Length-scales

Angstrom = 1Å = 1/10,000,000,000 meter = 10-10 m

Nanometer = 10 nm = 1/1,000,000,000 meter = 10-9 m
Micrometer = 1μm = 1/1,000,000 meter = 10-6 m
Millimeter = 1mm = 1/1,000 meter = 10-3 m

Interatomic distance ~ a few Å

A human hair is ~ 50 μm
Elongated bumps that make up the data track on CD are ~ 0.5 μm
wide, minimum 0.83 μm long, and 125 nm high
 Atomic Structure and Bonding
 Understanding of inter-atomic bonding is the first
step towards understanding/explaining materials
properties
Review of Atomic Structure
Electrons, Protons, Neutrons, Quantum mechanics
of atoms, Electron states, The Periodic Table

Atomic Bonding in Solids

Bonding Energies and Forces
Secondary Bonding (Van der Waals)
Periodic Table Three types of Dipole Bonds
• Molecules and Molecular Solids

Primary Interatomic Bonds

Ionic
Covalent
Metallic
 Review of Atomic Structure

Charges:

Electrons and protons have negative and positive charges

of the same magnitude, 1.6 × 10-19 Coulombs.
Neutrons are electrically neutral.

Masses:
Protons and Neutrons have the same mass, 1.67 × 10-27 kg.

Mass of an electron is much smaller, 9.11 × 10-31 kg and

can be neglected in calculation of atomic mass.
 Review of Atomic Structure
# protons gives chemical identification of the element
# protons = atomic number (Z)

# neutrons (N) defines isotope number

For a given element, the number of protons (Z) is the same for all
atoms, but the number of neutrons (N) may be variable. Thus atoms
of some elements have two or more different atomic masses,
which are called isotopes.

The atomic mass (A) = mass of protons + mass of

neutrons
 Atomic mass units. Atomic weight.
 The atomic mass unit (amu) is often used to express atomic
weight.

 1 amu is defined as 1/12 of the atomic mass of the most

common isotope of carbon atom that has 6 protons (Z=6) and six
neutrons (N=6).

 Mproton ≈ Mneutron = 1.66 x 10-24 g = 1 amu.

 The atomic mass of the 12C atom is 12 amu.

 The atomic weight of an element = weighted average of the

atomic masses of the atoms naturally occurring isotopes.

 Atomic weight of carbon is 12.011 amu.

 The mole unit
 The atomic weight is often specified in mass per mole

 A mole is the amount of matter that has a mass in grams equal to

the atomic mass in amu of the atoms (A mole of carbon has a
mass of 12 grams)

 The number of atoms in a mole is called the Avogadro number,

NA = 6.023 × 1023.

NA = 1 gram/1 amu.
 One mole of a substance contains 6.023 x 1023 (Avogadro’s
number) atoms or molecules

 1 amu/atom (or molecule) = 1 g/mol

 For example, the atomic weight of iron is 55.85 amu/atom, or

55.85 g/mol. Sometimes use of amu per atom or molecule is
convenient; on other occasions g (or kg)/mol is preferred.
 Some simple calculations
The number of atoms per cm3, n, for material of density d(g/cm3) and
atomic mass M (g/mol):

n = NA × d / M

Graphite (carbon): d = 2.3 g/cm3, M = 12 g/mol

n = 6×1023 atoms/mol × 2.3 g/cm3 / 12 g/mol = 11.5 × 1022 atoms/cm3

Diamond (carbon): d = 3.5 g/cm3, M = 12 g/mol

n = 6×1023 atoms/mol × 3.5 g/cm3 / 12 g/mol = 17.5 × 1022 atoms/cm3

Water (H2O): d = 1 g/cm3, M = 18 g/mol

n = 6×1023 molecules/mol × 1 g/cm3 / 18 g/mol = 3.3 × 1022 molecules/cm3
 Electrons in Atoms (I)
 In the Bohr model, the electrons form a cloud
around the nucleus, of radius of 0.05 – 2 nm

 This picture looks like a mini planetary system. But

quantum mechanics tells us that this analogy is not
correct.
 Electrons in Atoms (II)
 Electrons move not in circular orbits, but in 'fuzzy‘ orbits

 Actually, we cannot tell how it moves, but only can say what is
the probability of finding it at some distance from the nucleus

 Only certain “orbits” or shells of electron probability densities

are allowed

 The shells are identified by a principal quantum number n,

which can be related to the size of the shell, n = 1 is the
smallest; n = 2, 3 .. are larger. This quantum number is related
to the distance of an electron from the nucleus, or its position.

 Each “orbit” or shell can accommodate only a maximum

number of electrons, which is determined by quantum
mechanics
 Electrons in Atoms (II)
The most inner K-shell can accommodate only two electrons,
called s electrons; the next L-shell two s-electrons and six p-
electrons; the M-shell can host two s-electrons, six p-electrons,
and ten d-electrons; and so on

The filling of the electron shells starts with the lowest energy
shell/sub-shell and proceeds upwards

The second quantum number l, defines subshells within each

shell.

Two more quantum numbers characterize states within the

subshells.
Bohr and Wave Mechanics
models
 Electrons in Atoms (III)
 The quantum numbers arise from solution of
Schrodinger’s equation

 " Pauli Exclusion Principle: only one electron can have a

given set of the four quantum numbers

 The Number of Available Electron States in Some of the

Electron Shells and Subshells
 Electrons in Atoms (III)

Subshells by energy:
1s,2s,2p,3s,3p,4s,3d,4s,4p,5s,4d,5p,6s,4f,…
 Valence electrons
 Electrons that occupy the outermost filled shell –
the valence electrons – they are responsible for
bonding.

 " Electrons fill quantum levels in order of

increasing energy (only n, l make a significant
difference).

 Example: Iron, Z = 26: 1s22s22p63s23p63d64s2

Periodic Table
 Periodic Table
Elements in the same column (Elemental Group)
share similar properties.

Group number indicates the number of electrons

available for bonding.

0: Inert gases (He, Ne, Ar...) have filled subshells:

chem. inactive

IA: Alkali metals (Li, Na, K…) have one electron in

outermost occupied s subshell - eager to give up
electron – chem. active

VIIA: Halogens (F, Br, Cl...) missing one electron in

outermost occupied p shell - want to gain electron -
chem. active
 Periodic Table - Electronegativity

 Electronegativity - a measure of how willing atoms are to accept

electrons, measure of the attraction an atom has for electrons in a
bond formed with another atom

 Subshells with one electron - low electronegativity

 Subshells with one missing electron -high electronegativity

 Electronegativity increases from left to right

 Metals are electropositive – they can give up their few valence

electrons to become positively charged ions
Periodic Table - Electronegativity
Bonding Energies and Forces

This is typical potential well for two interacting atoms

Bonding Energies and Forces
 The principles of atomic bonding are best illustrated by
considering the interaction between two isolated atoms as
they are brought into close proximity from an infinite
separation.

 At large distances, the interactions are negligible; but as

the atoms approach, each exerts forces on the other.

 These forces are of two types, attractive and repulsive,

and the magnitude of each is a function of the separation
or interatomic distance.

 The origin of an attractive force FA depends on the

particular type of bonding that exists between the two
atoms.

 Its magnitude varies with the distance

 Bonding Energies and Forces
 Ultimately, the outer electron shells of the two atoms begin to
overlap, and a strong repulsive force FR comes into play.

 The net force FN between the two atoms is just the sum of both
attractive and repulsive components

 FN = FR + FA

 The net force is also a function of the inter-atomic separation

 When FA and FR balance, or become equal, there is no net force

 FR + F A = 0

A state of equilibrium exists.


Bonding Energies and Forces
The centers of the two atoms will remain separated by the
equilibrium spacing r0 ,

 For many atoms, r0 is approximately 0.3 nm (3 Å).

 Once in this position, the two atoms will counteract any attempt to
separate them by an attractive force, or to push them together by a
repulsive action

 Sometimes it is more convenient to work with the potential

energies between two atoms instead of forces. Mathematically,
energy (E) and force (F) are related as

E   Fdr
r
E N   FN dr

r r
E N   FR dr   FA dr
 
The electron volt (eV) – energy unit convenient
for description of atomic bonding

Electron volt - the energy lost / gained by an electron

when it is taken through a potential difference of one
volt.
E=q×V
For q = 1.6 x 10-19 Coulombs
V = 1 volt

1 eV = 1.6 x 10-19 J
 Bonding in Solids
 In solid materials, a complex condition exists since force and
energy interactions in many atoms must be considered

 Each atom may be associated with a unique bonding energy , the

magnitude and the shape of the energy-inter-atomic separation
curve vary from material to material

 A number of material properties depend on the bonding energy, E0 ,

the curve shape, and bonding type

 For example, materials having large bonding energies typically also

have high melting temperatures

 At room temperature, solid substances are formed for large bonding

energies, whereas for small energies the gaseous state is favored;
liquids prevail when the energies are of intermediate magnitude.
 Bonding in Solids
 In addition, the mechanical stiffness (or modulus of elasticity) of
a material is dependent on the shape of its force-versus-
interatomic separation curve .

 The slope for a relatively stiff material at the r = r0 position on

the curve will be quite steep; slopes are shallower for more
flexible materials.

 The expansion of a material upon heating (that is, its linear

coefficient of thermal expansion) is also related to the shape of
its E0-versus-r0 curve

 A deep and narrow ‘‘trough,’’ which typically occurs for

materials having large bonding energies, normally correlates
with a low coefficient of thermal expansion and relatively small
dimensional alterations for changes in temperature
 Types of Bonding
Primary bonding: e- are transferred or shared

Strong (100-1000 KJ/mol or 1-10 eV/atom)

Ionic: Strong Coulomb interaction among negative ions and

positive ions. Example - Na+Cl-

Covalent: electrons are shared between the molecules, to

saturate the valency. Example - H2

Metallic: the atoms are ionized, loosing some electrons from the
valence band. Those electrons form an ‘electron sea’, which binds the
charged nuclei in place
Secondary Bonding: no e- transferred or shared

 Interaction of atomic/molecular dipoles

 Weak (< 100 KJ/mol or < 1 eV/atom)

 " Fluctuating Induced Dipole (inert gases, H2, Cl2…)

 " Permanent dipole bonds (polar molecules - H2O, HCl...)

 " Polar molecule-induced dipole bonds

 Ionic Bonding (I)

Formation of ionic bond:

1.Mutual ionization occurs by electron transfer
 Ion = charged atom
 Anion = negatively charged atom
 Cation = positively charged atom

2. Ions are attracted by strong coulombic interaction

 Oppositely charged atoms attract

 An ionic bond is non-directional (ions may be
attracted
to one another in any direction
Example: NaCl
Na has 11 electrons, 1 more than needed
for a full outer shell (Neon)

Cl has 17 electron, 1 less than needed for a

full outer shell (Argon)
 Ionic Bonding (II)

Electron transfer reduces the energy of the system of

atoms, that is, electron transfer is energetically favorable

Note relative sizes of ions: Na shrinks and Cl expands

Ionic bonds: very strong, nondirectional bonds

 Covalent Bonding (I)
In covalent bonding, electrons are shared between the
molecules, to saturate the valency..

Formation of covalent bonds:

Cooperative sharing of valence electrons
Can be described by orbital overlap
Covalent bonds are HIGHLY directional
Bonds - in the direction of the greatest orbital overlap
Covalent bond model: an atom can covalently bond with at most
8-N’, N’ = number of valence electrons

Example: Cl2 molecule. ZCl =17 (1S2 2S2 2P6 3S2 3P5)
N’ = 7, 8 - N’ = 1 → can form only one covalent bond
 Covalent Bonding II

 Many nonmetallic elemental molecules (H2, Cl2, F2 ,

etc.) as well as molecules containing dissimilar
atoms, such as CH4, H2O, HNO3 , and HF, are
covalently bonded

 This type of bonding is found in elemental solids

such as diamond (carbon), silicon, and germanium
and other solid compounds composed of elements
that are located on the right-hand side of the
periodic table, such as gallium arsenide (GaAs),
indium antimonide (InSb), and silicon carbide (SiC)
 Covalent Bonding (III)
Example: Carbon materials. Zc = 6 (1s2 2s2 2p2)
N’ = 4, 8 - N’ = 4 → can form up to four covalent bonds
 Covalent Bonding (IV)
The potential energy of a system of covalently interacting atoms
depend not only on the distances between atoms, but also on angles
between bonds…
 Covalent Bonding (V)
 Covalent bonds may be very strong, as in diamond, which
is very hard and has a very high melting temperature,
3550°C (6400°F), or they may be very weak, as with
bismuth, which melts at about 270°C (518°F).

 This type of bond is typified by polymeric materials in

which the basic molecular structure being a long chain of
carbon atoms that are covalently bonded together with
two of their available four bonds per atom.

 The remaining two bonds normally are shared with other

atoms, which also covalently bond.
Bond Energy
 Mixed Character Bonds
 It is possible to have inter-atomic bonds that are partially ionic
and partially covalent, and, in fact, very few compounds exhibit
pure ionic or covalent bonding

 For a compound, the degree of either bond type depends on

the relative positions of the constituent atoms in the periodic
table or the difference in their electronegativities

 The wider the separation (both horizontally— relative to Group

IVA—and vertically) from the lower left to the upper-right-
handcorner (i.e., the greater the difference in electronegativity),
the more ionic the bond

 Conversely, the closer the atoms are together (i.e., the smaller
the difference in electronegativity), the greater the degree of
covalency
 Ionic character

 The percent ionic character of a bond between elements A

and B (A being the most electronegative) may be
approximated by the expression

% ionic character
  1  exp  0.25X A  X B   X100
2
 Metallic Bonding I
 This type of bonding is found in metals and their alloys

 Metallic materials have one, two, or at most, three valence

electrons

 In the proposed model, these valence electrons are not bound

to any particular atom in the solid and are more or less free to
drift throughout the entire metal.

 They may be thought of as belonging to the metal as a whole, or

forming a ‘‘sea of electrons’’ or an ‘‘electron cloud.’’

 The remaining non-valence electrons and atomic nuclei form

what are called ion cores, which possess a net positive charge
equal in magnitude to the total valence electron charge per atom
Metallic Bonding II
 Metallic Bonding III

 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
nondirectional in character.

 In addition, these free electrons act as a ‘‘glue’’ to hold the ion

cores together.

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

(0.7 eV/atom) for mercury to 850 kJ/mol (8.8 eV/atom) for
tungsten.

 Metallic bonding is found for Group IA and IIA elements in the

periodic table, and, in fact, for all elemental metals.
 Bonding Types and Material
Properties
 Some general behaviors of the various material types (i.e., metals,
ceramics, polymers) may be explained by bonding type

 For example, metals are good conductors of both electricity and

heat, as a consequence of their free electrons

 By way of contrast, ionically and covalently bonded materials are

typically electrical and thermal insulators, due to the absence of
large numbers of free electrons

 Furthermore, we note that at room temperature, most metals and

their alloys fail in a ductile manner; that is, fracture occurs after the
materials have experienced significant degrees of permanent
deformation
 Bonding Types and Material
Properties
 This behavior is explained in terms of deformation
mechanism , which is implicitly related to the characteristics
of the metallic bond

 Conversely, at room temperature ionically bonded materials

are intrinsically brittle as a consequence of the electrically
charged nature of their component ions
 Secondary Bonding (I)
 Secondary = van der Waals = physical (as opposite to chemical
bonding that involves e- transfer) bonding results from interaction of
atomic or molecular dipoles and is weak, ~0.1 eV/atom or ~10 kJ/mol

An electric dipole exists whenever there is some separation of

positive and negative portions of an atom or molecule

Permanent dipole moments exist in some molecules (called polar

molecules) due to the asymmetrical arrangement of positively and
negatively regions (HCl, H2O).
 Secondary Bonding (I)
 Polar molecules can induce dipoles in adjacent non-polar molecules.

 The bonding results from the coulombic attraction between the positive
end of one dipole and the negative region of an adjacent one

 Dipole interactions occur between induced dipoles, between induced

dipoles and polar molecules (which have permanent dipoles), and
between polar molecules

 Bonds between adjacent polar molecules – permanent dipole bonds –

are strongest among secondary bonds.

 Hydrogen bonding, a special type of secondary bonding, is found to

exist between some molecules that have hydrogen as one of the
constituents
 Secondary Bonding (I)

 The liquefaction and, in some cases, the solidification of the

inert gases and other electrically neutral and symmetric
molecules such as H2 and Cl2 are realized because of this type
of bonding

 Melting and boiling temperatures are extremely low in materials

for which induced dipole bonding predominates; of all possible
intermolecular bonds, these are the weakest
 Dipoles
 A dipole may be created or induced in an atom or molecule that is
normally electrically symmetric; that is, the overall spatial
distribution of the electrons is symmetric with respect to the
positively charged nucleus

 All atoms are experiencing constant vibrational motion that can

cause instantaneous and short-lived distortions of this electrical
symmetry for some of the atoms or molecules, and the creation of
small electric dipoles
 Dipoles
 One of these dipoles can in turn produce a
displacement of the electron distribution of an adjacent
molecule or atom, which induces the second one also to
become a dipole that is then weakly attracted or bonded
to the first; this is one type of van der Waals bonding.

 These attractive forces may exist between large

numbers of atoms or molecules, which forces are
temporary and fluctuate with time.
 Secondary Bonding (II)
Example: hydrogen bond in water. The H end of the molecule is
positively charged and can bond to the negative side of another
H2O molecule (the O side of the H2O dipole)

“Hydrogen bond” – secondary bond formed between two permanent

dipoles in adjacent water molecules.
 Summary (I)

Examples of bonding in Materials:

Metals: Metallic
Ceramics: Ionic / Covalent
Polymers: Covalent and Secondary
Semiconductors: Covalent or Covalent / Ionic
Summary (II)
 Types of Solids
Crystalline material: atoms self-organize in a periodic array

Single crystal: atoms are in a repeating or periodic array over the

entire extent of the material

Polycrystalline material: comprised of many small crystals or grains

Amorphous: lacks a systematic atomic arrangement

 Crystal structure
 To discuss crystalline structures it is useful to consider
atoms as being hard spheres with well-defined radii.

 In this hard-sphere model, the shortest distance between

two like atoms is one diameter.

 We can also consider crystalline structure as a lattice of

points at atom/sphere centers.
 Unit Cell
 The unit cell is the smallest structural unit or building block that
can describe the crystal structure.

 The entire crystal is generated by the repetition of the unit cell

Example of 3D crystalline structure:

 Different choices of unit cells possible, generally choose

parallelepiped unit cell with highest level of symmetry
 Metallic Crystal Structures
 Metals are usually (poly)crystalline; although formation of
amorphous metals is possible by rapid cooling

 The atomic bonding in metals is non-directional

⇒ no restriction on numbers or positions of nearest-neighbor atoms
⇒ large number of nearest neighbors and dense atomic packing

 Atom (hard sphere) radius, R, defined by ion core radius -

typically 0.1 - 0.2 nm

 The most common types of unit cells are the faced centered
cubic (FCC), the body-centered cubic (FCC) and the hexagonal
close-packed (HCP).
Face-centered cubic Crystal Structure (I)
(FCC)
 Atoms are located at each of the corners and on the centers of
all the faces of cubic unit cell

 Cu, Al, Ag, Au have this crystal structure

Face-centered cubic Crystal Structure (II)

 The hard spheres or ion cores touch one another across a face
diagonal ⇒ the cube edge length, a , and the atomic radius, R are
related by

a= 2R√2
 The coordination number, CN = the number of closest neighbors
to which an atom is bonded = number of touching atoms, CN = 12

 Number of atoms per unit cell, n = 4.

 For an atom that is shared with m adjacent unit cells, we only

count a fraction of the atom, 1/m
Face-Centered Cubic Crystal Structure (III)

 For the FCC crystal structure, each corner atom is shared

among eight unit cells, whereas a face-centered atom belongs
to only two.

 Therefore, one eighth of each of the eight corner atoms and

one half of each of the six face atoms, or a total of four whole
atoms, may be assigned to a given unit cell.

 The cell comprises the volume of the cube, which is generated

from the centers of the corner atoms

 Corner and face positions are really equivalent; that is,

translation of the cube corner from an original corner atom to
the center of a face atom will not alter the cell structure.
Face-Centered Cubic Crystal Structure (IV)
In FCC unit cell we have:

6 face atoms shared by two cells: 6 x 1/2 = 3

8 corner atoms shared by eight cells: 8 x 1/8 = 1

Atomic packing factor, APF = fraction of volume occupied by

hard spheres = (Sum of atomic volumes)/(Volume of cell)

= 0.74 (maximum possible)

FCC can be represented by a stack of close-packed planes (planes

with highest density of atoms)
Body-Centered Cubic (BCC) Crystal
Structure (I)
 Atom at each corner and at center of cubic unit cell

 Cr, α-Fe, Mo have this crystal structure

Body-Centered Cubic Crystal Structure (II)

The hard spheres touch one another along cube diagonal

⇒ the cube edge length, a= 4R/√3

The coordination number, CN = 8

 Number of atoms per unit cell, n = 2

 Center atom (1) shared by no other cells: 1 x 1 = 1

 8 corner atoms shared by eight cells: 8 x 1/8 = 1

Atomic packing factor, APF = 0.68

 Corner and center atoms are equivalent

Hexagonal Close-Packed Crystal Structure
(I)
 HCP is one more common structure of metallic crystals

 Six atoms form regular hexagon, surrounding one atom in the center

 Another plane is situated halfway up unit cell (c-axis), with 3

additional atoms situated at interstices of hexagonal (close-packed)
planes

 Cd, Mg, Zn, Ti have this crystal structure

 Hexagonal Close-Packed Crystal Structure (II)

 Unit cell has two lattice parameters a and c. Ideal ratio c/a = 1.633

 The coordination number, CN = 12 (same as in FCC)

 Number of atoms per unit cell, n = 6.

 3 mid-plane atoms shared by no other cells: 3 x 1 = 3

 12 hexagonal corner atoms shared by 6 cells: 12 x 1/6 = 2

 2 top/bottom plane center atoms shared by 2 cells: 2 x 1/2 = 1

 Atomic packing factor, APF = 0.74 (same as in FCC)

 All atoms are equivalent

 Density Computations
 Since the entire crystal can be generated by the repetition of the
unit cell, the density of a crystalline material, ρ = the density of the
unit cell = (atoms in the unit cell, n ) × (mass of an atom, M) / (the
volume of the cell, Vc)

 Atoms in the unit cell, n = 2 (BCC); 4 (FCC); 6 (HCP)

 Mass of an atom, M = Atomic weight, A, in amu (or g/mol) is given

in the periodic table. To translate mass from amu to grams we have
to divide the atomic weight in amu by the Avogadro number
NA = 6.023 × 1023 atoms/mol

 The volume of the cell, Vc = a3 (FCC and BCC) a = 2R√2 (FCC);

a = 4R/√3 (BCC) where R is the atomic radius
 Density Computations

 Thus, the formula for the density is:

nA

Vc N A

n = number of atoms associated with each unit cell

A = atomic weight
VC volume of the unit cell
NA Avogadro’s number (6.023 x 1023 atoms/mol)
 Example
Copper has an atomic radius of 0.128 nm (1.28Ǻ ), an FCC crystal
structure, and an atomic weight of 63.5 g/mol. Compute its
theoretical density and compare the answer with its measured
density of 8.94 g/cm3
 ceramic crystal structures
 Ceramics are composed of at least two elements

 Their crystal structures are generally more complex than those

for metals.

 The atomic bonding in these materials ranges from purely ionic

to totally covalent

 Many ceramics exhibit a combination of these two bonding

types, the degree of ionic character being dependent on the
electronegativities of the atoms.

 For those ceramic materials for which the atomic bonding is

predominantly ionic, the crystal structures may be thought of as
being composed of electrically charged ions instead of atoms.

 The metallic ions, or cations, are positively charged and the non
metallic ions, or anions, which are negatively charged.
ionic character examples
 ceramic crystal structures
 Two characteristics of the component ions in crystalline
ceramic materials influence the crystal structure: the
magnitude of the electrical charge on each of the
component ions, and the relative sizes of the cations and
anions.

 The crystal must be electrically neutral; that is, all the cation
positive charges must be balanced by an equal number of
anion negative charges.

 The chemical formula of a compound indicates the ratio of

cations to anions, or the composition that achieves this
charge balance.

 For example, in calcium fluoride, CaF2 .

 ceramic crystal structures
 The second criterion involves the sizes or ionic radii of the
cations and anions, rC and rA, respectively.

 Because the metallic elements give up electrons when

ionized, cations are ordinarily smaller than anions, and,
consequently, the ratio rC/rA is less than unity.

 Each cation prefers to have as many nearest-neighbor

anions as possible.

 The anions also desire a maximum number of cation

nearest neighbors.
 ceramic crystal structures
 Stable ceramic crystal structures form when those anions
surrounding a cation are all in contact with that cation

 The coordination number (i.e., number of anion nearest

neighbors for a cation) is related to the cation–anion radius ratio

 For a specific coordination number, there is a critical or minimum

rC/rA ratio for which this cation–anion contact is established

 This ratio may be determined from pure geometrical

considerations
 Example
Show that the minimum cation-to-anion radius ratio for the coordination
number 3 is 0.155.
Coordination numbers for various
cation-anion ratios
 Coordination numbers
 For rC/rA ratios less than 0.155, the very small cation is bonded
to two anions in a linear manner.

 If rC/rA has a value between 0.155 and 0.225, the coordination

number for the cation is 3.

 This means each cation is surrounded by three anions in the

form of a planar equilateral triangle, with the cation located in
the center.

 The coordination number is 4 for rC/rA between 0.225 and

0.414; the cation is located at the center of a tetrahedron, with
anions at each of the four corners.
 Coordination numbers
 For rC/rA between 0.414 and 0.732, the cation may be thought
of as being situated at the center of an octahedron surrounded
by six anions, one at each corner

 The coordination number is 8 for rC/rA between 0.732 and 1.0,

with anions at all corners of a cube and a cation positioned at
the center

 For a radius ratio greater than unity, the coordination number is

12

 The most common coordination numbers for ceramic materials

are 4, 6, and 8.
 AX-type crystal structures

 Some of the common ceramic materials are those in which

there are equal numbers of cations and anions

 These are often referred to as AX compounds, where A denotes

the cation and X the anion

 There are several different crystal structures for AX compounds;

each is normally named after a common material that assumes
the particular structure.
 Rock Salt
 The most common AX crystal structure is the sodium chloride
(NaCl), or rock salt, type.

 The coordination number for both cations and anions is 6, and

therefore the cation–anion radius ratio is between 0.414 and
0.732.

 A unit cell for this crystal structure is generated from an FCC

arrangement of anions with one cation situated at the cube center
and one at the center of each of the 12 cube edges.
 Rock Salt
 An equivalent crystal structure results from a face centered
arrangement of cations.

 Thus, the rock salt crystal structure may be thought of as two

interpenetrating FCC lattices, one composed of the cations, the
other of anions.

 Some of the common ceramic materials that form with this crystal
structure are NaCl, MgO, MnS, LiF, and FeO
 Cesium Chloride Structure
 The coordination number is 8 for both ion types.

 The anions are located at each of the corners of a cube,

whereas the cube center is a single cation.

 Interchange of anions with cations, and vice versa, produces

the same crystal structure.

 This is not a BCC crystal structure because ions of two different

kinds are involved.
 Zinc Blende Structure
A third AX structure is one in which the coordination number is 4;
that is, all ions are tetrahedrally coordinated.

This is called the zinc blende, or sphalerite, structure, after the

mineralogical term for zinc sulfide (ZnS).

All corner and face positions of the cubic cell are occupied by S
atoms, while the Zn atoms fill interior tetrahedral positions.

An equivalent structure results if Zn and S atom positions are

reversed.

Thus, each Zn atom is bonded to four S atoms, and vice versa.

 Zinc Blende Structure

 Most often the atomic bonding is highly covalent in

compounds exhibiting this crystal structure

 Examples include ZnS, ZnTe, and SiC.

 AmXp-type crystal structures
 If the charges on the cations and anions are not the same, a
compound can exist with the chemical formula AmXp , where m
and/or p  1.

 An example would be AX2 , for which a common crystal

structure is found in fluorite (CaF2). The ionic radii ratio rC/rA for
CaF2 is about 0.8 which gives a coordination number of 8.
 AmXp-type crystal structures

 Calcium ions are positioned at the centers of cubes, with

fluorine ions at the corners.

 The chemical formula shows that there are only half as many
Ca2+ ions as F- ions, and therefore the crystal structure would
be similar to CsCl , except that only half the center cube
positions are occupied by Ca2 + ions.

 One unit cell consists of eight cubes.

 Other compounds that have this crystal structure include UO2 ,

PuO2 , and ThO2
 AmBnXp-type crystal structures
 It is also possible for ceramic compounds to have more than one
type of cation; for two types of cations (represented by A and B),
their chemical formula may be designated as AmBnXp .

 Barium titanate (BaTiO3), having both Ba2+ and Ti4+ cations, falls into
this classification.

 This material has a perovskite crystal structure

 At temperatures above 120°C, the crystal structure is cubic.

Ba2+ ions are situated at all eight

corners of the cube and a single Ti4+
is at the cube cente, with O2- ions
located at the center of each of the
six faces.
 density computations—ceramics
 It is possible to compute the theoretical density of a
crystalline ceramic material from unit cell data in a manner
similar to that for metals.

 In this case the density may be determined using the

relation:

n'  AC   AA 

VC N A

n’ = the number of formula units1 within the unit cell

AC = the sum of the atomic weights of all cations in the formula unit
AA = the sum of the atomic weights of all anions in the formula unit
VC = the unit cell volume
NA = Avogadro’s number, 6.023 x 1023 formula units/mol
 Example
On the basis of crystal structure, compute the theoretical
density for sodium chloride. How does this compare with its
measured density of 2.16g/cm3?
 Polymorphism and Allotropy
Some materials may exist in more than one crystal structure, this is
called polymorphism. If the material is an elemental solid, it is called
allotropy.

An example of allotropy is carbon, which can exist as diamond,

graphite, and amorphous carbon.

Pure, solid carbon occurs in three crystalline forms – diamond,

graphite; and large, hollow fullerenes.
Two kinds of fullerenes
are shown here: buckminsterfullerene (buckyball) and carbon
Single Crystals and Polycrystalline Materials
 Single crystal: atoms are in a repeating or periodic array over the
entire extent of the material

 Polycrystalline material: comprised of many small crystals or grains.

 The grains have different crystallographic orientation.

 There exist atomic mismatch within the regions where grains meet.

 These regions are called grain boundaries.

 Anisotropy
 Different directions in a crystal have a different packing

 For instance, atoms along the edge of FCC unit cell are more
separated than along the face diagonal

 This causes anisotropy in the properties of crystals, for instance, the

deformation depends on the direction in which a stress is applied

 In some polycrystalline materials, grain orientations are random, so

bulk material properties are isotropic

 Some polycrystalline materials have grains with preferred

orientations (texture), so properties are dominated by those relevant
to the texture orientation and the material exhibits anisotropic
properties
 Non-Crystalline (Amorphous) Solids
In amorphous solids, there is no long-range order. But
amorphous does not mean random, in many cases there is
some form of short-range order.

Schematic picture of
amorphous SiO2 structure
Amorphous structure from
simulations by E. H. Brandt
 Imperfections in Solids
“Crystals are like people, it is the defects in them which
tend to make them interesting!” - Colin Humphreys.

Defects in Solids
0D, Point defects
" vacancies
" interstitials
" impurities, weight and atomic composition
1D, Dislocations
" edge
" screw
2D, Grain boundaries
" tilt
" twist
3D, Bulk or Volume defects
Atomic vibrations