Chapter 3.

The Structure of Crystalline

Solids
CRYSTAL STRUCTURES CRYSTALLINE AND
1.Fundamental Concepts NONCRYSTALLINE
2.Unit Cells MATERIALS
3.Metallic Crystal Structures 13. Single Crystals
4.Density Computations
14. Polycrystalline Materials
5.Polymorphism and Allotropy
6.Crystal Systems 15. Anisotropy
7.Materials of Importance—Tin (Its 16. X-Ray Diffraction:
Allotropic Transformation) Determination of Crystal
CRYSTALLOGRAPHIC POINTS, Structures
DIRECTIONS, AND PLANES 17. Noncrystalline Solids
8. Point Coordinates
9. Crystallographic Directions
10. Crystallographic Planes
11. Linear and Planar Densities
12. Close-Packed Crystal Structures
 Introduction

Matter can be subdivided into two states-solid and fluid, of which

the later is subdivided into liquid and gaseous state. Matter can also
be subdivided into condensed stated and gaseous state where
condensed state is subdivided into the solid and liquid state.

Although very little of the matter in the universe is in the solid

state, solids constitute much of the physical world around us and a
large part of the modern technology is based on the special
characteristics of the various solid materials.
 Fundamental Concepts
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 situated in a repeating or periodic
array over large atomic distances; that is, long-range order
exists, such that upon solidification, the atoms will position
themselves in a repetitive three-dimensional pattern, in
which each atom is bonded to its nearest-neighbor atoms.
All metals, many ceramic materials, and certain polymers
form crystalline structures under normal solidification
conditions. For those that do not crystallize, this long-range
atomic order is absent thus this is what we call as
noncrystalline or amorphous materials
A crystal or crystalline solid is a solid material whose constituents
(such as atoms, molecules or ions) are arranged in a highly ordered
microscopic structure, forming a crystal lattice that extends in all
directions.
Single crystal
When the periodicity in crystal pattern extends throughout a
certain piece of materials, one speaks of a single crystal or unit
crystal or mono-crystal. Rock salt, calcites, quartz, etc. are
examples of common single crystal.
Polycrystalline solids (Polymorphism)

When the periodicity in the crystal structure is interrupted at

so-called grain boundaries, the crystal is said to be polycrystalline. In
this case the size of the grains or crytallites is smaller than the size of
the pattern unit which forms the periodicity. The size of the grain in
which the structure is periodic may vary from macroscopic
dimensions to several angstroms. In general, the grains in such a
solid are not related in shape to the crystal structure, the surface
being random in shape rather than well defined crystal planes. Rock,
sand, metals, salts, etc. are some examples of polycrystalline solids.
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
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 materials: atoms
are situated in a repeating or
periodic array over large
atomic distances

• Crystalline structure: how

atoms, ions, or molecules are
arranged spatially

• Lattice: a three-dimensional
array of points coinciding with
atom position
Unit Cell

• Small repeating units in a crystal

• Basic structural unit or building block of the crystal structure
• A highest level of geometrical symmetry
• Unit cells for most crystal structures are parallelepipeds or prisms
having three sets of parallel faces; one is drawn within the
aggregate of spheres (Figure 3.1c), which in this case happens to be
a cube.
• A unit cell is chosen to represent the symmetry of the crystal
structure, wherein all the atom positions in the crystal may be
generated by translations of the unit cell integral distances along
each of its edges
The 10 Most Important Examples of Crystalline Solids
Source:https://www.lifepersona.com/the-10-most-important-examples-of-cristalline-solids

1- Table salt
Sodium chloride is the most representative example of a crystalline
solid and has a FCC crystal structure with a cubic system.
In addition to being used in the kitchen, it has several applications in
industrial processes.
2- Alumina
Its chemical formula is Al2O3 and forms an octahedral structure.
The industrial applications of this compound are mainly as thermal
and electrical insulator. It is also used as part of coatings that prevent
oxidation.
3- Barium chloride
Barium chloride (BaCl2) is a whitish crystal with an orthogonal
structure.
In the industry it is used mainly as a reagent in purity tests and for the
manufacture of salts.
4- Diamond
Diamond is the most famous carbon allotrope for its beauty and value.
It has a cubic crystalline system and is the hardest material known.
Diamonds are used both in jewelry and in industry. In the latter they
are mainly used as cutting tools due to their extraordinary hardness
properties.
5- Quartz
Silicon dioxide (SO2) can be present as quartz. It is a trapezohedral
trigonal white crystalline structure.
It is a very abundant mineral. Like diamond, it is used in the industry
as well as in the creation of electronic devices and jewelry.
6- Calcium oxalate
Calcium oxalate is produced in some poisonous plants.
They usually occur irregularly and are also present in some processes
for the creation of beer.
7- Acetylsalicylic acid
Generally known as aspirin, it is a crystalline solid that is synthesized
as a medication to treat pain and inflammation.
It was discovered in 1853 and is still used today.
8- Sugar
Sucrose, as a polymer of glucose and fructose, is a white crystal with a
sweet taste that is used as a sweetener in world cuisine.
It has a complex structure and a good amount of calories per gram, so it
is used as a nutrient to obtain energy.
9- Calcium nitrate
It is a component of some fertilizers that provide nitrogen and calcium
to the soil for the plants to absorb.
It has a structure that allows it to be highly soluble in water.
10- Ice
Ice is the solid form of water. Due to its polar covalent bonds it has a
lower density than water in liquid state and its crystalline structure is
arranged in the form of hexagons.
Ice is very used every day and the properties it has compared to other
solids makes it an element of great importance for life.
Amorphous Solids
Amorphous solids are rigid structures but they lack a well-
defined shape. They do not have a geometric shape. So they are non-
crystalline. This is why they do not have edges like crystals do. The
most common example of an amorphous solid is Glass.
Gels, plastics, various polymers, wax, thin films are also good
examples of amorphous solids.
It is the opposite extreme of a single crystal. These types of
solids have neither reticular nor granular structure. At most causes
exhibit short range orderness in their structure. Glass and plastic are
common example of this class. When the size of the grains or
crystallites becomes comparable to the size of the pattern unit, we
speak of amorphous substances. A typical feature of these substances
is that they have no definite melting points. As their temperature is
increased, they gradually become soft; their viscosity drops, and
begins to behave like ordinary viscous liquids.
Metallic Crystal Structure

• tend to be densely packed

• 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.
• have the simplest crystal structures
- Three relatively simple crystal structures are found for most of the common
metals: face centered cubic, body-centered cubic, and hexagonal close-packed.
Atomic packing factor

In crystallography, atomic packing factor (APF) or packing

fraction is the fraction of volume in a crystal structure that is
occupied by atoms. It is dimensionless and always less than unity.
For practical purposes, the APF of a crystal structure is determined
by assuming that atoms are rigid spheres. The radius of the spheres
is taken to be the maximal value such that the atoms do not overlap.
It is defined as the ratio of the actual volume occupied by the
spherical atoms to the total available of the structure. It is also
known as relative pacing density, efficiency or packing fraction. For
one-component crystals (those that contain only one type of atom),
the APF is represented mathematically by
The Face-Centered Cubic Crystal Structure

The 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. It is aptly called the face-centered cubic (FCC)
crystal structure. Some of the familiar metals having this crystal
structure are copper, aluminum, silver, and gold
 FACE CENTERED CUBIC STRUCTURE
(FCC)
• Close packed directions are face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

• Coordination # = 12

Adapted from Fig. 3.1(a),

Callister 6e.

9
(Courtesy P.M. Anderson)
Two other important characteristics of a crystal structure are the
coordination number and the atomic packing factor (APF). For
metals, each atom has the same number of nearest-neighbor or
touching atoms, which is the coordination number. For face-centered
cubics, the coordination number is 12. This may be confirmed by
examination of Figure 3.1a; the front face atom has four corner
nearest-neighbor atoms surrounding it, four face atoms that are in
contact from behind, and four other equivalent face atoms residing in
the next unit cell to the front, which is not shown. The APF is the sum
of the sphere volumes of all atoms within a unit cell (assuming the
atomic hard-sphere model) divided by the unit cell volume—that is,
(3.2) For the FCC structure, the atomic packing factor is 0.74, which
is the maximum packing possible for spheres all having the same
diameter. Computation of this APF is also included as an example
problem. Metals typically have relatively large atomic packing factors
to maximize the shielding provided by the free electron cloud.
The Body-Centered Cubic Crystal Structure

Another common metallic crystal structure also has a cubic unit cell
with atoms located at all eight corners and a single atom at the cube
center. This is called a body-centered cubic (BCC) crystal structure.
BODY CENTERED CUBIC STRUCTURE
(BCC)
• Close packed directions are cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

• Coordination # = 8

Adapted from Fig. 3.2,

Callister 6e.

(Courtesy P.M. Anderson) 7

 ATOMIC PACKING FACTOR: BCC
• APF for a body-centered cubic structure = 0.68
Close-packed directions:
length = 4R
= 3a
Unit cell c ontains:
1 + 8 x 1/8
= 2 atoms/unit cell
R
Adapted from a
Fig. 3.2,
Callister 6e. atoms volume
4
unit cell 2 ( 3a/4 ) 3
3 atom
APF =
volume
a3
unit cell
8
The Hexagonal Close-Packed Crystal Structure

Not all metals have unit cells with cubic symmetry; the final
common metallic crystal structure to be discussed has a unit cell
that is hexagonal. Figure 3.3a shows a reduced sphere unit cell for
this structure, which is termed hexagonal close-packed (HCP)
 Characteristics of Selected Elements at 20C
At. Weight Density Crystal Atomic radius
Element Symbol (amu) (g/cm 3 ) Structure (nm)
Aluminum Al 26.98 2.71 FCC 0.143
Argon Ar 39.95 ------ ------ ------
Barium Ba 137.33 3.5 BCC 0.217
Beryllium Be 9.012 1.85 HCP 0.114
Boron B 10.81 2.34 Rhomb ------ Adapted from
Table, "Charac-
Bromine Br 79.90 ------ ------ ------ teristics of
Cadmium Cd 112.41 8.65 HCP 0.149 Selected
Elements",
Calcium Ca 40.08 1.55 FCC 0.197 inside front
Carbon C 12.011 2.25 Hex 0.071 cover,
Callister 6e.
Cesium Cs 132.91 1.87 BCC 0.265
Chlorine Cl 35.45 ------ ------ ------
Chromium Cr 52.00 7.19 BCC 0.125
Cobalt Co 58.93 8.9 HCP 0.125
Copper Cu 63.55 8.94 FCC 0.128
Flourine F 19.00 ------ ------ ------
Gallium Ga 69.72 5.90 Ortho. 0.122
Germanium Ge 72.59 5.32 Dia. cubic 0.122
Gold Au 196.97 19.32 FCC 0.144
Helium He 4.003 ------ ------ ------
Hydrogen H 1.008 ------ ------ ------ 15
 DENSITIES OF MATERIAL CLASSES
Graphite/
metals >
ceramic > polymer s
s Metals/
Alloys
Ceramics/ Polymers
Composites/
fibers
Semicond
30
Why? Based on data in Table B1, Callister
Platinum
Metals have... 20 Gold, W
Tantalum
*GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-Reinforced
• close-packing Epoxy composites (values based on
60% volume fraction of aligned fibers
(metallic bonding) 10 Silver, Mo
Cu,Ni
in an epoxy matrix).
Steels
• large atomic mass

 (g/cm 3 )
Tin, Zinc
Zirconia
Ceramics have... 5
Titanium
4 Al oxide
• less dense packing Diamond
Si nitride
3
(covalent bonding) Aluminum Glass -soda
Concrete
Glass fibers
Silicon PTFE
• often lighter elements 2 Magnesium G raphite
GFRE*
Carbon fibers
Silicone CFRE *
Polymers have... PVC
PET
Aramid fibers
AFRE *
• poor packing 1 PC
HDPE, PS
PP, LDPE
(often amorphous)
• lighter elements (C,H,O) 0.5 Wood
Composites have... 0.4
0.3
• intermediate values Data from Table B1, Callister 6e.
16