Session 2 T1 Bonding PDF

Universidad
Carlos III de Madrid Aerospace Materials I

www.uc3m.es CIENCIA E INGENIERÍA DE MATERIALES
TOPIC 1. BONDING IN SOLIDS
• Introduction
• Bonding in solids
• Ionic bonding
• Covalent bonding
• Metallic
e a c bonding
bo d g
• Secondary bonding
• Bonding and properties in materials
Dpt. Materials Sci. and Eng. and Chemical Eng. UC3M Aerospace Materials I
Topic 1: Bonding in solids
INTRODUCTION
Nature of bonding <> properties <> type of materials <>

Processing and applications
Applications
Properties
Structure
Processing
Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Ionic Bonding
• Ionic bonding is due to electrostatic force of attraction

between cations and anions.
• It can form
f between
b t metallic
t lli andd nonmetallic
t lli elements.
l t
• Electrons are transferred from electropositive to
electronegative
g atoms
Bonding forces  F electrostatic attraction between opposite charged

ions.
Electropositive Electronegative
Electron
Element Atom
Transfer
Electrostatic
Cation Attraction Anion
+ve charge -ve charge
IONIC BOND
Ionic Bonding
© 2003 Brooks/Cole Publishing / Thomson Learning™
• An ionic bond is created between two unlike atoms with

different electronegativities.
• When sodium donates its valence electron to chlorine,
chlorine each
becomes an ion; attraction occurs, and the ionic bond is
formed.
• When a metal forms a cation,
cation its radius reduces and when a
nonmetal forms an anion, its radius increases
• Pure ionic bond: ideal.
•  Always exists covalent participation
Ionic Bonding
The electronegativity variations
Ionic Bonding
LATTICE ENERGY:
Energy released when a mole of
ionic solid is formed from its ions in
the g
gas state.
Born-Haber cycle for KCl.
Ionic Bonding
Ion Arrangements in Ionic Solids
• Ionic bonds are Non Directional

• Geometric arrangements are present in solids to
maintain electric neutrality.
neutrality
Ionic packing
I NaCl
In N Cl
and CsCl
CsCl NaCl
• As the ratio of cation to anion radius decreases, fewer
anion surround central cation.
• Ionic compounds are crystalline solids
Ionic Bonding
Interionic Energies for Ion Pairs
• Net potential energy (binding energy) for a pair of oppositely
charged
g ions =
2
E net  ZZe1 2

b
 4  a n
  o
2
a0
 o
Attraction Repulsion
p
Energy Energy
Energy Energy (Z1 ,Z2: number of electrons removed or added

Released Absorbed e=: electron charge= 1.6 x 10-19 C)
o : p
permitivityy of space
p = 8.85 x 10-12 C2/Nm2
b: constant
• Enet is minimum when ions are n: 5-9 (Born exponent)
r: interionic distance
at equilibrium separation
di t
distance a0
Ionic Bonding
LATTICE ENERGY:
Many properties are dependant on the lattice energy
(melting point, hardness, thermal expansion coefficient)
When the ion size   lattice

energy  and Tm 
Valence +1
Valence +2
Valance number   lattice
energy   Tm 
Ionic Bonding
• General properties of ionic compounds

Strong electrostatic attraction  High melting and evaporation points
Hard and brittle solids at room temperature
They do not conduct electricity (except in molten state or when

dissolved in water)
Water soluble.
Ionic Bonding
© 2003 Brooks/Cole Publishing / Thomson

Learning™
When voltage is applied to an ionic material, entire ions must move to

cause a current to flow. Ion movement is slow and the electrical
conductivity is poor
Covalent Bonding
• In Covalent bonding, outer s and p electrons are

shared
s a ed between
bet ee two
t o atoms
ato s to obtain
obta nobleob e gas
configuration.
• Takes p place between elements
with small differences in
electronegativity
g y and close by
y
in periodic table.
y g , a bond is formed between 2 atoms
• In Hydrogen,
by sharing their 1s1 electrons Overlapping Electron Clouds
Electron
Pair
H
H + H H H H
1s1 Hydrogen
Electrons Molecule
Covalent Bonding
Generally it forms between the non metallic elements of the periodic

table
Examples:
Covalent Bonding
Examples:
In silicon, with a valence of four, four covalent bonds must be formed
Covalent bonds are directional. In silicon, a tetrahedral structure is

formed, with angles of 109.5° required between each covalent bond
Covalent Bonding
Examples:
The tetrahedral structure of silica (Si02), which contains covalent bonds

between silicon and oxygen atoms
Covalent Bonding
POLAR COVALENT BOND

• Nonpolar bonds: sharing of the bonding
electrons is equal between the atoms and
the bonds.
• Polar covalent bond: Sharing of the
bonding electrons is unequal (HF, NaF).
Dipole moment
µ=Qxd
d = Distance between atoms;

Q =charge
Units: Debye, D; 1 D = 3.33 10-30 C·m
% ionic character  1  e   0.25  X A  X B 2

100% Xi : electronegativity of element i
Covalent Bonding
Bond Length, Bond order and Bond Energy
For a given pair of

atoms, with higher bond
order, the bond length
will decrease;; as bond
length decreases, bond
energy will increase (H2,
F2, N2)
Covalent Bonding
• Properties of the compounds with covalent bonds

 Covalent Solids
Formed by a system of continuous covalent bonds
Non conductive LATTICES both in the solid and in the molten state
Diamond boron nitride,
Diamond, nitride quartz (SiO2),
) silicon carbide (SiC)
Hard and incompressible
Tm high, non volatile
insoluble
graphite Diamond
Substances with covalent bonds
Metallic Bonding
• Atoms in metals are closely packed in crystal

structure.
• Loosely bounded valence electrons are attracted
towards nucleus of other atoms.
• Electrons
El t spreadd outt among atoms
t forming
f i
electron clouds. Positive Ion
• These free electrons are
reason for electric
conductivity and ductility
• Since outer electrons are
shared by y manyy atoms,,
metallic bonds are
Non-directional
Valence electron charge cloud
Metallic Bonding
The metallic bond forms

when atoms give up their
valence electrons, which
then form an electron sea
sea.
The positively charged
atom cores are bonded by
mutual attraction to the
negatively charged
electrons
Metallic Bonding
• Overall energy of individual atoms are lowered

by metallic bonds
• Minimum energy between atoms exist at
equilibrium
ilib i di
distance a0
• Fewer the number of valence electrons involved,
lower is the bonding energy.
energy
 Example:- Na Bonding energy 108KJ/mol,
g temperature
Melting p 97.7oC
• Higher the number of valence electrons involved,
higher is the bonding energy.
 Example:- Ca Bonding energy 177KJ/mol,
Melting temperature 851oC
Metallic Bonding
Metallic Bonds and Material Properties
The bond energies and the melting point of metals vary

greatly depending on the number of valence electrons and
electronic configuration.
Metallic Bonding
Metallic Bonds and Mate
Material
ial Properties
P ope ties
• Pure metals are significantly more malleable than
ionic
o c or
o covalent
co a e t networked
et o ed materials.
ate a s
• Strength of a pure metal can be significantly
g alloying.
increased through y g
• Pure metals are excellent conductors of heat and
electricity.
Metallic Bonding
When voltage is
applied to a metal, the
electrons in the
electron sea can easily
move and carry a
current
Metallic Bonding
• Band theory
– Alkaline metals
– Alkaline earth metals
*(ns) (debonding)
ns E = valence
band
(ns)(bonding )
Energy M2 M3 MN metallic crystal
Metallic Bonding
conduction band
conduction band
band gap
conduction band band gap
empty states
valance
band valance band valance band valance band
filled states
Secondary Bonding
• Secondary bonds are due to attractions of

electric dipoles in atoms or molecules.
• Dipoles are created when positive and negative
charge centers exist.
moment=μ =Q
Dipole moment Q.d
d
+q -q q= Electric charge
d = separation
ti didistance
t
d
• There two types of bonds permanent and
fluctuating.
Secondary Bonding
Fluctuating Dipoles
• Weak secondary y bonds in noble gasses.

g
• Dipoles are created due to asymmetrical
distribution of electron charges.
• Electron cloud charge changes with time.
Symmetrical Asymmetrical
distribution Distribution
of electron charge (Changes with time)
Secondary Bonding
Permanent Dipoles
Dipoles that do not fluctuate with time are

called
ll d Permanent
P t di
dipoles.
l
 Examples:-
Examples:
Symmetrical No Dipole
CH4 Arrangement moment
Of 4 C-H
C H bonds
b d
Asymmetrical
Creates
CH3Cl Tetrahedral
Dipole
arrangement
Secondary Bonding
H d ogen Bonds
Hydrogen
Hydrogen bonds are Dipole-Dipole interaction
between
bet ee polar
po a bonds
bo ds containing
co ta g hydrogen
yd oge atom.
ato
 Example :-
 In water, dipole is created due to asymmetrical
arrangement of hydrogen atoms.
 Attraction between positive oxygen pole and negative
hydrogen pole.
105 0
O
Hydrogen
H B d
Bond
Secondary Bonding
(a) In polyvinyl chloride

(PVC), the chlorine atoms
attached to the polymer
chain have a negative charge
and the hydrogen atoms are
positively
p y charged.
g The
chains are weakly bonded by
van der Waals bonds. This
additional bonding makes
PVC stiffer
stiffer, (b) When a force
is applied to the polymer, the
van der Waals bonds are
broken and the chains slide
past one another
Bonding and properties in materials
Primary bonds: (strong)
-Ionic bond: Transfer of e-  cations and anions  Fcoulomb (non

(150-370 kcal/mol) directional)
- Covalent bond: Sharing e- (directional)

(125-300 kcal/mol)
- Metallic bond: e- shared externally and very little tightened by the nucleus
(25-200 kcal/mol) (non directional)
SHACKELFORD, J.F. “Introduction to materials science foe engineers”,
Secondary bonds - weak (Van der Waals)
Permanent dipole 1-10 kcal/mol It forms between molecules:
•that present constant dipole moment μ

•made of atoms with different electronegativity that are
united with covalent bonding.
Fluctuatingg dipole:
p < 2 kcal/mol.
/ It forms in non
polar molecules in crystalline lattice
•Instantaneous fluctuations of electron charge

distribution  fluctuating dipoles
Hydrogen bond 7 kcal/mol in H2O (permanent

dipole):
• In molecules with H and electronegative atoms
(Polar covalent bond: O-H, N-H, F-H).
• Asymmetric distribution of charge  Permanent
dipole
• The minimum energy is the binding or potential energy, or energy

required to create or break the bond
• Materials with high binding energy have high melting temperatures
and hardness
• A high binding energy (steep slope), greater force required to stretch
the bonds; thus higher elastic (Young
(Young's)
s) modulus.
modulus
• Coefficient of thermal expansion (change in linear dimension of a

material per degree temperature): related to strength of atomic
bonds.
• Materials that display a steep curve with a deep interatomic
energy (IAE) trough, caused by strong atomic bonding, have low
linear coefficients of thermal expansion.
Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M 46 Aerospace Materials I
Secondary bonds (Van der Waals):

Examples
Variation of melting points of molecular

hidrates
Type off
T Melting
M lti andd Mechanical
M h i l
Bond Solubility
substance boiling points properties
Depends on the
Soft in the solid
COVALENT Molecular Low polarity of the
state
molecules
Atomic,
At i
Very hard Insoluble in all
COVALENT covalent or Very high
brittle solvents
lattice
Soluble in
IONIC Ionic High Hard and brittle
polar solvents
Ductile and Insoluble in all

METALLIC Metallic High
workable solvents
Nature of bonding  properties  type of materials
Type of material Character of bonding Examples
Metal Metallic Fe steels

Fe,
Ceramic and glasses Ionic/ covalent Silica (SiO2)
Polymers Covalent and secondary Polyethylene –(CH2)-
Questions
• Compare and contrast metallic and covalent primary bonds in

terms of
– a)) th
the nature
t off the
th bond,
b d
– b) the valence of the atoms involved, and
– c)) the ductility
y of the materials bonded in these ways.
y
• Titanium is stiffer than aluminum, has a lower thermal expansion
coefficient than aluminum, and has a higher melting temperature
than aluminum. On the same g graph,
p , carefully
y and schematically
y
draw the potential well curves for both metals and showing how
the physical properties are manifested in these curves.
• Would you expect MgO or magnesium to have the higher modulus
of elasticity? Explain.
• Aluminum and silicon are side-by-side in the periodic table. Which
would you expect to have the higher modulus of elasticity (E)?
Explain.
Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M 50 Aerospace Materials I

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Universidad

Carlos III de Madrid Aerospace Materials I

TOPIC 1. BONDING IN SOLIDS

Nature of bonding <> properties <> type of materials <>

• Ionic bonding is due to electrostatic force of attraction

Bonding forces  F electrostatic attraction between opposite charged

© 2003 Brooks/Cole Publishing / Thomson Learning™

• An ionic bond is created between two unlike atoms with

The electronegativity variations

Born-Haber cycle for KCl.

Ion Arrangements in Ionic Solids

• Ionic bonds are Non Directional

Energy Energy (Z1 ,Z2: number of electrons removed or added

When the ion size   lattice

• General properties of ionic compounds

They do not conduct electricity (except in molten state or when

© 2003 Brooks/Cole Publishing / Thomson

When voltage is applied to an ionic material, entire ions must move to

• In Covalent bonding, outer s and p electrons are

Generally it forms between the non metallic elements of the periodic

Covalent bonds are directional. In silicon, a tetrahedral structure is

The tetrahedral structure of silica (Si02), which contains covalent bonds

POLAR COVALENT BOND

d = Distance between atoms;

Units: Debye, D; 1 D = 3.33 10-30 C·m

% ionic character  1  e   0.25  X A  X B 2

For a given pair of

• Properties of the compounds with covalent bonds

• Atoms in metals are closely packed in crystal

The metallic bond forms

• Overall energy of individual atoms are lowered

Metallic Bonds and Material Properties

The bond energies and the melting point of metals vary

Energy M2 M3 MN metallic crystal

• Secondary bonds are due to attractions of

• Weak secondary y bonds in noble gasses.

Dipoles that do not fluctuate with time are

(a) In polyvinyl chloride

Primary bonds: (strong)

-Ionic bond: Transfer of e-  cations and anions  Fcoulomb (non

- Covalent bond: Sharing e- (directional)

SHACKELFORD, J.F. “Introduction to materials science foe engineers”,

Secondary bonds - weak (Van der Waals)

Permanent dipole 1-10 kcal/mol It forms between molecules:

•that present constant dipole moment μ

•Instantaneous fluctuations of electron charge

Hydrogen bond 7 kcal/mol in H2O (permanent

• The minimum energy is the binding or potential energy, or energy

• Coefficient of thermal expansion (change in linear dimension of a

Secondary bonds (Van der Waals):

Variation of melting points of molecular

Ductile and Insoluble in all

Nature of bonding  properties  type of materials

Type of material Character of bonding Examples

Metal Metallic Fe steels

• Compare and contrast metallic and covalent primary bonds in

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