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You are on page 1of 59

Structure in Materials

amorphous.

Yes, this means all solid stuff on Earth

and even in the universe.

Whats the difference?

Crystals have long range order.

Amorphous solids lack long range order.

Very ordered

No order

Examples of crystalline

solids

Sand

Salt, sugar

Diamonds, gemstones

Metals

Ceramics

Most solids are

crystalline!

Examples of

amorphous solids

Glass

Some polymers

Polyvinyl chloride

A few metals, in some

rare instances

Space lattice

Space lattice: An imaginary network of lines,

with atoms at the intersection of lines,

representing the arrangement of atoms.

Unit cell

Unit cell = the block of atoms which repeats itself to

form a space lattice.

Space Lattice

Unit Cell

According to Bravais,

fourteen standard unit cells

can describe all possible

lattice networks.

a=b=c

= = = 90

Simple

Body Centered

Face centered

Tetragonal

a =b c

= = = 90

Simple

Body Centered

Orthorhombic

a b c

= = = 90

Simple

Base Centered

Body Centered

Face Centered

Rhombohedral

a =b = c

= = 90

Simple

Hexagonal

a= b c

= = 90, = 120

Simple

Monoclinic

a b c

= = 90

Base

Centered

Simple

Triclinic

a b c

90

Simple

90% of the metals have one of the following three

HCP is a denser

crystal structures:

version of simple

hexagonal crystal

structure.

Body Centered

Cubic

BCC

Face Centered

Cubic

FCC

Hexagonal Close

Packed

HCP

Please click on the image below to begin a short

tutorial on body centered crystal structure

contains audio commentary)

cubic_unit_cells_7_new_BCC.mpg

BCC unit cell has one atom at each corner of

the cube and one at the center of the cube.

Each atom has 8 nearest neighbors.

Therefore, the coordination number is 8.

Examples of BCC solids:

Chromium (a=0.289 nm)

Iron (a=0.287 nm)

Sodium (a=0.429 nm)

atom at the corners and 1

full atom at the center.

Therefore each unit

cell

You

will be

has

building a model

of this in lab!

(8 x 1/8 ) + 1 = 2 full

atoms

diagonally in the cube,

2a a 3a 4R

2

You will be

calculating this

in lab!

a

2 a

constant, a =

4R

3

How dense is the unit cell?

Look at all that

empty space

between

atoms!

Volume of unit cell

Vatoms =

2 R3

3

Vunit cell =

a3

Volume of unit cell

= 8.373R3

4R

You will be

calculating this

in lab!

= 12.32

R3

3

8.723

R

Therefore APF = 12.32 R3 = 0.68

Please click on the image below to begin a short

tutorial on body centered crystal structure

contains audio commentary)

cubic_unit_cells_8_new_FCC.mpg

FCC structure is

represented as

one atom at

each corner of

the cube

and one at the

center of each

cube face.

Atom at

corner of

cube

Atom at

corner of

cube

Atom at

center of

face

Atom at

corner of

cube

Atom at

center of

face

Atom at

corner of

cube

Atom at

corner of

cube

Atom at

corner of

cube

Atom at

center of

face

Atom at

corner of

cube

Coordination number for FCC structure is 12

Atomic Packing Factor is 0.74, which is

higher/denser than for BCC

Examples of FCC solids:

Aluminum (a = 0.405)

Gold (a = 0.408)

Lead

Each unit cell has eight 1/8

atoms at corners and six

atoms at the center of six faces.

Therefore each unit cell has

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

across the cubic face diagonal

Therefore, lattice

4R

constant a

=

2

2a 4R

cubic_unit_cells_9_new.mpg

cubic_unit_cells_10_new_NaCl.mpg

cubic_unit_cells_11_new_Zn_blend.mpg

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 have higher APF by attaining HCP structure

instead of the simple hexagonal structure.

The coordination number is 12, APF = 0.74.

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.

(2 x 6 x 1/6) + (2 x ) + 3 = 6 atoms

Examples of HCP solids:

Cobalt (a = 0.2507 nm, c/a = 1.62)

Please click on the image below to begin a short

tutorial on the structure of crystalline solids.

contains audio commentary)

The 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 opposite of positive

directions.

Atom positions are

located using unit

distances along the

axes.

In cubic crystals, direction indices are vector

components of directions resolved along each axes,

resolved to smallest integers.

Direction indices are position coordinates of the unit

cell where the direction vector emerges from the cell

surface, converted to integers.

Please click on the image below to begin a short

tutorial on crystallographic directions.

Extend the direction vector until it

emerges from the surface of cubic cell

z

(1,1/2,1)

points of emergence and origin

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

= (1,1/2,1)

y

(0,0,0)

emergence by that of origin

integers?

NO

YES

Are any of the direction

vectors negative?

YES

Represent the indices in a square

bracket without comas with a

over negative index (Eg: [121])

2 x (1,1/2,1)

= (2,1,2)

Convert them to

smallest possible

integer by multiplying

by an integer.

NO

Represent the indices in a square

bracket without comas (Eg: [212] )

Determine direction indices of the given vector.

Origin coordinates are (3/4 , 0 , 1/4).

Emergence coordinates are (1/4, 1/2, 1/2).

Subtract 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 [ 2 2 1 ]

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

y

x

Please click on the image below to begin a short

tutorial on cubic crystal planes.

contains audio commentary)

Choose a plane that does not pass

through the origin

of the plane

Find the reciprocals of the intercepts

Fractions?

Place a bar over the

negative indices

Yes

Clear fractions by

multiplying by an integer

to determine smallest set

of whole numbers

are miller indices of cubic crystal plane

for x,y and z axes. Eg: (111)

z

(100)

y

x

x

x,y & z axes are 1, and

Taking reciprocals we get

(1,0,0).

Miller indices are (100).

*******************

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).

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.

The reciprocals are (1,-1, )

The intercepts are x=1, y=-1 and z= (parallel to z

axis)

To show this plane in a

single unit cell, the

origin is moved along

the positive direction

of y axis by 1 unit.

(110)

Direction indices of a direction perpendicular to a crystal

plane are the same as the Miller indices of the plane.

Example:

the same Miller indices is given by:

hkl

a

2

h k l

used (hkil) called MillerBravais 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.

Basal Planes:

Intercepts a1 =

a2 =

a3 =

c=1

(hkil) = (0001)

Prism Planes :

For plane ABCD,

Intercepts a1 = 1

a2 =

a3 = -1

c=

(hkil) = (1010)

Indicated by 4 indices [uvtw].

u,v,t and w are lattice vectors in a1, a2, a3 and c directions

respectively.

Example:

For a1, a2, a3 directions, the direction indices are

[ 2 1 1 0], [1 2 1 0] and [ 1 1 2 0] respectively.

Both FCC and HCP are close packed and

have APF 0.74.

FCC crystal is close packed in (111) plane

while HCP is close packed in (0001) plane.

Plane A

a void

b void

Consider a layer

of atoms (Plane A)

Another layer (plane B)

of atoms is placed in a

void of plane A

Third layer of atoms placed

in b voids of plane B. (Identical

to plane A.)

HCP crystal.

Plane A

Plane B

a void

b void

in a voids of plane B. Resulting

In 3rd Plane C.

FCC crystal.

Plane A

Plane B

Plane A

Plane B

Plane A

Plane C

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

912C

-273C

Iron

BCC

1394C 1539C

Iron

FCC

Iron

BCC

Information about crystal structure can be obtained using

x-rays.

The x-rays used are about the same wavelength (0.050.25 nm) as the distance between crystal lattice planes.

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

X-Ray Diffraction

Crystal planes of target metal act as mirrors reflecting

X-ray beam.

If rays leaving a set of planes

are out of phase (as in case

of arbitrary angle of incidence)

no reinforced beam is

produced.

If rays leaving are in phase,

reinforced beams are

produced.

Powdered specimens are used for X-ray diffraction analysis

since the random orientation facilitates different angles of

incidence.

A radiation counter detects the angle and intensity of the

diffracted beam.

Unknown

metal

Crystallographic

Analysis

sin 2 A

0.75

2

sin B

FCC

crystal

Structure

sin 2 A

0.5

2

sin B

BCC

crystal

Structure

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.

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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