CRYSTAL STRUCTURE

ATOMIC STRUCTURE
 Mc Graw Hill p84

Amethyst
SiO2

(a) Celestite SrSO4

(c)

Halite
NaCl

(b) Pyrite
FeS2 (d)
Matter
1. Solids – crystalline
non-crystalline (amorphous)
2. Liquids
3. Gases

What is a Crystalline solid? :

A crystal or crystalline solid is a solid material, whose constituent
atoms, molecules, or ions are arranged in an orderly repeating pattern
extending in all three spatial dimensions (long range order). So a
crystal is characterized by regular arrangement of atoms or molecules

Non-Metallic crystals: Ice, Carbon, Diamond, Graphite, NaCl, KCl

etc…
Metallic Crystals: Silicon, Copper, Silver, Aluminium, Tungsten,
Magnesium etc…
 Diamond

single crystal Si

silicon

Amorphous Si
Properties of crystalline solid :
1. have an orderly arranged units, practically incompressible.
2. show a definite melting point and sharp transition from solid to
liquid state.
3. Crystals are anisotropic (properties
change depending on direction)
eg. Graphite

4. have various crystalline forms (seven crystal systems or shapes).

cubic, tetragonal, hexagonal, trigonal, orthorhombic,
monoclinic, and triclinic.
Amorphous Solid (Non-crystalline)
Solid is composed of randomly orientated atoms , ions, or
molecules that do not form defined patterns or lattice structures.
Amorphous materials have order only within a few atomic or
molecular dimensions (short range or no order at all)
Isotropic (physical, mechanical properties are independent on
directions)
glass, amorphous carbon (a-C), amorphous Si, most plastics
Properties of amorphous solid :
1. Random non-oriented molecules.
2. Do not have definite melting points.
3. Formed favorably through rapid cooling
Crystalline ceramic non crystalline ceramic
(glasses)
Non crystalline plastic

silicon

Oxygen
noncrystalline SiO2 crystalline SiO2

Metallic glass

Understanding lattice :
crystal structure = lattice + basis.
Basis = Group of atoms or
molecules identical in
composition or A group of
atoms which describe
crystal structure
Lattice = Lattice points
are infinitesimal points in
space
Don't mix up atoms
with lattice points
Lattice Points do not
necessarily lie at the
centre of atoms
 Order of arrangement of atoms in space :
Short vs. Long Range
• No Order - atoms or molecules are in
random order (amorphous)
• Short Range Order - atoms or molecules
are only arranged within closest neighbors
• Long Range Order - atoms or molecules
are arranged in a regular repetitive pattern or
lattice.
Definition of lattice = An infinite array of points in space, in
which each point has identical surroundings to all others
UNIT CELL
The smallest component of the crystal
(group of atoms, ions or molecules),
which when stacked together with pure
translational repetition reproduces the
whole crystal.
NaCl

CsCl
The unit cell in the above diagram is a cube, consisting
of 6 faces, 12 edges and 8 vertices. The unit cell consists
of 1/4 Na+ ions per edge and a Na+ ion in the center of
the cube. The total number of Na+ ions in the unit cell is:

The unit cell consists of 1/8 Cl- ions per corner and 1/2
Cl- ions per edge of the cube. The total number of Cl-
ions in the unit cell is:

The unit cell contains 4 Na+ and 4 Cl- ions. This makes
sense because the ratio of Na+ to Cl- ions in NaCl is 1:1.
The NaCl unit cell can be repeated to form solid NaCl,
and therefore must have the same ratio of Na+ to Cl-.
Counting Atoms in 3D Cells

Remember ! - an atom shown as part of a unit cell

does not contribute a whole atom to the cell unless it
is wholly enclosed within the unit cell.

Atoms in different positions in a cell are shared by

differing numbers of unit cells

Vertex (corner) atom shared by 8 cells  1/8 atom per cell

Edge atom shared by 4 cells  1/4 atom per cell
Face center atom shared by 2 cells  1/2 atom per cell
Body unique to 1 cell  1 atom per cell
 Edge atom
(1/4 – atom per cell)

Vortex atom
(1/8 per atom
cell)

Body atom
(1 atom per
cell) Face atom
(1/2 per atom cell)
What is the formula of this
material?

Composition?
 formula YBa2Cu3O7

Y center = 1
Ba center = 2
Cu, top and bottom corner =
8x1/8=1
Cu, edge =8x1/4=2
O, edge =12x1/4= 3
O, face =8x1/2=4
Two classes of lattices:
1. Bravais
All lattice points are
equivalent
2. non-Bravais.
some of the lattice
points are non-
equivalent.

Crystal systems and Bravais lattice

1. By assigning specific values for axial lengths and
axial angles, different unit cells can be constructed.
2. 14 Types of unit cells also know as Bravais lattices.
3. These unit cells are grouped into 7 different
crystalline structures systems.
 Interaxial angles
(a, b, g)
Axial lengths
(a, b, c)

Space lattice of ideal crystalline solid Unit cell

showing
lattice constants
 BRAVAIS

note that
spheres in this
picture
represent lattice
points, not
atoms!
System Number of Lattice Symbol Restriction on crystal
Lattices cell angle
Cubic 3 SC, BCC, FCC a=b=c
α =β =γ=90°
Tetragonal 2 ST, BCT a=b≠c
α=β =γ=90°
Orthorhombic 4 SO, BCO, BSCO, a≠b≠ c
FCO α=β =γ=90°
Monoclinic 2 SM a≠b≠ c
BSCM α=β=90 °≠β
Triclinic 1 ST a≠b≠ c
α≠β≠γ
Rhombohedral 1 SR a=b=c
(trigonal) α=β =γ <120° ,≠90°
Hexagonal 1 SH a=b≠c
α =β =90° , γ=120o

S=simple, b=body, f=face, bs=base, c=centered

Primitive = simplest
QUESTION 2
Here are the three different crystallographic planes for
a unit cell of a hypothetical metal.
The circles represents atoms:
a) Draw and name the crystal system of the unit cell?
b) What would this crystal structure be called?
c) State the position of atom X in the crystal structure.
 Metallic Crystal Structures
• Tend to be densely packed.
• Reasons for dense packing:
- Typically, only one type of 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, more stable energy arrangement.
- Electron cloud shields cores from each other
• Have three crystal structures.

We will examine three such structures...

 The majority of
metals (90%)
have one of
three well-
packed crystal
structures:
1. Body centered
cubic (BCC)
2. Face centered
cubic (FCC)
3. Hexagonal
close packed
(HCP)
 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

 FCC arrangement the densest packing
12 nearest atom neighbors, CN = 12
Stacking sequence ABCABC.
Found in aluminum, copper, and nickel.

Cubic lattice
structure
Dense packing
Two lattice parameters, c and a, describe the
hcp unit cell where c/a is 1.633. ratio <1.633,
atoms are compressed in the c-axis direction,
ratio > 1.633, the atoms are elongated along the
c-axis
12 nearest atom neighbors, CN = 12
Hexagonal lattice
structure
 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
 Simple Cubic Structure (SC)
• Rare due to low packing density (only Po has this structure)
• Close-packed directions are cube edges.

Coordination # = 6
(# nearest neighbors)
 Atomic Packing Factor (APF)
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 p (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 (a), Tantalum, Molybdenum

• Coordination # = 8

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

 Atomic Packing Factor: BCC
• APF for a body-centered cubic structure = 0.68
3a

2a
P91
Close-packed directions: McGraw
R Hill
a length = 4R = 3 a

atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
3 volume
a
unit cell
The body-centred cubic
(bcc) structure is the most
stable form for lithium
metal at 298 K (25°C).
The closest Li-Li
separation is 304 pm
implying a lithium
metallic radius of 152 pm.
In the BCC lattice, every
lithium atom is
surrounded by eight other
nearest neighbour lithium
atoms organised into a
cubic array.
 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

• Coordination # = 12

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

 Atomic Packing Factor: FCC
• 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 p ( 2a/4) 3
3 atom
APF =
3 volume
a
unit cell
Halite crystal (FCC)
Halite is the mineral form
of sodium chloride, NaCl, Metals - Aluminum
crystal structure
commonly known as rock
salt.
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
Hexagonal close packed (HCP)
Deviation from hard sphere model in calculating volume

Garnet
crystal

HCP structure is denser than simple hexagonal structure

Lattice constant, a = 2 x r and

 For HCC :

Garnet crystal
SUMMARY
Ideal atomic packing factors of all crystal structures :
Simple cubic: 0.52
Body-centered cubic: 0.68
Hexagonal close-packed: 0.74
Face-centered cubic: 0.74 Diamond cubic: 0.34
Relationship between atoms size (r) and unit cell dimensions
for FCC, BCC and simple cubic structure.

FCC BCC SC

Side of unit 2r
cell
Face 4r
diagonal
Body 4r
diagonal
http://highered.mcgraw-
hill.com/sites/0073529249/student_view0/chapter3/tutorials.html#
(Chapter 3 – Tutorials - Structure of crystalline solid)
 Theoretical Density, r
Mass of Atoms in Unit Cell
Density = r =
Total Volume of Unit Cell

nA
r =
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadro’s number
= 6.023 x 1023 atoms/mol
 Theoretical Density, r

• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
R
a a = 4R/ 3 = 0.2887 nm

atoms
g
unit cell 2 52.00 rtheoretical = 7.18 g/cm3
mol
r= ractual = 7.19 g/cm3
a3 6.023 x 1023
volume atoms
unit cell mol
 Densities of Material Classes
In general Graphite/
rmetals > rceramics > rpolymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
30
Why? Platinum
20 Gold, W
Metals have... Tantalum

• close-packing
10 Silver, Mo
(metallic bonding) Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia

r (g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
• less dense packing 3
Diamond
Si nitride
Aluminum Glass -soda
• often lighter elements Concrete
Silicon PTFE
Glass fibers
GFRE*
2 Carbon fibers
Polymers have... Magnesium Graphite
Silicone CFRE*
Aramid fibers
PVC
• low packing density PET
PC
AFRE*
1 HDPE, PS
(often amorphous) PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood

• intermediate values 0.3

 Crystals as Building Blocks
Single crystal : a crystalline solid with perfection of repeated
arrangement of atoms, and this arrangement is extended
throughout the entirety of the specimen
• Some engineering applications require single crystals:
--diamond single --turbine blades
crystals for abrasives

• Properties of crystalline materials

often related to crystal structure.
--Ex: Quartz fractures more easily
along some crystal planes than
others.
 Polycrystals
Anisotropic
• Most engineering materials are polycrystals. Properties
change
depend on
direction of
measurement

1 mm

Isotropic

Polycrystalline materials are made up of

many small crystals or grains which are
mostly randomly oriented.
Behavior and Crystallographic Direction
• Anisotropic - Physical properties depend on
the crystallographic direction (in which
measurements are taken)
Example of Physical properties that are anisotropic in nature:
elastic modulus, electrical conductivity, index of reflection

• Isotropic - Physical properties are independent

of the crystallographic direction
 Single vs Polycrystals
• 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 mm
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
anisotropic.
 Polymorphism p114 Mc Graw Hill
 Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
example: iron system
titanium
liquid
a, b-Ti
1538ºC
BCC -Fe
carbon
diamond, graphite 1394ºC
FCC g-Fe
912ºC
BCC a-Fe
Now that we know how atoms arrange themselves to form
crystals, we need a way to identify directions and planes of
atoms.

Why?
- Deformation under loading (slip) occurs on certain
crystalline planes and in certain crystallographic directions.
Before we can predict how materials fail, we need to know
what modes of failure are more likely to occur.

- Other properties of materials (electrical conductivity,

thermal conductivity, elastic modulus) can vary in a crystal
with orientation  crystals are anisotropic
Directions and planes are described using three integers -
Miller Indices
Miller indices used to express lattice
planes and directions
• x, y, z are the axes (on arbitrarily
positioned origin)
• a, b, c are lattice parameters (length of
unit cell along a side)
• h, k, l are the Miller indices for planes
and directions -
expressed as planes: (hkl) and directions:
[hkl]
Atom positions in cubic unit cells

Positive axes
x-axis (coming out of paper), y-axis (to the right of paper), z-axis (to the top of paper)
Atomic positions is Point Coordinates
Point position specified in terms of its
z coordinates as fractional multiples of the
111
unit cell edge lengths
c
Point coordinates for unit cell
center are
y a/2, b/2, c/2 (½ ,½, ½)
000
a b
x  Point coordinate for one of the unit
z 2c cell corner is (1,1,1)


  Translation: integer multiple of

y lattice constants  identical
b position in another unit cell
b
 Crystal Directions

[210]

Directions
A direction is written as three numbers enclosed in
square brackets [hkl] and no commas between number,
with a line over a number if it is a negative.
 Crystallographic Directions
Algorithm (Procedures to determine directions)
z 1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of unit cell
dimensions a, b, and c
Subtract coordinates
Determine the
of point of
coordinates of point
y of emergence (head)
Emergence (head) by
that of origin (tail)
and origin (tail)
x
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas [hkl]

ex: head =(1, 0, ½) => 2, 0, 1 => [ 201 ]

tail = (0, 0, 0)

-1, 1, 1 => [ 111 ] where overbar represents a negative index

 Q: Sketch the [210] directions within a cubic unit cell: z

[210] = divide by 2 = [1 ½ 0]

Q: The cubic unit cell in Figure 1 has three indicated directions.

What are the Miller indices for those directions?
Direction A Direction B Direction C y

½
x
Head ½11 010 1½0
Tail 010 ½01 010
h’ ½-0=½ 0–½=-½ 1–0=1
k’ 1–1=0 1–0=1 ½-1=-½
z

l’ 1–0=1 0 – 1 = -1 0–0=0 Direction

A

Clear X2 X2 X2 ½ ½
fraction
h’ 1 -1 2
k’ 0 2 -1 0
l’ 2 -2 0 C
y
Direction
½ B
Indices [102] [12 2 ] [210 ] x
Figure 1
Families of crystallographic equivalent directions
(atom spacing along the direction is equal):

families of directions <uvw>

< 100 >  [100], [010], [001], [010], [001], [100]

Cubic edge

< 111 >  [111], [11 1 ], [1 1 1], [ 1 11],

Cubic body
diagonal
[ 1 1 1 ], [ 1 1 1], [ 1 1 1 ], [1 1 1 ]

< 110 >  [110], [011], [101], [1 1 0], [01 1 ], [10 1 ]

Cubic face
diagonal
 Linear Density (arises from direction)
Number of atoms
 Linear Density of Atoms  LD =
Unit length of direction vector

[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm

# atoms
a 2
LD = = 3.5 nm -1
length 2a
 Crystal Planes

Equispaced parallel
planes have same
Miller indices
 Sets of equivalent lattice planes
Family of Planes {hkl}
related by crystal symmetry
Ex: {100} = (100),(010), (001), (100), (010), (001)
 Crystallographic Planes
 Miller Indices:

 Algorithm
1. Read off intercepts of plane with axes in
terms of a, b, c (plane must not pass through
origin, if it does, MUST moves the origin)
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no commas i.e., (hkl)
 Intercepts  -1 -1/4
z
3/4

y
1/3

x
0

0
y
x

Intercepts -1 -5/12 

Moves existing plane to get intercept.

If green line moves to intercept x = -1

2 1 5
Similarly, Blue line moves -  = - , therefore will intercept y = -5/12
3 4 12
 1. Intercepts 1 5/12 
3/4
2. Reciprocals 1/1 1/(5/12) 1/
1/3 1 12/5 0
3. Reduction 5 12 0

0 4. Miller Indices (5 12 0)
y

Intercepts 1 5/12 

Moves existing plane to get intercept.

If blue line moves to intercept x = 1

Similarly, green line moves 3 - 1 = 5 , therefore will intercept y = 5/12

4 3 12
 Crystallographic Planes
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 (200) a b
x
 Crystallographic Planes
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

Q: Sketch a plane having a Miller indices of (632)

1. Take reduction (divide by

smallest integer)
6/2 3/2 2/2  3 3/2 1
2. Take reciprocal
1/(3) 1/(3/2) 1/(1)  1/3 2/3 1
3. Intercept is
x=1/3 y=2/3 z=1
4. Sketch on unit cell diagram
 Planar Density
Equiv. no. of atoms whose centres
are intersected by selected area
Planar Density of Atoms  PD =
Selected area of plane

1 + ¼(4) atoms
PD110 =
( a) (a)

= 17.2 atoms/nm2
 Planar Density of (100) Iron
Solution: At T < 912C iron has the BCC structure.
2D repeat unit

(100) 4 3
a= R
3
Side
face

Radius of iron R = 0.1241 nm

atoms
1
1 atoms atoms
19
Planar Density = = 2 = 12.1 = 1.2 x 10
a2 4 3 nm 2 m2
R
area 3
 Planar Density of (111) Iron
Solution (cont): (111) plane 1 atom in plane/ unit surface cell

2a atoms in plane
atoms above plane
atoms below plane

3
h= a
2
2
 4 3  16 3 2
area = 2 ah = 3 a = 3 
2
R  = R
atoms  3  3
1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
nm 2 m2
16 3 2
R
area 3
Calculate the planar densities of the (010) and (020) planes in a
simple cubic polonium, which has a lattice parameter of 0.334 nm.
Conclude whether the (010) and (020) planes are equivalent.

http://highered.mcgraw-
hill.com/sites/0073529249/student_view0/chapter3/tutorials.html#
(Chapter 3 – Tutorials – Determination of Crystallographic Directions)
example a b c
1. Intercepts  1 
2. Reciprocals 1/ 1/ 1 1/ 
0 1 0
z
3. Reduction 0 1 0
4. Miller Indices (010)

example a b c
1. Intercepts  1/2  y

2. Reciprocals 1/  1/1/2 1/

x
0 2 0
3. Reduction 0 2 0
4. Miller Indices (020)

No atoms are centered on the (020) plane. Therefore the planar

density will be zero. For (010) plane planar density = 8.96x104
atoms/cm2
 HCP Crystallographic Directions
z
Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of unit
a2 cell dimensions a1, a2, a3, or c
3. Adjust to smallest integer values
- 4. Enclose in square brackets, no commas
a3
[uvtw] a
a1
2
a2 -a3
2

ex: ½, ½, -1, 0 => [ 1120 ] a3

a1
2
dashed red lines indicate
projections onto a1 and a2 axes a1
 HCP Crystallographic Directions
 Hexagonal Crystals
 4 parameter Miller-Bravais lattice coordinates are
related to the direction indices (i.e., u'v'w') as follows.

[ u 'v 'w ' ]  [ uvtw ]

1
u = (2 u ' - v ')
3
a2
1
v = (2 v ' - u ')
- 3
a3
t = - (u +v )
w = w'
a1
 Crystallographic Planes (HCP)
 In hexagonal unit cells the same idea is used
z

example a1 a2 a3 c
1. Intercepts 1  -1 1
2. Reciprocals 1 1/ -1 1
1 0 -1 1 a2

3. Reduction 1 0 -1 1
a3

4. Miller-Bravais Indices (1011) a1

 Crystallographic Planes

 We want to examine the atomic packing of

crystallographic planes
 Iron foil can be used as a catalyst. The atomic
packing of the exposed planes is important.
a) Draw (100) and (111) crystallographic planes
for Fe.
b) Calculate the planar density for each of these planes.
 X-Ray Diffraction

 Diffraction gratings must have spacings comparable to the

wavelength of diffracted radiation.
 Can’t resolve if diffraction spacings  
 Spacing is the distance between parallel planes of atoms.
 X-Rays to Determine Crystal Structure
• Incoming X-rays diffract from crystal planes.

reflections must
be in phase for
a detectable signal
extra 
q q
distance
travelled
by wave “2” spacing
d between
planes

Measurement of X-ray
n
critical angle, qc, intensity d=
(from 2 sin qc
allows computation of
detector)
planar spacing, d.
q
qc
 X-Ray Diffraction Pattern
z z z
c c c

y (110) y y
a b a b a b
Intensity (relative)

x x x (211)

(200)

Diffraction angle 2q

Diffraction pattern for polycrystalline a-iron (BCC)

 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.