Covalent Bonding

• Similar electronegativity  share electrons

• bonds determined by valence – s & p orbitals
dominate bonding
• Example: CH4
shared electrons
H from carbon atom
C: has 4 valence e-, CH 4
needs 4 more
H: has 1 valence e-, H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
are comparable. atoms

Adapted from Fig. 2.10, Callister & Rethwisch 3e.

1
 • Ionic-Covalent Mixed Bonding
 (X A X B )2 
 
4

% ionic character = 1 e x (100%)
 
   
where XA & XB are Pauling electronegativities

Ex: MgO XMg = 1.3
XO = 3.5
 (3.5 1.3 )2 
  
% ionic character  1  e 4  x (100%)  70.2% ionic
 
 

2
 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 3e.

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -
Adapted from Fig. 2.14,
Callister & Rethwisch 3e.
secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer second

a ry b o n secondary bonding
d i ng

3
 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
4
 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”

5
 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 
6
 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
second
a ry b o n
d i ng
small E
large 

7
Chapter 3: Structures of Metals & Ceramics
ISSUES TO ADDRESS...

• How do atoms assemble into solid structures?

• How does the density of a material depend on

its structure?

• How do the crystal structures of ceramic

materials differ from those for metals?

• When do material properties vary with the

sample (i.e., part) orientation?

8
 Energy and Packing
• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, ordered packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, ordered packed structures tend to have lower

energies.
9