2.1. Atomic Structure: Structures of Engineering Materials

9/5/2014
Module 2.
Structures of Engineering Materials
1. Atomic Structure
2. Atomic Bonding
Prof. Dr. Ir. Bondan T. Sofyan, M.Si.
2.1. Atomic Structure
9/5/2014
Atomic Structure
All materials consist of elements and all elements consist of
atoms. Each atoms has its own characteristics has different
properties see Periodic Table
Atomic Structure
proton
neutron
e-
BOHR ATOM
orbital electrons:
n = principal
quantum number
1
n=3 2
Adapted from Fig. 2.1,
Callister 6e.
Nucleus: Z = # protons
= 1 for hydrogen to 94 for plutonium
N = # neutrons
Atomic mass A Z + N
9/5/2014
ELECTRON ENERGY STATES

Electrons...
Incre
easing energy
have discrete energy states

py lowest available energy
gy state.
tend to occupy
4p
n=4
4s
n=3
3s
2
n=2
n=1
2s
1s
3d
3p
2p
Callister 6e.
STABLE ELECTRON CONFIGURATIONS

Stable electron configurations...
have complete s and p subshells
tend to be unreactive.
Z Element Configuration
2
He
1s2
Adapted from Table 2.2,
Callister 6e.
10
Ne
1s22s 22p6
18
Ar
1s2 2s22p63s23p6
36
Kr
1s2 2s22p63s23p63d10 4s24p6
9/5/2014
SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.

Element
Atomic #
Hydrogen
1
Helium
2
Lithi
Lithium
3
Beryllium
4
Boron
5
Carbon
6
...
Neon
10
Sodium
11
Magnesium
12
Aluminum
13
...
Argon
18
...
...
Krypton
36
Electron configuration
1s 1
1s 2
(stable)
1s 22s 1
1s 22s 2
Adapted from Table 2.2,
1s 22s 22p 1
Callister 6e.
1s 22s 22p 2
...
(stable)
1s 22s 22p 6
1s 22s 22p 63s 1
1s 22s 22p 63s 2
1s 22s 22p 63s 23p 1
...
1s 22s 22p 63s 23p 6
(stable)
...
(stable)
1s 22s 22p 63s 23p 63d 10 4s 24 6
Why? Valence (outer) shell usually not filled completely.

Columns: Similar Valence Structure
Li Be
Na Mg
K
Ca Sc
Rb Sr
Cs Ba
Metal
Nonmetal
Intermediate
accept 2e
accept 1e
in
nert gases
give up 1e
e up 2e
give
give up 3
3e
THE PERIODIC TABLE
He
Ne
Cl
Ar
Se Br Kr
Te
Xe
Po At Rn
Adapted
from Fig. 2.6,
Fr Ra
Callister 6e.
Electropositive elements:
Readily give up electrons
to become + ions.
Electronegative elements:
Readily acquire electrons
to become - ions.
9/5/2014
ELECTRONEGATIVITY
Ranges from 0.7 to 4.0,

Large values: tendency to acquire electrons.
H
2.1
Cl
3.0
Br
2.8
He
Ne
Ar
Kr
-
Sr
1.0
I
2.5
Xe
-
Cs
0.7
Ba
0.9
At
2.2
Rn
-
Fr
0.7
Ra
0.9
Li
1.0
Na
0.9
Be
1.5
Mg
1.2
K
0.8
Rb
0.8
Ca
1.0
F
4.0
Ti
1.5
Cr
1.6
Fe
1.8
Smaller electronegativity
Ni
1.8
Zn
1.8
As
2.0
Larger electronegativity
Adapted from Fig. 2.7, Callister 6e. (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.
2.1. Atomic Bonding
9/5/2014
Atoms may form two types of bond:

Primary
P
i
b
bonds:
d
a. Ionic bond
b. Covalent bond
c. Metallic bond
Secondary bonds:
a. Van der Waal bond
b. Hydrogen bond
9/5/2014
Ionic Bonding
Primary Bonds
Electrons are directly transferred from one atom to another and

localised. Atoms are bonded by coulombic force. Bonds are nondirectional.
IONIC BONDING
Occurs between + and - ions.

Requires electron transfer.
Large difference in electronegativity required.
Example: NaCl
Na (metal)
unstable
Cl (nonmetal)
unstable
electron
Na (cation)
stable
Coulombic
Attraction
Cl (anion)
stable
9/5/2014
However, more energy is released as Na+ and Cl- ions are getting
closer.
The attractive energy , EA, is given by:
EA =
1
4 0 r
( Z1e)( Z 2e)
where 0 is the permittivity of free space (8.85 x 10-12 F/m), Z1 and

Z2 are the valences of the two ions, e is the electronic charge
(1.602 x 10-19 C) and r is the separation of the ions.
g
is for the energy
gy released in forming
g
In convention, negative
bonds and positive for the energy required to break bonds.
At a separation, r*, the energy released equals the 1.5eV

required to transfer the electrons. So at separations smaller than
this there will be a net release of energy and so the bond is
stable.
EA
The variation of the attractive coulomb interaction,

EA, with ionic separation, r.
9/5/2014
The approaching ions also suffer a repulsive force due to the interaction of
the inner electron shells of the two ions.
A repulsive energy, ER, is given by:
ER =
B
rn
where n is an exponent ~8 and B is an empirical constant.

ER
The variation of the repulsive interaction, Ur, with

ionic separation, r.
ER
EA
9/5/2014
The overall energy of interaction, Etot, is the combination of the

attractive energy, EA and the repulsive energy, ER.
Etot =
1
4 0 r
( Z1e)( Z 2e) +
B
rn
ETOT
EW
The equilibrium spacing between the two ions, given as r0, is

where the energy of interaction is a minimum.
r0 = bond length
Structure of Salt (NaCl)
Schematic model
Lattice
10
9/5/2014
MORE EXAMPLES: IONIC BONDING

Predominant bonding in Ceramics
NaCl
MgO
g
CaF2
CsCl
H
2.1
Li
1.0
Be
1.5
Na
0.9
Mg
1.2
K
0.8
Ca
1.0
Rb
0.8
He
O
F
3.5 4.0
Ne
-
Cl
3.0
Ar
-
Br
2.8
Kr
-
Sr
1.0
I
2.5
Xe
-
Cs
0.7
Ba
a
0.9
At
2.2
Rn
-
Fr
0.7
Ra
0.9
Ti
1.5
Cr
1.6
Fe
1.8
Ni
1.8
Zn
1.8
As
2.0
Acquire electrons
Give up electrons
Adapted from Fig. 2.7, Callister 6e. (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.
COVALENT BONDING
Requires shared electrons
Example: CH4
C: has 4 valence e,
e
needs 4 more
CH4
H: has 1 valence e,
needs 1 more
Electronegativities
are comparable.
shared electrons
from carbon atom
H
shared electrons
from hydrogen
atoms
Adapted from Fig. 2.10, Callister 6e.
10
11
9/5/2014
EXAMPLES: COVALENT BONDING
H
2.1
Li
1.0
Na
0.9
K
0.8
Be
1.5
Mg
1.2
Ca
1.0
Rb
0.8
Cs
0.7
Sr
1.0
Ba
0.9
Fr
0.7
Ra
0.9
column IVA
c
H2O
H2
C(diamond)
SiC
Ti
1.5
Cr
1.6
Fe
1.8
Ni
1.8
Zn
1.8
Ga
1.6
C
2.5
Si
1.8
Ge
1.8
F2
He
O
2.0
As
2.0
F
4.0
Cl
3.0
Br
2.8
I
2.5
Sn
1.8
Pb
1.8
At
2.2
Ne
-
Cl2
Ar
Kr
Xe
Rn
-
G A
GaAs
Ad t d ffrom Fi
Adapted
Fig. 2
2.7,
7 Callister
C lli t 6
6e. (Fig.
(Fi 2
2.7
7 iis
adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright
1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.
Molecules with nonmetals

Molecules with metals and nonmetals
Elemental solids (RHS of Periodic Table)
Compound solids (about column IVA)
11
Covalent Bonding
Sharing electrons between adjacent atoms. Bonds are directional.
The energy released, Ua,
associated with electron sharing:
Ur =
a
rn
where r is the distance between

the two atoms, n is ~6, and a is
a constant.
If the two atoms become too close

together, the repulsive energy Ur is
given by:
g
y
Ur =
b
rm
where m is an exponent (~12) and b is a

constant.
The overall covalent interaction

energy Utot is given by:
U tot =
a
b
+
rn rm
12
9/5/2014
Covalent bonding in a
molecule of methane
(CH4)
Metallic Bonding
In a metal, valence electrons leave their parent atoms and combine to
form an electron "gas" which freely wander around metal ions.
The electrons are completely delocalized and provide a bonding

force between the metal ions. The bonding between the atoms is
non-directional.
13
9/5/2014
Metallic Bonding
1. The complete delocalization

of the electrons means
metal "ions" are readily
i t h
interchangeable
bl different
diff
t
alloys.
2. The electrons are easy to
move metals are good
electrical conductors.
3. The metal ions p

pack
together very well metals
have high densities and
assume simple
crystallographic structures.
Primary bond for metals

and their alloys
12
SECONDARY BONDING
Arises from interaction between dipoles
Fluctuating dipoles van der waals
ex: liquid H2
asymmetric electron
H2
H2
clouds
- secondary +
bonding
H H
H H
secondary
bonding
Permanent dipoles-molecule induced hydrogen bond

-general
g
case:
-ex: liquid HCl
H Cl
-ex: polymer
s e c on
dary
secondary
bonding
secondary
bonding
H Cl
bond
in
Callister 6e.
Callister 6e.
g
13
14
9/5/2014
Secondary Bonds
Van der Waal Bonding
A dipole may be formed when the
electrical symmetry for some atoms
or molecules is instantaneously
distorted. Two opposite dipoles may
attract each and form a weak
eak bond
bond.
Bonds in the condensed halogen
molecules, such as liquid and solid
forms of Cl2, Br2 and I2.
The energy of the Van der Waals bond
U tot =
a
b
+
rn rm
where r is the distance between the two atoms, n is an

exponent ~6, m ~12 and a and b are constants.
Van der Waals bond:
the weakest bond
forces fluctuate with time
non-directional
15
9/5/2014
Hydrogen Bonds
When a single hydrogen electron is
shared with dissimilar atoms in
covalent bonding, a net positive
charge is displaced towards the
hydrogen atom. The positively
charged hydrogen can form a
hydrogen bond with the negative
end of a neighboring molecule.
Hydrogen Bonds
Approximately 30 times weaker
than a normal covalent bond,
because only one of the
contributing atoms is supplying
electrons to it.
Relatively easily broken.
Directional.
Such bonds may also exist in
many
a y po
polymers
y e s linking
gd
discrete
sc ete
chain molecules together.
16
9/5/2014
Interatomic Forces
The bonding force, F, varies as a function of the separation, r, between
atoms.
F(r)
dU
F=
dr
The variation of force between two atoms, F, as a

function of atomic separation
Mixed Bonds
Some engineering materials have mixed bonds.
In ceramic: ionic/covalent mixed bonds. e.g. SiO2.
In polymer: covalent/secondary mixed bond.
17
9/5/2014
Two atoms of similar electronegativity form either a

metallic bond or covalent bond.
Two atoms of different electronegativity form partial ionic
bond. The ionic character increases with the difference in
electronegativity.
For a AB compound:
e.g. NaCl:
|ENa-ECl|= |0.9-3.0|=2.1
highly
hi hl iionic
i
e.g SiC:
|ESi-EC|= |1.8-2.5|=0.7
highly covalent
PROPERTIES FROM BONDING: TM

Bond length, r
F
Melting Temperature, Tm
Energy (r)
r
ro
Bond energy, Eo
Energy (r)
smaller Tm
unstretched length
ro
r
Eo=
bond energy
larger Tm
Tm is larger if Eo is larger.
18
9/5/2014
Bond Strength and Melting Point

Bonding Type
Substance
Ionic
Bonding Energy
(kJ/mol)
Melting
Temperature (oC)
NaCl
640
801
MgO
1000
2800
Si
450
1410
C (diamond)
713
>3550
Hg
68
-39
Al
324
660
Fe
406
1538
849
3410
Ar
77
7.7
-189
189
C
Covalent
l t
Metallic
Van der Waals

Hydrogen
Cl2
31
-101
NH3
35
-78
H2O
51
PROPERTIES FROM BONDING: E

Elastic modulus, E
length, Lo
undeformed
cross
sectional
area Ao
deformed
Elastic modulus
F
L
=E
Ao
Lo
E ~ curvature at ro
Energy
unstretched length
ro
E is larger if Eo is larger.
smaller Elastic Modulus

larger Elastic Modulus
16
19
9/5/2014
PROPERTIES FROM BONDING:

Coefficient of thermal expansion,
coeff. thermal expansion
length, Lo
unheated, T1
L
Lo
heated, T2
= (T2-T1)
~ symmetry at ro
Energy
ro
is larger if Eo is smaller.
larger
smaller
17
SUMMARY: BONDING
Type
Ionic
C
Covalent
l t
Metallic
Secondary
Bond Energy
Large!
Variable
llarge-Diamond
Di
d
small-Bismuth
Variable
large-Tungsten
small-Mercury
smallest
Comments
Nondirectional (ceramics)
Directional
semiconductors,
i
d t
ceramics
i
polymer chains)
Nondirectional (metals)
Directional
inter-chain
inter
hain (polymer)
inter-molecular
There is an equilibrium spacing between two atoms determined by an

attractive force associated with electrostatic attraction and a repulsive force
associated with the interaction of inner shell electrons.
The nature of bonding has a strong effect on the properties of materials.
20
9/5/2014
SUMMARY: BONDING
Ceramics
Large bond energy
(Ionic & covalent bonding):
Variable bond energy
Metals
(Metallic bonding):
Polymers
moderate Tm
moderate E
moderate
Directional Properties
(Covalent & Secondary):

s e c on
dary
large Tm
large E
small
bond
in
Secondary bonding dominates

small T
small E
large
18
21

2.1. Atomic Structure: Structures of Engineering Materials

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

2.1. Atomic Structure: Structures of Engineering Materials

Uploaded by

Copyright:

Available Formats

9/5/2014

Prof. Dr. Ir. Bondan T. Sofyan, M.Si.