Adama Science and Technology

University
School of Mechanical and Chemical
Engineering

Introduction to Engineering Materials

The Structure of Crystalline Solids

By :Belete K.
 Learning Objective

On completion of this topic you will be able to understand:

 Unit cell
 Crystal structure of metals: FCC, BCC and HCP
 Atomic packing factor (APF)
 Theoretical densities of metals
 Polymorphism and Allotropy
 Crystal system and lattice parameter
 Crystallographic points, directions and planes
 Linear and planer density
 Single crystal and polycrystalline
 Crystalline and non-crystalline

Notice: (Optional reading) this part may not covered during the lecture, if so not tested
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 Introduction

 The properties of some materials are directly related to their crystal

structures.

 Significant property differences exist between crystalline and

noncrystalline materials having the same composition.
-- Dense, ordered packed structures tend to have lower energies.

 In the processing – structure – properties – performance scheme,

this relationship is very important especially for crystalline solids

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 Crystal structures

 Solid materials may be classified according to the regularity with

which atoms or ions are arranged with respect to one another.

 A crystalline material is one in which the atoms are arranged in a

repeating or periodic array over large atomic distances; that is,
• Long-range order exists, this can be achieved upon solidification,
• The atoms will position themselves in a repetitive 3-D pattern,
• Atom is bonded to its nearest neighbor atoms.

 All metals, many ceramic and certain polymers form crystalline

structures under normal solidification conditions.

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 Cont’d
Solids

Amorphous Crystalline
 Lacks symmetric arrangement of  Atoms are arranged in a repetitive
atoms, show a short ranged order three dimensional pattern, will
exhibit long range order
 Occurs for –complex structures
– rapid cooling  Typical of –metals, many ceramics
and some polymers

SiO2
SiO2 5
 Cont’d
 Some of the properties of crystalline solids depend on the crystal
structure of the material, the manner in which atoms, ions, or
molecules are arranged.

 When describing crystalline structures, it is

useful to consider atoms as being hard
spheres with well-defined radii. In this
hard-sphere model, the shortest distance hard-sphere model
between two like atoms is one diameter of
the hard sphere.

 We can also consider crystalline structure as

a lattice means a three-dimensional array of
points coinciding with atom positions (or
sphere centers).

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 Unit cell
 A unit cell is a structural unit or building block that can describe the
crystal structure. Repetition of the unit cell generates the entire crystal.

 Thus, in describing crystal structures, it is often convenient to

subdivide the structure into small repeat entities (unit cells).

 Different choices of unit cells possible, we will consider

parallelepiped unit cell with highest level of symmetry

• unit cell is smallest region in space, when

repeated, completely describe the crystal
structure
• its geometry is defined in terms of 6 lattice
parameters:
3 edges length (a, b, c)
3 interaxial angles
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 Metallic Crystal Structure

 Metals usually polycrystalline solids, is comprised of a collection of

many single crystals
amorphous metal possible by rapid cooling

 Atomic bonding in metals are metallic and thus non-directional 

large number of nearest neighbors and dense atomic packing

 Atom (hard sphere) radius, R:

defined by ion core radius: ~0.1 - 0.2 nm

 Most common unit cells

Faced-centered cubic (FCC)
Body-centered cubic (BCC)
Hexagonal close-packed (HCP).

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12/11/17
 Cont’d

Characteristics of metallic structure:

 Tend to be densely packed, (planes with highest density of atoms)

 Have several reasons for dense packing,
• Typically, only one 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.
• Electron cloud shields cores from each other
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 Have the simplest crystal structures.
 Face centered cubic (FCC) Crystal Structure
 Many metals have a cubic unit cell geometry, with atoms located at corners
and on centers of faces of the cubic
 Some family of metals having FFC crystal structure, such as Cu, Al, Ag, Au,
Pb, Ni, Pt
 Each corner atom is shared among eight unit cells, whereas a face-centered
atom belongs to only two

a b

two representations of the FCC unit cell c

Figure 3.1 For the FCC cubic crystal structure, (a) a hard sphere unit cell representation,
(b) a reduced-sphere unit cell, and (c) an aggregate of many atoms.
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 Cont’d

a
 Hard spheres touch along face diagonal
 the cube edge length, a= 22R
 The coordination number, CN = number of closest neighbors =
number of touching atoms, CN = 12
 Number of atoms per unit cell, n = 4.
FCC unit cell:
• 6 face atoms shared by two cells: 6 x 1/2 = 3
• 8 corner atoms shared by eight cells: 8 x 1/8 = 1
 Atomic packing factor, APF

Volume of atoms in unit cell

APF =
Volume of unit cell
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 Cont’d
• ABCABC... Stacking Sequence
• 2D Projection

Fig. Close-packed stacking sequence for face-centered cubic.

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Cont’d

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 Body centered cubic (BCC) Crystal Structure
 Another common metallic crystal structure also has a cubic unit cell,
with atoms located at each corners and one atom at the center of the
cube.
 Some family of metals having BCC crystal structure are Cr, W, Fe (),
Ta, Mo
 Center and corner atoms touch one another along cube diagonals

b
a c

Figure 3.2 For the BCC cubic crystal structure, (a) a hard sphere unit cell representation,
(b) a reduced-sphere unit cell, and (c) an aggregate of many atoms. 19
 Cont’d

 Hard spheres touch along cubic diagonal

 the cube edge length, a= 4R/3
 The coordination number, CN = 8
 Number of atoms per unit cell, n = 2.
BCC unit cell:
• Center atom not shared: 1x1 = 1
• 8 corner atoms shared by eight cells:
2a R 8 x 1/8 = 1
a  Atomic packing factor, APF = 0.68
a

 Corner and center atoms are equivalent

 The coordination number for the BCC crystal structure is 8, whereas

FCC has 12 CN. Thus, the CN of BCC is lower than FCC, it is also true
the atomic packing factor BCC (0.68) lower than FCC (0.74).

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 Cont’d
• APF for a body-centered cubic structure = 0.68

3a

2a
Close-packed directions:
R
Adapted from a length = 4R = 3a
Fig. 3.2(a), Callister &
Rethwisch 8e.

atoms
4 volume
unit cell 2  ( 3 a/4 ) 3
3 atom
APF =
volume
a3
= 0.68 unit cell
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 Hexagonal closed-packed (HCP) Crystal Structure
 HCP has a hexagonal unit cell, in which the top and bottom faces of the
unit cell consist of six atoms form regular hexagons surrounding one
atom in the center.
 And another plane that provides three additional atoms to the unit cell
is situated halfway between the top and bottom planes.
-- atoms in this midplane have as nearest neighbors atoms (close-packed plane)
 Some family of metals having HCP crystal structure are: cadmium,
magnesium, titanium, and zinc

Figure 3.3 For the hcp crystal structure, (a) a reduced-sphere unit cell (a and c represent the short and
long edge lengths, respectively), and (b) an aggregate of many atoms. 22
 Cont’d
 Unit cell has two lattice parameters a and c.
ideal ratio c/a = 1.633
 The coordination number, CN = 12 (same as in FCC)

 Number of atoms per unit cell, n = 6.

 3 mid-plane atoms not shared: 3 x 1 = 3
 12 hexagonal corner atoms shared by 6 unit cells:
12 x 1/6 = 2
 2 top/bottom plane center atoms shared by 2 unit cells:
2 x 1/2 = 1
 Atomic packing factor, APF = 0.74 (same as in FCC)

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 Cont’d

• ABAB... Stacking Sequence

• 2D Projection

Fig. Close-packed plane stacking sequence for hexagonal closed packing.

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 Theoretical Density, 

Mass of Atoms in Unit Cell

Density =  =
Total Volume of Unit Cell
nA
 =
VC N A

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadro’s number
= 6.022 x 1023 atoms/mol
Atoms in unit cell, n = 2 (BCC); 4 (FCC); 6 (HCP)

Volume of the cell, Vc = a3 (FCC and BCC)

a = 22R (FCC); a = 4R/3 (BCC)
where R is the atomic radius

Atomic weight and atomic radius values of elements are found in the table.c
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 Chromium has an atomic radius of 0.125 nm, an BCC crystal structure,
and an atomic weight of 52.0 g/mol. Compute its theoretical density and
compare the answer with its measured density.

Cr has a BCC crystal structure

A = 52.0 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
R a = 4R/ 3 = 0.2887 nm (1nm=10-7 cm)
a

atoms
g
unit cell 2 52.00
mol theoretical = 7.18 g/cm3

= actual = 7.19 g/cm3

a3 6.022 x 1023
volume atoms

unit cell mol

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 Polymorphism and Allotropy
 Polymorphism, in materials science, is the ability of a solid material to
exist in more than one crystalline form under different conditions of
temperature and pressure.
 Polymorphism can potentially be found in any crystalline material
including polymers, minerals, and metals, and is related to allotropy,
which refers to elemental solids.
Carbon: three crystalline forms Iron system: three crystalline forms
liquid
 graphite: layered structure – parallel
1538ºC
hexagonal arrays of carbon atoms
BCC -Fe
 diamond: tetrahedral carbon –
1394ºC
hardest material known
FCC -Fe
 Fullerenes: spherical cluster of 60
carbon atoms, C60 912ºC
BCC -Fe
 Carbon nanotubes: sheet of graphite
rolled into a tube, 27
 Single Crystals and Polycrystalline Materials
 Single crystal: the periodic and repeated
arrangement of toms is perfect and extends
throughout the entirety of the specimen
without interruption.
 Single crystals are normally difficult to
grow, because the environment must be
carefully controlled.

 Polycrystalline material: comprised of

many small crystals or grains. The grains
have different crystallographic orientation.
 There exist atomic mismatch within the
regions where grains meet. These regions
are called grain boundaries.

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 Cont’d
 The small grains grow by the successive addition from the surrounding
liquid of atoms to the structure of each.

(a) (b)

(c) (d)

Various stages in the solidification: (a) Small crystallite nuclei. (b) Growth of the crystallites. (c)
Upon completion of solidification, grains having irregular shapes have formed. (d) The grain
structure as it would appear under the microscope.
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 Anisotropy
 Different directions in a crystal have different packing. For instance:
atoms along the edge of FCC unit cell are more separated than along the
face diagonal.

 This causes anisotropy in crystal properties, for instance, the

deformation depends on direction in which a stress is applied.

 In some polycrystalline materials, grain orientations are random, so bulk

material properties are isotropic

 Some polycrystalline materials have grains with preferred orientations

(texture): material exhibits anisotropic properties

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 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.

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 Cont’d

 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).

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 Examples
Below are listed the atomic weight, density, and atomic radius for three
hypothetical alloys. For each determine whether its crystal structure is
FCC, BCC, or simple cubic and then justify your determination.

Answer
we need, by trial and error, to calculate the density using the equation and
compare it to the value cited in the problem

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For SC, BCC, and FCC crystal structures
n = 1 (SC) 2 (BCC) 4 (FCC)
a = 2R(SC) 4R/3 (BCC) 22R (FCC)
Volume of the cell, Vc = a3 (SC, FCC and BCC)

For alloy A, Let us calculate  assuming a BCC crystal structure

Therefore, its crystal structure is a BCC.

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For SC, BCC, and FCC crystal structures
n = 1 (SC) 2 (BCC) 4 (FCC)
a = 2R(SC) 4R/3 (BCC) 22R (FCC)

Volume of the cell, Vc = a3 (SC, FCC and BCC)

For alloy A, Let us calculate  assuming a simple cubic crystal structure

Therefore, its crystal structure is simple cubic. 35

For SC, BCC, and FCC crystal structures
n = 1 (SC) 2 (BCC) 4 (FCC)
a = 2R(SC) 4R/3 (BCC) 22R (FCC)

Volume of the cell, Vc = a3 (SC, FCC and BCC)

For alloy A, Let us calculate  assuming a BCC crystal structure

Therefore, its crystal structure is a BCC.

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The unit cell for uranium has orthorhombic symmetry, with a, b, and c
lattice parameters of 0.286, 0.587, and 0.495 nm, respectively. If its
density, atomic weight, and atomic radius are 19.05 g/cm3, 238.03
g/mol, and 0.1385 nm, respectively, compute the atomic packing factor.

Answer
In order to determine the APF for U, we need to compute both the unit cell
volume (Vc) and the total sphere volume (Vs)

In which the total sphere volume is a product of number of spheres in unit cell and
volume of a single sphere

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The value of n may be calculated as:

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Below is a unit cell for a hypothetical metal.
To which crystal system does this unit cell belong?
What would this crystal structure be called?
Calculate the density of the material, given that its atomic weight is 141 g/mol.

Answer
The unit cell belongs to the tetragonal crystal system since a =b ≠ c and

The crystal structure would be called body-centered tetragonal.
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As with BCC, n = 2 atoms/unit cell. Also, for this unit cell

the density is equal to

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