Crystal Structure and Analysis

by

Dr. Abdul Faheem Khan

Department of Materials Engineering,

Institute of Space Technology, Islamabad
Textbooks
1. Modern Ceramics Engineering David R.
Richerson, Taylor and Francis

2. Introduction to Glass Science & Technology, 2nd

Edition, Rs.C
Assessment or Evaluation
Quizzes 10%
Assignments 05%
Presentations 10%
OHT Exam 30%
Final Exam 45%
Project Nil
Total 100%
Atomic Bonding & Crystal
Structure
Modern Ceramics Engineering
Ceramics
They contain both metallic and nonmetallic elements.
Characterized by their higher resistance to high temperatures
and harsh environments than metals and polymers.
Typically good insulators to passage of both heat and
electricity.
Less dense than most metals and alloys.
They are harder and stiffer, but brittle in nature.
They are mostly oxides, nitrides, and carbides of metals.
Wide range: traditional (clay, silicate glass, cement) to
advanced (carbides, pure oxides, non-silicate glasses).

E.g.: Glass, Porcelain, Minerals, etc.

 A ceramic is
an inorganic, nonmetallic, solid material
comprising metal, nonmetal or metalloid atoms
primarily held in ionic and covalent bonds.
 Review of Atomic Structure
Atoms = nucleus (protons and neutrons) + electrons

Mass (g) Charge (C)

Proton 1.673 x 10-24 +1.602 x 10-19
Neutron 1.675 x 10-24 0
Electron 9.109 x 10-24 -1.602 x 10-19

Atomic mass = # protons + # neutrons

Atomic number (Z) = # protons

chemical identification of element

Isotope number # neutrons

Electronic Structure of Atom

Photon:
E = hv
h is the planks constant = 6.63 x 10 -34 J-s

E = hc/
Electron being excited or lose due to discrete energy levels, wavelengths intensities

E = - 2me4 / n2h2 = (-13.6 / n2) ev (n = 1, 2, 3, .)

Electron orbit

Proton: charge +e Proton: charge +e

Mass m, velocity v

r, for H = 0.05 nm

v
n=3, paschen series,
n=4, Bracket series,
n=5, pfund series
Ionization Energy
The minimum energy required to remove an electron from the atom.

Heisenbergs Uncertainty Principle

The position and momentum of a small particle such as an electron can not be
determined simultaneously.
Probability of finding the electron in an Hydrogen atom is high at a radius of about
0.05 nm.
Quantum numbers

1.Principle quantum number, n: corresponds to the main energy levels

2.The subsidiary quantum number, l:Subenergy levels within the main
energy levels. Allowed values of l are 0 (s), 1(p), 2(d), 3(f), 4. n-1. s,p,d,f are
oribitals or subenergy levels or subshell.
3.The magnetic quantum number, ml: Spatial orientation of a single
atomic orbital and has little effect on the energy of an electron. Permissible values
are l to +l.
4.Electron spin quantum number, m s: specifies two allowed spin
directions for an electron spinning on its own axis. Two electrons may occupy the
same orbital if they have opposite spin.

Pauli exclusion principle: no two electrons can have the same

set of four quantum numbers
Maximum number of electrons for Principle shell: 2n2

Atomic size

Electronic configurations of the elements

Electronic structure and chemical reactivity

Outermost electrons completely filled (Ne, Ar, Kr, Xe and Rn)

 Electrons in Atoms (III)

Subshells by energy: 1s,2s,2p,3s,3p,4s,3d,4s,4p,5s,4d,5p,6s,4f,

Electrons fill levels in order of increasing energy (only n, make a
significant difference).
Example: Iron, Z = 26: 1s22s22p63s23p63d64s2

Outermost shell the valence electrons

responsible for bonding. 16
 Periodic Table

Elements in same column share similar properties.

Group number number of electrons available for bonding

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

IA: Alkali metals (Li, Na, K) one electron in outer shell eager to give up electron
chem. active

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

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

Electronegativity - how willing atoms are to

accept electrons
Subshells with one electron - low electronegativity
Subshells with one missing electron -high electronegativity
Electronegativity increases from left to right

Metals are electropositive can give up their few valence electrons

to become positively charged ions
 Bonding Energies and Forces

Energy, E repulsion
Potential

0
attraction

equilibrium

Typical potential between two atoms

Repulsion when they are brought close together
Related to Pauli principle
(As electron clouds overlap energy increases)

Attractive part: at large distances

(Depends on type of bonding)
 Types of Bonding
Primary Bonding: e- are transferred or shared
Strong (100-1000 KJ/mol or 1-10 eV/atom)

Ionic:
Example - Na+Cl
Strong Coulomb interaction between
a positive atom (lost an electron, Na+) and
a negative atom (an extra electron, Cl-)

Covalent: electrons shared between the atoms.

Example - H2

Metallic:
Atoms lose some electrons from valence band
Those electrons are shared by all the material

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 dipoles (polar molecules - H2O, HCl...)

 Ionic Bonding (I)
Mutual ionization by electron transfer
(remember electronegativity table) Occurs between + and -
Anion = negatively charged atom ions.
Cation = positively charged atom Large difference in
electronegativity required.
Ions are attracted by strong coulombic interaction
Oppositely charged atoms attract
An ionic bond is non-directional

Example: NaCl
Na has 11 electrons, 1 more than needed for a full outer shell (Neon)

11 Protons Na 1S2 2S2 2P6 3S1 donates e-

10 e- left
11 Protons Na 1S 2S 2P
+ 2 2 6
Cl has 17 electron, 1 less than needed for a full outer shell (Argon)

17 Protons Cl 1S2 2S2 2P6 3S2 3P5 receives e-

18 e-
17 Protons Cl- 1S2 2S2 2P6 3S2 3P6
 Ionic Bonding (II)
e-
Na Cl Na+ Cl-
3s1 Half-filled 3p

Electron transfer reduces energy of the system

The ionic bonding forces are due to
Na shrinks and Cl expands electrostatic or coulombic force of attraction of
oppositely charged ions.

bonds forms due to decrease in pot. energy

Ionic bonds: very strong, nondirectional bonds

 Reduces the size of Na atom due to electron to proton
ratios.
Increases the size of Cl atom due to electron to proton
ratios.

0.192nm 0.099nm 0.095nm 0.181nm

 Bonding Energies and Forces
a0
Potential Energy

Ut=Ur+Ua

E0 E0 bond energy
F= dE/da
a0 equilibrium distance
a0
at a0, dE/da = 0, Fa = Fr
Tensile
(+)
Force

Compressive
(-)

24
Examples: Ionic Bonding
Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (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.
Ions arrangement in ionic solids

Elemental ions have approximately spherical shape charge distributions

Elemental cations are smaller than their atoms and anions are larger
Non-directional due to electrostatic attraction of symmetrical charges
The larger the difference in
Electronegativities, the
Greater would be the ionic
character
Bonding energies of ionic solid
Ionic solids have high melting temp. Why???

Ions packing without preferred orientationelectrostatic attraction of symmetrical

charges does not require any orientation
Charge Neutrality

May have extremely complex structures. Considering only geometric arrangement

of ions:
CsCl & Nacl
In CsCl, eight Cl- ions can surround a central Cs+ ion where in NaCl only six.
For CsCl, cation to anion radius ratios is larger than Nacl.

As the cation to anion radius ratios is reduced, fewer anions can sorround a central
Cation in this type of structure.

Lattice energy decrease as the ion increases in a group

Covalent Bonding
Small differences in Electronegativity
Sharing of electrons
After sharing energy decreases

Covalent Bonding Hydrogen molecule

 Covalent Bonding in Carbon

Carbon forms two covalent bonds

In some cases it forms four covalent bonds sp3 by hybridization

1s 2s 2p orbitals (half filled) 1s Four half filled orbitals

(sp3 orbitals)
Carbon in the form of diamond exhibit sp3 tetrahedral covalent bonding
Sp3 hybrid orbitals are directed symmetrically towards the corners of a tetrahedron

High hardness, high bond strength

and melting temp.
Covalent bonding in carbon-containing molecule

Benzene
 Covalent Bonding
Potential energy of system of covalent bonds

P.E.=

Depend on distances between atoms

35
AND angles between bonds
Metallic bonding
Occurs in the solids metals, that atoms are packed relatively close together in a
definite pattern, such that their outer electrons are attracted to the nucleus of
many neighbors (12 nearest neighbors for Cu)

Solid metals are visualized as positive

ion cores (atoms without their valence
elections)

Valence electrons are spread among

atoms in the form of low density
electron charge cloud or electron
gas. These electrons are weakly
bonded to positive ion cores and can
move in the crystal (free electrons).
In metallic bonding, no conditions of charge neutrality or electron pair is required
Non-directional due to bonding of valence electrons to many atoms
Secondary bonding
Secondary bonds are weak in contrast to primary bonds
Driving force for the secondary bonds is the attraction of the electric diploes

Electric diploes are created when two equal and opposite charges are separated
 SECONDARY BONDING
Arises from interaction between dipoles
Fluctuating dipoles
asymmetric electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding Adapted from Fig. 2.13,
bonding
Callister & Rethwisch 8e.

Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -
Adapted from Fig. 2.15,
Callister & Rethwisch 8e.
secondary
-ex: liquid HCl H Cl bonding H Cl

secon
-ex: polymer dary
bond secondary bonding
ing
The charge value multiplied by the separation distance between the positive and
negative charges the dipole moment

= qd

Fluctuating dipoles

It may arise due to non-symmetrical distribution of charges like nobel gases.

Weak inter-atomic forces (nearby atoms) due to which non-directional bonds.







Symmetrical charge distribution
Non-symmetrical charge distribution
 Permanent dipoles
Many molecules have such dipole moments due to non-uniform distributions of
positive and negative charges on the various atoms. Such is the case with polar
compounds like hydroxide (OH), where electron density is shared unequally
between atoms.

e.g., C-H bonds are arranged in a tetrahedral structure so zero dipole and CH3Cl
Non-symmetrical distribution of three C-H bonds and one C-Cl resulting in a net
dipole moment.

Hydrogen Bonding (special case of a permanent dipole-dipole interaction)

Water consist of two hydrogen atoms and one oxygen atom
Each hydrogen atom is covalently bonded with hydrogen atom via shared pair of
electrons

Hydrogen has positive charge centre and oxygen has negative charge centre
 Summary: Bonding
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Covalent Variable Directional

large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
inter-molecular
 Properties From Bonding: Tm
Bond length, r Melting Temperature, Tm
Energy
r

Bond energy, Eo ro
r
Energy smaller Tm

unstretched length
ro larger Tm
r
Eo = Tm is larger if Eo is larger.
bond energy
 Properties From Bonding :
Coefficient of thermal expansion,
length, L o coeff. thermal expansion
unheated, T1
L L
=(T2 -T1)
heated, T2 Lo

~ symmetric at ro
Energy
unstretched length
ro
r is larger if Eo is smaller.

Eo
larger

Eo smaller
Summary: Primary Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
secon
dary
bond small E
ing
large
Mixed bonding
1. Ionic-covalent bonding
2. Metallic-covalent bonding
3. Metallic-ionic bonding

1. Ionic-covalent bonding

Most covalent bonded molecules have some ionic binding and vice versa
Greater the difference in electronegativies, greater the ionic character of the bond
e.g, GaAs (3-5) and ZnSe (2-6)

2. Metallic-covalent bonding

In the transition metals involving dsp bonding orbitals

3. Metallic-ionic bonding

Significant difference in electronegativities that forms intermetallic compound

(NaZn13).