EME1166 MATERIALS SCIENCE

Chapter 2
Crystalline And Noncrystalline
Structures

Chapter 2 - 1
 2.1 INTRODUCTION
Ø Properties of some materials are directly related to their crystal
structures
Ø Example; magnesium, which has a certain crystal structure,
is more brittle than gold, which has a different crystal
structure.
Ø There are also significant differences in material properties between
the crystalline and noncrystalline materials which have the
same chemical composition
Ø Example; noncrystalline ceramics are normally optically
transparent; where else for the same composition ceramic
but in crystalline form, tends to be translucent/opaque
Ø This chapter discusses:
1. Concepts of crystallinity and non crystallinity
2. Crystal structure concepts
3. Single crystals, polycrystalline materials and noncrystalline
materials
4. X-ray diffraction techniques to determine crystal structures
–
Chapter 2 - 2
 2.2 CRYSTAL STRUCTURES
2.2.1 FUNDAMENTAL CONCEPTS
Ø Solids materials can be classified according to the
regularity with which the atoms or ions are arranged with
respect to another
Ø A crystalline material is a material where the atoms are
arranged in a repeating array over large atomic
distances.
Ø Upon solidification. The atoms will position
themselves in a repetitive three-dimensional
pattern; where each atom is bonded to its nearest
neighbor.
Ø Examples: all metals, many ceramic materials and
certain polymers.
Ø Noncrystalline or amorphous materials are materials that
do not crystallize since long-range atomic order is absent.
Ø Some of the properties of crystalline materials depend on
the crystal structure of the material; which is how the
atoms, ions or molecules are spatially arranged.
Ø There are many different crystal structures; from the relatively
Chapter 2 - 3
simple structures for metals to complex structures for
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling

"Amorphous" = Noncrystalline noncrystalline SiO2

Chapter 2 - 4
Ø ATOMIC HARD-SPHERE MODEL
Ø The model/theory where the atoms (ions) described in
crystalline structures are assumed to solid spheres
having well-defined diameters.
Ø The spheres represent nearest-neighbor atoms which
touch one another.
Ø Below figure shows the hard-sphere model for the
atomic arrangement found in some common
elemental metals. All atoms are identical in the
example.
Ø
Ø
Ø
Ø
Ø
Ø
Ø
Ø
Ø Lattice is used to describe the three-dimensional
array of points coinciding with atom positions
(sphere centers) Chapter 2 - 5
 2.2.2 UNIT CELLS
Ø In a crystalline solid, small groups of atoms form a repetitive pattern.
Ø The crystalline structure is subdivided into small repeat entities called
unit cells.
Ø For most crystal structures, unit cells are parallelepipeds or prisms
having three sets of parallel faces.
Ø The unit cell represents the symmetry of the crystal structure.
Ø Therefore all the atom positions in the crystal may be generated by
translations of the unit cell integral distances along each of its
edges.
Ø The unit cell is the basic structural unit or building block of the crystal
structure.
Ø Furthermore, more than a single unit cell may be chosen for a
particular crystal structure; however, we generally will use the unit
cell which has the highest level of geometrical symmetry.
Ø

Chapter 2 - 6
 2.2.3 METALLIC CRYSTAL
STRUCTURES
Ø Atomic bonding is metallic and nondirectional in nature; therefore
there are minimal restrictions to the number and position of
nearest-neighbors atoms.
Ø As a result, for most metallic crystal structures, there are
relatively large numbers of nearest neighbors and dense
atomic packings.
Ø For metals, based on the atomic hard-sphere model, each sphere
represents an ion core.
Ø Coordination number - the number of atomic or ionic nearest
neighbors.
Ø For metals, each atom has the same number of nearest-
neighbors or touching atoms; which is the coordination
number.
Ø Atomic Packing Factor (APF) is the sum of the sphere volumes of
all atoms within a unit cell (explained further in next SLIDE).
Ø There are three simple structures found for most of the common
metals:
i. Face-centered cubic
ii. Body-centered cubic Chapter 2 - 7
 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
volume
atoms atom
a 4
unit cell 1 π (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
Chapter 2 - 8
i. Face-Centered Cubic Crystal Structure
Ø Face-centered cubic (FCC) crystal structure found for many metals
has a unit cell of cubic geometry, with atoms located at each of
the corners and the centers of all the cube faces.
Ø Examples of metals having
FCC structure are chromium,

iron and tungsten.

Ø
Ø

Chapter 2 - 9
Ø The spheres (ion cores) in Figure (c) from the previous slide, touch
one another across a face diagonal.
Ø The cube edge length is a.
Ø Atomic radius R. a = 2R 2
Ø Corner and face positions are really equivalent – translation of the
cube corner from an original corner atom to the center of a face
atom will not alter the cell structure
Ø In the FCC crystal structure,
Ø each corner atom is shared among eight unit cells
Ø Each face-centered atom is shared by two unit cells.
Ø The coordination number for FCC is 12. Referring to Figure (a) in
the previous slide,
Ø the front face atom is in contact with four corner nearest-
neighbor atoms surrounding it
Ø four face atoms in contact from behind
Ø another four equivalent face atoms from the next unit cell to
the front (not shown)
Ø FCC has an APF of 0.74, which is the maximum packing possible for
spheres all having the same diameter.
Ø Metals have relatively large APF in order to maximize the shielding
provided by the free electron clouds.
Chapter 2 - 10
 Atomic Packing Factor: FCC
• APF for a face-centered cubic structure = 0.74
maximum achievable APF
Close-packed directions:
length = 4R = 2 a
2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister & atoms volume
Rethwisch 8e. 4
unit cell 4 π ( 2a/4) 3 atom
3
APF =
volume
a3
unit cell
Chapter 2 - 11
ii. Body-Centered Cubic Crystal Structure
Ø BCC also has a cubic unit cell with atoms located at all eight
corners and a single atom at the cubic center.
Ø Center and corner atoms touch another along cube diagonals, and
unit cell length a and atomic radius R are related through
Ø
4R
a=



3


Chapter 2 - 12
Ø Examples of metals having BCC crystal structure are chromium, iron
and tungsten.
Ø Two atoms are associated with each BCC cell
Ø Equivalent of one atom from eight corners (each of which
is shared among eight unit cells)
Ø Single center atom which is wholly contained within the cell.
Ø Corner and center atom positions are equivalent.
Ø Coordination number for BCC crystal structure is 8.
Ø Each center atom has as nearest neighbors its eight corner
atoms
Ø The APF is 0.68 only.


Chapter 2 - 13
 Atomic Packing Factor: BCC
• APF for a body-centered cubic structure = 0.68
3a

2a

Close-packed directions:
Adapted from R length = 4R = 3 a
Fig. 3.2(a), Callister &
Rethwisch 8e.
a
atoms volume
4 3
unit cell 2 π ( 3a/4) atom
3
APF =
volume
a3
unit cell Chapter 2 - 14
 iii. Hexagonal Close-packed Crystal
Structure
Ø FCC and BCC had unit cells with cubic symmetry. For HCP crystal
structure, the unit cell is hexagonal.
Ø Figure (a) shows a reduced-sphere unit cell and (b) shows an
assemblage of several HCP unit cells.
Ø The top and bottom faces of the unit cell consists of six atoms that
form regular hexagons and surround a single atom in the center
Ø Another plane provides additional three atoms to this unit cell is
positioned between the top and bottom planes.
Ø


Chapter 2 - 15
Ø The atoms in this midplane have as nearest neighbors atoms in both
of the adjacent two planes
Ø The equivalent of six atoms is contained in each of the unit cell
Ø One-sixth of each of the 12 top and bottom face corner
atoms
Ø One-half of each of the 2 center face atoms
Ø All 3 midplane interior atoms
Ø The ratio of the long (c) and short (a) unit cell dimensions should
ideally be 1.633.
Ø The coordination number for HCP crystal structure is also 12.
Ø The APF for HCP is also the same as for FCC; which is 0.74.
Ø Examples of metals having HCP crystal structure are cadmium,
magnesium, titanium and zinc.


Chapter 2 - 16
 FCC Stacking Sequence
• ABCABC... Stacking Sequence
• 2D Projection
B B
C
A
A sites B B B
C C
B sites B B
C sites

A
• FCC Unit Cell B
C

Chapter 2 - 17
 Hexagonal Close-Packed Structure
(HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection

A sites Top layer

c
B sites Middle layer

A sites Bottom layer

a Adapted from Fig. 3.3(a),
Callister & Rethwisch 8e.

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633 Chapter 2 - 18
 2.2.4 DENSITY COMPUTATIONS
ØThe theoretical density of the metallic solid can be calculated if the
crystal structure is known.

Mass of Atoms in Unit Cell

Density =  = Total Volume of Unit Cell

nA
 =
VC NA

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
Chapter 2 - 19
 •

• Ex: Cr (BCC)
 A = 52.00 g/mol
 R = 0.125 nm
 n = 2 atoms/unit cell

R
Adapted from a a = 4R/ 3 = 0.2887 nm
Fig. 3.2(a), Callister &
Rethwisch 8e.
atoms
g
unit cell 2 52.00  = 7.18 g/cm3
mol theoretical
= ρ actual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol Chapter 2 - 20
 Densities of Material Classes
In general Graphite/
ρ metals > ρ ceramics >ρ polymers Metals/
Alloys
Ceramics/ Polymers
Composites/
fibers
Semicond
30
Why? Platinum
B ased on data in Table B1, Callister
20 Gold, W *GFRE, CFRE, & AFRE are Glass,
Metals have: Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
10 Silver, Mo
(metallic bonding) Cu,Ni
in an epoxy matrix).
Steels
• often large atomic masses Tin, Zinc
Zirconia
5
Ceramics have:
ρ (g/cm3 )
Titanium
4 Al oxide
• less dense packing 3
Diamond
Si nitride
• often lighter elements Aluminum Glass -soda
Concrete
Glass fibers
Silicon PTFE GFRE*
2
Polymers have: Magnesium Graphite
Silicone
Carbon fibers
CFRE*
PVC Aramid fibers
• low packing density PET AFRE*
1 PC
(often amorphous) HDPE, PS
PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have: 0.4
Wood

• intermediate values 0.3

Data from Table B.1, Callister & Rethwisch, 8e.
Chapter 2 - 21
 2.2.5 POLYMORPHISM AND
ALLOTROPY
ØSome metals and non metals may have more than one crystal
structure. This phenomenon is called polymorphism.
ØWhen found in elemental solids, it is called allotropy
ØThe prevailing crystal structure depends on both the temperature and
external pressure.
ØExample:
ØCarbon:
ØGraphite is the stable polymorph in ambient condition
ØDiamond is formed at extremely high pressures
ØPure iron:
ØBCC crystal structure at room temperature
ØFCC crystal structure at 912°C
ØModification of the density and other physical properties normally
accompanies a polymorph transformation

Chapter 2 - 22