between valence and conduction bands.
The impurity levels work as electron donor, that is, electrons are excited from donor
levels to conduction band.
CoO works as p-type semiconductor due to cation-deficiency defect, where
vacancies form at Co sites. Some Co2+ ions change to Co3+ ions for charge
compensation. The extra positive charges are not localized at specific Co sites and
move as positive holes, resulting in the electrical conduction. Theoretically, Co
vacancies are assumed to trap positive holes. It means that the vacancies are
positively charged and release positive holes. According to the electron energy
band model, the positively charged vacancies work as electron acceptor. Electrons
in valence band are excited to the acceptor levels and leave positive holes as charge
carrier in the valence band.
1.3.4 Defects in Solid Solution
Solid solution between definite compounds with different ionic valences forms point
defects to keep charge balance. The solid solutions of c-ZrO2 with CaO and Y2O3 are
typical. The equilibrium equation in CaO-doped ZrO2 is written as follows:
CaO ¼ CaZr 00 þ VO • • þ OO x ð1:4Þ

Fig. 1.16 Dependence of

oxide ion conductivity on
Ca content in CaxZr1-X O2-X
Ca2+ is substituted for Zr4+. Since the positive charges are deficient, oxygen vacan-
cies form. Through the oxygen vacancies, O2 ions easily diffuse, resulting in oxide
ion conduction. As shown in Fig. 1.16, the electrical conductance increases with an
increase in Ca content owing to the formation of oxygen vacancies. However, it
decreases at high Ca content. This is caused by the association between CaZr00 and
VO•• with the Coulombic force, because the associated vacancies cannot be used for
oxide ion conduction.
Electrical conductivity of nonstoichiometric metal-oxide semiconductor can be
controlled by doping of definite metal oxide with different ionic valences. The
equilibrium equation in doping of Al2O3 to n-type semiconductor, ZnO, is written
as follows:
Al2 O3 ¼ 2AlZn • þ 2OO x þ 2e0 þ 1=2O2 , ð1:5Þ
where Al3+ is substituted for Zn2+ with release of O2. The concentration of electron
increases by Al2O3 doping, leading to the increase in electrical conductivity of
n-type semiconductor. The equilibrium equation in doping of Li2O to p-type semi-
conductor, CoO, is written as follows:
Li2 O þ 1=2O2 ¼ 2LiCo 0 þ 2h • þ 2OO x , ð1:6Þ
where Li+1 is substituted for Co2+ with introduction of O2. The Li2O doping forms
positive holes, which is the same meaning as disappearance of electrons. This causes
the increase in electrical conductivity of p-type semiconductor. Higher-valence
metal ions are doped to n-type semiconductor, while lower-valence metal ions are
doped to p-type semiconductor. This type of semiconductor is called valence-
controlled semiconductor, and applied to control the electrical properties of many

oxide semiconductors.
1.4 Network Structure of Silicate
Ceramics have been developed on the basis of technologies of pottery and porcelain.
The main components are SiO2 and Al2O3. They are abundant in the earth’s crust as
seen in the Clarke number, O 49.5%, Si 25.8%, and Al 7.56%, and exist as silicates
with alkali and alkaline earth oxides (Na2O, CaO, etc.). Silicates are traditional
materials, but important in ceramic industries. The feature is the polymerized
network structure of Si-O bonds with highly covalent behavior, and they are
understood as inorganic polymers.
Fundamental unit of silicate is SiO4 tetrahedron, and they are connected at the
corner of tetrahedron in various manners, forming network structures in one, two,
and three dimensions. Typical structures are illustrated in Fig. 1.17. Connection
mode of SiO4 unit is ordered with O/Si atomic ratio ranging in 2 O/Si 4. When
O/Si ¼ 4, SiO4 exists as monomer. They are polymerized to chain, layer, and steric
structure: one-dimensional chain or ring at O/Si ¼3, two-dimensional layer at
O/Si ¼ 2.5, and pure SiO2 at O/Si ¼ 2. The polymerization degree is low at high
O/Si ratio, including Na+, K+, Mg2+, Al3+, OH, etc. for charge compensation.
(a) One dimensional chain (b) Two dimensional layer
OH
Al
O, OH
Si
O
(c) Layer structure of kaolinite (d) Three dimensional cage

(zeolite)
Fig. 1.17 Typical network structures of silicates by one-, two-, and three-dimensional
arrangements
Chrysotile, Mg6(OH)6Si4O11∙H2O, has double-chain structure. This is natural

inorganic fiber and called asbestos. This has been widely used as heat-insulating
material, but the use is now prohibited owing to the hazardous nature of sharp
crystalline fiber. Kaolin has double-layer structure consisting of SiO4 and AlO6
layers. The composition is written as (OH)3Al2(OH)∙Si2O5 according to the layer
structure. SiO4 and AlO6 layers are covalently bonded through oxygen. The van der
Waals force works between the double layers. When kaolin is kneaded with water,
H2O molecules are intercalated between the double layers, causing plasticity. After
drying, it solidifies due to removing H2O molecules. This phenomenon has been
applied for shaping of pottery and porcelain. The other layer structures are found in
talc and mica. Mica is exfoliative. Mica films have been applied as insulating sheet in
electrical parts. Zeolite forms spherical cage consisting of SiO4 and AlO4 tetrahedron
units. This is featured for pore size at nanometer level in the network, providing
various functions of molecular sieve, ion exchange, and adsorption of organic
substances.
1.5 Glass Structure
Glass is amorphous solid which is frozen as it is from supercooled liquid. Typical

inorganic glass is SiO2-based one. The structural features of oxide glasses are
summarized as follows:
(1) The number of cation bonded to oxygen is one or two: M-O and M-O-M bonds
are allowed.
(2) The oxygen coordination number of cation is 4 or less.
(3) Oxygen polyhedron shares corner, but does not share edge and face.
(4) Oxygen polyhedron should share at least 3 corners.
The conditions, (1), (2), and (3), are required to allow flexibility of glass structure,
but the condition, (4), is required to hold the structure. The covalent valence number
of oxygen is two, but the number of cation bonded to oxygen can become three
or over in ionic crystals, causing rigid framework. The bond angle at the corner of
SiO4 tetrahedron is flexible, allowing amorphous random structure of glass.
Glass components are classified into glass former, intermediate and modifier.
Glass former is fundamental component to constitute glass: SiO2, B2O3, P2O5, etc.
Intermediate works as a part of glass former and improves the property of glass:
Al2O3 and ZnO improve chemical stability, and PbO increases refractive index to
produce crystal glass. Modifier lowers melting point and viscosity: Na2O, K2O,
CaO, etc., because Si-O networks are cut off as following equation:
j j
j
S i O S i þNa2 O ! 2 S i O þ 2Naþ

ð1:7Þ
j j j
: Si : O : Na : Ca
(a) Crystalline silica (b) Quartz glass (c) Soda-lime glass
Fig. 1.18 Network structures of crystalline silica and amorphous silica glasses (2D model)
Network structures of glasses are illustrated in Fig. 1.18. Silica crystal has regular
structure. Quartz glass is pure glass. It is produced by fusion of quartz crystal, and
called fused quartz or fused silica. SiO4 units are randomly connected, which
is different from regular arrangement in quartz. The quartz glass has been applied
as high-grade refractory glass because of high melting point, low thermal expansion
coefficient, and high thermal shock resistance. However, it is expensive. Soda-lime
glass includes Na2O and CaO as modifier. The composition of practical soda-lime
glass is SiO2 65–75, Al2O3 0.5–4, CaO 5–15, and Na2O 10–20 in wt%. Na+ and Ca2+
are incorporated into SiO2 network. The low melting point makes it easy to
produce usual flat glasses. Borosilicate glass includes B2O3. The addition of B2O3
to SiO2 network weakens the glass because the number of bonds decreases by
doping of BO3 triangle compared to SiO4 tetrahedron. The simultaneous addition
of Na2O and B2O3 forms BO4 tetrahedron, yielding stable glass. The composition of
practical borosilicate glass is SiO2 65–75, B2O3 5–12, Al2O3 1–5, CaO 5–8, Na2O
8–14, and K2O 1–5 in wt%. Since the borosilicate glass is superior in thermal
and chemical stability, it has been used as laboratory glasses and kitchen utensils.
The famous commercial name is “Pyrex.”
1.6 Highly Ordered Structure by Dimensional Control
Materials are constructed from atoms or molecules by chemical bonding to form

crystal or amorphous structure. Crystals and amorphous phases form assembled
structures and bring out their functions. From the practical viewpoint, morphological
control is important for their applications. The morphology of material is hierarchi-
cally classified as follows: zero-dimension (particle), one-dimension (fiber),
two-dimension (film), and three-dimension (bulk). They are totally termed the highly
ordered structure. Table 1.3 summarizes highly ordered structures: morphology,
characterization, and application.
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THE ARCTIC WORLD.
CHAPTER I.
THE NORTH POLE—THRESHOLD OF THE UNKNOWN WORLD—THE
CIRCUMPOLAR REGIONS—THE FLORA OF THE NORTH—LIFE IN THE
POLAR WORLD—THE NORTH-WEST AND NORTH-EAST PASSAGES.
s the reader knows, the Poles are the two extremities of the
axis round which the Earth revolves. It is to the North Pole,
and the regions surrounding it, that the following pages will be
devoted.
The inhabitants of Western Europe, and more particularly those
of the British Isles, have a peculiar interest in the North Polar
Regions. Deriving their wealth and importance from their commercial
enterprise, and that commercial enterprise leading their ships and
seamen into the furthest seas, they have necessarily a vital concern
in the discovery of the shortest possible route from that side of the
Earth which they inhabit to the other, or eastern side; and this, more
particularly, because the East is rich in natural productions which are
of high value to the peoples of the West.
Now a glance at the map will show the reader that the traders of
Western Europe—the British, the French, the Dutch, the
Scandinavians—are situated on the northern shores of the Atlantic
Ocean, and that, to reach the Pacific Ocean or the Indian, only two
routes are at present open. For instance, they may cross the Atlantic
to the American coast, and, keeping southward, strike through
Magellan’s stormy Strait or round the bleak promontory of Cape
Horn into the Pacific, and then, over some thousands of miles of
water, proceed to Australia or Hindustan or China; or they may keep
along the African coast to the Cape of Good Hope, its southernmost
point, and so stretch across the warm Tropical seas to India and the
Eastern Archipelago. A third, an artificial route, has indeed of late
years been opened up; and ships, entering the Mediterranean, may
pass through the Suez Canal into the Red Sea. But this last-named
route is unsuitable for sailing-ships, and all three routes are laborious
and slow. How greatly the distance would be shortened were it
possible to navigate the Northern Seas, and, keeping along the north
coast of the American continent, to descend Behring’s Strait into the
Pacific! In other words, were that North-West Passage practicable,
which, for three centuries, our geographers and explorers so
assiduously and courageously toiled to discover! But a still shorter
route would be opened up, if we could follow a line drawn from the
British Islands straight across the North Pole to Behring’s Sea and
the Aleutian Archipelago. This line would not exceed 5000 miles in
length, and would bring Japan, China, and India within a very short
voyage from Great Britain. We should be able to reach Japan in
three or four weeks, to the obvious advantage of our extensive
commerce.
Hitherto, however, all efforts to follow out this route, and to throw
open this great ocean-highway between Europe and Asia, have
failed. Man has been baffled by Nature; by ice, and frost, and winds,
and climatic influences. With heroic perseverance he has sought to
gain the open sea which, it is believed, surrounds the Pole, but a
barrier of ice has invariably arrested his progress. His researches
have carried him within about 500 miles of the coveted point; but he
is as yet unable to move a step beyond this furthest limit of
geographical discovery. Immediately around the North Pole, within a
radius of eight to ten degrees or more, according to locality, still lies
an Unknown Region, on the threshold of which Science stands
expectant, eagerly looking forward to the day when human skill and
human courage shall penetrate its solitudes and reveal its secrets.
This Unknown Region comprises an area of 2,500,000 square
miles; an immense portion of the terrestrial surface to be shut out
from the knowledge of Civilized Man. Its further exploration, if
practicable, cannot but be rich in valuable results. Not only would it
furnish the shortest route from the West to the East, from
progressive Europe to conservative Asia, from the Atlantic to the
Pacific, but it could not fail to add in a very important degree to our
stores of scientific information. Sir Edward Sabine is surely right
when he says, that it is the greatest geographical achievement which
can be attempted, and that it will be the crowning enterprise of those
Arctic researches in which England has hitherto had the pre-
eminence.
We may briefly indicate to the reader some of the advantages
which might be expected from exploration in the Unknown Region. It
would unquestionably advance the science of hydrography, and lead
to a solution of some of the more difficult problems connected with
the Equatorial and Polar ocean-currents, those great movements of
the waters of which, as yet, we know so little.
A series of pendulum observations, it is said, at and near the
North Pole, would be of essential service to the science of geology.
We are unable, at present, for want of sufficient data, to form a
mathematical theory of the physical condition of the Earth, and to
ascertain its exact configuration. No pendulum observations have
been taken nearer than 600 or 620 miles to the North Pole.
Again: what precious information respecting the strange and
wonderful phenomena of magnetism and atmospheric electricity
would certainly be acquired! How much we have yet to learn in
reference to the Aurora, which can be learned only in high latitudes,
and at or near the point which apparently represents a magnetic
focus or centre!
It has also been pointed out by Mr. Markham that the climate of
Europe is largely affected by the atmospheric conditions of the Polar
area, in which the development of extremely low temperatures
necessarily leads to corresponding extreme changes of pressure,
and other atmospheric disturbances, whose influence extends far
into the Temperate Zone. For the satisfactory appreciation of these
phenomena, says Mr. Markham, a precise knowledge is required of
the distribution of land and water within the Polar Region; and any
addition to our knowledge of its unknown area, accompanied by
suitable observations of its meteorology, cannot fail to afford
improved means of understanding the meteorology of our own
country, and of the Earth generally.
There can be no doubt, too, that geology would profit, if we could
push our researches nearer to the Pole, and force our way through
the great barrier of the Polar ice. It is highly desirable, too, that we
should know more of that interesting class of animals, the Mollusca,
both terrestrial and aquatic, fresh-water and salt-water. Again: what a
wide field of inquiry is opened up by the Polar glaciers; their extent,
their elevation, their range, and the effects produced by the slow but
continuous motion of those huge ice-rivers over the surface of the
country. And the botanist has a right to calculate upon the discovery
of many precious forms of vegetable life in the Unknown Region.
The Arctic flora is by no means abundant, but it is peculiarly
interesting. In Greenland, besides numerous mosses, lichens, algæ,
and the like, flourish three hundred kinds of flowering plants, all of
which are natives of the Scandinavian peninsula; and Dr. Joseph
Hooker remarks that they exhibit scarcely any admixture of American
types, though these are found on the opposite coast of Labrador. It
would seem probable that in the warm period which preceded the
Glacial Age, the Scandinavian flora spread over the entire area of
the Polar Regions; but that during the Age of Ice it was gradually
driven within its present limits, only the hardier types surviving the
blight of the long lingering winter.
And what would be the gain to the zoologist? Why, it is a well-
known fact that life abounds in the Arctic waters, and especially
those minute organisms which play so important a part in the
formation of sedimentary deposits, and help to build up the terrestrial
crust. We have much to learn, moreover, of the habits and habitats
of the fish, the echinoderms, the molluscs, the corals, the sponges of
the extreme Northern Seas.
There are questions connected with the migrations of birds which
can be elucidated only by an exploration of the Unknown Region.
Multitudes which annually visit our shores in the winter and spring,
return in summer to the far North. This is their regular custom, and
obviously would not have become a custom unless it had been found
beneficial. Therefore we may assume that in the zone they frequent
they find some water which is not always frozen; some land on which
they can rest their weary feet; and an adequate supply of nourishing
food.
From Professor Newton we adopt, in connection with this
consideration, a brief account of the movements of one class of
migratory birds,—the Knots.[1]
The knot, or sandpiper, is something half-way between a snipe
and a plover. It is a very active and graceful bird, with rather long
legs, moderately long wings, and a very short tail. It swims
admirably, but is not often seen in the water; preferring to assemble
with its fellows on the sandy sea-shores, where it gropes in the sand
for food, or fishes in the rock-pools and shallow waters for the small
crustaceans. It is known both as the red and the ash-coloured
sandpiper, because it changes the colour of its plumage according to
the season of the year; a bright red in summer, a sober ashen-gray
in winter. Now, in the spring the knot seeks our island in immense
flocks, and after remaining on the coasts for about a fortnight, can be
traced proceeding gradually northwards, until it finally takes leave of
us. It has been noticed in Iceland and Greenland, but not to stay; the
summer there would be too rigorous for its liking, and it goes further
and further north. Whither? Where does it build its nest, and hatch its
young? We lose all trace of it for some weeks: what becomes of it?
Towards the end of summer back it comes to us in larger flocks
than before, and both old birds and young birds remain upon our
coasts until November, or, in mild seasons, even later. Then it wings
its flight to the south, and luxuriates in blue skies and balmy airs until
the following spring, when it resumes the order of its migrations.
Commenting upon these facts, Professor Newton infers that the
lands visited by the knot in the middle of summer are less sterile
than Iceland or Greenland; for certainly it would not pass over these
countries, which are known to be the breeding-places for swarms of
water-birds, to resort to regions not so well provided with supplies of
food. The food, however, chiefly depends on the climate. Wherefore
we conclude that beyond the northern tracts already explored lies a
region enjoying in summer a climate more genial than they possess.
Do any races of men with which we are now unacquainted inhabit
the Unknown Region? Mr. Markham observes that although scarcely
one-half of the Arctic world has been explored, yet numerous traces
of former inhabitants have been found in wastes which are at
present abandoned to the silence and solitude. Man would seem to
migrate as well as the inferior animals, and it is possible that tribes
may be dwelling in the mysterious inner zone between the Pole and
the known Polar countries.
The extreme points reached by our explorers on the ice-bound
Greenland coast are in about 82° on the west, and 76° on the east
side; these two points lying about six hundred miles apart. As man
has dwelt at both these points, and as they are separated from the
settlements further south by a dreary, desolate, uninhabitable
interval, it is not an extravagant conjecture that the unknown land to
the north has been or is inhabited. In 1818 a small tribe was
discovered on the bleak Greenland coast between 76° and 79° N.;
their southward range being bounded by the glaciers of Melville Bay,
and their northward by the colossal mass of the Humboldt Glacier,
while inland their way is barred by the Sernik-sook, a great glacier of
the interior. These so-called Arctic Highlanders number about one
hundred and forty souls, and their existence “depends on open pools
and lanes of water throughout the winter, which attract animal life.”
Wherever such conditions as these are found, man may be found.
We know that there are or have been inhabitants north of the
Humboldt Glacier, on the very threshold of the Unknown Region; for
Dr. Kane’s expedition discovered the runner of a sledge made of
bone lying on the beach immediately to the north of it. The Arctic
Highlanders, moreover, cherish a tradition that herds of musk-oxen
frequent an island situated far away to the north in an iceless sea.
Traces of these animals were found by Captain Hall’s expedition, in
1871–72, as far north as 81° 30′; and similar indications have been
noted on the eastern side of Greenland. In 1823, Captain Clavering
found twelve natives at Cape Borlase Warren, in lat. 79° N.; but
when Captain Koldewey, of the German expedition, wintered in the
same neighbourhood, in 1869, they had disappeared, though there
were traces of their occupancy, and ample means of subsistence.
Yet they cannot have gone southward, owing to insuperable natural
obstacles; they must have moved towards the North Pole.
We have thus indicated some of the results which may be
anticipated from further researches in the Unknown Region. It is not
to be forgotten, however, that “the unexpected always happens,” and
it is impossible to calculate definitely the consequences which may
ensue from a more extensive investigation. “Columbus,” it has been
justly said, “found very few to sympathize with him, or perceive the
utility of the effort on his part to go out into the unknown waste of
waters beyond the Strait of Gibraltar, in search of a new country.
Who can, at this time, estimate the advantages which have followed
upon that adventure? If now it should be possible to reach the Pole,
and to make accurate observations at that point, from the relation
which the Earth bears to the sun and to the whole stellar universe,
the most useful results are very likely to follow, in a more thorough
knowledge of our globe.”
The reader has now before him the particulars which will enable
him to form an idea of the extent and character of the undiscovered
region of the Pole. Roughly speaking, it is bounded by the 80th
parallel of latitude on the European side, except at a few points
where our gallant explorers have succeeded in crossing the
threshold; on the Asiatic side it descends as low as 75°; and to the
west of Behring Strait as low as 72°. Thus, it varies from 500 or 600
to 1400 or 1500 miles across. Below these parallels, and bounded
by the Arctic Circle, or, in some places, by the 60th parallel, extends
a vast belt of land and water which is generally known as the Arctic
or Circumpolar Regions. These have been more or less thoroughly
explored; and it is to a description of their principal features, their
forms of animal and vegetable life, and their natural phenomena, that
we propose to devote the present volume.
A DESERT OF ICE IN THE ARCTIC REGION.
It is important to remember that the northern shores of Europe,
Asia, and America are skirted by the parallel of 70°, and that the belt
between the 70th and 80th parallels, having been partially explored
by the seamen and travellers of various nations, intervenes as a kind
of neutral ground between the known and the unknown. We may,
indeed, formulate our statement thus; from the Pole to the 80th
degree stretches the unknown; from the 80th to the 70th, the partially
known; while, south of the 70th, we traverse the lands and seas
which human enterprise has completely conquered.
The Circumpolar Zone includes the northernmost portions of the
three great continents, Europe, Asia, and America; and by sea it has
three approaches or gateways: one, through the Northern Ocean,
between Norway and Greenland; another, through Davis Strait,—
both these being from the Atlantic; and a third, through Behring
Strait,—the entrance from the Pacific.
It will be seen that the Circumpolar Regions, as they are now
understood, and as we shall describe them in the following pages,
extend to the south of that imaginary line drawn by geographers
round the North Pole, at a distance from it equal to the obliquity of
the ecliptic, or 23° 30’. Within this circle, however, there is a period of
the year when the sun does not set; while there is another when he
is never seen, when a settled gloom spreads over the face of nature,
—this period being longer or shorter at any given point according as
that point is nearer to or further from the Pole.
But as animal and vegetable life are largely affected by climate, it
may be justly said that wherever an Arctic climate prevails there we
shall find an Arctic or Polar region; and, hence, many countries
below even the 60th parallel, such as Kamtschatka, Labrador, and
South Greenland, fall within the Circumpolar boundary.
The waters surrounding the North Pole bear the general
designation of the Arctic Ocean. But here again it is almost
impossible to particularize any uniform limit southward. It joins the
Pacific at Behring Strait in about lat. 66° N., and consequently in this
quarter extends fully half a degree beyond the Arctic Circle. At
Scoresby Sound, as at North Cape, where it meets the Atlantic, it is
intersected by the parallel of 71°, and consequently falls short of the
Arctic Circle by about 4° 30’.
In the Old World, the Polar Ocean, if we include its gulfs,
extends, in the White Sea, fully two degrees beyond the Arctic
Circle; while at Cape Severo, the northernmost point of Asia, in lat.
78° 25’ N., it is 11° 55’ distance from it. Finally, in the New World it is
everywhere confined within the Circle; as much as 5° at Point
Barrow, about 7° 30’ at Barrow Strait, and about 3° at the Hecla and
Fury Strait.
We may add that, so far as temperature is concerned, the great
gulfs known, in memory of their discoverers, as Davis Strait, Baffin
Bay, and Hudson Bay, are portions of the Arctic Ocean.
Of the more southerly area of this great ocean, the only section
which has been adequately explored to a distance from the
continent, and in the direction of the Pole, is that which washes the
north-east of America. Here we meet, under the collective name of
the Polar Archipelago, with the following islands:—Banks Land,
Wollaston Land, Prince Albert Land, Victoria Land, Prince Patrick
Island, Princess Royal Islands, Melville Island, Cornwallis Island,
North Devon, Beechey Island, Grinnell Land, and North Lincoln.
Further to the east lie Spitzbergen, Jan Mayen Island, Novaia
Zemlaia, New Siberia, and the Liakhov Islands. The chief straits and
inlets are Lancaster Sound, Barrow Strait, Smith Sound, Regent
Inlet, Hecla and Fury Strait, Wellington Channel, and Cumberland
Sound; while further westward are Belcher Channel, Melville Sound,
M’Clintock Channel, Banks Strait, and Prince of Wales Strait.
The Arctic Lands comprehend two well-defined sections, or
zones; that of the forests, and the treeless wastes.
To the latter belong the islands within the Arctic Circle, and also a
considerable tract of the northern continents, forming the “barrens” of
North America, and the “tundras” and “steppes” of European Russia
and Siberia.
The treeless character of this vast area of wilderness is owing to
the bleak sea-winds which drive, without let or hindrance, across the
islands and level shores of the Polar Ocean, compelling even the
most vigorous plant to bend before them and creep along the
ground.
Drearier scenes are nowhere presented than these stony
tundras, or their boundless swamps. Almost the only vegetation are
a few gray lichens, a few dull blackish-looking mosses; the stunted
flowers or crawling grasses that here and there occur do not relieve
the uniform desolation,—they serve simply to enhance its gloomy
character. In summer, indeed, the tundras are full of life; for the
spawning instinct of the salmon and the sturgeon impels them to
enter their rivers and seek the quiet recesses of their mysterious
lakes. The reindeer assemble in numerous herds to feed on the
herbage warmed into temporary vitality by the upward-slanting sun;
the whirr of countless wings announces the coming of the migratory
birds to breed, and feed their young, on the river-banks and the level
shores; and in their trail arrive the eagle and the hawk, intent on
prey.
But with the first days of September a change passes over the
scene. Animal life hastens to the more genial south; the birds
abandon the frozen wastes; the reindeer retires to the shelter of the
forests; the fish desert the ice-bound streams; and a terrible silence
reigns in the desolate wilderness, broken only by the harsh yelp of a
fox or the melancholy hooting of a snow-owl. For some eight or nine
months a deep shroud or pall of snow lies on the whitened plains. No
cheerful sunbeams irradiate it with a rosy glow; the sky is dull and
dark; and it seems as if Nature had been abandoned to eternal
Night.
But blank and dreary as the limitless expanse of snow appears, it
is the security of man in these far northern regions. It affords the
necessary protection to the scanty vegetable life against the rigour of
the long winter season. In Rensselaer Bay, Dr. Kane found, when the
surface temperature had sunk to -30°, a temperature at two feet
deep of -8°, at four feet deep of +2°, and at eight feet deep of +26°,
or no more than 6° below freezing-point. Hence, underneath their
thick frozen pall, the Arctic grasses and lichens maintain a struggling
existence, and are able to maintain it until thoroughly resuscitated by
the summer sun. It is owing to this wise and beneficent provision
that, in the highest latitudes, the explorer discovers some feeble
forms of vegetation. Thus, as Hartwig reminds us, Morton gathered a
crucifer at Cape Constitution, in lat. 80° 45’ N.; and Dr. Kane, on the
banks of the Minturn River, in lat. 78° 52’, met with a flower-growth
which, though fully Arctic in its type, was gaily and richly coloured—
including the purple lychnis, the starry chickweed, and the hesperis,
among the festuca and other tufted grasses.
In the tundras, the most abundant vegetable forms, next to the
lichens and mosses, are the grasses, the crucifers, the saxifrages,
the caryophyles, and the compositæ. These grow fewer and fewer
as we move towards the north, but the number of individual plants
does not decrease. Where the soil is fairly dry, we shall find an
extensive growth of lichens; in moister grounds, these are
intermingled with the well-known Iceland moss. Lichens are
everywhere, except in the sparse tracts of meadow-land lying at the
foot of sheltering hills, or in those alluvial inundated hollows which
are thickly planted with “whispering reeds” and dwarf willows.
It is not easy to trace exactly the boundary between the tundras
and the forest zone. The former descend to the south, and the latter
advances to the north, according to the climatic influences which
prevail; following the isothermic lines of uniform temperature, and not
the mathematical limits of the geographical parallels of latitude.
Where the ground undulates, and hilly ridges break the fury of the icy
blasts, the forests encroach on the stony treeless region; but the
desolate plains strike into the wooded zone in places where the
ocean-winds range with unchecked sway.
THE SWAMPS OF THE OBI.

The southernmost limit of the “barrens” is found in Labrador,
where they descend to lat. 57°; nor is this to be wondered at, when
we remember the peculiar position of that gloomy peninsula, with icy
seas washing it on three sides, and cold winds sweeping over it from
the north. On the opposite coasts of Hudson Bay they do not strike
lower than 60°; and they continue to rise as we proceed westward,
until in the Mackenzie Valley we find the tall forest growth reaching
as far north as 68° or even 70°. Thence they recede gradually, until,
on the bleak shore of Behring Sea, they do not rise higher than 65°.
Crossing into the eastern continent, we find them beginning, in the
land of the Tuski (or Tchuktche), in 63°, and from thence encroaching
gradually upon the tundras until, at the Lena, they reach as high as
71°. From the Lena to the Obi the tundras gain upon the forests, and
in the Obi Valley descend below the Arctic Circle; but from the Obi to
the Scandinavian coast the forests gain upon the tundras,
terminating, after many variations, in lat. 70°.
IN THE FOREST ZONE OF THE NORTH.
The result to which this rapid survey brings us is, that the
“tundras” or “barrens” of Europe, Asia, and America occupy an area
larger than the whole of Europe. The Siberian wilderness is more
extensive than the African Sahara or the South American Pampas.
But of still vaster area are the Arctic forest regions, which stretch in
an “almost continuous belt” through three quarters of the world, with
a breadth of from 15° to 20°—that is, of 1000 to 1400 miles. And it is
a peculiarity of these Circumpolar woods, that they are almost wholly
composed of conifers, and that frequently a wide space of ground is
covered for leagues upon leagues with a single kind of fir or pine.
“This is the forest primeval. The murmuring pines and the hemlocks,
Blended with moss, and in garments green, indistinct in the twilight,
Stand like Druids of eld, with voices sad and prophetic,
Stand like harpers hoar, with beards that rest on their bosoms.”
The American species, however, differ from the Asiatic or

European. While in the Hudson Bay territories grow the white and
black spruce,[2] the Canadian larch,[3] and the gray pine[4]; in
Scandinavia and Siberia, the Siberian fir and larch,[5] the Picea
olovata, and the Pinus umbra flourish. But both in the Old World and
the New the birch advances beyond the fir and pine, and on the
banks of the rivers and the shores of the lakes dwarf willows form
immense and almost impenetrable thickets. The Arctic forests also
include various kinds of ash, elder, and the service tree; and though
orchard trees are wholly wanting, both man and beast find a great
boon in the bilberries, cranberries, bog-berries, and the like, which
grow plentifully in many localities.
The area of the Arctic flora comprises Greenland, in the western
hemisphere, and extends considerably to the south of the Arctic
Circle, especially on the coasts, where it reaches the parallel of 60°
N. lat., and even overpasses it.
In Greenland the vegetation is more truly of an Arctic character
than even in Iceland. The valleys are covered with marsh-plants and
dingy mosses; the gloomy rocks are encrusted with lichens; while
the grasses on the meadow-lands that border the fiords and inlets
are nearly four times less varied than those of Iceland.
The flora of Iceland is approximative to that of Great Britain; yet
only one in every four of British plants is included in it. The total
number of species may be computed at eight hundred and seventy,
of which more than half blossom; this proportion is greater than
prevails in Scotland, but then only thirty-two are of woody texture.
They are scattered about in groups according as they prefer a
marshy, volcanic, dry, or marine soil. Many bloom in the immediate
vicinity of the hot springs; some not far from the brink of the basin of
the Great Geyser, where every other plant is petrified; and several
species of confervæ flourish in a spring the waters of which are hot
enough, it is said, to boil an egg.
From the nature of the Arctic forests, the reader will be prepared
to learn that they are not inhabited, like those of the Tropics, by
swarms of animals; or made musical by the songs of birds, like our
European woods. Even the echoes are silent, except when the
hoarse wind bears to them the peculiar cry of the reindeer, the howl
of the wolf, or the sharp scream of some bird of prey. Insect life,
however, is active and abundant; and our Arctic travellers have
suffered greatly from the legions of gnats which haunt their swampy
recesses.
Passing from the forest region into the treeless wastes, we may
glance once again at their strikingly impressive features. North of the
62nd parallel no corn can ripen, on account of the fatal power of the
winds which pour down from the Arctic Ocean. As we advance to the
northward, a wide-spread area of desolation stretches before us: salt
steppes, stony plains, boundless swamps, and lakes of salt and
fresh water. So terrible is the cold that the spongy soil is perpetually
frozen to the depth of some hundred feet below the surface; and the
surface itself, though not thawed until the end of June, is again ice-
bound by the middle of September. One of the most graphic
sketches with which we are acquainted of the extreme Siberian
desert is furnished by Admiral von Wrangel, who travelled during the
winter from the mouth of the Kolyma to Behring Strait.
Here, he says, endless snows and ice-crusted rocks bound the
horizon; Nature lies shrouded in all but perpetual winter; life is a
constant conflict with privation and with the terrors of cold and
hunger; the grave of Nature, containing only the bones of another
world. The people, and even the snow, throw off a continual vapour;
and this evaporation is instantly changed into millions of needles of
ice, which make a noise in the air like the sound of torn satin or the
rustle of thick silk. The reindeer take to the forest, or crowd together
for heat; and the raven alone, the dark bird of winter, still smites the
frosty air with heavy laborious wing, leaving behind him a long trail of
thin vapour to mark the course of his solitary flight. The trunks of the
thickest trees are rent with a loud clang, masses of rock are torn
from their sites, the ground in the valleys is split into a myriad
fissures, from which the waters that are underneath bubble up,
throwing off a cloud of smoke, and immediately congealing into ice.
The atmosphere grows dense; the glistening stars are dimmed. The
dogs outside the huts of the Siberians burrow in the snow, and their
howling, at intervals of six or eight hours, interrupts the general
silence of winter.
The abundance of fur-bearing animals in the less rigorous parts
of the tundras has induced the hardy Russians to colonize and build
towns on these confines of the Frozen World. Yakutsk, on the river
Lena, in 62° 1′ 30″ N., may be regarded, perhaps, as the coldest
town on the Earth. The ground is perpetually frozen to the depth of
more than 400 feet, of which three feet only are thawed in summer,
when Fahrenheit’s thermometer frequently marks 77° in the shade.
Yet in winter the rigour of the climate is so extreme that mercury is
constantly frozen for two and occasionally even for three months.
From the data set forth in the preceding pages, the reader will
conclude that, as indeed results from physical laws, the line of
perpetual snow will be found to descend lower and lower on
advancing to the Pole. By the line of perpetual snow we mean, of
course, the limit above which a continual frost endures. Now, this
limit varies according to climate. The lower the temperature, the
lower the snow-line; the higher the temperature, the higher the snow-
line. In the Tropics it does not sink below the summits of the loftiest
mountains. Thus, at 1° from the Equator, where the mean
temperature at the sea-level is 84°.2, the snow-line must be sought
at the elevation of 15,203 feet; in 51° 30’ lat., the latitude of London,
it is usually found at about 5900 feet; in lat. 80°, where the mean
temperature is 33°.6, it sinks to 457 feet. These figures, however,
represent its normal elevations; but temperature, as we all know, is
greatly affected by local circumstances, and therefore the perpetual
snow-line varies greatly in height. Owing to causes already
explained, the snow-line in the Circumpolar Regions sinks to a very
low level; and, therefore, many mountainous regions or elevated
table-lands, such as Spitzbergen, Greenland, and Novaia Zemlaia,
which, in a more temperate climate, would bloom with emerald
slopes and waving woods, are covered with huge glaciers and fields
of ice, with apparently interminable reaches of untrodden snow.
It should be noted, however, that nowhere does the perpetual
snow-line descend to the water’s edge; nowhere has the spell of
winter absolutely crushed the life out of all vegetation. Lichens and
grasses, on which the reindeer gains its hardy subsistence, are
found near lat. 80°; even on the awful plains of Melville Island the
snow melts at midsummer; and the deserts of New Siberia afford
food for considerable numbers of lemmings. As far as man has
reached to the north, says a popular and accurate writer, vegetation,
when fostered by a sheltered situation and the refraction of solar
heat from the rocks, has everywhere been found to rise to a
considerable altitude above the level of the sea; and should there be
land at the North Pole, we may reasonably suppose that it is
destitute neither of animal nor vegetable life. It would be quite wrong
to conclude that the cold of winter invariably increases as we
approach the Pole, the temperature of a land being controlled by
many other causes besides its latitude. Even in the most northern
regions visited by man, the influence of the sea, particularly where
favoured by warm currents, considerably mitigates the severity of the
winter, while at the same time it diminishes the heat of summer. On
the other hand, the large continental tracts of Asia or America that
slope towards the Pole, possess a more rigorous winter and a fiercer
summer than many coast lands or islands situated far nearer to the
Pole. For example: the western shores of Novaia Zemlaia, fronting a
wide expanse of sea, have an average winter temperature of only
-4°, and a mean summer temperature which rises very little above
the freezing-point of water (+ 36° 30’); while Yakutsk, situated in the
centre of Siberia, and 20° nearer to the Equator, has a winter
temperature of -36° 6’, and a summer of + 66° 6’.
But though such are the physical conditions of the Polar Regions,
it must not be supposed that Nature wears only a severe and
repellent aspect. There is something beautiful in the vast expanse of
snowy plain when seen by the light of a cloudless moon; something
majestic in the colossal glaciers which fill up the remote Arctic
valleys; something picturesque in the numerous icebergs which
grandly sail down the dark Polar waters; something mysterious and
wonderful in the coruscations of the Aurora, which illuminates the
darkness of the winter nights with the glory of the celestial fires. The
law of compensation prevails in the far North, as in the glowing and
exuberant regions of the Tropics.

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Materials Chemistry of Ceramics

Transparent Ceramics: Materials, Engineering, and

Ultra High Temperature Ceramics Materials for Extreme

The chemistry of medical and dental materials Second

Chemically Bonded Phosphate Ceramics. Twenty-First

Chemistry of High Energy Materials 4 ed 4th Edition

Physics and Chemistry of Carbon-Based Materials: Basics

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ISBN 978-981-13-9934-3 ISBN 978-981-13-9935-0 (eBook)

© Springer Nature Singapore Pte Ltd. 2019

Inorganic chemistry is based on the understanding of various elements on the Earth,

Fukuoka, Japan Junichi Hojo

1 Crystal Structures of Inorganic Materials . . . . . . . . . . . . . . . . . . . . 1

Junichi Hojo Faculty of Engineering, Kyushu University, Fukuoka, Japan

Shu Yin Institute of Multidisciplinary Research for Advanced Materials, Tohoku

Junichi Hojo and Miki Inada

Keywords Chemical bonding · Crystal · Glass · Defect structure · Dimensional

© Springer Nature Singapore Pte Ltd. 2019 1

1.1 Fundamental Structures and Properties of Materials

Powder Crystal grain Grain boundary

Forming Die pressing

Sintering Pressureless sintering

1.2 Crystal Structure of Inorganic Material

1.2.1 Packing Manner of Rigid Spheres

(c) Cubic closed packing (CCP)

(d) Hexagonal closed packing (HCP)

manner of spheres, the stable packing is based on triangular arrangement. When

1.2.2 Coordination Conﬁguration

(a) 3-coordination (b) 4-coordination

(c) 6-coordination (d) 8-coordination

1.2.3 Covalent Crystals

Fig. 1.5 Crystal structure empty p orbital pared electrons

Diamond has three-dimensional network structure consisting of carbon tetrahedrons

1.2.4 Ionic Crystals

1.2.4.1 Coordination Number and Crystal Structure

: Cation : Anion : Cation : : Anion

Fig 1.7 Wurtzite structure

(a) Hexagonal column (b) Rhombohedral column

Fig. 1.8 Crystal structures

(a) Rock salt (b) CsCl

1.2.4.2 Various Chemical Compositions

1.2.4.3 Solid Solution and Complex Compound

Fig. 1.10 Crystal structure

Fig. 1.11 Crystal structure

1/4, 3/4 1/4, 3/4

1/4, 3/4 1/4, 3/4

Fig. 1.12 Crystal structure

(a) Cubic lace (b) Ion displacement in tetragonal

1.3 Defect Structures in Crystal

1.3.1 Point Defects

1.3.2 The Schottky Defect and the Frenkel One

null ¼ V00Ca þ 2VF• null ¼ VU þ 2VO• •

BeO null ¼ V00Be þ VO• • AgBr, AgCl X

1.3.3 Nonstoichiometric Defects

Compounds of typical elements have deﬁnite compositions depending on the ionic

ZnO ¼ Zni x þ 1=2O2 ð1:1Þ

Znix ¼ Zni • þ e0 ð1:2Þ

1.3.4 Defects in Solid Solution

CaO ¼ CaZr 00 þ VO • • þ OO x ð1:4Þ

Fig. 1.16 Dependence of

Al2 O3 ¼ 2AlZn • þ 2OO x þ 2e0 þ 1=2O2 , ð1:5Þ

Li2 O þ 1=2O2 ¼ 2LiCo 0 þ 2h • þ 2OO x , ð1:6Þ