Chapter 3.ppt - 0

CHAPTER
3
Crystal Structures
and
Crystal Geometry
3-1
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display
Chapter Objectives
1.
Describe what crystalline and noncrystalline (amorphous)

materials are.
2.
Learn how atoms and ions in solids are arranged in space and
identify the basic building blocks of solids.
3.
Describe the difference between atomic structure and crystal

structure for solid material.
4.
Distinguish between crystal structure and crystal system.
5.
Explain why plastics cannot be 100% crystalline in structure.
6.
Explain polymorphism or allotropy in materials.
7.
Write the designation for atom position, direction indices, and

Miller indices for cubic crystals. Specify what are the three
densely packed structures for most metals. Determine MillerBravais indices FCC and BCC structure. Be able to draw
directions and planes in cubic crystals.
MATERIALS AND PACKING

Crystalline materials...
atoms pack in periodic, 3D arrays
typical of: -metals
-many ceramics
-some polymers
crystalline SiO2
Adapted from Fig. 3.18(a),
Callister 6e.
Noncrystalline materials...
Si
Oxygen
atoms have no periodic packing

occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline
noncrystalline SiO2
Adapted from Fig. 3.18(b),
Callister 6e.
The Space Lattice and Unit Cells
CRYSTAL STRUCTURE - Atoms, arranged in repetitive 3Dimensional 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
3-2
Unit Cell
Crystal Systems and Bravais Lattice
3-3
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
Seven Crystal System
Fourteen Bravais Lattices
Chapter 3 - 8
METALLIC CRYSTALS
tend to be densely packed.
have several reasons for dense packing:
- typically, only one element is present, so all a

radii are the same.
- metallic bonding is not directional.
- nearest neighbor distances tend to be small in
order to lower bond energy.
have the simplest crystal structures.
We will look at three such structures...
Chapter 3 - 9
Intro
1. SIMPLE CUBIC STRUCTURE (SC)

Rare due to poor packing (only Po has this structure)
Close-packed directions are cube edges.
Coordination # = 6
(# nearest neighbors)
(Courtesy P.M. Anderson)
Chapter 3 - 11
Coordination Number
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
atoms
unit cell
a
R=0.5a
close-packed directions
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.19,
Callister 6e.
APF =
volume
atom
4
(0.5a)3
1
3
a3
volume
unit cell
Chapter 3 - 13
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
Figure 3.3
3-7
HCP Structure
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
Body Centered Cubic (BCC) Crystal

Structure
(a)
Hard-sphere unit
cell model
(b)
Reduced-sphere
unit cell model
(c)
An aggregate of
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
constant,
3-9
a=
4R
3
ATOMIC PACKING FACTOR: BCC

APF for a body-centered cubic structure = 0.68
Close-packed directions:
length = 4R
= 3a
R
Adapted from
Fig. 3.2,
Callister 6e.
Unit cell contains:

1 + 8 x 1/8
=2 atoms/unit cell
a
atoms
volume
4
( 3a/4)3
2
unit cell
atom
3
APF =
volume
a3
unit cell
Chapter 3 - 18
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 :
3-11
Aluminum (a = 0.405)
Gold (a = 0.408)
Face Centered Cubic (FCC)

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

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

across cubic face diagonal
Therefore, lattice
constant,
3-12
4R
2
Figure 3.7
ATOMIC PACKING FACTOR: FCC

APF for a body-centered cubic structure = 0.74
Close-packed directions:
length = 4R
= 2a
Adapted from
Fig. 3.1(a),
Callister 6e.
Unit cell contains:

6 x 1/2 + 8 x 1/8
=4 atoms/unit cell
atoms
volume
4
3
( 2a/4)
4
unit cell
atom
3
APF =
volume
3
a
unit cell
Chapter 3 - 23
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)
Hard-sphere
unite cell model
(b)
Reduced-sphere
unite cell model
Sect. 02 stops here 25/5/11
(c)
An aggregate of
many atoms
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 ) + 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)
Hard-sphere
unite cell model
(b)
Reduced-sphere
unite cell model
(c)
An aggregate of
many atoms
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.
3-15
Figure 3.10 b
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
emerges from surface of cubic cell
z
(1,1/2,1)
Determine the coordinates of point

of emergence and origin
Subtract coordinates of point of
Emergence by that of origin
Are all are
integers?
YES
Are any of the direction
vectors negative?
NO
YES
Represent the indices in a square
bracket without comas with a
over negative index (Eg: [121])
3-17
(1,1/2,1) - (0,0,0)
= (1,1/2,1)
y
(0,0,0)
2 x (1,1/2,1)
= (2,1,2)
The direction indices are [212]

Convert them to
smallest possible
integer by multiplying
by an integer.
NO
Represent the indices in a square
bracket without comas (Eg: [212] )
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
3-18
221
Figure EP3.6
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)
y
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
Fractions?
Place a bar over the
Negative indices
Clear fractions by
multiplying by an integer
to determine smallest set
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

(1,0,0).
Miller indices are (100).
y
x
*******************
Figure 3.14
3-21
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).
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.
******************************
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.
3-22
Figure EP3.7 a
Figure EP3.7 c
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:-
(110)
[110]
Figure EP3.7b
Interplanar spacing between parallel closest planes with same

miller indices is given by
d
3-24
hkl
k l
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
Comparison of FCC and HCP crystals
3-28
Both FCC and HCP are close packed and

have APF 0.74.
FCC crystal is close packed in (111) plane
After W.G. Moffatt, G.W. Pearsall, & J. Wulff, The Structure and Properties of Materials, vol. I: Structure, Wiley, 1964, p.51.)
Comparison of FCC and HCP crystals
3-28
Both FCC and HCP are close packed and

have APF 0.74.
HCP is close packed in (0001) plane.
After W.G. Moffatt, G.W. Pearsall, & J. Wulff, The Structure and Properties of Materials, vol. I: Structure, Wiley, 1964, p.51.)
Structural Difference between HCP and

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

of atoms is placed in a
Void of plane A
Plane A
Plane B
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 B
Plane A
Plane B
Plane A
Plane C
Figure 3.20
3-29
Structural Difference between HCP and

FCC
HCP
FCC
Chapter 3 - 46
HEXAGONAL CLOSE-PACKED STRUCTURE (HCP)

ABAB... Stacking Sequence
3D Projection
2D Projection
A sites
Top layer
B sites
Middle layer
A sites
Bottom layer
Adapted from Fig. 3.3,

Callister 6e.
Coordination # = 12
APF = 0.74
Chapter 3 - 47
FCC STACKING SEQUENCE

ABCABC... Stacking Sequence
2D Projection
A
A sites
B sites
B
C
B
C
B
B
C
B
C sites
FCC Unit Cell
A
B
C
Chapter 3 - 49
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.
9120C
-2730C
Iron
BCC
3-33
Liquid
Iron
13940C 15390C
Iron
FCC
Iron
BCC
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 (0.050.25 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
3-35
X-Ray spectrum of
Molybdenum is obtained when
Molybdenum is used as target
metal.
K and K are characteristic
of an element.
For Molybdenum K 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
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 4tetrahedron 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.
Exercises
1.
Define the following terms: (a) crystalline solid, (b) long-range order, (c)
short-range order, and (d) amorphous.
2.
Define the following terms: (a) crystal structure. (b) space lattice, (c)
lattice point, (d) unit cell, (e) motif, (f) lattice constants
3.
What are the three most common metal crystal structures? List five metals
that have each of these crystal structures.
4.
For a BBC unit cell, (a) how many atoms are there inside the unit cell, (b)
what is the coordination number for the atoms, (c) what is the
relationship between the length of the side a of the BCC unit cell and the
radius of its atoms, and (d) APF = 0.68 or 68%
5.
For an FCC unit cell, (a) how many atoms are there inside the unit cell,
4R
(b) What is the coordination number for the atoms, (c) shows a and
2
(d) what is the atomic packing factor?
6.
List the atom positions for the eight corner and six face-centered atoms of the
FCC unit cell.
7.
What is the notation used to indicate a family or form of cubic crystallographic

planes?
8.
Draw the following directions in a BCC unit cell and list the position
coordinates of the atoms whose centers are intersected by the direction
vector:
(a) [100]
9.
6.
(b) [110]
(c) [111]
Draw direction vectors in unit cells for the following cubic directions:
(a)
1 1 1
(b)
1 10
(c)
12 1
(d)
1 13
(g)
122
(h)
123
(i)
021
(j)
233
(e)
(k)
101
12 1
(f) 321
(l)
223
What are the indices of the directions shown in the unit cubes of Figure below?
11. Draw
in unit cubes the crystal planes

indices:
1 1 1
12 1
321
(a)
(b)
(c)
102
213

302
(g)
(h)
(i)
(j)
that have the following Miller
20 1
(d)
212
3 12
(f)
33 1
(232)
(e)
133
(k)
(l)
12.
What are the Miller indices of the cubic cyrsyallographic planes shown in Fig.
below?
13.
An unknown material is being analyzed using X-ray diffraction techniques.

However, the diffraction patterns are extremely broad (no clear peaks are
visible). (a) What does this tell you about the material? (b) What are some of
the tests that you can perform to help identify the material or narrow the
possibilities?
14.
Draw a schematic diagram of an x-ray tube used for x-ray diffraction, and
indicate on it the path of the electrons and X rays.
15.
What is the characteristic x-ray radiation? What is its origin?
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CHAPTER

Describe what crystalline and noncrystalline (amorphous)

Describe the difference between atomic structure and crystal

Distinguish between crystal structure and crystal system.

Explain why plastics cannot be 100% crystalline in structure.

Explain polymorphism or allotropy in materials.

Write the designation for atom position, direction indices, and

MATERIALS AND PACKING

atoms have no periodic packing

The Space Lattice and Unit Cells

Properties of solids depends upon crystal structure

SPACE LATTICE - An imaginary network of lines, with

Unit cell is that block of

Materials arranged in short

Crystal Systems and Bravais Lattice

Only 7 different types of unit cells (i.e. cubic,

According to Bravais (1811-1863), 14 standard unit

The 4 basic types of unit cells are:

Seven Crystal System

Fourteen Bravais Lattices

- typically, only one element is present, so all a

1. SIMPLE CUBIC STRUCTURE (SC)

(Courtesy P.M. Anderson)

ATOMIC PACKING FACTOR, APF

Principal Metallic Crystal Structures

90% of the metals have either Body Centered Cubic

HCP is denser version of simple hexagonal crystal

Body Centered Cubic (BCC)

Represented as one atom at each corner of cube and

Each atom has 8 nearest neighbors.

Therefore, coordination number is 8.

Chromium (a=0.289 nm)

Figure 3.4 a&b

Body Centered Cubic (BCC) Crystal

BCC Crystal Structure

Each unit cell has eight 1/8

Therefore each unit cell has

Atoms contact each

ATOMIC PACKING FACTOR: BCC

Unit cell contains:

Face Centered Cubic (FCC)

FCC structure is represented as one

Coordination number for FCC structure

Atomic Packing Factor is 0.74

Face Centered Cubic (FCC)

FCC Crystal Structure (Cont..)

Each unit cell has eight 1/8

Atoms contact each other

ATOMIC PACKING FACTOR: FCC

Unit cell contains:

Hexagonal Close-Packed Structure

The HCP structure is represented as an atom at each

Atoms attain higher APF by attaining HCP structure

The coordination number is 12, APF = 0.74.

Figure 3.8 a&b

Sect. 02 stops here 25/5/11

HCP Crystal Structure (Cont..)

Each atom has six 1/6 atoms at each of top and

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.

*having physical properties, as conductivity,

Atom Positions in Cubic Unit Cells