KKKR 1233 C

KKKR 1233
MATERIALS SCIENCE & ENGINEERING
FUNDAMENTALS OF MATERIALS SCIENCE &

ENGINEERING
NOR YULIANA YUHANA (PhD)

Level 3, Faculty of Engineering and Built Environment,
Department of Chemical and Process Engineering.
MOHD SHAIFUL SAJAB (PhD)

Level 1, Faculty of Engineering and Built Environment,
Research Center for Sustainable Process Technology (CESPRO).
KKKR 1233 ATOMIC STRUCTURE & ATOMIC BONDING IN SOLIDS
INTRODUCTION
Bonding:
• What promotes bonding?
• What types of bond are there?
• What properties are inferred from bonding?
ELECTRONIC STRUCTURE
Electrons have wavelike and particulate properties.

This means that electrons are in orbitals defined by a
probability.
Each orbital at discrete energy level is determined by
quantum numbers.
Quantum # Designation
n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)
l = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,…, n-1)
ml = magnetic 1, 3, 5, 7 (-l to +l)
ms = spin ½, -½
BOHR ATOM
orbital electrons:
n = principal
quantum number 1
n=3 2
Nucleus: Z = # protons
= 1 for hydrogen to 94 for plutonium
N = # neutrons
Atomic mass A ≈ Z + N
BOHR ATOM
ELECTRON ENERY STATES
Electron
• Have discrete energy states.

• Tend to occupy lowest available energy.
STABLE ELECTRON CONFIGURATIONS
Stable electron configurations:

• Have complete s and p subshells.
• Tend to be unreactive.
SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.

• Why? Valence (outer) shell usually not filled completely.
SURVEY OF ELEMENTS
• Valence electrons – those in unfilled shells
• Filled shells more stable
• Valence electrons are most available for bonding and tend to control the
chemical properties
– example: C (atomic number = 6)
1s2 2s2 2p2
valence electrons
Valence electrons determine all of the following properties:

• Chemical
• Electrical
• Thermal
• Optical
ELECTRONIC CONFIGURATION
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2
4d
4p N-shell n = 4 valence
electrons
3d
4s
Energy 3p M-shell n = 3
3s
2p L-shell n = 2
2s
1s K-shell n = 1
ELECTRONIC CONFIGURATION
PERIODIC TABLE
Columns = similar valence structure.

ELECTRONEGATIVITY
• Ranges from 0.7 to 4.0.

• Large values: tendency to acquire electron.
IONIC BONDING
• Occurs between + and – ions.

• Requires electron transfer.
• Large difference in electronegativity required.
• e.g NaCl
IONIC BONDING
• Predominant bonding in ceramics.

COVALENT BONDING
• Requires shared electron.

• e.g. CH4
• C: has 4 valence e, needs 4 more
• H: has 1 valence e, needs 1 more
Electronegativity are comparable.
COVALENT BONDING
H2O
column IVA
H2 F2
C(diamond)
H He
2.1
SiC - Cl2
Li Be C O F Ne
1.0 1.5 2.5 2.0 4.0 -
Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -
K Ca Ti Cr Fe Ni Zn Ga Ge As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 1.6 1.8 2.0 2.8 -
Rb Sr Sn I Xe
0.8 1.0 1.8 2.5 -
Cs Ba Pb At Rn
0.7 0.9 1.8 2.2 -
Fr Ra
0.7 0.9 GaAs
• Molecules with nonmetals.
• Molecules with metals and nonmetals.
• Elemental solids (RHS of periodic table)
• Component solids (about column IVA)
SECONDARY/VAN DER WAALS BONDING
Arises from interaction between dipoles
• Fluctuating dipoles.
• Permanent dipoles-molecules induced.

BONDING
Type Bond Energy Types
Ionic Large Non-directional

(Ceramics)
Covalent Variable: e.g. Large- Directional
diamond, Small- (Semiconductors,
Bismuth Ceramics, Polymer
chains)
Metallic Variable: e.g. Large- Non-directional
Tungsten, Small- (Metals)
Mercury
Secondary Smallest Directional
Inter-chain (Polymer)
Inter-molecular
PROPERTIES FROM BONDING: MELTING TEMPERATURE, Tm
Bond length, r
• Tm is larger if Eo is larger.
Bond energy, Eo
PROPERTIS FROM BONDING: ELASTIC MODULUS, E
Elastic modulus, E
• E is curvative at ro.
• E is larger if Eo is larger.
PROPERTIS FROM BONDING: THERMAL, α
Coefficient of thermal expansion, α
coeff. thermal expansion

• α ∼ symmetry at ro.
∆L
= α (T2-T1) • α is larger if Eo is smaller.

Lo
PRIMARY BONDS
KKKR 1233 THE STRUCTURE OF CRYSTALINE SOLIDS
INTRODUCTION
Structure of solids:
• How do atoms assemble into solid structures?
• How does the density of material depend on its structure?
• When do material properties vary with the sample (i.e. part) orientation?
INTRODUCTION
ENERGY AND PACKING
Structure of solids:
• Dense, ordered packed structures tend to have lower energies.
• 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
MATERIALS AND PACKING
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.23(a),
Callister & Rethwisch 8e.
Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.23(b),
Callister & Rethwisch 8e.
METALLIC CRYSTAL STRUCTURES
How can we stack metal atoms to minimize empty
space?
2-dimensions
vs.
Now stack these 2-D layers to make 3-D structures

METALLIC CRYSTAL STRUCTURES
• Tend to be densely packed.

• Typically, only one element is present, so all atomic radii are the same.
• Metallic bonding is not directional.
• Nearest neighbor distances tend to be small in order to lower bond energy.
• Electron cloud shields cores from each other
• Have the simplest crystal structures
UNIT CELL
– the subdivision of a lattice that still remains the overall characteristics
of the entire lattice
• 8 unit cells
• Lattice can be constructed by stacking identical
unit cells the entire
UNIT CELL
SIMPLE CUBIC STRUCTURE
• Rare due to low packing density (only Po has this structure)
• Close-packed directions are cube edges.
• Coordination # = 6
(# nearest neighbors)
ATOMIC PACKING FACTOR
Volume of atoms in unit cell*

APF =
Volume of unit cell
*assume hard spheres
• APF for a simple cubic structure = ?
a
R=0.5a
close-packed directions
contains 8 x 1/8 =
1 atom/unit cell
Volume of atoms in unit cell*

APF =
Volume of unit cell
*assume hard spheres
• APF for a simple cubic structure = 0.52
volume
atoms atom
a 4
unit cell 1 π (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
BODY CENTERED CUBIC STRUCTURE (BCC)
• Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.
ex: Cr, W, Fe (α), Tantalum, Molybdenum

2 atoms/unit cell: 1 center + 8 corners x 1/8

• APF for a body-centered cubic structure = 0.68
R
a
• APF for a body-centered cubic structure = 0.68
3a
2a
Close-packed directions:
R length = 4R = 3 a
a
atoms volume
4
unit cell 2 π ( 3a/4) 3
3 atom
APF =
3 volume
a
unit cell
FACE CENTERED CUBIC STRUCTURE (FCC)
• Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.
ex: Al, Cu, Au, Pb, Ni, Pt, Ag

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

• APF for a face-centered cubic structure = ?
maximum achievable APF
2a
a
• APF for a face-centered cubic structure = 0.74
maximum achievable APF
Close-packed directions:
length = 4R = 2 a
2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
atoms volume
4
unit cell 4 π ( 2a/4) 3
3 atom
APF =
volume
a3
unit cell
FCC STACKING SEQUENCE
• ABCABC... Stacking Sequence
• 2D Projection
B B
C
A
A sites B B B
C C
B sites B B
C sites
A
• FCC Unit Cell B
C
HEXAGONAL CLOSE-PACKED STRUCTURE (HCP)
• ABAB... Stacking Sequence

• 3D Projection • 2D Projection
A sites Top layer

c
B sites Middle layer
A sites Bottom layer

a
• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633
POLYCRYSTAL
• Most engineering materials are polycrystals. Anisotropic
1 mm
• Nb-Hf-W plate with an electron beam weld. Isotropic

• Each "grain" is a single crystal.
• If grains are randomly oriented,
overall component properties are not directional.
• Grain sizes typically range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
SINGLE VS POLYCRYSTAL
• Single Crystals E (diagonal) = 273 GPa
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
E (edge) = 125 GPa
• Polycrystals
-Properties may/may not 200 µm
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
anisotropic.
POLYMORPHISM
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
α, β-Ti
1538ºC
BCC δ-Fe
carbon
diamond, graphite 1394ºC
FCC γ-Fe
912ºC
BCC α-Fe
CRYSTAL SYSTEM
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
7 crystal systems
14 crystal lattices
a, b, and c are the lattice constants

POINT COORDINATES
z
111 Point coordinates for unit cell
c center are
a/2, b/2, c/2 ½½½
000
y
a b
Point coordinates for unit cell
x • corner are 111
z 2c
•
Translation: integer multiple of
• • lattice constants  identical
b y position in another unit cell
b
POINT COORDINATES
POINT COORDINATES
CRYSTALLOGRAPHIC DIRECTION
Direction in the Unit Cell (Miller indices)
PROCEDURE
- Using the right handed coordinate system, determine the coordinates of
two point that lie on the direction
- Subtract the coordinates of the ‘tail’ point from the coordinates of the
‘head’ point
- Clear fraction and/or reduce the results obtained from the subtraction to
lowest integers
- Enclose the number in square bracket [ ]. If a negative sign is produced,
represent the negative sign with bar over the number.
CRYSTALLOGRAPHIC DIRECTION
Direction A
1. Two points are 1, 0, 0, and 0, 0, 0
2. 1, 0, 0 – 0, 0, 0 = 1, 0, 0
3. No fraction to clear or integers to reduce
4. [100]
CRYSTALLOGRAPHIC PLANES
• Miller Indices: Reciprocals of the (three) axial
intercepts for a plane, cleared of fractions &
common multiples. All parallel planes have same
Miller indices.
• Algorithm
1. Read off intercepts of plane with axes in
terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no
commas i.e., (hkl)
PROCEDURE
1. Identify the points at which the plane intercepts the x,y and z
coordinates in terms of the number of lattice parameters. If the plane
passes through the origin, the origin of the coordinates system must be
moved!
2. Take reciprocal of these intercepts
3. Clear fractions but do not reduce to the lower integers
4. Enclosed the resulting numbers in parentheses ( ). Again, negative
numbers should be written with a bar over the number
z
example a b c
1. Intercepts 1 1 ∞ c
2. Reciprocals 1/1 1/1 1/∞
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2 ∞ ∞ c
2. Reciprocals 1/½ 1/∞ 1/∞
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100) a b
x
z
example a b c c
1. Intercepts 1/2 1 3/4 •
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3 • y
•
3. Reduction 6 3 4 a b
4. Miller Indices (634) x

EXCERCISE
SUMMARY
• Atoms may assemble into crystalline or

amorphous structures.
• Common metallic crystal structures are FCC, BCC, and
HCP. Coordination number and atomic packing factor
are the same for both FCC and HCP crystal structures.
• We can predict the density of a material, provided we
know the atomic weight, atomic radius, and crystal
geometry (e.g., FCC, BCC, HCP).
• Crystallographic points, directions and planes are
specified in terms of indexing schemes.
Crystallographic directions and planes are related
to atomic linear densities and planar densities.
SUMMARY
• Materials can be single crystals or polycrystalline.

Material properties generally vary with single crystal
orientation (i.e., they are anisotropic), but are generally
non-directional (i.e., they are isotropic) in polycrystals
with randomly oriented grains.
• Some materials can have more than one crystal
structure. This is referred to as polymorphism (or
allotropy).
• X-ray diffraction is used for crystal structure and
interplanar spacing determinations.

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KKKR 1233

MATERIALS SCIENCE & ENGINEERING

FUNDAMENTALS OF MATERIALS SCIENCE &

NOR YULIANA YUHANA (PhD)

MOHD SHAIFUL SAJAB (PhD)

Electrons have wavelike and particulate properties.

• Have discrete energy states.

Stable electron configurations:

Most elements: Electron configuration not stable.

– example: C (atomic number = 6)

1s2 2s2 2p2

Valence electrons determine all of the following properties:

ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

Columns = similar valence structure.

• Ranges from 0.7 to 4.0.

• Occurs between + and – ions.

• Predominant bonding in ceramics.

• Requires shared electron.

• Permanent dipoles-molecules induced.

Type Bond Energy Types

Ionic Large Non-directional

Coefficient of thermal expansion, α

coeff. thermal expansion

= α (T2-T1) • α is larger if Eo is smaller.

• Non dense, random packing Energy

• Dense, ordered packing Energy

Now stack these 2-D layers to make 3-D structures

• Tend to be densely packed.

Volume of atoms in unit cell*

Volume of atoms in unit cell*

ex: Cr, W, Fe (α), Tantalum, Molybdenum

2 atoms/unit cell: 1 center + 8 corners x 1/8

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

• ABAB... Stacking Sequence

A sites Top layer

A sites Bottom layer

• Coordination # = 12 6 atoms/unit cell

• Nb-Hf-W plate with an electron beam weld. Isotropic

a, b, and c are the lattice constants

4. Miller Indices (634) x

• Atoms may assemble into crystalline or

• Materials can be single crystals or polycrystalline.

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