MST2122 – Metals, Ceramics and

Composite materials
Semester II
Unit 1
Atomic structure and Bonding

Crystal structure – Lattice/Basis- Miller indices-Points groups-space groups

Symmetry operations

Ceramic crystal structures – Pauling rules

Diffusion

Defects

Metals and alloys

Atomic configuration
PERIODIC TABLE DEPICTING ELECTRONIC CONFIGURATION

Pinterest.com – original contributor not known

METALS IN THE PERIODIC TABLE

Ref: Dr. Richard R. Lindeke course slides

 Tutorials – practice problems

https://www.chm.uri.edu/weuler/chm401/studyaids/
atomicstructurepracticeproblems_answers.html

Warning:
For Bonding in solids, please refer to the class lectures based on
“Introduction to Solids” by Azaroff – use the materials in the subsequent
slides for complementary knowledge
Chemical Bonding
• The chemical and physical properties of crystals
depend almost entirely on the forces that bind the
atoms together in a crystal structure. Forces known
collectively as chemical bonds.

• Chemical bonding depends on the electronic structure

of the atoms involved, in particular the valence
electrons in the outermost shells, and on the size of the
ion or atom.
Chemical Bonding
• In general we recognize 4 different types of chemical
bonds, although as we will see, all bond types are
transitional from one type to another.
Types of Chemical Bonds
• Ionic
• Covalent
• Metallic
• Van der Waals
• Hydrogen Bond
 Ionic Bond
• There is a tendency for atoms to lose or gain electrons and become
ions in order to achieve the stable electronic configuration with
completely filled outer electron shells.
• Positively charged ions are called cations and negatively charged
ions are called anions.

• These ions can achieve various values of electronic charge

depending on the number of electrons gained or lost.
• For example, Na has one electron in its outermost shell. It will
tend to give up this electron to become Na+1 ion.

• Similarly, Cl has 7 electrons in its outermost shell and would

like to gain an electron to become Cl -1ion

• Once these atoms become Na +1 and Cl-1, the force of

attraction between the oppositely charged ions results in an
ionic bond.
• Formed between atoms of very different electronegativity (Refer slide
11)
• The less electronegativity atom completely donates one or more
electron to the more electronegative atom. The resulting ions are
held together by electrostatic attraction
• Most important for bonding between oxygen and Mg, Si, Al, Na, K
• Hence, the primary bonding type in silicate and oxide minerals

• Ionic bonds are non-directional in nature,

that is the attractive forces occur from all
directions.
What are the typical properties of ionically bonded
compounds?
• D nDissolves easily polar solvents like water (H2O is a polar solvent)
• Tend to form crystals with high symmetry.
• Moderate hardness and density.
• High melting temperatures.
• Generally poor conductors of heat and electricity (they are good
materials for thermal and electrical insulation).
 Covalent Bonds
• Elements near the right hand side of the periodic table tend to bond
to each other by covalent bonds to form molecules that are found in
crystal structures.

• For example Si and O form an SiO4-4 molecule that can bind to other
atoms or molecules either covalently or ionically.

• Covalent bonds can also be thought of as shared electron bonds.

Covalent bonds develop when atoms can achieve the a stable outer shell
electron configuration by sharing electrons with another atom. This
results in each of the atoms having a stable electronic configuration part
of the time
• Carbon has four electrons in its outer
shell and needs 4 more to achieve the
stable electronic configuration.

• C atom share electrons with 4 other C

atoms to form covalent bonds. This
results in compounds like diamond or
graphite that are held together by strong
covalent bonds between Carbon atoms.
 Covalent Bonds
• Formed between atoms of similar electronegativity
• Atoms are held together by “Sharing electrons”
• Sulfide minerals
• Most organic compounds

Covalent bonds are very strong directional

bonds, that is they occur along the zone where
the electrons are shared.
Covalently bonded crystals have the following properties:

• Relatively insoluble in polar solvents like water.

• High melting temperatures.

• Generally form crystals structures of low symmetry.

• Tend to have high hardness.

• Generally poor conductors of heat and electricity.

• In reality, bonding between atoms usually does not
take place as pure covalent or pure ionic bonds, but
rather as a mixture of bond types.

• The amount of each type is determined by the

electronegativity difference between the atoms
involved.
Electronegativity
• For example, consultation of electronegativity chart shows Cl with a
value of 3.16 and Na with a value of 0.93. The electronegativity
difference is 2.3, suggesting that the dominant bonding type in NaCl is
ionic but “not only ionic”

• Even looking a larger electronegativity difference like for NaF, the

bonding would by only about 90% ionic. Bonding between Oxygen
atoms or between Carbon atoms, where the electronegativity
difference is 0, would result in pure covalent bonds.
Chemical Bonds
Very ionic Partially Covalent Very Covalent

Mg-O Al-O C-O as in (CO3)-2

Ca-O Si-O S-O as in (SO4)-2
Na-O Fe-S S-S as in (S2)

K-O Ti-O
A simple calculation of electronegativity difference for the
above mentioned combinations will justify their grouping
http://hyperphysics.phy-astr.gsu.edu/hbase/Chemical/bond2.html
Metallic Bonds
• None of the bond types discussed so far result in
materials that can easily conduct electricity. Pure
metals however, do conduct electricity easily and
therefore must be bonded in a different way.
Metallic Bonds
• This is the metallic bond, where positively charged atomic nuclei
share electrons leading to free electron clouds.

• In a sense, each atom is sharing electrons freely with other

atoms, and some of the electrons are free to move from atom to
atom.

• Since some of the electrons are free to move, metallically

bonded materials have high electrical conductivity.
When crystals are formed with metallic bonds they have the following
properties:

• Low to Moderate hardness.

• Usually very malleable and ductile.

• Good thermal and electrical conductors.

• Soluble only in acids.

• Crystals with high symmetry.

Residual Bonds
•Residual bonds are weak/strong bonds that involve the attraction of partially charged
atoms or molecules. These partial charges are created when electrons become
concentrated on one side of an atom or molecule to satisfy ionic or covalent bonds.
•This sometimes creates a polar atom or molecule which has a concentration of negative
charges on one side and a concentration of positive charges on the other side.
Residual Bonds
• When some residual bonds occur in a crystal
structure, they generally form planes or zones of easy
cleavage because of the weakness of the residual
bond.

• van der Waals/ Hydrogen bond

• Hydrogen Bonds - These occur in the special case of hydrogen,
because H has only one electron. When Hydrogen gives up this
electron to become H+1 ion or shares its single electron with another
atom in a covalent bond, the positively charged nucleus of the
hydrogen atom is exposed, giving that end of the H ion a residual +1
charge.
• This is what causes the H2O molecule to be a polar molecule seen
here.
• van der Waals Bonds are also residual bonds that result from
polarization of atoms or molecules.
• In the mineral graphite, the C atoms are held together by strong
covalent bonds, that result in concentrations of positive and negative
charges at either end of the C atoms. Bonding between sheets takes
place as a result of the slight attraction between these residual
charges from one sheet to another.
 Stable Ionic Structure of ceramics

• Ceramics are typical examples for complex arrangement of atoms

• More than one bonding type could be present and this has its influence on its properties

• Ionic bonding is dominant in ceramics

• Between an pair of oppositely charged ions there is an attractive force, that is

proportional to the products of their charges and inversely proportional to the square of
the distance between their centers. (Coulomb’s Law)
Lecture 1 – Basics of Crystallography
‘Crystallography’ is a branch of physics
that deals with the study of all possible types of crystals
and the physical properties of crystalline solids by the
determination of their actual structure by using X-rays,
neutron beams and electron beams.

Solids can broadly be classified into two types

based on the arrangement of units of matter.
The units of matter may be atoms, molecules or
ions.
Crystalline solids and
Non-crystalline (or) Amorphous
solids
 Crystalline materials

A substance is said to be crystalline when the

arrangement of units of matter is regular and
periodic.

A crystalline material has directional properties and

therefore called as anisotropic substance.

A crystal has a sharp melting point.

It possesses a regular shape and if it is broken, all

broken pieces have the same regular shape.
A crystalline material can either be a single
(mono) crystal or a polycrystal.

A single crystal consists of only one crystal,

whereas the polycrystalline material consists of
many crystals separated by well-defined
boundaries.

Examples
Metallic crystals – Cu, Ag, Al, Mg etc,
Non-metallic crystals – Carbon,Silicon,Germanium,
TEM image of Cordierite (Mg2Al4Si5O18) showing ordered structure typical of
crystalline structures

20A
ZnTe Crystal Electron Diffraction (ZnTe
Atomistic model of a
nanocrystalline solid
Coutesy: Dept of materials science
and engineering
University of Virginia
In amorphous solids, the constituent particles
are not arranged in an orderly manner. They
are randomly distributed.

They do not have directional properties and so

they are called as `isotropic’ substances.

They have wide range of melting point and do

not possess a regular shape.
Examples:
Glass, Plastics, Rubber etc.,
 Crystallography
Two-dimensional Packing:

Crystal is a regular and repeated arrangement of atoms in 2 or 3 directions

Understand the concept of “Unit Cell” and “Packing density”

Unit Cell is the minimum volume cell that can recreate the whole space
when translated in 2 or 3 directions – primitive cell
Identify and draw the unit cells for each of this atomic arrangement
Interstitial space:

Exercise:
1. Calculate the area per unit cell for square, oblique and hexagonal packing

2. How many interstices are present per unit cell?

3. Calculate the interstitial area for each of the packing

 Crystal = Lattice + Basis

Lattice is defined by fundamental translation vectors such as a and b such that

the arrangement looks identical when observed from each lattice point
 
Symmetry:

To define a crystal structure, you need to know,

What is a lattice?

What are the unit translation vectors?

What is the Basis?

What are the symmetry operations that recreate the lattice?

Symmetry operations can be (a) Translation (b) Rotation (c) Reflection

 Rotational symmetry elements can be

(1) Two-fold (◆) – Rotation of 180 can carry the crystal onto itself
(2) Three-fold (▲) –Rotation of 120  - ‘’-
(3) Four-fold (■) - Rotation of 90 
(4) Six-fold – Rotation of 60 

Five fold and Seven fold symmetry

elements do not count – as
pentagons and heptagons do not
result in filled space
(a) Only a two fold axis possible
(b) A two fold axis + 2 mirror planes
(c) A four fold axis + 2 mirror planes
(d) A six fold axis+2 mirror planes
Point Group Symmetry: Minimum number of symmetry elements which
completely defines the symmetry of the structure
A crystal symmetry is generally less than a lattice symmetry – most of the Basis are
some molecules rather than atoms
 What is the Professsor’s lattice
symmetry?

What is the point group?

What is the symmetry of his

structure?

What is the Pattern’s lattice symmetry?

What is the point group?

What is the symmetry of this structure?

Three dimensional Lattice types (totally
14 different types called Bravais lattice)

Triclinic is a general lattice

Rest 13 are special lattices

Most important ones:

(a) Simple Cubic lattice

(b) Body centered lattice
(c) Face centered lattice
(d) Hexagonal Close packed
Packing in three dimensions:

ABCABC packing leading to FCC

ABAB stacking leading to HCP packing

Most metals exist in either BCC, FCC or HCP structure

Interstitial Space:

Tetrahedral Holes

Octahedral Holes
Interstitial Spaces are crucial for alloying – a Foreign atom occupying the
octahedral or the tetrahedral holes available

Carbon steel is a classic example – Fe (BCC) can hold Carbon in the tetrahedral
interstitial sites (0.23 times that of Fe)

Calculate the diameter of the largest sphere that will fit into the octahedral
hole in FCC structure. We can consider the diameter of the spheres located at
FCC positions to be unity

Can you do the same for Tetrahedral hole in FCC?

What is the ratio of octahedral holes to tetrahedral holes in the FCC structure
Can you identify the tetrahedral interstitial site in a HCP lattice. How many such
sites may be present within a cell
Describing planes and directions:

Two examples to understand why understanding

directions and planes are important:

(i) Elastic modulus of Ti is greatest along the hexagonal

axis – when Ti turbine blades are manufactured, the
blade axis must be the axis along which the stiffness is
maximum

(ii) Silicon wafers (Si being diamond cubic) are cut parallel
to the cube faces – the ability to oxidize is better on cube
faces than the other planes
Miller indices of the plane are the reciprocals of the intercepts the plane makes
with the three axes (reduced to the smallest integers) – Miller Indices are written
in round brackets

The plane considered should not pass through the origin

 
Representation of directions: components of vector that starts from the origin,
along the direction
What are the close packed planes?
0.4 nm

0.4 nm
0.4 nm ?
(001) (110)
Ceramic crystal structures
• 
 Most of the Crystal Ceramic Crystal structures
structure basics are
the same for metals Grouping of Ions and Pauling rules:
and ceramics
Oxides, Halides, Silicates etc., known ceramics – predominantly ionic in
character
Five statements – Pauling’s rules – We will see each in detail
First rule:
Example: 1. A coordination polyhedron of anion formed about each cation
Potassium and 2. Cation-Anion distance = Sum of ionic radii
oxygen 3. Coordination number is determined by ionic radii ratio
RA = 1.33Å , 4. Cation coordination polyhedra is advocated
RB =1.40Å ,
RA / RB

KO = 0.95
When coordinating identically sized spheres (RA/RB is approx. 1)
1.C.N. =12

a. Hexagonal Close Packed (HCP)

b. Cubic Close packed (CCP)

2. Cubic Packing where the C.N. = 8 (cubic coordination) for 0.732 < RA/RB < 1.0

3. For 0.414 < RA/RB <0.732, C.N.=6 (The limiting value for the interior of octahedrally
coordinated anions relative size of 1 is in the range of R = 0.732 - 0.414)
 4. Tetrahedral coordination is the next smallest interior space with
RA/RB = 0.414 - 0.225

5. Triangular coordination is next smallest space with RA/RB = 0.225 -

0.155

6. Linear coordination is smallest where RA/RB < 0.155

Stablest structure is the one with maximum coordination

A larger co-ordination may be allowed at the expense of deformation and gain

of electrostatic energy – For central atoms with higher charge/anions have
high Z
Ionic Radii
Pauling’s Rules for Ionic Structures
Rule 1: The coordination number of a cation A by an anion B will be determined
by the radius ration of the ions A and B

R /R < 0.16
A B
3-fold coordination
0.16>R /R < 0.41
A B
4-fold coordination
0.41>R /R < 0.73
A B
6-fold coordination
0.73>R /R < 1.00
A B
8-fold coordination
1.00>R /R A B 12-fold coordination
 

Fourth and Fifth rules:

Separation of cations decreases as
polyhedras share edges, corners and
faces

Polyhedra formed about cations of low

C.N and higher charge – will prefer
corner sharing

The number of different constituents

are kept at minimum – stability of
structure in ceramics
 Zincblende structure

TiO2 (distorted cubic close packed)

Wurtzite (HCP structure) – BeO, ZnS
 Flourite structure
Corundum structure

Cesium Chloride

https://www.seas.upenn.edu/~chem101/sschem/
ionicsolids.html
(Website is more informative on various Ceramic
structures)
Perovskite structure

Assignment: BaTiO3, belonging to perovskite family is an interesting Ferroelectric material

1. What is the lattice type?
2. What are the coordination numbers of ions
3. Does the structure obey Pauling’s rules
32 Octahedral interstices per unit cell

64 tetrahedral interstices per unit cell

 Defects in ceramics - Structural imperfections

Frenkel disorder – Creation Schottky disorder – Creation of equal number of

of equal number of anion and cation vacancies
vacancies and interstitials
Location of atoms +valence state/electronic energy level of the defect

Ofcourse, apart from the above mentioned two types of disorders, we have substitutional
and interstitial solid solutions (illustrate!) – cases very similar to metals
Kroger wink Notation

For a composition M-X, where M is a cation and X is an anion

Type of defects Kroger Wink Notation
Vacant Lattice sites VM, VX
Interstitial atoms Mi, Xi
Misplaced atoms MX
Associated Centers (VMVX), (XIXM)
Solute LM, SX, Li
Free electrons, electron holes e’, h
Charged defects For NaCl, V’Na=VNa+e’,
VCl=VCl+h
Charged defects are rudimentary to the understanding of ceramics:
Let us discuss the examples of Zni, Ca substitution Na in NaCl , Non-stoichiometric FeO
 Defect “Chemistry” – Formulation of reaction equations

Defect interactions – conceptualized by mass-action equilibria just like chemical

reactions
1. Site relation – the number of sites should always be in correct proportion – equal
proportion for MX, X sites twice that of M for MX2
2. Site creation – Introducing or eliminating a VM should not violate the factor 1 “Site
relation” – VM, VX, XM, MM, XX
3. Mass balance – A mass balance must be maintained as in any chemical equation
4. Electrical neutrality – This condition is said to be maintained if both sides of the defect
reaction equation has the same effective charge – example, refer to creation of Na,Cl
vacant sites in NaCl
5. Surface sites – No special indication for surface sites – may consider case by case
Solid solution of CaCl2 in KCl

Possibility I

Possibility II

Both equations preserve site relation, electrical neutrality, mass balance etc.

What is the factor that picks one of them to actually happen?

 20.02.2017
Ofcourse the Energy – the solid solubility in a host lattice can never happen if it increases
the total energy of the crystal
G=E+PV-TS
Randomness
Structural energy

Two contradictory examples:

(1) MgO- NiO – starting phases have same crystal structure

(2) MgO-Al2O3 – starting phases have different crystal

structure
 MgO-Al2O3 Solid Solution diagram

Substitutional Solid solution: Substitution of one ion for another

Several examples exist – Al2O3-Cr2O3, ThO2-UO2 etc. including the above discussed case

In most of the cases, “You cannot keep adding!”

What are the factors that decides the extent of substitution at a given temperature?
Factors affecting the extent of solubility:
1. Size factor: RA/RB>15%, the solubility drops to less than 1% - most important
2. Valency factor
3. Chemical affinity: Highly reactive phases do not tend to dissolve much in each other
4. Structure type: The end phases must be isostructural

How the difference in valency is overcome to form extensive solid solutions

(1) through exchangeable ion adsorbed on particle surfaces
(2) Vacant sites compensate charge difference Example MgAl2O4-Al2O3 (Refer to spinel
structure)
For Al3+ substituting Mg2+, Al2O3 2AlMg+V’’Mg+3OO

For every 2 Al3+ added, 3 Mg2+ is removed – leaving one vacant site
End member is -Al2O3 (fcc anion packing with 1/9 of cation sites vacant!)

(3) For CaO added to ZrO2 (fluorite),

Case by case difference depending on the valency of cation added – lower valency than host
What happens when CaCl2 is added to KCl? Actually the solid
solubility is very poor. What does the reaction look like:
CaCl2 CaK+V’K+2ClCl

What is the role of processing temperature in determining

the extent of solid solution and creation of defects?

Density calculations from unit cell edge length:

Total weight of the ions per unit cell: (No of sites X fraction
occupied X Atomic Weight)/6.023X1023
Density=Total weight of ions per unit cell/Volume For composition Zr0.85Ca0.15O0.85, unit cell
edge is 5.131Å
Ref: Diness and Roy, Solid state Communication, 3, 123
(1965)
A divergence between the observations at room
temperature and the equilibrium situation at higher
temperatures

Interstitial Solid Solution:

1. Size factor
2. Valency factor
3. Chemical affinity
No structure type (Actually the structure of host phase
matters!)
Once again, the charge balance needs to be maintained
– through formation of defects or substitutional solid
solution or changes in electronic structure
Consider dissolving ZrO2 in Y2O3, 2 ZrO2 2 ZrY +3OO+O’’i – creates
oxygen interstitials for site relation and electrical neutrality.
The other possible defect reaction: 3ZrO2 3ZrY+6Oo+V’’Y

Cation vacancies
 Frenkel disorder

Energy required to create Configurational Entropy

Energy of
vacant and interstitial sites
perfect crystal

For N normal sites and equal number of interstitial sites, depending on number of ways N
atoms can be arranged is given by,

Apply ni=nv, then

Minimizing the free energy, one can get,

Example of Silver Bromide:

Applying the law of mass action:

 Mass action constant:

Assuming a small concentration of defects,

-------------------------------------------------------------------------------------------------------------------------
Assignment:
If Δh=1.1 eV for AgBr and assuming exp(s/2k)=0,30 and 100, calculate relative Frenkel
defect concentration at from RT to 1000C (in steps of 100 C). Plot the log(n/N) as a
function of 1/T.
-------------------------------------------------------------------------------------------------------------------------
Energy change in accommodating a Frenkel defect depends on structure and ion
characteristics!
Examples of NaCl (h=7 to 8 eV), CaF2 (h=2.8 eV, entropy term 104), AgBr (h=1.1 eV,
entropy term 30 to 1500)
Calculations are relatively difficult especially when correction for ionic polarizability is
important! What happens in oxides?
 Y2O3 is a typical example

Even under substitutional solution, this relation is upheld

Schottky disorder: Example NaCl

The Enthalpy to create point defects calculated from Born-Mayer cycle :

(1) creation of charged imperfections in crystals by removal of ions
(2) Transformation of gaseous ions into atoms
(3) formation of compound from gaseous atoms.

For NaCl (derived from a research paper by Fumi and Tosi)

Calculations tough for oxides in general due to influence of following factors:
Coulombic interactions, Born repulsions and polarization effects (large uncertainties
are associated with these parameters)
Schottky defect requires lattice perturbations – grain boundaries, surfaces – basically
where the ions that escape, tend to get harbored

For MgO,

What happens when Al2O3 is added to MgO!

Oxygen vacancies disappear in proportion to maintain the above equation

Order-disorder transformation

Most metals tend to be disordered, not very general in oxides

Mostly the disorderness influences the second coordination

Order parameter
Assignment: Identify some ceramic/ionic systems that undergo order-disorder
transformation. Report the parameters in a table
• Order-disorder transformation is very common in metals – AB alloys –
disorder energy ED is less
• Ionic crystals – order-disorder related to either cation substructure or
anion substructure
• If Valency/structure are similar, then only coloumbic energy dictates
the disorder energy - example NiO-MgO or Al2O3-Cr2O3
• Valency is different – example: Li2Fe2O4 and Li2TiO3 – both rock salt
structure
• ZnO1-xFx or (NH4)3MoO3F3 – disorder in anion sites
• Order-disorder transformation in Ferrites – classic examples

Low temperature phase is ordered – high temperature phases exhibits

disorderness
Polymorphs: Special structures – Should
also know about polytypes