LECTURE 3

Crystal Structure of Metals & Ceramics

~Dr. Norfhairna Baharulrazi
Crystal Structure of
Metals & Ceramics
 Learning Outcome
Week Topic Learning Outcome

3-4 Structure of Crystalline Solids: It is expected that students are able to:
Metals and Ceramics

•Unit cell and crystal geometry •Define unit cell

•Principal metallic crystal structures•Sketch isometric or oblique diagrams of cubic
•Atomic positions in cubic unit cells unit cells (BCC, FCC, SC)
•Directions in cubic unit cells •Determine atomic position in a unit cell
•Miller indices for crystallographic •Determine direction in cubic unit cells
•Planes in cubic unit cells •Assign Miller index for direction in cubic cell
•Mass, planar and linear density •Assign Miller index for a plane in cubic cell
•Calculate:
(Section 3.1, 3.2, 3.3.1, 3.3.2, 3.4, –Coordination Number (CN)
3.5, 3.6, 3.9 & 3.12) –Atomic Packing Factor (APF)
–Density (mass, linear and planar)

-3- *BCC, body-centered cubic; FCC, faced-centered cubic

 Broad Classes of Solids
Crystalline SiO2
• Crystalline solids
– Atoms pack in periodic, orderly 3D arrays
– Possess well-defined shapes
– Typical of:
• Metals and alloys
• Many ceramics Si
• Some polymers Oxygen

Noncrystalline SiO2
• Noncrystalline (amorphous) solids
• Atoms have no periodic packing
• Occurs for:
• Complex structures
• Rapid cooling

-4-
 Space Lattice and Unit Cells
• Crystalline solid/material–Atoms arranged in repetitive 3D pattern,
in LRO*. Long Order
Range
• Amorphous materials–Materials arranged in SRO*.
Short Range Order
• Properties of solids depends on crystal structure and bonding
force.

• Atomic arrangement in
crystalline solids:
– Referring the atoms to the
points of intersection of a
network of lines in 3D

→ SPACE LATTICE.
-5-
*LRO, long-range order ; SRO, short-range order
 Space Lattice

• An imaginary network of lines in 3D.

• Intersection of the lines──lattice point
→represents 1 atom.
• There is an infinite number of lattice
points.

• Atoms in crystalline solids occupy the

lattice points.

• Repetitive sub-divisions are observed

↑lattice in the space lattice ── UNIT CELL.
point
11 atom)

-6-
 Unit Cell

Lattice Points Space Lattice

• Block of atoms which repeats itself
to form space lattice.

• The smallest sub-division of the

crystal that retains the overall
characteristics of the total crystal.

• Thus, unit cells are the building

blocks of a crystal.
Unit Cell

-7-
 Unit Cell (cont..)

Inter-axial angles

Lattice constants

Axial lengths

All 7-unit cell systems are variations of these lattice constants.

-8-
 Structure of Metals
Why metals?

• Structures of pure metals are the easiest to describe

• Their atoms can be treated as identical perfect spheres.

• Also, in pure metals, only 1 type of element is present,

• Thus, all atomic radii are equal.
(radius)

• Same case for structures of inert gases (He, Ne, Ar, etc.) at very low
temperatures.

• In metals, atoms occupy specific positions in the space lattice to form an

ordered, repetitive and 3-D pattern.

• Metals have the simplest crystal structure – cubic.

-9-
 Crystal Systems & Bravais Lattices

• Only 7 different unit cell systems are necessary to

create all point lattices.

• According to Bravais*, 14 standard unit cells can

describe all possible lattice networks.

• 4 basic types of unit cells are:

*Bravais A (1811–1863). French crystallographer who derived the 14 possible arrangement of points in space

-10-
 Basic Types of Unit Cell
Simple Body-centered

-
center

• Atoms at the lattice points. • 1 atom in the body center.

Face-centered Base-centered
- Another 2

Every plane atom of

hmelatm
at
center
base and opposite
• 1 atom centered in every • 1 atom each on 2 opposite
plane composing the unit sides.
cell.
-11-
 Types of Unit Cell

• Cubic Unit Cell

 a=b=c
 α = β = γ = 90°
Simple Body-centered Face-centered

• Tetragonal
 a =b ≠ c
 α = β = γ = 90°
Simple Body-centered

-12-
 Types of Unit Cell (cont..)

• Orthorhombic
Simple Base-centered
 a≠ b≠ c
 α = β = γ = 90°

Face-centered Body-centered

• Rhombohedral
a=b=c
 α = β = γ ≠ 90° Simple
-13-
 Types of Unit Cell (cont..)
• Hexagonal
 a≠ b≠ c
 α = β = γ = 90°

• Monoclinic
 a≠ b≠ c
 α = β = γ = 90°
Simple Base-centered

• Triclinic
 a≠ b≠ c
 α = β = γ = 90°
Simple
-14-
 Principal Metallic Crystal Structures
• 90% of the metals have either
• Body Centered Cubic (BCC),
• Face Centered Cubic (FCC) or BCC Structure

• Hexagonal Close Packed

(HCP) crystal structure.

FCC Structure

• HCP is denser version of simple

hexagonal crystal structure (will
not be discussed).
HCP Structure
-15-
 Unit Cell Analysis

QUESTIONS TO ANSWER Atomic configuration in

FCC unit cell

What are the basic structural parameters, R

E.g. lattice constant or side of cube? 2R
How many atoms per unit cell? R
What is the volume per unit cell? a
What is the atomic packing factor (APF)?
What is the closed-packed direction?
What is the coordination number?
What is the relationship between lattice constant, a
and the atomic radius, R?
What are linear densities of close-packed directions?
What are planar densities of every plane?
2 a  4R

-16-
 Coordination Number

• The number of neighbors

→The coordination number
(CN) of the crystal structure.

• Simple cubic structure

• 1 atom directly touches (i.e.
forms bond) 6 other atoms.

• Thus, CNSC is 6.

-17-
 How to Count Number of Atoms Per Unit Cell
• Corner atom shared by 8 cells => 1/8 atom per unit cell.
• Edge atom shared by 4 cells => 1/4 atom per unit cell
• Face atom shared by 2 cells => 1/2 atom per unit cell.
• Body unique to 1 cell => 1 atom per unit cell.
How many atoms per cell for
body-centered cubic?
And, face-centered cubic?

-18-
 SC Unit Cell
• Only polodium (Po) has this structure.

• Number of atoms per unit cell: (8

corners x 1/8) = 1

• Volume of atom per unit cell = Volume

of 1 sphere = (4/3)πR3

• Atomic packing factor (APF): fraction

of volume occupied by hard spheres =
0.52

• Closed-packed direction = direction

where atoms are in continuous contact:
Along the cube edge.

• CN = 6

-20-
 SC Unit Cell

-21-
 Atomic Packing Factor (APF) for SC Unit Cell
Volume of the atoms inside the unit cell
APF =
Volume of the unit cell
Volume
atom
atoms 4 4
unit cell (1) πR3 (1) π (0.5a)3
3 3
= = 0.52
a3 a3
Volume
unit cell
• APF─volume fraction of the cell that is
occupied by matter.

• Close-packed direction = along cube edge.

A

a = 2R • Contains 8 x1/8 = 1 atom per unit cell.

B
F- G-
-22-
 BCC Crystal Structure
• Represented as 1 atom at each
corner of cube and 1 at the center
of cube.

• Each atom has 8 nearest

neighbors.

• Therefore, CNBCC is 8.

• Examples :-
 Chromium (a=0.289 nm)
 Iron (a=0.287 nm)
 Sodium (a=0.429 nm) (this file opens in a new window and
contains audio commentary)

-23-
 BCC Unit Cell
• Each unit cell has eight 1/8 atom at
corners and 1 full atom at the center.

• Therefore each unit cell has

(8x1/8 ) + 1 = 2 atoms
• Atoms contact each other at cube
diagonal

• Therefore, a* = 4R
3
*a, lattice constant
-24-
 APF* of BCC Structure
Volume of atoms in unit cell
APF =
Volume of unit cell

 4π R 3 
Vatoms = 2  3  = 8.378R3
 

3
 4R 
Vunit cell = a3 =   = 12.32 R3
 3

8.378 R 3
Therefore APF = 12.32 R3 = 0.68

*APF, atomic packing factor

-25-
 BCC Crystal Structure

-26-
 FCC Crystal Structure

• Represented as 1 atom each at

the corner of cube and at the
center of each cube face.

• CN for FCC structure is 12

• APF is 0.74

• Examples :-
 Aluminum (a = 0.405 nm)
(this file opens in a new window and
 Gold (a = 0.408 nm) contains audio commentary)

-27-
 FCC Unit Cell
• Each unit cell has 8 1/8 atom at
corners and 6 1/2 atoms at the
center of 6 faces.

• Therefore each unit cell has

(8x1/8 ) + (6 x 1/2) = 4 atoms

• Atoms contact each other across
cubic face diagonal

• Therefore, a* = 4R
2
*a, lattice constant
-28-
 FCC Unit Cell

-29-
 How to Determine a* for FCC
• Geometry along close-packed direction (face diagonal)
relates a* and R.

AB  2 a  4R Close-packed direction = face diagonal

4R
a  Cube edge length, a = 4R/√2 or a =
2 2R√2.
*a, lattice constant
-30-
 APF for FCC Unit Cell
Volume of the atoms inside the unit cell
APF =
Volume of the unit cell

atoms
Volume
2a unit cell
atom
4
4 π( 2a/4)3
3
APF =
a3 Volume
unit cell
a a
APF = 0.74

• This means that 74% of the unit cell is filled with matter
and 26% is empty space (voids).
-31-
Example 1
• Iron at 20C is Body-centered Cubic (BCC) with atoms of atomic
radius 0.124 nm. Calculate the lattice constant a for the cube
edge of the iron unit cell.
Humber atom :
1+811-8) R'-0.124hm 412=53 a
410.124) a
22 atoms
9=0.2864 nm
Tutorial 1
Molybdenum at 20C is Body-centered Cubic (BCC) has an atomic
① radius 0.140 nm. Calculate the lattice constant a in nanometers.

Tutorial 2:
Gold at 20C is Face-centered Cubic (FCC) has a lattice constant of
②
0.40788 nm. Calculate a value for the atomic radius of a gold
atom in nanometers.

Tutorial 3:
③
Verify the atomic packing factor for the FCC structure is 0.74
 SE §
,g¥§iÉ
"
E-
'
É →
¥
"
≈É¥±
¥¥
•
¥ÉÉ ?
S
:
? é
¥
;¥
LECTURE 3 – Part 2
Crystal Structure of Metals & Ceramics
Dr. Norfhairna Baharulrazi
 Atom Positions in Cubic Unit Cells
• Locate atoms–Cartesian coordinate
system.
• In a cubic unit cell
y axis is the direction to the
right.
x axis is the direction
coming out of the paper.
z axis is the direction
towards top.
-ve directions are to the
opposite of +ve directions.

Atomic positions are located using unit distances

along the axes.

-2-
 Direction Indices in Cubic Unit Cells
• Vector components of directions resolved along each axes, reduced
to smallest integers.

• Position coordinates of unit cell where the direction vector emerges

from cell surface, converted into integers.

• Represented → square brackets

[112]
→ without comma

-3-
 Procedure to Find Direction Indices
Produce the direction vector till it emerges (1,1/2,1) - (0, 0, 0)
from surface of cubic cell z
= (1,1/2,1)
(1,1/2,1)
2 x (1, 1/2, 1)
Determine the coordinates of point of •
= (2, 1, 2)
emergence and origin. y
(0,0,0)
Subtract coordinates of point of x
emergence by that of origin
The direction indices are [212]
Are all are No
integers? Convert them to
smallest possible
Yes integer by multiplying
by an integer.
Are any of the
direction
vectors -ve?
No
Yes
Represent the indices in a
Represent the indices in a square
square bracket without
bracket without comas with a
comas (Eg: [212])
-4- over -ve index (E.g. [121])
 Example of Direction Indices

-5-
Example of Direction Indices
 Direction Indices – Example 2
• Determine direction indices of the given vector below. Origin (tail)
coordinates are (3/4 , 0, 1/4). Emergence (arrow tip) coordinates are
(1/4, 1/2, 1/2).

Subtracting origin coordinates

from emergence coordinates,

(1/4, 1/2, 1/2) - (3/4 , 0, 1/4)

= (-1/2, 1/2, 1/4)

Multiply by 4 to convert all

fractions to integers

4 x (-1/2, 1/2, 1/4) = (-2, 2, 1)

Direction indices = [2 2 1]
-7-
 Direction Indices – Example 3

• Determine the indices for the direction shown in the accompanying figure.

Projections of this vector onto the x, y,

and z axes →a/2, b, and 0c,

Become 1/2, 1, and 0 in terms of

the unit cell parameters

Reduction – multiply by the factor 2

Direction indices = [120]

-8-
 Direction Indices – Example 4
• Draw a [110] direction within a cubic unit cell.

gio] 0
"

'
•0
Elio]
<

-9-
 Tutorial 4

(-3, 4, -2)

-10-
 Miller Indices For Crystallographic Planes In Cubic Unit Cells

• Sometimes it is necessary to refer to specific lattice

planes of atoms within a crystal structure,

• Or it may be of interest to know the crystallographic

orientation of a plane or group of planes in a crystal
lattice.

• To identify crystal planes in cubic crystal structures, the

Miller notation system is used

-13-
 Miller Indices

• Refer to specific lattice planes z Miller Indices =(111)

of atoms.

• They are reciprocals of the

fractional intercepts (with y
fractions cleared) that the plane
makes with the crystallographic
x, y and z axes of 3 nonparallel x
edges of the cubic unit cell.

-14-
 Crystal Planes in Cubic Unit Cells
• Just as with crystal directions, different crystal planes
will have different characteristics and indices.
¥
1¥ ¥
÷ I
v1
'
my
÷ 1110 ) I 1111)
, ,
to 0
g. ,
yin , ,
2=00 #
0
2-
_ is to 0
1100 )

:& ¥, :3
6

1×2
n
3
y :} %-)
:{
2=1 'T .
1 2

16 } ,
, 2)

-15-
 Find Miller Indices – Procedure
Make sure plane does not pass through
origin. Otherwise, select new origin.

Determine where the plane intercepts at each

axis, i.e. the x, y and z intercepts of the plane.

Find the reciprocal of each intercept

Any Yes
fractions Clear fractions by
? multiplying by an
No integer (least common
multiple) to determine
the smallest set of
Any –ve whole numbers
indices?
Yes
No
Place a ‘bar’ over the
Enclose in parenthesis (hkl) where h, k, l –ve indices
are Miller indices of cubic crystal plane for
-16- x, y and z axes. E.g.: (111)
 Miller Indices – Example

Example
x y z
1. Intercepts ½ 1 ¾
2. Reciprocals 1/(½) 1/1 1/(¾)

2 1 4/3
3. Clear fractions 6 3 4
4. Miller Indices 634 •

-17-
 Miller Indices – Example
z
• Intercepts of the plane at x, y & z
(100) ∞ axes are 1, ∞ and ∞.
y • Taking reciprocals we get (1, 0, 0).
• Miller indices are (100).
1 ∞
x

• Intercepts are 1/3, 2/3 & 1.

• Taking reciprocals we get (3, 3/2, 1).
• Multiplying by 2 to clear fractions, we
get (6, 3, 2).
•

• Miller indices are (632).

-18-
 Miller Indices – Example 6
• Determine the Miller indices of the plane that intersects the following
coordinates: (1, ¼, 0), (1, 1, ½), (¾, 1, ¼), and all coordinate axes.

• Intercepts: New
plane
 x= –1/2 ACD
 y= –3/4
10.0,t)  z= +1/2

⑤ • Reciprocals:
⑧
⑧
1-E,0,0)
 1/x= –2
B

& &  1/y= –4/3

20.-5,0)
n
 1/z= +2
(576)
• Clear fractions by multiplying by 3,
SoBy
*

E2O
E
Miller indices is [6 4 6]
-19-
 Draw Miller Indices – Example 7

• Draw the plane (101).

• Take reciprocals of the indices, we
get (1 ∞ 1).
• Intercepts of the plane are x=1, y=
∞ (parallel to y) and z=1.

• Plot the plane (2 2 1).

• Take reciprocals of the indices, we
get (1/2 1/2 1).
• Intercepts of the plane are x=1/2, y=
1/2 and z=1.

-20-
 Draw Miller Indices – Example 8
I -
I 0

• Plot the plane (110) 1- ÷ :

• Reciprocals are (1,-1, ∞) I -1W

• Intercepts are x=1, y=-1 and z= ∞ (parallel to z axis)

(110)
Note new
origin

O
• • y
•

x
-21-
Draw in unit cubes the crystal planes that have
the following Miller indices:
a) 1 1 1 b) 1 2 1  c) 302   
a) 1- ± -4 b) 1- ± :-, g- to ±
I -
I -1 I
-

I -

I § is
-

± -
( Iit )

✗ • New
origin
✗

✗ ¥:£
×

2: -

-22-
 a- I 1- I

Determine the Miller indices of the cubic

y=¥ ¥ ¥
)
crystallographic plane shown in Figure EP3.8a.
2=0 To 0

-
5

-
12

Is -120 )
 Tutorial 7
What are the Miller indices of the cubic
crystallographic planes shown below?

-24-
-25-
LECTURE 3 – Part 3
Crystal Structure of Metals & Ceramics
Dr. Norfhairna Baharulrazi
 Volume, Planar, and
Linear Density
Unit-Cell Calculations
 Volume Density
Example: Copper (FCC) has atomic mass of 63.54 g/mol and atomic
radius of 0.1278 nm. Find volume density of copper.

Mass of a unit cell, m

ρv =
Volume of a unit cell, Vc

• Lattice constant, a = 4R/√2 = 4(0.1278nm) /√2 = 0.361 nm.

• Volume of FCC unit cell = a3 = (0.361 nm)3 = 4.7 × 10−29 m3 = 4.7 × 10−23 cm3.
• FCC has 4 atoms per unit cell.

• Mass of unit cell: 4 𝑎𝑡𝑜𝑚𝑠 𝑔

63.54
𝑚 = 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑚𝑜𝑙
= 4.22 × 10−23 g/unit cell
6.023 × 10 𝑎𝑡𝑜𝑚𝑠/𝑚𝑜𝑙

4.22  10 22 g/unit cell

ρv   8.98g/cm3
4.7  10 cm /unit cell
23 3

-3-
 Planar Atom Density in BCC
Example: Calculate ρPD on (110) plane of a BCC iron crystal. Lattice
constant a = 0.2887 nm.

Equivalent number of atoms whose

centers are intersected by a given plane
ρPD =
Area of the given plane

• Plane intersects center of 5 atoms (4 for ¼ atoms and 1 full atom).

• Equivalent number of atoms in (110) plane: 2 atoms.
• Area of (110) plane: √2 a2

1 2
2
1 PD   17.2 atoms/nm2

2 0.287 
2
3 4

-4-
 Linear Density
Example: Calculate the linear density of an FCC copper crystal along
[110]. Lattice constant a = 0.361 nm.

Number of atomic diameters intersected by

selected length of line in direction of interest
ρl =
Selected length of line

• [110] direction intersects 2 half diameters and

1 full diameter.
• Therefore, it intersects ½ + ½ + 1 = 2 full
diameters.
• Length of [110] line: √2 a

2 atoms 2 atoms
ρl    3.92 atoms/nm
2a 2 0.361

-5-
 Densities of Material Classes
Graphite/
Metals/ Composites/
ρmetals > ρceramics > ρpolymers Alloys
Ceramics/ Polymers
Fibers
Semicond
30
• Metals have...
●Platinum
*GFRE, CFRE & AFRE are Glass,
20 Carbon & Aramid Fiber-Reinforced
• Close-packing (metallic ●Gold, W Epoxy composites (values based
bonds) ●Tanlanum
on 60% volume fraction of aligned
• Large atomic mass fibers in an epoxy matrix)
10 ●Silver, Mo
●CU, Ni
●Steels
• Ceramics have... ●Tin, Zinc

ρ(g/cm3)
●Zirconia
• Less dense packing (covalent 5
bonds) ●Titanium
4 ●Al oxide
●Diamond
• Often lighter elements 3 ●Si nitride
●Aluminum ●Glass-soda ●Glass fibers
●Concrete ●PTFE
2 ●Silicon ●GFRE*
• Polymers have... ●Magnesium ●Graphite
●Silicone
●Carbon fibers
●CFRE*
• Poor packing (often ●PVC
●PET
●Aramid fibers
●AFRE*
amorphous) 1 ●PC
●HDPE, PS,
• Lighter elements (C,H,O) PP, LDPE

0.5
• Composites have...
0.4
●
●Wood
●
• Intermediate values
0.3
-6-
 Tutorial 8 14atoms).
Calculate a value for the density of FCC platinum in grams per
cubic centimeter from its lattice constant a of 0.39239 nm and its
atomic mass of 195.09 g/mol.

a =
0.39239nm AM:195.09
g/mo)
as
4(195.09)
"gall
v M
1.2963x10
=
= =

6.02x1023
=10.39239)"
0.06042 nm) cell

1.2963x10"glcell
P =
0.06042nmlull

=2 -

1454x1020g/nm"

-7-
 Tutorial 9
f atom
The lattice constant for BCC tantalum at 20C is 0.33026 nm and its
density is 16.6 g/cm3. Calculate a value for its relative atomic
mass?

a3 = 3.6022x10:29m3
166glan" a 0.33026
=
nm

p= 0.33026 x10.9m
186cm3 i

16.69
p= cm3 |m3
m pa3
=

:13600000g/m3 :16600000(3.6022x1529)
=
5.9797x10-g
c(AM)
19797x(0-2: 6.02x 1023

An:
179.99g/mol
-8-
 Tutorial 10
Calculate the planar atomic density in atoms per square millimetre for the following
crystal planes in BCC chromium, which has a lattice constant of 0.28846 nm:
a) 100 b) 110 c) 111

-9-
 Tutorial 11
Calculate the linear atomic density in atoms per millimetre for the following
directions in BCC vanadium, which has a lattice constant of 0.3039 nm:
a) 100 b) 110 c) 111

-10-
 Polymorphism or Allotropy: Iron
• Metals have the ability of to exist in more than 1 crystalline form
or structure
→POLYMORPHISM
• According to Gibbs’ phase rule, these changes in crystalline
phases are dependent on intensive variables such as P* and T*.

• Fe can exist in BCC or FCC form depending on temperature.

• Other E.g: Titanium, Carbon
Liquid Iron

-273°C 912°C 1394°C 1539°C

α-Iron γ-Iron δ-Iron

BCC FCC BCC

-11- *P, pressure; T, temperature

 Polymorphism or Allotropy: Carbon
Pure, solid carbon occurs in three crystalline forms
→diamond; graphite; and large, hollow fullerenes.

• Layer structure – aromatic layers;

• Weak van der waal’s forces

between layers;

• Planes slide easily – makes good

lubricant
Tetrahedral carbon

• Wrap graphite sheet by curving

into ball or tube;

• Like soccer ball of C60–C70

Carbon nanotube Buckminster fullerene (buckyball)

-12-
 Atomic Radii and Crystal Structures

a FCC = face-centered cubic; HCP = hexagonal close-packed; BCC = body-centered cubic

b A nanometer (nm) equals 10-9 m; to convert from nanometers to angstrom unit (Å), multiply the
nanometer value by 10.

-13-