Crystal Structure

SUBCONTENT:
Crystal structures.
Fundamental Concept Unit cell Material crystal system Efficiency of atomic packing Polymorphism and allotropic transformation Crystallography plane and direction

LEARNING OBJECTIVE
You should be able:

Differentiate between crystalline, noncrystalline, single crystal and polycrsytal.

Derive the relationship between unit cell edge length and atomic radius for face centered and body centered cubic Compute density and atomic packing factors for crystal Specify the miller indices for crystallography plane and direction Relate the crystal structure with material properties

Fundamental concept: Classification of solid materials

Solid materials

Crystalline Material

Noncrsytalline material (Amorphous)

Single Crystal

polycrystal

Fundamental concept: Crystalline material

Crystalline material- atoms, molecules or ion packed in a regularly ordered, repeating pattern, extending in 3 spatial dimension. Properties of crystalline materials depend on the crystal structure

Crystal structure
is a unique arrangement of atoms in a crystal. composed of a unit cell

 Formation crystal structure depends

Chemistry of fluid Condition under which is being solidified Ambient pressure

Crystallization-Process forming crystalline structures.

Crystalline materials... atoms pack in periodic, 3D arrays typical of: -metals -many ceramics -some polymers

crystalline SiO2

Noncrystalline materials... atoms have no periodic packing occurs for: -complex structures -rapid cooling
noncrystalline SiO2

"Amorphous" = Noncrystalline

Amorphous

Crystal

No recognizable longrange order

Atoms are disordered

No lattice

Entire solid is made up of atoms in an orderly array

All atoms arranged on a common lattice

Polycrystalline

Completely ordered In segments

Different lattice orientation for each grain

SINGLE VS POLYCRYSTALS
Single Crystals
-Properties vary with direction: anisotropic. -Example: the modulus of elasticity (E) in BCC iron:

Polycrystals
-Properties may/may not vary with direction. -If grains are randomly oriented: isotropic.
(Epoly iron = 210 GPa) 200 mm

-If grains are textured, anisotropic.

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 Some engineering applications require single crystals:

--diamond single crystals for abrasives --turbine blades

Most engineering materials are polycrystals.

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grain

Unit cell - smallest structural unit or building block that can describe the crystal structure. Repetition of the unit cell generates the entire crystal. Primitive unit cell- smallest possible unit cell one can construct. Lattice parameters- spacing between unit cells in various direction.

Concept test
which one is unit cell

1.5 CRYSTAL SYSTEM AND CRYSTALLOGRAPHY

Crystal System
The crystal systems are a grouping of crystal structures that used to describe their lattice. Each crystal system consists of a set of three axes in a particular geometrical arrangement. There are only 7 crystal systems that atoms can pack together to produce an infinite 3D space lattice : cubic, hexagonal, tetragonal, rhombodhedral, orthorhombic, monoclinic, triclinic. By adding additional lattice point to 7 basic crystal systems form 14 Bravais lattice. However, most metals exhibit one of three crystal structure BCC, FCC & HCP The atomic arrangements in the different crystal systems
affect

mechanical behavior.

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BRAVAIS LATTICE
BRAVAIS LATTICE - describe the geometric arrangement of the lattice points and the translational symmetry of the crystal.

Figure : The 14 Bravais conventional unit cells are grouped according to crystal system. The dots indicate lattice points that when allocated on faces or at corners, are shared by other identical lattice unit cells.

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CRYSTAL STRUCTURE OF METALS

SIMPLE CUBIC (SC)

FACE CENTRED CUBIC (FCC)

BODY CENTRED CUBIC (BCC)

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HEXAGONAL CLOSED PACK (HCP)

CRYSTAL STRUCTURE OF METALS

Most metals (about 90%) crystallize upon solidification into three densely packed crystal structures as shown below (BCC,FCC,HCP). However, simple cubic crystals are rather rare which can be viewed as simple cubic grid.
Types of crystal structure Simple cubic Cube where atoms lie on a grid. No. of atom at corner = 8x1/8 = 1 atom Total no. of atom in 1unit cell = 1 atom Examples Manganese

Body centered cubic (BCC)

*Lower ductility but a higher yield strength than FCC metals.

Cube with an atom at each corner and one in the center. No. of atom at corner = 8x1/8 = 1 atom No. of atom at center = 1 atom Total no. of atom in 1unit cell = 2 atoms

Chromium, Tungsten(W), Molybdenum, Vanadium(V)

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Types of crystal structure

Examples

Face centered cubic (FCC)

* Atoms for FCC are more densely packed than BCC.

Cube with an atom at each corner, one in the center and one in the center of each side of the cube. No. of atom at corner = 8x1/8 = 1 atom No. of atom at face = 6x1/2 = 3 atom Total no. of atom in 1unit cell = 4 atoms

Aluminum, Nickel, Copper, Gold, Lead, Platinum

Hexagonal close-packed (HCP)

Because of the spacing of the lattice structure, rows of atoms do not easily slide over one another in HCP --- have lower plasticity and ductility than cubic structures. *Atoms are as densely packed as in the FCC unit cell. Difference--Arrangement of the atoms

Hexagon with a reference atom that is surrounded by 12 atoms that are equal distance from the reference atom. No. of atom at corner for top face = 6x1/6 = 1 atom No. of atom at corner for bottom face = 6x1/6 = 1 atom No. of atom at centre = 3 atoms No. of atom at centre for top face = 1x1/2 = 1/2 atom No. of atom at centre for bottom face = 1x1/2 = 1/2 atom Total no. of atom in 1unit cell = 6 atoms

Magnesium, Beryllium, Zinc, Cadmium, Titanium, Zirconium (Zr)

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Summary
a (lattice constant) Atoms/unit cell Coordination No. Examples

Simple cubic

a = 2R

CsCl

BCC

a = 4R/3

Many metals: -Fe, Cr, Mo, W

Many metals : Ag, Au, Cu, Pt

FCC

a = 4R/2 or a = 2R2

12

HCP

a = 2R c = 1.633 a

12

Many metals : Co, Mg, Ti, Zn

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ATOMIC PACKING FACTOR

Atomic packing factor (APF) is defined as the efficiency of atomic arrangement in a unit cell. It is used to determine the most dense arrangement of atoms. It is because how the atoms are arranged determines the properties of the particular crystal. It is represented mathematically by :

APF = no. of atom/unit cell, n x volume of atoms in the unit cell, (Vs) volume of the unit cell, (Vc)

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EXAMPLE
Calculate the APF for Simple Cubic (SC)?

APF for a simple cubic structure = 0.52

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EXERCISE
Calculate the APF for BCC and FCC ?

a) BCC

b) FCC

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DENSITY COMPUTATIONS
A knowledge of the crystal structure of a metallic solid permits computation of its density through the relationship :
=
Where
n = number of atoms associated with each unit cell A = atomic weight Vc = volume of the unit cell NA = Avogadros number (6.023 x 1023 atoms/mol)

nA Vc NA

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EXAMPLE
Calculate the density for nickel (simple cubic structure). Note that the unit cell edge length (a) for nickel is 0.3524 nm.
The volume (V) of the unit cell is equal to the cell-edge length (a) cubed. V = a3 = (0.3524 nm)3 = 0.04376 nm3

Since there are 109 nm in a meter and 100 cm in a meter, there must be 107 nm in a cm. 109 x 1m = 107 nm/cm 1 m 100 cm
We can therefore convert the volume of the unit cell to cm3 as follows. 4.376 x 10-2 nm3 x [1 cm ]3 = 4.376 x 10-23 cm 3 107 nm The mass of a nickel atom can be calculated from the atomic weight of this metal and Avogadros number. 58.69g Ni x 1 mol = 9.746 x 10-23 g/atom 1 mol 6.023 x 1023 atoms
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1(9.746 x 10-23 g/unit cell) = 2.23 g/cm3 4.376 x 10-23 cm 3/unit cell

EXERCISE
Copper has an atomic radius of 0.128 nm, FCC crystal structure and an atomic weight of 63.5 g/mol. Compute its density and compare the answer with its measured density.
Element Symbo l Atomic Number Atomic weight (amu) 52.00 58.93 63.55
Density of solid, 20oC (g/cm3)

Crystal structure, 20oC

Atomic radius (nm) 0.125 0.125 0.128

Chromium Cobalt Copper Solution :

Cr Co Cu

24 27 29

7.19 8.9 8.94

BCC HCP FCC

nA Vc NA

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Polymorphism allotropic transformation

the ability of a solid material to exist in more than one form or crystal structure. Example: Carbon and iron

Allotropy: Carbon

Graphite

Diamond

ALLOTROPIC TRANSFORMATION
A material that can exist in more than one lattice structure (depending on temperature-heating@cooling) allotropic. An allotropic material is able to exist in two or more forms having various properties without change in chemical composition. E.g : When metals are heated slowly from room temperature to their melting points (liquid state), most metals (Cu,Al) do not change their crystalline lattice structure before becoming a liquid. However, this in not the case with steel, Ti, iron and many iron alloys.

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Upon heating, pure iron experiences two changes in crystal structure.

At room temperature, it exists as ferrite,or iron (BCC).

When we heat it to 912C, it experiences an allotropic transformation to austenite,or iron (FCC). At 1394C, austenite reverts back to a BCC phase called ferrite.

Allotropy of iron(Fe)
BCC (delta iron-high T) FCC (austenite-moderate T) BCC (alfa iron-low T)

1538C 1394C

912C 768C

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MILLER INDICES
Miller indices is used to label the planes and directions of atoms in a crystal.

Why Miller indices is important? To determine the shapes of single crystals, the interpretation of X-ray diffraction patterns and the movement of a dislocation , which may determine the mechanical properties of the material.

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MILLER INDICES OF A PLANE

How to determine crystal plane indices?
i) Determine the points at which a given crystal plane intersects the three axes, say at (a,0,0),(0,b,0), and (0,0,c). If the plane is parallel an axis, it is given an intersection .
ii) Take the reciprocals of the three integers found in step (i).

iii) Label the plane (hkl). These three numbers are expressed as the smallest integers and negative quantities are indicated with an overbar,e.g : a.

Axis Interceptions Reciprocals Reduction (if necessary) Enclosed

(h

k
31

l)

Figure : Planes with different Miller indices in cubic crystals

EXAMPLE : CRYSTAL PLANE INDICES

Axis Interceptions Reciprocals Reduction (if necessary) Enclosed (2 1 2) X Y 1 1 Z

0 1

Axis
Interceptions Reciprocals Reduction (if necessary) Enclosed

X
1

Y
1

Z
1

0
(1 1
32

1)

Axis

Interceptions Reciprocals Reduction (if necessary) Enclosed

1 1

1 1

0
(1 1 0)

Axis Interceptions Reciprocals Reduction (if necessary) Enclosed

X 1 1

Z 2
5/6

(1

2)

Two numbers in one axes 33

Axis

Interceptions Reciprocals Reduction (if necessary)

1 1

Enclosed

(0

2)
Plane pass through origin

Axis

Interceptions Reciprocals Reduction (if necessary) Enclosed

1 1

0
(0 1 0)

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Determine the Miller Indices plane for the following figure below?
Axis
a)

Answer :
1

Intercepts

a) (121) b) (210) 1
1 0

Reciprocals
Reduction
(if necessary)

c) (111)

Enclosed

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b)

Answer : a) (121) b) (210)

0 1

Axis Intercepts Reciprocals Reduction

(if necessary)

c) (111)

Enclosed

c)

Answer :
1

Axis Intercepts

a) (121)

b) (210)
1

Reciprocals
Reduction
(if necessary)

c) (111)

c)

Enclosed

d)

Answer :
1

Axis Intercepts Reciprocals Reduction

(if necessary)

a) (121)

b) (210)
1

c) (111)

c)

Enclosed

Determine the Miller indices of a cubic crystal plane that intersects the position coordinates A (1, 1/4, 0), B (1, 1, 1/2) , C (3/4, 1, 1/4) and D (1/2, 1, 0) ?

Axis Intercepts Reciprocals Reduction

(if necessary)

Enclosed

Answer : ( 6 4 6 )

Draw the following Miller Indices plane.

a) ( 1 0 0 ) b) ( 0 0 1 )

c) ( 1 0 1 )
d) ( 1 1 0 ) e) ( 0 1 1 ) f) ( 2 2 1 ) g) ( 1 3 1 )

h) ( 0 1 0 )

MILLER INDICES OF A DIRECTION

How to determine crystal direction indices?
i) Determine the length of the vector projection on each of the three axes, based on .

ii) These three numbers are expressed as the smallest integers and negative quantities are indicated with an overbar. iii) Label the direction [hkl].
Axis Head (H) Tail (T) Head (H) Tail (T) Reduction (if necessary) Enclosed
* No reciprocal involved. 41

Figure : Examples of direction

X x2 x1 x2-x1 Y y2 y1 y2-y1 Z z2 z1 z2-z1

[h

l]

EXAMPLE : CRYSTAL DIRECTION INDICES

Axis Head (H) Tail (T) Projection (H-T) Reduction (if necessary) * 2 Enclosed X 1 0 1 2 [2 Y 0 0 0 0 0 Z

1 1]

0 1 1

Axis Head (H) Tail (T) Projection (H-T) Enclosed

X 1 0 1 [1

Y 0 1 1 1

1
0 0 0 0]

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Determine the Miller Indices direction for the following figure below?
a)
1

Axis
Answer : a) (121) b) (210) 1
1 0

Head Tail Projection

(Head Tail)

c) (111)

c)

Reduction
(if necessary)

Enclosed

b)

Answer :

Axis

a) (121)
1 b) (210) 1 0

Head
Tail

c) (111)

Projection
(Head Tail)

Reduction
(if necessary)

Enclosed

c)
1

Answer : a) (121) b) (210) 1

0

Axis

Head
Tail

Projection
(Head Tail)

c) (111)

c)

Reduction
(if necessary)

Enclosed

d)
1

Answer : a) (121) b) (210) 1

0

Axis

Head
Tail

Projection
(Head Tail)

c) (111)

c)

Reduction
(if necessary)

Enclosed

e)
1

Answer : a) (121) b) (210) 1

0

Axis

Head
Tail

Projection
(Head Tail)

c) (111)

c)

Reduction
(if necessary)

Enclosed

f)
1

Answer : a) (121) b) (210) 1

0

Axis

Head
Tail

Projection
(Head Tail)

c)

(111)

c)

Reduction
(if necessary)

Enclosed

Determine the direction indices of the cubic direction between the position coordinates TAIL (3/4, 0, 1/4) and HEAD (1/4, 1/2, 1/2)?

Axis Head Tail Projection

(Head Tail)

Reduction
(if necessary)

Enclosed
Answer : [ 2 2 1 ]

Determine the direction indices of the cubic direction between the position coordinates TAIL (1, 0, 1/2) and HEAD (0, 1, 1/3)?

Axis Head Tail Projection

(Head Tail)

Reduction
(if necessary)

Enclosed
Answer : [ 6 6 1 ]

Draw the following Miller Indices direction.

a) [ 1 0 0 ] b) [ 1 1 1 ] c) [ 1 1 0 ] d) [ 1 1 0 ]

e) [ 1 1 2 ]

NOTE (for plane and direction):

PLANE Make sure you enclosed your final answer in brackets () with no separating commas (hkl)

DIRECTION Make sure you enclosed your final answer in brackets () with no separating commas [hkl] FOR BOTH PLANE AND DIRECTION Negative number should be written as follows : -1 (WRONG)

1 (CORRECT)

Final answer for labeling the plane and direction should not have fraction number do a reduction.
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