STRUCTURES OF

SOLIDS
ENGR. ANA LORRAINE M . DALILIS, RChE
OBJECTIVES

•To distinguish among metals,

ceramics, and composites based
on their structure and
composition at the atomic level.
•Atomic arrangement plays an
important role in determining the
microstructure and behavior of a
solid.
•Solid materials can be classified
according to the regularity with
which the atoms or ions are
arranged with respect to one
another.
Basic Concepts:
Solid materials may be classified
according to the regularity with
which the atoms or ions are
arranged:

a)Crystalline material
b)Non-crystalline material

4
•Crystal structure – is the manner in
which atoms, ions, or molecules
are spatially arranged. In other
words, it refers to the size, shape ,
and atomic arrangement.
•Atomic hard sphere model – used
to represent the atoms or ions
when describing crystalline
structure.
•Unit Cell – a relatively small
repeating unit
- made up of a unique
arrangement of atoms
•Lattice - an infinite array of
discrete points with identical
environment
Materials and Packing
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of:
-metals
-many ceramics
-some polymers

crystalline SiO2
Adapted from Fig. 3.23(a),
Callister & Rethwisch 8e.

Si Oxygen
7
Materials and Packing
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline

noncrystalline SiO2
Adapted from Fig. 3.23(b),
Callister & Rethwisch 8e.
Crystalline Solids
- Solids in which atoms are
arranged in an orderly repeating
pattern
- usually have flat surfaces, or
faces, that make definite angles
with one another.
Examples of Crystalline Solids
sodium chloride, quartz, and diamond.
Amorphous solids
• Greek words for “without form”,
lack the order found in
crystalline solids.
• They do not have the well-
defined faces and shapes of a
crystal.
Examples of Amorphous Solids
Familiar amorphous solids are rubber,
glass, and obsidian (volcanic glass).
•All metals and many ceramic
materials form crystalline structures
under normal solidification.
•Non-crystalline or amorphous
materials
-the atoms are arranged
haphazardly, disorganized
- no repetitive pattern of atom.
Examples: glass and rubber.
- some can be made crystalline
when subjected to higher
temperature or by stretching.
Examples: asphalt when
subjected to high temperature
- rubber when stretched.
•Unit cell - subdivision of the
crystalline lattice that still retains
the overall characteristic of the
entire lattice.
-basic structural unit or
building block of the
crystal structure by virtue of
its geometry and the atom
positions within.
• Coordination number – the number of
atoms touching a particular atom of the
number of nearest neighbors.
• It is an indication of how tightly and
efficiently atoms are packed together.
• Atomic Packing Factor (APF) – the fraction
of space occupied by atoms, assuming
that atoms are hard spheres.
(𝑛𝑜. 𝑜𝑓𝑎𝑡𝑜𝑚𝑠 𝑝𝑒𝑟 𝑐𝑒𝑙𝑙)(𝑣𝑜𝑙 𝑜𝑓 𝑒𝑎𝑐ℎ 𝑎𝑡𝑜𝑚)
𝐴𝑃𝐹 =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
Or
𝑣𝑜𝑙 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑎 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
𝐴𝑃𝐹 =
𝑡𝑜𝑡𝑎𝑙 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑣𝑜𝑙𝑢𝑚𝑒
STRUCTURES OF
METALS AND
CERAMICS
METALS
• The positions of the lattice points are defined by the
lattice vectors a and b. Beginning from any lattice
point it is possible to move to any other lattice point
by adding together whole-number multiples of the
two lattice vectors.*
•OBLIQUE LATTICE - most general
type of lattice.
-the lattice vectors are of
different lengths and the angle c
between them is of arbitrary size,
which makes the unit cell an
arbitrarily shaped parallelogram.
•SQUARE LATTICE - results when
the lattice vectors are equal in
length and perpendicular to
each other.
•RECTANGULAR LATTICE - if the two
vectors are perpendicular to
each other but of different
lengths, a is formed.
•HEXAGONAL LATTICE - a and b
are the same length and c is
120°
3D Crystals
If we place a lattice point
at each corner of a unit
cell, we get a primitive
lattice. It is also possible to
generate what are called
centered lattices by
placing additional lattice
points in specific locations
in the unit cell.
•A body-centered cubic
lattice has one lattice point
at the center of the unit cell
in addition to the lattice
points at the eight corners.
• A face-centered cubic
lattice has one lattice point
at the center of each of the
six faces of the unit cell in
addition to the lattice points
at the eight corners.
 Structure Axes Angles between
Axes
1. Cubic a=b=c All angles = 90°
2. Tetragonal a=b=c All angles = 90°
3. Orthorhombic a=b=c All angles = 90°
4. Hexagonal a=b=c Two angles = 90°
One angle = 120°
5. Rhombohedral a = b = c All angles are
equal, none
6. Monoclinic a=b=c equals 90°
Two angles = 90°
7. Triclinic a=b=c One angle (β) is
not 90°
All angles are
different and
none equals 90°
Filling the Unit Cell
• To generate a crystal structure, we
need to associate an atom or group of
atoms with each lattice point. In the
simplest case, the crystal structure
consists of identical atoms, and each
atom lies directly on a lattice point.
When this happens, the crystal structure
and the lattice points have identical
patterns.
Filling the Unit Cell
•Keep in mind that only
elements can form
structures of this type.
Filling the Unit Cell
•In most crystals the atoms are
not exactly coincident with
the lattice points. Instead, a
group of atoms, called a
motif, is associated with each
lattice point.
TWO IMPORTANT CHARACTERISTICS
OF CRYSTALS
1. No atoms lie on the lattice points.
Thus, to build up a structure you must
know the location and orientation of
the atoms in the motif with respect to
the lattice points.
2. Bonds can be formed between
atoms in neighboring unit cells.
(metallic, ionic, and network-
covalent solids)
Metallic Crystal Structures
• Tend to be densely packed.
• 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
• Have the simplest crystal structures.

34
The Structures of Metallic
Solids
The crystal structures of many metals are
simple enough that we can generate
the structure by placing a single atom
on each lattice point.
Metals with a primitive cubic structure
are rare, one of the few examples being
the radioactive element polonium.
The Structures of Metallic
Solids
•Face-centered cubic (FCC)
metals: usually soft and ductile
•aluminum, lead, copper, silver,
and gold, Ag, Ni, Pt
The Structures of Metallic
Solids
•Body-centered cubic (BCC)
metals: less ductile but stronger
•iron, chromium, sodium, and
tungsten.
The Structures of Metallic
Solids
•Hexagonal Closed Packed
(HCP) Structure: usually brittle

•Zn
FCC Crystal Structure
• FIGURE 4

(a)A hard sphere unit cell representation

(b)reduced-sphere unit cell
(c)An aggregate of many atoms
Two other important characteristics of a crystal
structure:
Coordination number

 Is the number of atoms touching a particular

atom or the number of nearest neighbors.
 It is an indication of how tightly and efficiently
atoms are packed together.

Atomic Packing Factor (APF)

 The fraction of space occupied by atoms,
assuming that atoms are hard spheres.
Face Centered Cubic Structure (FCC)
• Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

• Coordination # = 12

Adapted from Fig. 3.1, Callister & Rethwisch 8e.

(Courtesy P.M. Anderson)

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8
44
•Number of atoms per unit cell, N,
can be computed as:
𝑵𝒇 𝑵𝒄
𝑵 = 𝑵𝒊 + +
𝟐 𝟖
Where Ni = number of interior
atoms
Nf = number of face atoms
NC = number of corner atoms

45
•For FCC crystal structure, there are 8
corner atoms (NC = 8), 6 face atoms
(Nf = 6), and no interior atoms (Ni = 0).
•Thus,
N=0 + 6 + 8
2 8
= 4 whole atoms may be assigned
to a given unit cell.

46
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
atoms volume
Fig. 3.1(a), 4
Callister & Rethwisch 8e.
unit cell 4 p ( 2a/4) 3
3 atom
APF =
3 volume
a
unit cell 47
The coordination number for FCC
metals, CN = 12,
• The front face atom has 4 corner
nearest neighbor atoms surrounding it,
• 4 face atoms that are in contact from
behind
• 4 other equivalent face atoms residing
in the next unit cell to the front.
BCC Crystal Structure
•Center and corner atoms touch
one another along cube
diagonals and unit cell length a
and atomic radius R are related
through:
4𝑅
𝑎=
3
Examples of BCC metals: Cr, Fe,
Mo, W
BCC Crystal Structure
Two atoms are associated with each
BCC unit cell; the equivalent of one
atom from the B corners , each of which
is shared among 8 unit cells, and the
single atom at the center.
The corner and center atom positions are
equivalent.
The coordination number for BCC is 8,
i.e., the center atom has 8 corners
equivalent to 8 neighboring atoms; AFP
for BCC = 0.68
Body-Centered Cubic Crystal
Structure
• FIGURE 5

(a)Hard sphere unit cell representation

(b)Reduced-sphere unit cell
(c)An aggregate of many atoms
Body Centered Cubic
Structure (BCC
•Also has a cubic unit cell with
atoms located at all 8 corners and
a single atom at the cube center
•Center and corner atoms touch
one another along cube
diagonals

52
Body Centered Cubic Structure (BCC)
• Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

ex: Cr, W, Fe (), Tantalum, Molybdenum

• Coordination # = 8

Adapted from Fig. 3.2,

Callister & Rethwisch 8e.
(Courtesy P.M. Anderson)
2 atoms/unit cell: 1 center + 8 corners x 1/8
53
 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 & a
Rethwisch 8e.

atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
3 volume
a
unit cell 54
Hexagonal Close-Packed
Crystal Structure
• FIGURE 6

A sites
c
B sites

A sites
a

(a) (b)
(a) Reduced-sphere unit cell (a and c represent the short and long
edge lengths, respectively)
(b) An aggregate of many atoms
The Hexagonal Close-Packed
Crystal Structure
• The unit cell is a skewed prism, shown
separately.
• The top and bottom faces of the unit cell consist
of 6 atoms that form regular hexagons and
surround a single atom in the center.
• Another plane lies in between the top and
bottom planes, this provides additional 3 atoms.
• An equivalent of 6 atoms is contained in each
unit cell, 1/6 of each of the 12 top and bottom
face corner atoms, ½ of each of the 2 center
face atoms and al 3 mid-plane interior atoms.
Hexagonal Close-Packed
Crystal Structure
• The coordination number and the atomic
packing factor for HCP are the same as
for FCC.
• CN = 12, APF = 0.74
• Examples of HCP metals: Cd, Mg, Ti, Zn,
Co
58
Simple Cubic Structure (SC)
• Rare due to low packing density (only Po has this
structure)
• Close-packed directions are cube edges.
• Coordination # = 6
(# nearest neighbors)

(Courtesy P.M. Anderson)

59
 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
4
a unit cell 1 p (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.24,
60
Callister & Rethwisch 8e.
 Summary of Crystal Structure

Atoms/ Coordination
Structure Cell No. APF
SC 1 6 0.52
BCC 2 8 0.68

FCC 4 12 0.74

HCP 6 12 0.74
 Density Computations
𝒏𝑨
• Theoretical density ρ=
𝑽𝒄 NA
• Where:
n = number of atoms associated with
each unit cell
A = atomic weight
VC = volume of unit cell
NA = Avogadro’s number

62
 Theoretical Density, 

• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
R
Adapted from
Fig. 3.2(a), Callister &
a a = 4R/ 3 = 0.2887 nm
Rethwisch 8e.
atoms
g
unit cell 2 52.00 theoretical = 7.18 g/cm3
mol
= actual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol 63
Show that the atomic packing factor for the
FCC crystal structure is 0.74

Given: FCC unit cell

Req’d: show that APF = 0.74
Sol’n:
APF = VT atoms in a unit cell .
V unit cell
APF = 4(4/3) p R3 = p .
16 R3 2 32
= 0.74

64
Copper has an atomic radius of 0.128
nm, an FCC crystal structure and an
atomic weight of 63.5 g/mol. Compute
its theoretical density and compare it
with the measured density, 8.94 g/cm3.
Given: Copper; FCC crystal
R = 0.128 nm = 1.28x10-8 cm 4𝑅
a=
A = 63.5 g/mol 2
Measured  = 8.94 g/cm3
Req’d:  & compare w/ measured
Sol’n:
= nA ;
Vc NA
65
n = 4 atoms/cell
Vc = a3
Na = 6.023x1023 atoms/mol
a = 4R/2 ; Vc = (4R /2)3 = 16R32

= n A .
162R3NA
= (4atoms/cell)(63.5g/mol)
16x2 x (1.28x10-8 cm)3
x (6.023x1023 atoms/mol)
= 8.8870 g/cm3
Determine the density of BCC iron, w/c has a lattice
parameter of 0.2866 nm. Compare the answer w/ the
measured density of 7.870 g/cm3.

Given: BCC Fe, a = 0.2866 nm, Meas.  = 7.87 g/cm3

Reqd:  and compare with meas. value
Soln:
 = n A ; n = 2 atoms/cell,
VC NA A = 55.85 g/mol
VC = a3

= 2 (55.85)
(2.866x10-8)3(6.023x1023)
= 7.8779 g/cm3 > meas. 

67
Show for the body centered cubic crystal
structure that the unit cell edge length a
and the atomic radius R are related
through a = 4R/3 .
Given: BCC 4R
Req’d: show that a = 4R/3
a2 a

Sol’n:

(4R)2 = a2 + (a2)2
16 R2 = 3 a2
R = a3 or a = 4R
4 3
 Densities of Material Classes
In general Graphite/
metals > ceramics > polymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
30
Why? Platinum
Based on data in Table B1, Callister
*GFRE, CFRE, & AFRE are Glass,
20 Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
(metallic bonding) Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia

 (g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
• less dense packing 3
Diamond
Si nitride
Aluminum Glass -soda
• often lighter elements Concrete
Silicon PTFE
Glass fibers
GFRE*
2 Carbon fibers
Polymers have... Magnesium Graphite
Silicone CFRE*
Aramid fibers
PVC
• low packing density PET
PC
AFRE*
1 HDPE, PS
(often amorphous) 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.
69
SEATWORK (1/4 sheet of paper)
• For each of the two-dimensional
structures shown here (a) draw the unit
cell, (b) determine the type of two-
dimensional lattice, and (c) determine
how many of each type of circle (white
or black) there are per unit cell.
COMPOSITES