Chapter 4

The Structure of Crystalline Solids

Chapter 3 - 52
 Concern
• Ch3: Fundamental concepts of crystal
structures
– Units cells
– Crystallographic
• Points
• Directions
• Planes
• Ch4: Addresses possible crystal structures
documented for known strands of materials
– Metals (Main focus)
– Ceramics
– Polymers
Chapter 3 - 53
 Metallic Crystal Structures
• Atomic bonding is METALLIC (hence, non-
directional*)
• This tends to pose less restrictions on the
possible nearest-neighbor atoms in terms of:
– Position
– Number
• i.e. This is what gives way for metallic crystal
structures to exhibit the characteristic:
– Relatively large numbers of immediate neighbors
– Dense atomic packing
• Hard sphere model assigns each sphere to
represent an ION CORE. Chapter 3 - 54
 Metallic Crystal Structures

Three relatively simple structures are

found for most common metals:

• Face-Centred Cubic [FCC]

• Body-Centred Cubic [BCC]

• Hexagonal Close-packed [HCP]

Chapter 3 - 55
 Face-Centered Cubic Structure (FCC)
Spheres/Ion cores touch each other along face diagonals.

In the hard sphere model

(given below) all atoms are ex: Al, Cu, Au, Pb, Ni, Pt, Ag
identical; the face-centered
atoms are shaded
• Coordination # = 12
differently only for ease of
viewing.

(Courtesy P.M. Anderson) Adapted from Fig. 3.1, Callister 7e.

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

Chapter 3 - 56
 Face-Centered Cubic Structure (FCC)
• In dealing with a given
crystalline system, it is
crucial to identify units
cell edge dimensions (in
this case “a”)
• This is often facilitated by
using the closely packed
direction* to obtain Adapted from Fig. 3.1, Callister 7e.

[ a = f (R) ]
where,
a : unit cell edge dimension
R : sphere/ion radius Chapter 3 - 57
Face-Centered Cubic Structure (FCC)
Adopting the
aforementioned
approach would yield:

𝑎 = 2𝑅 2

Derivation, illustrated in Adapted from Fig. 3.1, Callister 7e.

example 4.1

Chapter 3 -
 Number of Atoms per Unit Cell (N)
Depending on an atom’s location ➔ it
might be shared by neighboring unit
cells ➔ implying that only a fraction of a
given atom might actually be possessed
by a unit cell in consideration
Hence,
𝑁𝑓 𝑁𝑐
𝑁 = 𝑁𝑖 + +
2 8
Where,
Ni = No. of interior atoms
Nf = No. of face atoms
Nc = No. of corner atoms Chapter 3 - 59
How did the previous expression come
about?
For an FCC structure,

N=4

Would you be able to

regenerate this
outcome for “N”?? Adapted from Fig. 3.1, Callister 7e.

Chapter 3 - 60
 General remarks

Notice that the cell is

composed of the
VOLUME of the cube
that is generated by
the CENTRES of the
Adapted from Fig. 3.1, Callister 7e.

CORNER atoms

Chapter 3 - 61
 Other characteristics of crystal
structures
Coordination No.:
Number of nearest-
neighbor/ touching
atom.

For FCC it is 12.

Adapted from Fig. 3.1, Callister 7e.

Why??*
Chapter 3 - 62
 Other characteristics of crystal
structures
Volume of atoms in unit cell*
APF =
Volume of unit cell
*adopting hard-sphere model
For an FCC structure
APF = 0.74
How??
This is considered the
Adapted from Fig. 3.1, Callister 7e.

maximum packing possible

for spheres all having the
Chapter 3 - 63
same diameter.
Body-Centered Cubic Structure (BCC)

Closely packed direction would be….

Body diagonal (i.e. <111> from one edge

to opposite in a unit cell)

4𝑅
𝑎= & N=2
3 Chapter 3 - 64
Body-Centered Cubic Structure (BCC)

e.g. Cr, Fe & W

Coordination No. = 8

As the above is lower for BCC than is the

case for FCC then APF is also relatively
low (APF =0.68) Chapter 3 - 65
 Simple Cubic Structure (SC)

Given the low APF

exhibited by such a
structure ➔ none of
the metallic elements
is associated with it (Courtesy P.M. Anderson)

(going back to metallic

bonding only facilitating
highly dense packing)*

Chapter 3 - 66
 Simple Cubic Structure (SC)
• Notice that lack of density
in atomic packing here also
reflects in the low
coordination No. (that is 6)
➔ hence, APF is relatively*
LOW =0.524
• Highly packed direction is
along edge (i.e. <100>-
type directions)
Hence, your would expect
a = 2R Chapter 3 - 67
Not all METALS exhibit CUBIC
symmetry down to the unit cell

Some are

(hcp)
Chapter 3 - 68
 Hexagonal Close-Packed Structure
(hcp)
• Atoms in mid-plane have as
nearest neighbors atoms in
both adjacent planes.
• Notice: basal plane is closely
packed (i.e. a = 2R)
𝑁𝑓 𝑁𝑐
• 𝑁 = 𝑁𝑖 + + =6
2 𝟔
• a & c are short and long units
cell dimensions, respectively.
• c/a = 1.633 (Typically)
Though, it deviates from such
ideal value for some hcp metals Chapter 3 - 69
 Hexagonal Close-Packed Structure
(hcp)
• Coordination No. & APF are
IDENTICAL to those of FCC
(i.e. 12 & 0.74, respectively)

• Hints on similar approach to

atomic packing with key
distinction reflective of unique
units cell geometry of each.

• e.g. Cd, Mg, Ti & Zn Chapter 3 - 70

 Crystal Structure ➔ Theoretical ρ

This for solids if given by:

Mass of Atoms in Unit Cell
Density =  =
Total Volume of Unit Cell

nA A/NA allows for conversion

 = from atoms to equivalent
VC NA
grams
where n = No. of atoms/unit cell
A = atomic weight (g/gmol)
VC = Volume of unit cell = a3 for cubic
NA = Avogadro’s number
= 6.023 x 1023 atoms/gmol Chapter 3 -
 Polymorphism / Allotropy
• Two or more distinct crystal structures
for the same material
• Exhibited by metals and non-metals*
• PREVAILING crystal structure depends
on both:
– Temperature
– External Pressure/Stress

Chapter 3 - 72
 Carbon Polymorphs
Graphite: At
ambient
conditions

Diamond: At
extremely
high
pressures
Chapter 3 - 73
 Similarly…..

• Iron

BCC (@ Troom) ➔ FCC (@ 912°C)

• This in general is accompanied by:

– Adjustments to density

– Modifications of physical properties

Chapter 3 - 74
 Atomic Arrangement/Packing

• Atomic arrangement in a
crystallographic PLANE depends on
crystal structure

• e.g. notice atomic packing in <110>-

type planes of the 2 structures BCC &
FCC:

Chapter 3 - 75
Chapter 3 - 76
 Needless to say…

• Atomic packing in a given plane is

dependent on crystal
SYSTEM/GEOMETRY
• Recall, “Crystallographic
Equivalence*” is established for planes
of the same family+ ONLY for CUBIC
SYSTEMS

𝒆. 𝒈. 𝟏𝟎𝟎
ഥ𝟎𝟎 , 𝟎𝟏
= 𝟏𝟎𝟎 , 𝟎𝟏𝟎 , 𝟎𝟎𝟏 , 𝟏 ഥ𝟎 , (𝟎𝟎𝟏
ഥ)
Chapter 3 - 77
 However…..
• This is NOT TRUE for SYSTEMS inferior
in SYMMETRY
e.g. tetragonal
Where
𝟏𝟎𝟎 = 𝟏𝟎𝟎 , 𝟎𝟏𝟎 , 𝟏ഥ𝟎𝟎 , 𝟎𝟏
ഥ𝟎

Excluding
ഥ)
𝟎𝟎𝟏 , (𝟎𝟎𝟏
• Why is that??

Chapter 3 - 78
Chapter 3 - 79
 Linear & Planar Densities
For a particular materials,
• Equivalent DIRECTIONS <UVW> have
➔ identical LINEAR densities (LD) ➔
notice your calculations/visualization
➔1D (line)
• Equivalent PLANES {hkl} have ➔
identical PLANAR densities (PD) ➔
notice your calculations/visualization
➔2D (area)
Chapter 3 - 80
 𝑁𝑜.𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑐𝑒𝑛𝑡𝑒𝑟𝑒𝑑 𝑜𝑛 𝑑𝑖𝑟𝑒𝑐𝑡𝑖𝑜𝑛 𝑣𝑒𝑐𝑡𝑜𝑟
• 𝐿𝐷 =
𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑑𝑖𝑟𝑒𝑐𝑡𝑖𝑜𝑛 𝑣𝑒𝑐𝑡𝑜𝑟
−1 −1
𝑔𝑖𝑣𝑒𝑛 𝑖𝑛 (𝑒. 𝑔. 𝑛𝑚 𝑜𝑟 𝑚 )

𝑁𝑜.𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑐𝑒𝑛𝑒𝑡𝑒𝑑 𝑜𝑛 𝑎 𝑝𝑙𝑎𝑛𝑒

• 𝑃𝐷 =
𝑎𝑟𝑒𝑎 𝑜𝑓 𝑝𝑙𝑎𝑛𝑒
−2 −2
𝑔𝑖𝑣𝑒𝑛 𝑖𝑛 (𝑒. 𝑔. 𝑛𝑚 𝑜𝑟 𝑚 )

For practice,
get LD110 and PD110 for an FCC structure Chapter 3 - 81
Why study atomic packing and linear &
planar densities
• When metals deform plastically (i.e.
with no return)
• They do so through a mechanism know
as “Slip”
• Where does it occur??
In most closely packed PLANES and in
those PLANES along most densely
packed DIRECTIONS
Chapter 3 - 82
 RECALL….
MOST EFFICIENT packing of equal-size
spheres/atoms of metallic structures
are….
• FCC
• hcp
Exhibiting APF of 0.74

Chapter 3 - 83
 In the PAST FCC & hcp
structures were depicted using

UNIT CELL
representations
Chapter 3 - 84
However, FCC & hcp might also be
represented by:
Closely packed planes of atoms
stacked on top of each other.

“what distinguished FCC from hcp is

merely the STACKING SEQUENCE”

But, 1st what is a closely packed plane??

Chapter 3 - 85
 Closely Packed Planes
Planes having a maximum atom/sphere-
packing density
But, How can we stack metal atoms to minimize
empty space?
2-dimensions

vs.

Now stack these 2-D layers to make 3-D structures

Chapter 3 - 86
• Centers of all atoms in one
close-packed plane (BLUE)
are labelled “A”
• Notice in (BLUE) basal plane
2 sets of equivalent “triangular
depressions” each formed by
3 adjacent atoms
• Up Vertices ➔ B positions
• Down Vertices ➔ C positions Chapter 3 - 87
• Either B- or C-positions
may host the NEXT closely-
packed plane.
• SO FAR, the stacking
sequence is termed “AB”*
• The real distinction
between FCC and hcp lies
in the choice of positioning
the 3rd stacked plane in
sequence Chapter 3 - 88
 For hcp
• The 3rd plane will rest with
centers of it’s atoms aligned
DIRECTLY above those in
plane “A”
• i.e. stacking sequence is
“ABABAB…”
• Of course, “ACACAC…”
would be equivalent
• Such close packed planes
for hcp are of the (0001)-
type Chapter 3 - 89
For hcp
Notice the
correspondence
between the close-
packed plane stacking
REPRESENTATION and
the unit cell
REPRESENTATION

Chapter 3 - 90
For FCC

• Centers of 3rd plane situated over “C”

sites of 1st plane
• Stacking sequence ➔
“ABCABCABC…”
• i.e. atomic alignment repeats every
3rd plane
• Notice we’re stacking (111)-type
planes here
Chapter 3 - 91
For FCC
• 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
Notice the (111)-type
plane stacking here

Chapter 3 - 92
 For FCC
Notice the correspondence between the close-
packed plane stacking REPRESENTATION and
the unit cell REPRESENTATION

Chapter 3 - 93