CH 3 - Crystal Structures Geometry - Ok

CHAPTER
3
Crystal Structures
and
Crystal Geometry
3-1
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display
Intro
The Space Lattice and Unit Cells

• CRYSTAL STRUCTURE - Atoms, arranged in repetitive 3-
Dimensional pattern, in long range order (LRO) .
• Properties of solids depends upon crystal structure and
bonding force.
• SPACE LATTICE - An imaginary network of lines, with
atoms at intersection of lines, representing the arrangement
of atoms.
Space Lattice
• Unit cell is that block of
atoms which repeats itself
to form space lattice.
• Materials arranged in short
range order are called
amorphous materials Unit Cell
3-2
Crystal Systems and Bravais Lattice
• Only 7 different types of unit cells (i.e.

cubic, tetragonal, orthorhombic,
rombohedral, hexagonal, monoclinic,
triclinic) are necessary to create all point
lattices.
• According to Bravais (1811-1863), 14
standard unit cells can describe all
possible lattice networks.
• The 4 basic types of unit cells are:
 Simple
 Body Centered
 Face Centered
 Base Centered
3-3
Types of Unit Cells
• Cubic Unit Cell

 a=b=c
 α = β = γ = 900
Simple Body Centered
Figure 3.2
Face centered
• Tetragonal
 a =b ≠ c
 α = β = γ = 900
Simple Body Centered

3-4 After W.G. Moffatt, G.W. Pearsall, & J. Wulff, “The Structure and Properties of Materials,” vol. I: “Structure,” Wiley, 1964, p.47.)
Types of Unit Cells (Cont..)
• Orthorhombic
 a≠ b≠ c
 α = β = γ = 900
Simple Base Centered
Body Centered
Face Centered
• Rhombohedral Figure 3.2

 a =b = c
 α = β = γ ≠ 900
Simple
Types of Unit Cells (Cont..)
• Hexagonal
 a≠ b≠ c
 α = β = γ = 900 Simple
• Monoclinic
 a≠ b≠ c
 α = β = γ = 900 Base
Centered
Simple
• Triclinic Figure 3.2
 a≠ b≠ c
 α = β = γ = 900
Simple
Principal Metallic Crystal Structures
• 90% of the metals have either Body Centered Cubic

(BCC), Face Centered Cubic (FCC) or Hexagonal
Close Packed (HCP) crystal structure.
• HCP is denser version of simple hexagonal crystal
structure.
BCC Structure FCC Structure HCP Structure

Figure 3.3
3-7
Body Centered Cubic (BCC) Crystal Structure
• Represented as one atom at each corner of cube and

one at the center of cube.
• Each atom has 8 nearest neighbors.
• Therefore, coordination number is 8.
• Examples :-
 Chromium (a=0.289 nm)
 Iron (a=0.287 nm)
 Sodium (a=0.429 nm)
Figure 3.4 a&b

3-8
Coordination Number
Body Centered Cubic (BCC) Crystal Structure
(a) (b) (c)

Hard-sphere unit Reduced-sphere An aggregate of
cell model unit cell model many atoms
BCC Crystal Structure (Cont..)
• 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, lattice
4R
constant, a=
3
3-9
Atomic Packing Factor of BCC Structure

Sect. 02& 04
stops here
7/6/2012 Volume of atoms in unit cell
Atomic Packing Factor =
Volume of unit cell
 4 R 3 
Vatoms = 2.  = 8.373R3
 
 3 
3
 4R 
V unit cell = a3 =   = 12.32 R3
 
 3 
8.723 R3
Therefore APF = 12.32 R3 = 0.68
3-10
Face Centered Cubic (FCC) Crystal Structure
• FCC structure is represented as one atom each at the

corner of cube and at the center of each cube face.
• Coordination number for FCC structure is 12
• Atomic Packing Factor is 0.74
• Examples :-
 Aluminum (a = 0.405)
 Gold (a = 0.408)
3-11
Face Centered Cubic (FCC) Crystal Structure
(a) (b) (c)

Hard-sphere Reduced-sphere An aggregate of
unite cell model unite cell model many atoms
FCC Crystal Structure (Cont..)
• Each unit cell has eight 1/8

atom at corners and six ½
atoms at the center of six
faces.
• Therefore each unit cell has
(8 x 1/8)+ (6 x ½) = 4 atoms
• Atoms contact each other

across cubic face diagonal
Therefore, lattice
4R
constant, a =
2 Figure 3.7
3-12
Hexagonal Close-Packed Structure
• The HCP structure is represented as an atom at each

of 12 corners of a hexagonal prism, 2 atoms at top and
bottom face and 3 atoms in between top and bottom
face.
• Atoms attain higher APF by attaining HCP structure
than simple hexagonal structure.
• The coordination number is 12, APF = 0.74.
Figure 3.8 a&b

3-13 After F.M. Miller, “Chemistry: Structure and Dynamics,” McGraw-Hill, 1984, p.296
(a) (b) (c)

HCP Crystal Structure (Cont..)
• Each atom has six 1/6 atoms at each of top and bottom
layer, two half atoms at top and bottom layer and 3 full
atoms at the middle layer.
• Therefore each HCP unit cell has
(2 x 6 x 1/6) + (2 x ½) + 3 = 6 atoms
• Examples:-
 Zinc (a = 0.2665 nm, c/a = 1.85)
 Cobalt (a = 0.2507 nm, c.a = 1.62)
• Ideal c/a ratio is 1.633.

(to behave *isotropically)
*having physical properties, as conductivity,

elasticity, etc., that are the same regardless of the
direction of measurement
3-14 After F.M. Miller, “Chemistry: Structure and Dynamics,” McGraw-Hill, 1984, p.296
(a) (b) (c)

Atom Positions in Cubic Unit Cells
• Cartesian coordinate system is used to locate atoms.

• 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.
 Negative directions are to the opposite of positive
directions.
• Atom positions are

located using unit
distances along the
axes.
Figure 3.10 b
3-15
Directions in Cubic Unit Cells
• In cubic crystals, Direction Indices are vector

components of directions resolved along each axes,
resolved to smallest integers.
• Direction indices are position coordinates of unit cell
where the direction vector emerges from cell surface,
converted to integers.
Figure 3.11
3-16
Procedure to Find Direction Indices

Produce the direction vector till it
z
emerges from surface of cubic cell
(1,1/2,1)
(1,1/2,1) - (0,0,0)
Determine the coordinates of point = (1,1/2,1)
of emergence and origin y
(0,0,0) 2 x (1,1/2,1)
Subtract coordinates of point of x = (2,1,2)
Emergence by that of origin
The direction indices are [212]
Are all are NO Convert them to
integers? smallest possible
YES integer by multiplying
Are any of the direction by an integer.
vectors negative?
NO
YES
Represent the indices in a square
Represent the indices in a square
bracket without comas with a
bracket without comas (Eg: [212] )
over negative index (Eg: [121])
3-17
Direction Indices - Example

• Determine direction indices of the given vector.
Origin coordinates are (3/4 , 0 , 1/4).
Emergence 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)
Therefore, the direction indices are
 221
Figure EP3.6
3-18
Miller Indices
• Miller Indices are used to refer to specific lattice

planes of atoms.
• They are reciprocals of the fractional intercepts (with
fractions cleared) that the plane makes with the
crystallographic x,y and z axes of three nonparallel
edges of the cubic unit cell.
z Miller Indices =(111)
x
3-19
Miller Indices - Procedure

Choose a plane that does not pass
through origin
Determine the x,y and z intercepts

of the plane
Find the reciprocals of the intercepts
Clear fractions by
Fractions?
multiplying by an integer
Place a ‘bar’ over the to determine smallest set
Negative indices of whole numbers
Enclose in parenthesis (hkl) where h,k,l

are miller indices of cubic crystal plane
For x,y and z axes. Eg: (111)
3-20
Miller Indices – Examples (to determine plane)
• Intercepts of the plane at

z
x,y & z axes are 1, ∞ and ∞
(100) • Taking reciprocals we get
y (1,0,0).
x • Miller indices are (100).
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).
Figure 3.14
3-21
Miller Indices – Examples (to plot plane)
• Plot the plane (101)

Taking reciprocals of the
indices we get (1 ∞ 1).
The intercepts of the plane are
x=1, y= ∞ (parallel to y) and z=1.
Figure EP3.7 a
******************************
• Plot the plane (2 2 1)
Taking reciprocals of the
indices we get (1/2 1/2 1).
The intercepts of the plane are
x=1/2, y= 1/2 and z=1.
Figure EP3.7 c
3-22
Miller Indices - Example

• Plot the plane (1 1 0)
The reciprocals are (1,-1, ∞)
The intercepts are x = 1, y = -1 and z = ∞ (parallel to z axis)
z
(1 1 0)
x
3-23
Miller Indices – Important Relationship
• Direction indices of a direction perpendicular to a

crystal plane are same as miller indices of the plane.
• Example:- z
(110) y
[110]
Figure EP3.7b
x
• Interplanar spacing between parallel closest planes

with same miller indices is given by
a
d hkl

2 2 2
h k l
3-24
Planes and Directions in Hexagonal Unit Cells
• Four indices are used (hkil) called as

Miller-Bravais indices.
• Four axes are used (a1, a2, a3 and c).
• Reciprocal of the intercepts that a crystal
plane makes with the a1, a2, a3 and c axes
give the h,k,i and l indices respectively.
Figure 3.16
3-25
Hexagonal Unit Cell - Examples

• Basal Planes:- Sect. 04
Intercepts a1 = ∞ Stop here
12/6/2012
a2 = ∞
a3 = ∞
c=1
(hkil) = (0001)
• Prism Planes :- Figure 3.12 a&b
For plane ABCD,
Intercepts a1 = 1
a2 = ∞
a3 = -1
c=∞
(hkil) = (1010)
3-26
Directions in HCP Unit Cells
• Indicated by 4 indices [uvtw].

• (u + v) = (- t)
• u,v,t and w are lattice vectors in a1, a2, a3 and c
directions respectively.
3-27
[uvtw]
(u + v) = (- t)
Comparison of FCC and HCP crystals
• Both FCC and HCP are close packed and

have APF 0.74.
• FCC crystal is close packed in (111) plane
Comparison of FCC and HCP crystals
• Both FCC and HCP are close packed and

have APF 0.74.
• HCP is close packed in (0001) plane.
Structural Difference between HCP and FCC

Plane A
Consider a layer ‘a’ void
of atoms (Plane ‘A’) ‘b’ void
Another layer (plane ‘B’) Plane A

of atoms is placed in ‘a’ Plane B
Void of plane ‘A’ ‘a’ void
‘b’ void
Third layer of Atoms placed Third layer of Atoms placed
in ‘b’ Voids of plane ‘B’. (Identical in ‘a’ voids of plane ‘B’. Resulting
to plane ‘A’.) HCP crystal. In 3rd Plane C. FCC crystal.
Plane A Plane A
Plane B Plane B
Plane A Plane C
Figure 3.20
3-29
Structural Difference between HCP and FCC
HCP FCC
Polymorphism or Allotropy
• Metals exist in more than one crystalline form. This is

caller polymorphism or allotropy.
• Temperature and pressure leads to change in
crystalline forms.
• Example:- Iron exists in both BCC and FCC form
depending on the temperature.
Liquid
Iron
-2730C 9120C 13940C 15390C
α Iron γ Iron δ Iron

BCC FCC BCC
3-33
Polymorphism or Allotropy
Iron Carbide
Phase Diagram
3-33
Crystal Structure Analysis
• Information about crystal structure are obtained using

X-Rays.
• The X-rays used are about the same wavelength (0.05-
0.25 nm) as distance between crystal lattice planes.
35 KV
(Eg:
Molybdenum)
Figure 3.25
3-34 After B.D. Cullity, “Elements of X-Ray Diffraction, “ 2d ed., Addison-Wesley, 1978, p.23.
X-Ray Spectrum of Molybdenum

• X-Ray spectrum of Molybdenum
is obtained when Molybdenum is
used as target metal.
• Kα and Kβ are characteristic of
an element.
• For Molybdenum Kα occurs at
wave length of about 0.07nm.
• Electrons of n=1 shell of target
metal are knocked out by
bombarding electrons.
• Electrons of higher level drop
down by releasing energy to
replace lost electrons
Figure 3.26
3-35
Amorphous Materials
• Random spatial positions of atoms

• Polymers: Secondary bonds do not allow
formation of parallel and tightly packed chains
during solidification.
 Polymers can be semicrystalline.
• Glass is a ceramic made up of SiO4 4-
tetrahedron subunits – limited mobility.
• Rapid cooling of metals (10 8 K/s) can give rise
to amorphous structure (metallic glass).
• Metallic glass has superior metallic properties.
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CHAPTER

The Space Lattice and Unit Cells

Crystal Systems and Bravais Lattice

• Only 7 different types of unit cells (i.e.

Types of Unit Cells

• Cubic Unit Cell

Simple Body Centered

Simple Body Centered

Types of Unit Cells (Cont..)

Simple Base Centered

• Rhombohedral Figure 3.2

Types of Unit Cells (Cont..)

• Triclinic Figure 3.2

Principal Metallic Crystal Structures

• 90% of the metals have either Body Centered Cubic

BCC Structure FCC Structure HCP Structure

Body Centered Cubic (BCC) Crystal Structure

• Represented as one atom at each corner of cube and

Figure 3.4 a&b

Body Centered Cubic (BCC) Crystal Structure

(a) (b) (c)

BCC Crystal Structure (Cont..)

• Each unit cell has eight 1/8

• Atoms contact each

Atomic Packing Factor of BCC Structure

Face Centered Cubic (FCC) Crystal Structure

• FCC structure is represented as one atom each at the

Face Centered Cubic (FCC) Crystal Structure

(a) (b) (c)

FCC Crystal Structure (Cont..)

• Each unit cell has eight 1/8

• Atoms contact each other

Hexagonal Close-Packed Structure

• The HCP structure is represented as an atom at each

Figure 3.8 a&b

(a) (b) (c)

HCP Crystal Structure (Cont..)

• Ideal c/a ratio is 1.633.

*having physical properties, as conductivity,

(a) (b) (c)

Atom Positions in Cubic Unit Cells

• Cartesian coordinate system is used to locate atoms.

• Atom positions are

Directions in Cubic Unit Cells

• In cubic crystals, Direction Indices are vector

Procedure to Find Direction Indices

Direction Indices - Example

Subtracting origin coordinates

• Miller Indices are used to refer to specific lattice

Miller Indices - Procedure

Determine the x,y and z intercepts

Find the reciprocals of the intercepts

Enclose in parenthesis (hkl) where h,k,l

Miller Indices – Examples (to determine plane)

• Intercepts of the plane at

Miller Indices – Examples (to plot plane)

• Plot the plane (101)

Miller Indices - Example

Miller Indices – Important Relationship

• Direction indices of a direction perpendicular to a

• Interplanar spacing between parallel closest planes

Planes and Directions in Hexagonal Unit Cells

• Four indices are used (hkil) called as