MME 2012-CERAMICS- II

Assist. Prof. Dr. Gülhan Çakmak

Room: 104

1
 LECTURES
Time: Tuesday 13:30-16:20 (Lecture)

Activities:
• Present new material

• Announce reading and homework

• Take quizzes and midterms*

*Make-ups given only for emergencies.

b 2
 Grading
• 2. midterm exams- 40 % (together with
laboratory reports)
• Pop-quizes-20 %
• Final Exam- 40 %

3
 COURSE MATERIAL
• Lecture Notes
• C.Barry Carter, M. Grant Norton] Ceramic Materials
• David Richerson Modern Ceramic Engineering

f 4
You will learn about:
• Summary of Previous knowledge
• Defects in ceramics
• Ceramic phase diagrams
• Mechanical and physical properties of materials
• Magnetic, optical and electrical properties of materials
• Glass materials
• Production of glasses
• Application of glass ceramics

a
 Introduction
• In materials science we often divide materials into distinct
classes. The primary classes of solid materials are ceramics,
metals, and polymers. This classification is based on the types of
atoms involved and the bonding between them.
• In this part we will define what we mean by a “ceramic” and will
also describe some of the general properties of ceramics.
• Since the classification of materials strongly depends on the
type of bonding and the type of bonding depens on the atomic
structure of the material, we will continue with atomic strucure
and bonding.

6
 ceramics
• Ceramics (ceramic materials) are non-metallic inorganic
compounds formed from metallic (Al, Mg, Na, Ti, W) or semi-
metallic (Si, B) and non-metallic (O, N, C) elements.
• Atoms of the elements are held together in a ceramic structure by
one of the following bonding mechanism: Ionic Bonding, Covalent
Bonding, Mixed Bonding (Ionic-Covalent).
• .They consist of arrays of interconnected atoms; there are no
discrete molecules.
• The majority of ceramics are compounds of metals or metalloids
and nonmetals. Most frequently they are oxides, nitrides, and
carbides. However, we also classify diamond and graphite as
ceramics.

7
 GENERAL PROPERTIES
Brittleness. This probably comes from personal
experiences such as dropping a glass beaker or a dinner
plate.
The reason that the majority of ceramics are brittle is the
mixed ionic–covalent bonding that holds the constituent
atoms together. At high temperatures (above the glass
transition temperature) glass no longer behaves in a brittle
manner; it behaves as a viscous liquid. That is why it is
easy to form glass into intricate shapes. So what we can
say is that most ceramics are brittle at room temperature
but not necessarily at elevated temperatures.
8
 GENERAL PROPERTIES
• Poor electrical and thermal conduction. The valence electrons are
tied up in bonds, and are not free as they are in metals. In metals it
is the free electrons—the electron gas—that determines many of
their electrical and thermal properties. Diamond, which we
classified as a ceramic in has the highest thermal conductivity of
any known material. The conduction mechanism is due to phonons,
not electrons.
• Ceramics can also have high electrical conductivity:
(1) the oxide ceramic, ReO3, has an electrical conductivity at room
temperature similar to that of Cu
(2) the mixed oxide YBa2Cu3O7 is an HTSC; it has zero resistivity below
92 K. These are two examples that contradict the conventional wisdom
when it comes to ceramics. 9
 GENERAL PROPERTIES
• Compressive strength. Ceramics are stronger in
compression than in tension, whereas metals have
comparable tensile and compressive strengths. This
difference is important when we use ceramic
components for load-bearing applications.
• Ceramics generally have low toughness, although
combining them in composites can dramatically
improve this property

10
 GENERAL PROPERTIES
• Chemical insensitivity. A large number of ceramics are
stable in both harsh chemical and thermal
environments. Pyrex glass is used widely in chemistry
laboratories specifically because it is resistant to many
corrosive chemicals, stable at high temperatures (it
does not soften until 1100 K), and is resistant to
thermal shock because of its low coefficient of thermal
expansion (33 × 10−7 K−1). It is also widely used in
bakeware
• Transparent. Many ceramics are transparent because
they have a large Eg. Examples include sapphire watch
covers, precious stones, and optical fibers.

11
• Some of the important properties of solid materials
depend on geometrical atomic arrangements, and also
the interactions that exist among constituent atoms or
molecules.
• In this part we will considers several fundamental and
important concepts—namely, atomic structure,
electron configurations in atoms and the periodic
table, and the various types of primary and secondary
interatomic bonds that hold together the atoms that
compose a solid.

12
 Background You need to know
• BONDING AND PROPERTIES

ISSUES TO ADDRESS...
• What promotes bonding?

• What types of bonds are there?

• What properties are inferred from bonding?

13
• An understanding of the behavior of electrons
in atoms and crystalline solids necessarily
involves the discussion of quantum
mechanical concept.
• however, we’ll not see the detailed
exploration of these principles.
• An early outgrowth of quantum mechanics
was the simplified Bohr atomic model.

14
 Each atom consists of a very small nucleus composed of protons and neutrons, which
is encircled by moving electrons.

Each chemical element is

BOHR ATOM characterized by the number of
protons in the nucleus, or the
orbital electrons: atomic number (Z).
n = principal For an electrically neutral or
quantum number 1
complete atom, the
n=3 2 atomic number also equals the
number of electrons

Adapted from Fig. 2.1,

Callister 6e.

Nucleus: Z = # protons
1 for hydrogen to 94 for plutonium
N = # neutrons The atomic mass (A) of a specific atom may be
expressed as the sum of the masses of protons and
Atomic mass A ≈ Z + N neutrons within the nucleus 15
 ELECTRON ENERGY STATES
Electrons...

• have discrete energy states

• tend to occupy lowest available energy state.

3 16
 This Bohr model was eventually found to
have some significant limitations because
of its inability to explain several
phenomena involving electrons.

A resolution was reached with a wave-

mechanical model, in which the electron
is considered to exhibit both wavelike and
particle-like characteristics.

With this model, an electron is no longer

treated as a particle moving in a discrete
orbital; rather, position is considered to
be the probability of an electron’s being
Figure compares Bohr at various locations around the nucleus.
and wave-mechanical In other words, position is described by a
models for the hydrogen probability distribution or electron cloud.
17
atom.
Using Wave Mechanics, every electron in an atom is characterized by four parameters
called quantum numbers. The size, shape, and spatial orientation of an electron’s
probability densities are specified by these quantum numbers.
Furthermore, Bohr energy levels separate into electron subshells, and quantum
numbers dictate the number of states within each subshell. Shells are specified by a
principal quantum number n, which may take on integral values beginning with
unity; sometimes these shells are designated by the letters K, L, M, N, O, and so
on, which correspond, respectively, to n 1, 2, 3, 4, 5, . . . 18
The second quantum number, l, signifies the subshell, which is denoted by a
lowercase letter—an s, p, d, or f; it is related to the shape of the electron subshell.

In addition, the number of these subshells is restricted by the magnitude of n.

Allowable subshells for the several n values are also presented in Table 2.1
The number of energy states for each subshell is determined by the third quantum
number,ml.
For an s subshell, there is a single energy state, whereas for p, d, and f subshells,
19
three, five, and seven states exist, respectively
 STABLE ELECTRON CONFIGURATIONS
Stable electron configurations...

• have complete s and p subshells

• tend to be unreactive.

Adapted from Table 2.2,

Callister 6e.

4 20
 SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.
Electron configuration
1s1
1s2 (stable)
1s22s1
1s22s2
1s22s22p1 Adapted from Table 2.2,
1s22s22p2 Callister 6e.
...
1s22s22p6 (stable)
1s22s22p63s1
1s22s22p63s2
1s22s22p63s23p1
...
1s22s22p63s23p6 (stable)
...
1s22s22p63s23p63d10 4s246 (stable)
• Why? Valence (outer) shell usually not filled completely.
5 21
At this point, comments regarding these electron
configurations are necessary.

First, the valance electrons are those that occupy the

outermost shell.
These electrons are extremely important
• they participate in the bonding between atoms to
form atomic and molecular aggregates.
• many of the physical and chemical properties of
solids are based on these valance electrons.

22
Classified according to electron configuration
THE PERIODIC TABLE
• Columns: Similar Valence Structure

Adapted
from Fig. 2.6,
Callister 6e.

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
23
 ELECTRONEGATIVITY
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell
University.
24
 ATOMIC BONDING IN SOLIDS
• An understanding of many of the physical
properties of materials is enhanced by a
knowledge of the interatomic forces that bind
the atoms together.
• Three different types of primary bond are
found in solids.
– Ionic
– Covallent
– Metallic

25
• For each type, the bonding necessarily
involves the valance electrons
• The nature of the bond depends on the
electron structure of constituent atoms.

These three types of bonding arises from the

tendency of atoms to assume stable electron
structures (like those of inert gases)

26
 IONIC BONDING
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl

27
 EXAMPLES: IONIC BONDING
NaCl
MgO
H He
2.1 CaF2 -
Li Be O F Ne
1.0 1.5 CsCl 3.5 4.0 -
Na Mg Cl Ar
0.9 1.2 3.0 -
K Ca Ti Cr Fe Ni Zn As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 2.0 2.8 -
Rb Sr I Xe
0.8 1.0 2.5 -
Cs Ba At Rn
0.7 0.9 2.2 -
Fr Ra
0.7 0.9

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell
University.
9 28
• Ionic bonding is non-directional→ the
magnitude of the bond is equal in all
directions around ion.
• For ionic materials to be stable , all positive
ions must have as nearest neighbors
negatively charged ions in a three dimensional
scheme.

29
 • Predominant bonding in Ceramics

Bonding Energies and Melting Temperatures for Various Substances

Bonding energies of ionic materials 600-1500 Kj/mol.

They are relatively large and high M.T.
Charactheristically hard and brittle and, electrically and thermally insulative. 30
 The crystal structure of an ionically bonded material is
determined by the number of atoms of each element required
for electrical neutrality and the optimum packing based on the
relative sizes of the ions.

Table shows ioniv radii for ions with C.N. Of 4 and 6. The relative size of the ions determines
the C.N. 31
The relative size of the ions determines the C. N.

Figure shows stable and unstable configurations.

Cation/anion:0.155-0.225→ C.N:3
Cation/anion:0.225-0.414→ C.N:4
Cation/anion:0.414-0.732→ C.N:6
Cation/anion:> 0.732 → C.N:8

32
33
Most of the ionic structures are close
packed. Bonding is associated with the s
electron shells (which have spherical
probabilitr distribution) and would be
non directional if purely ionic. However,
there is a tendency for increased
electron concentration between atom
centers, which provides a degree of non-
ionic character.

The degree of ionic character of a compound can

be estimated using the electronegativity scale
(shown in figure ) derived by Pauling.
Electronegativity is a measure of an atom’s ability
to attract electrons and is roughly proportional to
the sum of the energy needed to add an electron
(electron affinity) and to remove an electron
(ionization potential). The larger the
electonegativity difference between atoms in a
compound, the larger the degree of ionic character.
The semiemprical curve derived by Pauling is
shown in figure 34
35
36
 COVALENT BONDING
• covalent bonding occurs when two or more atoms share electrons such that
each achieves a stable filled electron shell.
Two atoms that are covalently bonded will each contribute at least one electron to the
bond, and the shared electrons may be considered to belong to both atoms.

Seen in ceramic materials and organic compounds

• Example: CH4

C: has 4 valence e,
needs 4 more
H: has 1 valence e,
needs 1 more
Electronegativities
are comparable.

Adapted from Fig. 2.10, Callister 6e. 37

Unlike metallic and ionic bonds, covalent bonds are
directional. Each covalent bond conisit of a pair of
electrons shared between two protons such that
the probability distribution for each electron
resembles a dumbbell. This produces the
directionality of the bond. The bonding of carbon
atoms to produce diamond is a good example.

38
• C-C covalent bonding
• C-…. 2p2 →four valance electrons available for bonding.
• Resulting in a structure in which each carbon atom is
covalently bonded to four carbon atoms in tetrahedral
orientattion.
• Central carbon atom→initial 2 electrons + from shared
electrons:10 electrons.
• This is equivalent to the filled outer shell of a neon atom
and is very stable condition.
• Outer carbon atoms of the tetrahedron is bonded
directionally to three additional carbon atoms in the
structure
39
The continuous periodic covalent bonding of carbon atoms in
diamond results in high hardness, high melting temperature, and
low electrical conductivity at low temperature. Silicon carbide has
similar covalent bonding and thus high hardness, high melting
temperatue and low electrical conductivity at low temperature.
Diatomic gasses (H2, O2, N2) are another example of covalent
bonding where molecules rather than interconnected solid
structures are formed.

40
 EXAMPLES:H2OCOVALENT BONDING

column IVA
H2 F2
C(diamond)
H He
2.1
SiC - Cl2
Li Be C O F Ne
1.0 1.5 2.5 2.0 4.0 -
Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -
K Ca Ti Cr Fe Ni Zn Ga Ge As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 1.6 1.8 2.0 2.8 -
Rb Sr Sn I Xe
0.8 1.0 1.8 2.5 -
Cs Ba Pb At Rn
0.7 0.9 1.8 2.2 -
Fr Ra
0.7 0.9
Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is GaAs
adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright
1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

• Molecules with nonmetals Cl2

• Molecules with metals and nonmetals
• Elemental solids (RHS of Periodic Table) diamond, Silicon
• Compound solids (about column IVA) GaAs, SiC
11 41
The directional bonding of covalent materials
results in structures that are not close packed. This
has a pronounced effect on the properties, in
particular density and thermal expansion. Close
packed materials (metals , ionic-bonded ceramics )
have relatively high thermal expansion
coefficients.
Close packed sytem→ thermal expansion is
acumullated throughout the structure
Covalent bonded ceramics→some of the
thermalgrowth of the individual atoms is absorbed
by the open space in the structure.
42
• Covalent bonding occurs between atoms of
similar electronegativity which are not close in
electronic structure to the inert gas
configuration.

• Atoms such as C, N, Si, Ge and Te are

intermediate electronegativity and form high
covalent structures.

• Atoms witha greater difference in

electronegativity form compounds having a less
covalent bond nature.
43
Example: what is the approximate degree
of covalent character of diamond ? of
Si3N4? And SiO2 ?

44
45
 IONIC AND COVALENT BOND
COMBİNATIONS
• Many ceramic materials have a combination of ionics and
covalent bonding.

A similar type of combined bonding results in the many silicate compositions that
are so important to ceramic technology. These silicate structures are based on the
SiO4 -4 tetrahedron and the various ways these terahedron can be linked.

Terahedra link by sharing corners.

Result: frame, chain, ring, layer structures

46
47
 METALLIC BONDING
• Arises from a sea of donated valence electrons
(1, 2, or 3 from each atom).
These valance electrons are
not bound to any particular
atom in the solid and more or
less free to drift througout the
entire metal.
‘sea of electron , ‘electron
cloud’.
The remaining non-valance
electron+ nuclei→ ion cores.

• Primary bond for metals and their alloys

12 48
• The free electrons shield the positively
charged ion cores from mutually repulsive
electrostatic forces, which they would
otherwise exert upon one another;
consequently, the metallic bond is non-
directional

49
Bonding energies and melting temperatures for several metals are
listed in Table .

Bonding may be weak or strong; energies range from 68 kJ/mol (0.7

eV/atom) for mercury to 849 kJ/mol (8.8 eV/atom) for tungsten. Their
respective melting temperatures are 39 and 3410C (38 and 6170F).

Metallic bonding is found in the periodic table for Group IA and IIA
elements and, in fact, for all elemental metals.
50
51
 SECONDARY BONDING
Secondary bonds are generally much weaker than primary
bonds, although they can be critical in determining both the
existence of a particular crystal structure and the properties of a
material.
The origin of van der Waals bonding (known also as the London
interaction) is weak electrostatic attraction between closely
spaced neutral atoms and molecules. The explanation for this
universally attractive force is that even a neutral atom has a
charge distribution that fluctuates very rapidly.
When two atoms are brought together the fluctuations in one
can induce a field around the other and this coupling results in
the attractive force. Although van der Waals bonding is present in
all crystalline solids it is important only when not overwhelmed
by strong bonding forces
13 52
 SECONDARY BONDING
Arises from interaction between dipoles
• Fluctuating dipoles

Adapted from Fig. 2.13, Callister 6e.

• Permanent dipoles-molecule induced

Adapted from Fig. 2.14,
-general case: Callister 6e.

Adapted from Fig. 2.14,

-ex: liquid HCl Callister 6e.

-ex: polymer

13 53
In ceramics, van der Waals bonding is important in
layered structures. In pyrophyllite, a layered
silicate, van der Waals bonds between the oxygen
ions in adjacent layers allow easy slip parallel to
the layers. In the mineral talc, van der Waals
bonds between the layers are even weaker than in
pyrophyllite. You can cleave talc with your
fingernail.

54
 SUMMARY: BONDING
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Variable Directional
Covalent large-Diamond semiconductors, ceramics
small-Bismuth polymer chains)

Variable
Metallic large-Tungsten Nondirectional (metals)
small-Mercury
Directional
Secondary smallest inter-chain (polymer)
inter-molecular

14 55
 SUMMARY: PRIMARY
Ceramics
BONDS
Large bond energy
large Tm
(Ionic & covalent bonding): large E
small a

Metals Variable bond energy

moderate Tm
(Metallic bonding):
moderate E
moderate a

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small T
small E
large a

18 56
CHAPTER 2: CRYSTAL STRUCTURES

ISSUES TO ADDRESS...
• How do atoms assemble into solid structures?
(for now, focus on metals)

• How does the density of a material depend on

its structure?

• When do material properties vary with the

sample (i.e., part) orientation?

1 57
Most ceramics are crystalline. The exception is glass, which
we usually discuss separately. Not only do the properties of
ceramic crystals depend on how the atoms or ions are
arranged, but the type and nature of defects also depend on
crystal structure.

Sixty-five (almost 90%) of the metallic elements are either

cubic or hexagonal. In ceramics, many of the most important
materials are neither cubic nor hexagonal, so we need to be
more familiar with the rest of the subject.
In order to understand the crystal structures in ceramics, we
first start with the crystal structure found in metallic materials
(easier one)
58
 MATERIALS AND PACKING
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers
crystalline SiO2
Adapted from Fig. 3.18(a),
Callister 6e.

Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling

"Amorphous" = Noncrystalline noncrystalline SiO2

Adapted from Fig. 3.18(b),
Callister 6e.

3 59
 METALLIC CRYSTALS
• tend to be densely packed.

• have several reasons for dense packing:

-Typically, only one element is present, so all atomic

radii are the same.
-Metallic bonding is not directional.
-Nearest neighbor distances tend to be small in
order to lower bond energy.
• have the simplest crystal structures.

We will look at three such structures...

4 60
 SIMPLE CUBIC STRUCTURE (SC)
• Rare due to poor packing (only Po has this structure)
• Close-packed directions are cube edges.

• Coordination # = 6
(# nearest neighbors)

(Courtesy P.M. Anderson)

5 61
 ATOMIC PACKING FACTOR

• APF for a simple cubic structure = 0.52

Adapted from Fig. 3.19,

Callister 6e. 6 62
 BODY CENTERED CUBIC STRUCTURE
(BCC)
• Close packed directions are cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

• Coordination # = 8

Adapted from Fig. 3.2,

Callister 6e.

(Courtesy P.M. Anderson) 7 63

 ATOMIC PACKING FACTOR:
• APF for a body-centered cubic structure = 0.68
BCC

Unit cell contains:

1 + 8 x 1/8
= 2 atoms/unit cell
R
Adapted from a
Fig. 3.2,
Callister 6e.

8 64
 FACE CENTERED CUBIC STRUCTURE
(FCC)
• Close packed directions are face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

• Coordination # = 12

Adapted from Fig. 3.1(a),

Callister 6e.

(Courtesy P.M. Anderson)

9 65
 ATOMIC PACKING FACTOR:
• APF for a body-centered cubic structure = 0.74
FCC

Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister 6e.

10 66
 FCC STACKING
• ABCABC... Stacking Sequence
SEQUENCE
• 2D Projection
A
B B
C
A
A sites B B B
C C
B sites B B
C sites

• FCC Unit Cell

11 67
 HEXAGONAL CLOSE-PACKED
STRUCTURE (HCP)
• ABAB... Stacking Sequence

• 3D Projection • 2D Projection

A sites

B sites

A sites
Adapted from Fig. 3.3,
Callister 6e.

• Coordination # = 12

• APF = 0.74

12 68
 THEORETICAL DENSITY, 

Example: Copper
Data from Table inside front cover of Callister (see next slide):
• crystal structure = FCC: 4 atoms/unit cell
• atomic weight = 63.55 g/mol (1 amu = 1 g/mol)
• atomic radius R = 0.128 nm (1 nm = 10 -7cm)

Result: theoretical Cu = 8.89 g/cm3

Compare to actual: Cu = 8.94 g/cm3
14 69
 Characteristics of Selected Elements at 20C
At. Weight Density Atomic radius
Element Symbol (amu) (g/cm3) (nm)
Aluminum Al 26.98 2.71 0.143
Argon Ar 39.95 ------ ------
Barium Ba 137.33 3.5 0.217
Beryllium Be 9.012 1.85 0.114
Boron B 10.81 2.34 ------ Adapted from
Table, "Charac-
Bromine Br 79.90 ------ ------ teristics of
Cadmium Cd 112.41 8.65 0.149 Selected
Elements",
Calcium Ca 40.08 1.55 0.197 inside front
Carbon C 12.011 2.25 0.071 cover,
Cesium Cs 132.91 1.87 0.265 Callister 6e.
Chlorine Cl 35.45 ------ ------
Chromium Cr 52.00 7.19 0.125
Cobalt Co 58.93 8.9 0.125
Copper Cu 63.55 8.94 0.128
Flourine F 19.00 ------ ------
Gallium Ga 69.72 5.90 0.122
Germanium Ge 72.59 5.32 0.122
Gold Au 196.97 19.32 0.144
Helium He 4.003 ------ ------
Hydrogen H 1.008 ------ ------ 15 70
 DENSITIES OF MATERIAL CLASSES
metals• ceramics• polymers
Why?
Metals have...
• close-packing
(metallic bonding)
• large atomic mass
Ceramics have...
• less dense packing
(covalent bonding)
• often lighter elements
Polymers have...
• poor packing
(often amorphous)
• lighter elements (C,H,O)
Composites have...
• intermediate values Data from Table B1, Callister 6e.
16 71
 MATERIALS AND PACKING
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers
crystalline SiO2
Adapted from Fig. 3.18(a),
Callister 6e.

Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling

"Amorphous" = Noncrystalline noncrystalline SiO2

Adapted from Fig. 3.18(b),
Callister 6e.

3 72
the properties of crystalline solids depend on the crystal structure
of the material, the manner in which atoms, ions, or molecules are
spatially arranged.

There is an extremely large number of different crystal structures all

having long-range atomic order; these vary from relatively simple
structures for metals to exceedingly complex ones, as displayed by
some of the ceramic and polymeric materials.

73
 CRYSTAL SYSTEMS
The atomic order in crystalline solids indicates that small groups of
atoms form a repetitive pattern. Thus, in describing crystal
structures, it is often convenient to subdivide the structure into
small repeat entities called unit cells.

The unit cell is the basic structural unit or building block of the
crystal structure and defines the crystal structure by virtue of its
geometry and the atom positions within.

Because there are many different possible crystal structures, it is

sometimes convenient to divide them into groups according to
unit cell configurations and/or atomic arrangements. One such
scheme is based on the unit cell geometry, that is, the shape of
the appropriate unit cell parallelepiped without regard to the
atomic positions in the cell.
74
 CRYSTAL SYSTEMS
Crystal Lattice: A three-dimensional array of points related by
translational symmetry. The translation can occur in three
independent directions giving three independent base vectors. We
can fully describe such a lattice by three vectors, a, b, c, and three
angles, α, β, γ. The special property of a crystal lattice is that the
lattice points are identical:

Unit Cell: The vectors a, b, c define a

cell. There is, in principle, an infinite
number of ways to define a unit cell in
any crystal lattice.
Lattice Parameters: The vectors a, b,
c and the angles α, β, γ are called the
75
lattice parameters of the unit cell.
Crystal System: There
are seven unique shapes
that can each be used to fill
three-dimensional space.
These are the seven crystal
systems into which all crystals
are classified.

76
 Bravais Lattices
Different options are available for stacking atoms in unit cell. For example, three options exist
for a cubic cell:
(1) At the eight corners
(2) At the eight corners plus at the center of each cube
(3) At the eight corners plus at the center of each face of the cube.

These atom positions are referred to as lattice points. Fourteen points are possible for lattice
points in the seven crystal systems (Bravais Lattices)

These are constructed as three separate types:

Primitive (P) lattices—one lattice point per
unit cell
Body-centered (I) lattices—a lattice point at 77
the corners and one in the center of the cell
A-, B-, C-, or F-centered lattices—a lattice
point at the corners and others at one (A, B, C)
or all three (F) of the faces
 Crystallographic Points,
Directions, and Planes
When dealing with crystalline materials, it often becomes
necessary to specify a particular point within a unit cell, a
crystallographic direction, or some crystallographic plane of
atoms. Labeling conventions have been established in which
three numbers or indices are used to designate point
locations, directions, and planes.
- a right-handed coordinate system consisting of three (x,
y, and z) axes situated at one of the corners and coinciding
with the unit cell edges,
- For some crystal systems—namely, hexagonal,
rhombohedral, monoclinic, and triclinic—the three axes
are not mutually perpendicular, as in the familiar
78
Cartesian coordinate scheme.
POINT COORDINATES
• The position of any
point located within a
unit cell may be
specified in terms of
its coordinates as
fractional multiples of
the unit cell edge
lengths (i.e., in terms
of a, b, and c).

79
Example: For the unit cell shown in the
accompanying sketch (a), locate the point having
coordinates ¼ 1 ½ .

80
Example:

81
Example :Specify point coordinates for all atom
positions for a BCC unit cell

82
83
84
 CRYSTALLOGRAPHIC DIRECTIONS
A crystallographic direction is defined as a line between two points,
or a vector.
The following steps are used to determine the three directional
indices:
1. A vector of convenient length is positioned such that it passes
through the origin of the coordinate system. Any vector may be
translated throughout the crystal lattice without alteration, if
parallelism is maintained.
2. The length of the vector projection on each of the three axes is
determined; these are measured in terms of the unit cell dimensions
a, b, and c.
3. These three numbers are multiplied or divided by a common
factor to reduce them to the smallest integer values.
4. The three indices, not separated by commas, are enclosed in
square brackets, thus: [uvw]. The u, v, and w integers correspond to
85
the reduced projections along the x, y, and z axes, respectively
For each of the three axes, there will exist both
positive and negative coordinates. Thus negative
indices are also possible, which are represented by a
bar over the appropriate index. For example, the [ ]
direction would have a component in the y direction.
Also, changing the signs of all indices produces an
antiparallel direction; that is, [ ] is directly opposite
to [ ] . If more than one direction (or plane) is to be
specified for a particular crystal structure, it is
imperative for the maintaining of consistency that a
positive–negative convention, once established, not
be changed.

86
Example: Determine the indices for the
direction shown in the accompanying figure.

87
88
89
Example: Draw a [11- 0] direction within a cubic
unit cell.

90
91
For some crystal structures, several nonparallel directions with
different indices are crystallographically equivalent; this means
that the spacing of atoms along each direction is the same. For
example, in cubic crystals, all the directions represented by the
following indices are equivalent: [100], [ 00], [010], [0 0], [001],
and [00 ]. As a convenience, equivalent directions are grouped
together into a family, which are enclosed in angle brackets,
thus: [100]. Furthermore, directions in cubic crystals having the
same indices without regard to order or sign—for example, [123]
and [ 1 2-3-]— are equivalent. This is, in general, not true for
other crystal systems. For example, for crystals of tetragonal
symmetry, [100] and [010] directions are equivalent, whereas
[100] and [001] are not.

92
 Hexagonal Crystals
a four-axis, or Miller–Bravais, coordinate system

The three a1, a2, and a3 axes

are all contained within a
single plane (called the basal
plane) and are at 120 angles
to one another. The z axis is
perpendicular to this basal
plane.

93
denoted by four indices, as [uvtw]; by
convention, the first three indices pertainto
projections along the respective a1, a2, and a3
axes in the basal plane.
Conversion from the three-index system to the
four-index system,

94
the [010] direction →

95
Reduced-scale coordinate axis
system for hexagonal unit cells that may be
used to plot crystallographic directions.

96
 Conversion and Construction of Directional
Indices for a Hexagonal Unit Cell

• (a) Convert the [111] direction into the four-

index system for hexagonal crystals.
(b) Draw this direction within a reduced-scale
coordinate system (per Figure 3.9).
(c) Now draw the [111] direction within a
hexagonal unit cell that utilizes a
three-axis (a1, a2, z) coordinate system.

97
98
b

99
c

100
 Determination of Directional Indices
for a Hexagonal Unit Cell
Determine the directional indices (four-index
system) for the direction shown in the
accompanying figure.

101
102
 CRYSTALLOGRAPHIC PLANES
The unit cell is the basis, with the three-axis coordinate system.

1. If the plane passes through the selected origin, either another parallel plane
must be constructed within the unit cell by an appropriate translation, or a
new origin must be established at the corner of another unit cell.

2. At this point the crystallographic plane either intersects or parallels each of

the three axes; the length of the planar intercept for each axis is determined
in terms of the lattice parameters a, b, and c.

3. The reciprocals of these numbers are taken. A plane that parallels an axis
may be considered to have an infinite intercept, and, therefore, a zero index.

4. If necessary, these three numbers are changed to the set of smallest integers
by multiplication or division by a common factor.

5. Finally, the integer indices, not separated by commas, are enclosed within
parentheses, thus: (hkl). 103
One interesting and unique characteristic of cubic
crystals is that planes and directions having the
same indices are perpendicular to one another;
however, for other crystal systems there are no
simple geometrical relationships between planes
and directions having the same indices.
104
• Determine the Miller indices for the plane
shown

105
Because the plane passes through the selected origin O, a new
origin must be chosen at the corner of an adjacent unit cell,
taken as and shown in sketch.

106
107
 Construction of Specified
Crystallographic Plane
Construct a (01-1) plane within a cubic unit cell.

108
109
 Atomic Arrangements
The atomic arrangement for a crystallographic
plane, which is often of interest, depends on the
crystal structure. Reduced sphere FCC
unit cell with
the (110) plane.

Atomic packing of an
FCC (110) plane.
Corresponding atom
positions from (a) are
indicated.

110
Draw reduced-sphere BCC unit cell with the
(110) plane.
(b)Draw atomic packing of a BCC (110) plane.

111
The circles represent atoms lying in the crystallographic
planes as would be obtained from a slice taken through
the centers of the full-sized hard spheres.
112
A “family” of planes contains all planes that are
crystallographically equivalent— that is, having the
same atomic packing; a family is designated by indices
that are enclosed in braces—such as {100}. For
example, in cubic crystals the (111) ………
…………..………
planes all belong to the {111} family.
tetragonal crystal structures, the {100} family
113
 Hexagonal Crystals
For crystals having hexagonal symmetry, it is desirable that equivalent planes
have the same indices; as with directions, this is accomplished by the Miller–
Bravais system shown
This convention leads to the four-index (hkil) scheme, which is
favored in most instances because it more clearly identifies
the orientation of a plane in a hexagonal crystal. There is
some redundancy in that i is determined by the sum of h and
k through

Otherwise the three h, k, and l indices are identical

for both indexing systems

114
Determination of Miller–Bravais Indices for a
Plane within a Hexagonal Unit Cell

115
 LINEAR AND PLANAR DENSITIES

the equivalency of nonparallel crystallographic

directions and planes
• Directional equivalency is related to linear density in
the sense that, for a particular material, equivalent
directions have identical linear densities.

• The corresponding parameter for crystallographic

planes is planar density, and planes having the same
planar density values are also equivalent.

116
Linear density (LD)

units of linear density →

[110] linear density for FCC is ?

planar density (PD)

units for planar density → Planar density: (110) plane within an FCC unit
cell ?
[110] linear density for FCC

the section of a (110) plane within an FCC unit

cell

118
 CLOSE-PACKED CRYSTAL STRUCTURES
face centered cubic and hexagonal close-packed
crystal structures have atomic packing factors of
0.74, which is the most efficient packing of
equal-sized spheres or atoms.
A portion of a close-packed
plane of atoms; A, B, and C
positions are indicated

Both crystal structures may be generated by the stacking of these close-

packed planes on top of one another; the difference between the two
structures lies in the stacking sequence.
Let the centers of all the atoms in one close-packed plane be labeled A. Associated
with this plane are two sets of equivalent triangular depressions formed by
three adjacent atoms, into which the next close-packed plane of atoms may rest.
Those having the triangle vertex pointing up are arbitrarily designated as B positions,
while the remaining depressions are those with the down vertices, which are
marked C .

A second close-packed plane may be

positioned with the centers of its atoms
over either B or C sites; at this point both are
equivalent. Suppose that the B
positions are arbitrarily chosen; the stacking
sequence is termed AB.

120
The real distinction between FCC
and HCP lies in where
the third close-packed layer is
positioned. For HCP, the centers of
this layer are
aligned directly above the original
A positions. This stacking
sequence, ABABAB . . . ,

These close-packed planes for

HCP are (0001)-type planes,
121
For the face-centered crystal structure, the centers of the third plane
are situated over the C sites of the first plane

This yields an ABCABCABC . . .

stacking sequence; that is, the atomic
alignment repeats every third plane. It
is more difficult to correlate the
stacking of close-packed planes to the
FCC unit cell.

These planes are of the (111) type; an FCC

unit cell is outlined on the upper left-hand
front face of Figure
122
 THE IMPORTANCE OF
CRYSTALLOGRAPHY
Understanding the crystalline structure of ceramics is critical to understanding many of
their properties.
• Diffusion. Often depends on the size and number of interstitial sites, both functions
of the crystal structure.
• Deformation by slip or twinning. In ceramics there are both crystallographic and
electrostatic considerations. The slip direction is usually along a close packed
direction. The slip plane will usually be a closely packed plane
• Piezoelectricity. Crystals must be noncentrosymmetric.
Thermal conductivity. Phonon conductivity is most efficient in simple crystal
structures formed by small
atoms.
• Fracture. Often crystallographic, but not always (e.g., glass and cubic zirconia).
• Cleavage. Always crystallographic. Cleavage planes have high atomic density, but we
also need to consider charge.
• Ferrimagnetism. In ferrimagnets the coordination number of the magnetic cation
(usually an Fe ion) determines its behavior in an applied magnetic field.
123