Quiz of Chapter 2

1) Which of the following electron

configurations is for an inert gas?

2) What type(s) of bonding would be

expected for rubber?
(A) Ionic bonding
(B) Metallic bonding
(C) Covalent bonding with some van der
Waals bonding
(D) van der Waals bonding

MSE : Introduction to Materials Science Chapter 3, Structure of solids 1

 Chapter Outline
How do atoms arrange themselves to form solids?

• Fundamental concepts and language

• Unit cells
• Crystal structures
➢Face-centered cubic
➢Body-centered cubic
➢Hexagonal close-packed
• Close packed crystal structures
• Density computations
• Types of solids
Single crystal
Polycrystalline
Amorphous

MSE : Introduction to Materials Science Chapter 3, Structure of solids 2

 Types of Solids
Crystalline material: atoms self-organize in a periodic
array
Single crystal: atoms are in a repeating or periodic array
over the entire extent of the material
Polycrystalline material: comprised of many small
crystals or grains

Amorphous: disordered – lack of a systematic atomic

arrangement
Crystalline Amorphous

SiO2
MSE : Introduction to Materials Science Chapter 3, Structure of solids 3
 Crystal structures
Why do atoms assemble into ordered structures (crystals)?
Energy of interatomic bond

Interatomic distance
0

Let’s consider nondirectional

bonding (like in metals)

Energy of the crystal < Energy of the amorphous solid

MSE : Introduction to Materials Science Chapter 3, Structure of solids 4

 Crystal structure

To discuss crystalline structures it is useful to consider

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

2R
-hard-sphere model

We can also consider crystalline structure as a lattice of

points at atom/sphere centers.

MSE : Introduction to Materials Science Chapter 3, Structure of solids 5

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

Example: 2D honeycomb net can

be represented by translation of
two adjacent atoms that form a unit
cell for this 2D crystalline structure

Example of 3D crystalline structure:

Different choices of unit cells possible

MSE : Introduction to Materials Science Chapter 3, Structure of solids 6

 Metallic Crystal Structures

➢Metals are usually (poly) crystalline; although

formation of amorphous metals is possible by rapid
cooling

➢As we learned in Chapter 2, the atomic bonding in metals

is non-directional ⇒ no restriction on numbers or
positions of nearest-neighbor atoms ⇒ large number of
nearest neighbors and dense atomic packing

➢Atomic (hard sphere) radius, R, defined by ion core

radius - typically 0.1 - 0.2 nm

➢The most common types of unit cells are

• faced-centered cubic (FCC)
• body-centered cubic (BCC)
• hexagonal close-packed (HCP)

MSE : Introduction to Materials Science Chapter 3, Structure of solids 7

 Face-Centered Cubic (FCC) Crystal Structure (I)
➢Atoms are located at each of the corners and on the
centers of all the faces of cubic unit cell
➢Cu, Al, Ag, Au have this crystal structure

Two representations
of the FCC unit cell

MSE : Introduction to Materials Science Chapter 3, Structure of solids 8

 Face-Centered Cubic Crystal Structure (II)

a
➢ The hard spheres touch one another across a face
diagonal ⇒ the cube edge length, a= 2R√2
➢ The coordination number, CN = the number of closest
neighbors to which an atom is bonded = number of
touching atoms, CN = 12
➢ Number of atoms per unit cell, n = 4. (For an atom
that is shared with m adjacent unit cells, we only count a
fraction of the atom, 1/m). In FCC unit cell we have:
6face atoms shared by two cells: 6×1/2 =3
8corner atoms shared by eight cells: 8×1/8 = 1
� Atomic packing factor, APF = fraction of volume
occupied by hard spheres = (Sum of atomic
volumes)/(Volume of cell) = 0.74 (maximum possible)
MSE : Introduction to Materials Science Chapter 3, Structure of solids 9
 Face-Centered Cubic Crystal Structure (III)

Let’s calculate the atomic packing factor for FCC crystal

a = 2R 2
R
a
APF = (Sum of atomic volumes)/(Volume of unit cell)
4
Volume of 4 hard spheres in the unit cell: ×4πR 3
3
Volume of the unit cell: a 3 = 16 R 3 2
16 3 16 R 3
APF = πR 2= π 3 2 = 0.74
3
➢ FCC crystal has APF of 0.74 , the maximum packing for a
system equal-sized spheres ⇒ FCC is a close-packed
structure
➢ FCC can be represented by a stack of close-packed
planes (planes with highest density of atoms)

MSE : Introduction to Materials Science Chapter 3, Structure of solids 1

0
Body-Centered Cubic (BCC) Crystal Structure (I)
Atom at each corner and at center of cubic unit cell
Cr, α-Fe, Mo have this crystal structure

MSE : Introduction to Materials Science Chapter 3, Structure of solids 11

 Body-Centered Cubic Crystal Structure (II)

a
➢ The hard spheres touch one another along cube diagonal
⇒the cube edge length, a= 4R/√3
➢ The coordination number, CN = 8
➢ Number of atoms per unit cell, n = 2
Center atom (1) shared by no other cells: 1 x 1 1 =
8corner atoms shared by eight cells: 8 x 1/8 = 1

➢ Atomic packing factor, APF = 0.68

MSE : Introduction to Materials Science Chapter 3, Structure of solids 12

 Hexagonal Close-Packed Crystal Structure (I)

➢ HCP is one more common structure of metallic crystals

➢ Six atoms form regular hexagon, surrounding one atom
in center. Another plane is situated halfway up unit cell
(c-axis), with 3 additional atoms situated at interstices of
hexagonal (close-packed) planes
➢ Cd, Mg, Zn, Ti have this crystal structure

MSE : Introduction to Materials Science Chapter 3, Structure of solids 13

 Hexagonal Close-Packed Crystal Structure (II)

➢ 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
3mid-plane atoms shared by no other cells: 3 x 1 = 3
12hexagonal corner atoms shared by 6 cells: 12 x 1/6 = 2
2top/bottom plane center atoms shared by 2 cells: 2 x 1/2=1

➢ Atomic packing factor, APF = 0.74 (same as in FCC)

MSE : Introduction to Materials Science Chapter 3, Structure of solids 14

 Close-packed Structures (FCC and HCP)
➢ Both FCC and HCP crystal structures have atomic
packing factors of 0.74 (maximum possible value)
➢ Both FCC and HCP crystal structures may be generated
by the stacking of close-packed planes
➢ The difference between the two structures is in the
stacking sequence

HCP: ABABAB... FCC: ABCABCABC…

MSE : Introduction to Materials Science Chapter 3, Structure of solids 15

 FCC: Stacking Sequence ABCABCABC...

Third plane is placed above the “holes” of the first plane

not covered by the second plane

MSE : Introduction to Materials Science Chapter 3, Structure of solids 16

 HCP: Stacking Sequence ABABAB...

Third plane is placed directly above the first plane of atoms

MSE : Introduction to Materials Science Chapter 3, Structure of solids 17

 Atomic Radii and Crystal Structures for 16 Metals

MSE : Introduction to Materials Science Chapter 3, Structure of solids 18

 Density Computations

Since the entire crystal can be generated by the repetition

of the unit cell, the density of a crystalline material, ρ = the
density of the unit cell = (atoms in the unit cell, n ) ×(mass
of an atom, M) / (the volume of the cell, Vc)

Atoms in the unit cell, n = 2(BCC); 4 (FCC); 6 (HCP)

Mass of an atom, M = Atomic weight, A, in amu or (g/mol)

is given in the periodic table. To translate mass from amu
to grams we have to divide the atomic weight in amu by
the Avogadro number NA = 6.023 ×1023 atoms/mol

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

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

Thus, the formula for the density is: nA

ρ=
Vc N A

Atomic weight and atomic radius of many elements you

can find in the table at the back of the textbook front cover.

MSE : Introduction to Materials Science Chapter 3, Structure of solids 19

 Polymorphism and Allotropy
Some materials may exist in more than one crystal
structure, this is called polymorphism. If the material is an
elemental solid, it is called allotropy.
An example of allotropy is carbon, which can exist as
diamond, graphite, and amorphous carbon.

Pure, solid carbon occurs in three crystalline forms – diamond,

graphite; and large, hollow fullerenes. Two kinds of fullerenes
are shown here: buckyball and carbon nanotube.

MSE : Introduction to Materials Science Chapter 3, Structure of solids 20

 Single Crystals and Polycrystalline Materials

Single crystal: atoms are in a repeating or periodic array

over the entire extent of the material
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.

A garnet single crystal that was

found in Tongbei, Fujian Province,
China

Schematic diagrams of the various stages in the solidification of a polycrystalline

material; the square grids depict unit cells. (a) Small crystallite nuclei. (b) Growth of the
crystallites; the obstruction of some grains that are adjacent to one another is also shown.
(c) Upon completion of solidification, grains having irregular shapes have formed. (d)
The grain structure as it would appear under the microscope; dark lines are the grain
boundaries.

MSE : Introduction to Materials Science Chapter 3, Structure of solids 20

 Single Crystals and Polycrystalline Materials

Grain Boundary

Atomistic model of a nanocrystalline solid by Mo Li

MSE : Introduction to Materials Science Chapter 3, Structure of solids 20
 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 the properties of crystals, for instance, the
deformation depends on the 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), so properties are dominated by those
relevant to the texture orientation and the material exhibits
anisotropic properties

MSE : Introduction to Materials Science Chapter 3, Structure of solids 23

 Non-Crystalline (Amorphous) Solids

In amorphous solids, there is no long-range order. But

amorphous does not mean random, in many cases there is
some form of short-range order.

Schematic picture of
amorphous SiO2 structure

Amorphous structure from

simulations by E. H. Brandt

MSE : Introduction to Materials Science Chapter 3, Structure of solids 24

 Summary

Make sure you understand language and concepts:

➢ Allotropy
➢ Amorphous
➢ Anisotropy
➢ Atomic packing factor (APF)
➢ Body-centered cubic (BCC)
➢ Coordination number
➢ Crystal structure
➢ Crystalline
➢ Face-centered cubic (FCC)
➢ Grain
➢ Grain boundary
➢ Hexagonal close-packed (HCP)
➢ Isotropic
➢ Lattice parameter
➢ Non-crystalline
➢ Polycrystalline
➢ Polymorphism
➢ Single crystal
➢ Unit cell

MSE : Introduction to Materials Science Chapter 3, Structure of solids 25