MATERIALS SCIENCE AND ENGINEERING

Chapter 3. Atomic and Ionic Arrangements

Prof. Dr. Gültekin GÖLLER

11.11.2020
Materials Science and Engineering

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 OBJECTIVES OF CHAPTER 3

• To learn classification of materials based on

atomic/ionic arrangements

• To describe the arrangements in crystalline solids

based on lattice, basis, and crystal structure

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 OUTLINE
3.1 Short-Range Order versus Long-Range Order
3.1.1 Lattice, Unit Cells, Basis, and Crystal Structures
 Lattice Parameters
 Number of Atoms per Unit Cell
 Atomic Radius versus Lattice Parameter
 Coordination Number
 Packing Factor
 Density
 The Hexagonal Lattice and Unit Cell
3.2 Allotropic or Polymorphic Transformations
3.3 Points, Directions, and Planes in the Unit Cell
 Coordinates of Points
 Directions in the Unit Cell
 Planes in the Unit Cell
 Miller Indices for Hexagonal Unit Cells
 Close-Packed Planes and Directions
 Isotropic and Anisotropic Behavior
 Interplanar Spacing

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OUTLINE (Cont.)

3.4 Interstitial Sites

3.5 Crystal Structures of Ionic Materials
 Electrical Neutrality
 Ionic Radii
 Sodium Chloride Structure
 Zinc Blende Structure
 Fluorite Structure
 Corundum Structure
3.6 Covalent Structures
 Diamond Cubic Structure
 Crystalline Silica
 Crystalline Polymers
3.7 Diffraction Techniques for Crystal Structure Analysis

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 SHORT-RANGE ORDER vs LONG-RANGE ORDER

• Short-range order - The regular and predictable

arrangement of the atoms over a short distance -
usually one or two atom spacing.
• Long-range order (LRO) - A regular repetitive
arrangement of atoms in a solid which extends over a
very large distance.

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SHORT-RANGE ORDER vs LONG-RANGE ORDER

 Arrangements of atoms and ions play an important role in

determining the microstructure and properties of a
material.

 Atoms
a) No order (monoatomic gases)
b) Short-range order (Glass)
c) Long-range order (Metals)

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 Metals, alloys, many ceramics and some polymers have
regular ordering of atoms ions that extends through the
material.

 The atoms form a regular repetitive, grid like pattern or

lattice.

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SHORT-RANGE ORDER vs LONG-RANGE ORDER

Levels of atomic
arrangements in
materials: (a) Inert
monoatomic gases have
no regular ordering of
atoms: (b,c) Some
materials, including water
vapor, nitrogen gas,
amorphous silicon and
silicate glass have short-
range order. (d) Metals,
alloys, many ceramics
and some polymers have
regular ordering of
atoms/ions that extends
through the material.
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 Basic Si-O tetrahedron in silicate glass.

(c) 2003 Brooks/Cole Publishing / Thomson

Learning™
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 Tetrahedral arrangement of C-H bonds in polyethylene
(c) 2003 Brooks/Cole Publishing / Thomson Learning™

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(a) Photograph of a silicon single crystal.
(b) Micrograph of a polycrystalline
stainless steel showing grains and grain
boundaries (Courtesy of Dr. A. J. Deardo, Dr. M. Hua and Dr. J.
Garcia.)

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Liquid crystal polymers behave as amorphous materials (liquid-like) in one
state. When an external stimulus (such as an electric field or a temperature
change) is provided, some polymer molecules undergo alignment and form
small regions that are crystalline, hence the name “liquid crystals.” These
materials have many commercial applications in liquid crystal display (LCD)
technology.
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AMORPHOUS MATERIALS

 Any material that exhibits only a short-range order of atoms

or ions is an amorphous material.
 Glasses Solid, non-crystalline materials (typically derived
from the molten state) that have only short-range atomic
order
 Glass-ceramics A family of materials typically derived from
molten inorganic glasses and processed into crystalline
materials with very fine grain size and improved mechanical
properties.

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AMORPHOUS MATERIALS

Amorphous Silicon Crystalline Silicon

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 (c) 2003 Brooks/Cole Publishing / Thomson Learning™

Blow-stretch process
Blowing and stretching process provide an occurring of small crystalline in
amorphous structure bring about strengthening of polymer

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 (c) 2003 Brooks/Cole Publishing / Thomson
Learning™

Classification of materials based on the type of atomic order.

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Lattice, Basis, Unit Cells, and Crystal Structures

 Lattice A collection of points that divide space into smaller

equally sized segments.
 Basis A group of atoms associated with a lattice point (same as
motif).
 Unit cell A subdivision of the lattice that still retains the overall
characteristics of the entire lattice.
 Atomic radius The apparent radius of an atom, typically
calculated from the dimensions of the unit cell, using close-
packed directions (depends upon coordination number).
 Packing factor The fraction of space in a unit cell occupied by
atoms.

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UNIT CELLS

 Unit cell - A subdivision of the lattice that still retains the

overall characteristics of the entire lattice.

Lattice Points Unit Cell

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Lattice, Basis, Unit Cells, and Crystal Structures

 Crystalline solids are a three dimensional collection of individual

atoms, ions, or whole molecules organized in repeating patterns.
These atoms, ions, or molecules are called lattice points and are
typically visualized as round spheres.

 The two dimensional layers of a solid are created by packing the

lattice point “spheres” into square or closed packed arrays.
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 By stacking identical unit cells, the entire lattice can be
constructed. There are seven unique arrangements, known
as crystal systems, which can be used to fill up a three-
dimensional space.
1) Cubic
2) Tetragonal
3) Orthorhombic
4) Rhombohedral (trigonal)
5) Hexagonal
6) Monoclinic
7) Triclinic

 Although there are 7 crystal systems, there are 14 distinct

arrangements of lattice points (Bravais Lattices).

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The 14 types of
Bravais lattices
grouped in 7
crystal systems.

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23
Characteristics of Seven Crystal Systems

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14 Bravais Lattices (video)

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 Lattice points are located at the corners of the unit cell
and, in some cases, at either faces or the center of the
unit cell.
For the cubic crystal system:
 Simple Cubic (SC)
 Body-Centered Cubic (FCC)
 Face-Centered Cubic (BCC)

SC BCC FCC

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(a) Illustration showing sharing
of face and corner atoms. (b)
The models for simple cubic
(SC), body centered cubic (BCC),
and face-centered cubic (FCC)
unit cells, assuming only one
atom per lattice point.
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LATTICE PARAMETER
The lattice parameters, which describes the size and shape of the
unit cell, include the dimensions of the sides of the unit cell and the
angles between the sizes.

1 Angstrom (Aº) = 10-1 nm = 10-10 m

(c) 2003 Brooks/Cole Publishing / Thomson Learning™

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Atomic Radius versus Lattice Parameter

(c) 2003 Brooks/Cole Publishing / Thomson

Learning™

4r 4r
a0  2r a0  a0 
3 2

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 Coordination Number
The coordination number is the number of atoms touching a
particular atom, or the number of neighbors for that particular atom.

Illustration of coordinations in (a) SC and (b) BCC unit cells. Six atoms
touch each atom in SC, while the eight atoms touch each atom in the
BCC unit cell. 30
 Coordination Number

Coordination Number (CN) = 4

Coordination Number (CN) = 6

Coordination Number (CN) = 12

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Coordination Number

CN  Radius of cation / Radius of anion

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Packing Factor

Fraction of space occupied by atoms, assuming that atoms are

hard spheres.

(number of atoms/cell) (volume of each atom)

Packing Factor =
volume of unit cell

Structure Packing Factor

SC 0.52
BCC 0.68
FCC 0.74

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Density

(atoms/cell) (atomic mass of each atom)

Density =
(volume of unit cell) (Avogadro number)

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The Hexagonal Close-Packed Structure

(c) 2003 Brooks/Cole Publishing / Thomson

Learning™

 The hexagonal close-packed (HCP) structure (left) and its unit cell.

 In metals with an ideal HCP, c0 / a0 = 1.633 35

36
Allotropic or Polymorphic Transformations

 Allotropy - The characteristic of an element being able to

exist in more than one crystal structure, depending on
temperature and pressure.

 Polymorphism - Compounds exhibiting more than one type

of crystal structure.

 The term allotropy is normally reserved for this behavior in pure

elements, while the term polymorphism is used for compounds.

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Example
Allotropic Transformation: Calculating Volume Changes in Polymorphs of
Zirconia

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SOLUTION (Cont.)

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Zirconia gas sensor consisting of stabilized zirconia.
(Image courtesy of Bosch © Robert Bosch GmbH.)

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Points, Directions, and Planes in the Unit Cell

 Miller indices - A shorthand notation to describe certain

crystallographic directions and planes in a material. A direction is
indicated by [ ] brackets. A negative number is represented by a
bar over the number.
 Directions of a form - Crystallographic directions that all have the
same characteristics, although their ‘‘sense’’ is different.
Denoted by < > brackets.
 Repeat distance - The distance from one lattice point to the
adjacent lattice point along a direction.
 Linear density - The number of lattice points per unit length
along a direction.
 Packing fraction - The fraction of a direction (linear-packing
fraction) or a plane (planar-packing factor) that is actually
covered by atoms or ions.
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Coordinates of Points

Coordinates of selected points in the unit cell. The number refers to

the distance from the origin in terms of lattice parameters.

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Directions in the Unit Cell

 Metals deform in directions along which atoms are in

closest contact.

 Properties of a material may depend on the direction

in the crystal along which the property is measured.

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Directions in the Unit Cell

a) Using a right-handed coordinate system, determine the

coordinates of two points that lie on the direction.

b) Subtract the coordinates of the “tail” point from the

coordinates of the “head” point to obtain the number of lattice
parameters traveled in the direction of each axis of the
coordinate system.

c) Clear fractions and/or reduce the results obtained from the

subtraction to lowest integers.

d) Enclose the numbers in square brackets [ ]. If a negative sign is

produced, represent the negative sign with a bar over the
number.
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Example - 7

Determine the Miller indices of directions A, B, and C.

Crystallographic directions and coordinates.

(c) 2003 Brooks/Cole Publishing /

Thomson Learning™

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SOLUTION
Direction A
1. Two points are 1, 0, 0, and 0, 0, 0
2. 1, 0, 0, -0, 0, 0 = 1, 0, 0
3. No fractions to clear or integers to reduce
4. [100]
Direction B
1. Two points are 1, 1, 1 and 0, 0, 0
2. 1, 1, 1, -0, 0, 0 = 1, 1, 1
3. No fractions to clear or integers to reduce
4. [111]
Direction C
1. Two points are 0, 0, 1 and 1/2, 1, 0
2. 0, 0, 1 -1/2, 1, 0 = -1/2, -1, 1
3. 2(-1/2, -1, 1) = -1, -2, 2
(c) 2003 Brooks/Cole Publishing /
Thomson Learning™

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Directions in the Unit Cell

1) A direction and its negative are not identical

-
[100] is not equal to [100].

2) A direction and its multiple are identical.

[100] = [200]

3) Certain groups of directions are equivalent.

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Directions in the Unit Cell

Equivalency of crystallographic directions of a form in cubic systems.

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 (c) 2003 Brooks/Cole Publishing / Thomson Learning™

Determining the repeat distance, linear density, and packing fraction for
[110] direction in FCC copper.

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 In here;
Start point[110] = 0,0,0
Next lattice point = 1/2,1/2,1/2
Lattice parameter of Cu = (a0)= 3.6151x10-8 cm

(c) 2003 Brooks/Cole

Atomic radius = (√2a0/4) = 1.2781x10-8 cm
Publishing /
Thomson Learning™

2 x3.6151x108
The distance between lattice points or repeat distance (√2a0/2) =
2
= 2.55x10-8 cm
Length of direction [110] = √2a0 =5.1125x10-8 cm

number of atoms centered on [110] 2

Linear density = =
length of direction 5.1125x10-8
= 3.9x107 lattice points/cm

Packing Fraction = (linnear density) x 2r

= (3.9x107)(2)(1.2781x10-8)
= 1.0 50
 Calculate the repeat distance, linear density,
and packing fraction for the [111] direction in
FCC copper.
In here;
Start point[111] = 0,0,0
Next lattice point = 1,1,1
Lattice parameter of Cu = (a0)= 3.6151x10-8 cm
Atomic radius = (√2a0/4) = 1.2781x10-8 cm

Repeat distance and length of direction (√3a0) = √3x(3.6151x10-8)

= 6.262x10-8 cm
number of atoms centered on [111]
Linear density = = 2x(1/2)/(6.262x10-8)
length of direction

= 1.597x107 lattice points/cm

Packing Fraction = (linnear density) x 2r = (1.597x107)(2)(1.278x10-8)
= 0.408 51
Planes in the Unit Cell

a) Identify the points at which the plane intercepts the x, y and z

coordinates in terms of the number of lattice parameters. If the
plane passes through the origin, the origin of the coordinate
system must be moved.

b) Take reciprocals of these intercepts.

c) Clear fractions but do not reduce to lowest integers.

d) Enclose the numbers in parentheses ( ). If a negative sign is

produced, represent the negative sign with a bar over the
number.

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Example - 8

Determining Miller Indices of Planes

Determine the Miller indices of planes A, B, and C in Figure.

(c) 2003 Brooks/Cole Publishing /

Thomson Learning™

Crystallographic planes and intercepts.

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SOLUTION
Plane A
1. x = 1, y = 1, z = 1
2.1/x = 1, 1/y = 1,1 /z = 1
3. No fractions to clear
4. (111)
Plane B
1. The plane never intercepts the z axis, so x = 1, y = 2, and z = 
2.1/x = 1, 1/y =1/2, 1/z = 0
3. Clear fractions:
1/x = 2, 1/y = 1, 1/z = 0
4. (210)
Plane C
1. We must move the origin, since the plane passes through 0, 0, 0. Let’s
move the origin one lattice parameter in the y-direction. Then, x = , y = -1,
and z = 
2.1/x = 0, 1/y = 1, 1/z = 0
3. No fractions to clear.
4. (0 1 0)
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Planes in the Unit Cell

1) A plane and its negative are identical

-
(020) is equal to (020).

2) A plane and its multiple are not identical.

(100) İs not equal to (200)

3) Certain groups of planes are equivalent.

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Planes in the Unit Cell

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Example - 9

Calculate the planar density and planar packing fraction for the
(010) and (020) planes in simple cubic polonium, which has a
lattice parameter of 0.334 nm.

(c) 2003 Brooks/Cole Publishing /

Thomson Learning™

The planar densities of the (010) and (020) planes in SC unit cells are
not identical.
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 SOLUTION
The total atoms on each face is one. The planar density is:
atom per face 1 atom per face
Planar density (010)   2
area of face (0.334)
 8.96 atoms/nm  8.96  10 atoms/cm
2 14 2

The planar packing fraction is given by:

(1 atom) (r )
2
area of atoms per face
Packing fraction (010)  
(a 0)
2
area of face
r 2
 2
 0.79
( 2r )
However, no atoms are centered on the (020) planes. Therefore, the
planar density and the planar packing fraction are both zero. The
(010) and (020) planes are not equivalent! 58
Example - 10

Draw (a) the [1 2 1] direction and (b) the [ 2 10] plane in a cubic unit
cell.

(c) 2003 Brooks/Cole Publishing / Thomson

Learning™

Construction of a (a) direction and (b) plane within a unit cell.

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SOLUTION

a. Because we know that we will need to move in the negative y-direction,

let’s locate the origin at 0, +1, 0. The ‘‘tail’’ of the direction will be located
at this new origin. A second point on the direction can be determined by
moving +1 in the x-direction, 2 in the y-direction, and +1 in the z direction
[Figure 3.24(a)].
[ 2 10]
b. To draw in the plane, first take reciprocals of the indices to
obtain the intercepts, that is:
x = 1/-2 = -1/2 y = 1/1 = 1 z = 1/0 = 
Since the x-intercept is in a negative direction, and we wish to draw the
plane within the unit cell, let’s move the origin +1 in the x-direction to 1,
0, 0. Then we can locate the x-intercept at 1/2 and the y-intercept at +1.
The plane will be parallel to the z-axis [Figure 3.24(b)].

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 Example - 11
Determining the Miller-Bravais Indices for Planes and Directions
Determine the Miller-Bravais indices for planes A and B and
directions C and D.

Miller-Bravais indices are

obtained for crystallographic
planes in HCP unit cells by
using a four-axis coordinate
system. The planes labeled A
and B and the direction
labeled C and D are those
discussed in Example 11.

(c) 2003 Brooks/Cole Publishing /

61
Thomson Learning™
SOLUTION

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SOLUTION (Continued)

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Planes in the Unit Cell

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Close-Packed Planes and Directions

 Atoms are in continuous contact.

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The ABABAB stacking sequence
of close-packed planes produces
the HCP structure.

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 (c) 2003 Brooks/Cole Publishing / Thomson Learning™

The ABCABCABC stacking sequence of close-packed planes produces

the FCC structure.

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Anisotropic Behavior

 A material is anisotropic if its properties depend on the

crystallographic direction along which the property is
measured.

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Interstitial Sites

 Interstitial sites - Locations between the ‘‘normal’’ atoms or

ions in a crystal into which another - usually different - atom or
ion is placed. Typically, the size of this interstitial location is
smaller than the atom or ion that is to be introduced.
 Cubic site - An interstitial position that has a coordination
number of eight. An atom or ion in the cubic site touches eight
other atoms or ions.
 Octahedral site - An interstitial position that has a coordination
number of six. An atom or ion in the octahedral site touches six
other atoms or ions.
 Tetrahedral site - An interstitial position that has a coordination
number of four. An atom or ion in the tetrahedral site touches
four other atoms or ions.
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 (c) 2003 Brooks/Cole Publishing / Thomson Learning™

The location of the interstitial sites in cubic unit cells. Only

representative sites are shown.

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Example - 12
Calculating Octahedral Sites
Calculate the number of octahedral sites that uniquely belong to
one FCC unit cell.

SOLUTION
The octahedral sites include the 12 edges of the unit cell, with the
coordinates.

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SOLUTION (Continued)

Each of the sites on the edge of the unit cell is shared between
four unit cells, so only 1/4 of each site belongs uniquely to each
unit cell.

Therefore, the number of sites belonging uniquely to each cell

is:

(12 edges) (1/4 per cell) + 1 center location

= 4 octahedral sites

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Interstitial Sites

 If the interstitial atom becomes too large, it prefers to

enter a site having a larger coordination number.

 An atom whose radius ratio is between 0.225 and 0.414

will enter a tetrahedral site; if its radius is larger than
0.414, it will enter an octahedral site instead.

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74
 Example - 13
Design of a Radiation-Absorbing Wall
We wish to produce a radiation-absorbing wall composed of 10,000
lead balls, each 3 cm in diameter, in a face-centered cubic
arrangement. We decide that improved absorption will occur if we
fill interstitial sites between the 3-cm balls with smaller balls. Design
the size of the smaller lead balls and determine how many are
needed.

Calculation of an octahedral
interstitial site.
(c) 2003 Brooks/Cole Publishing /
Thomson Learning™ 75
SOLUTION
First, we can calculate the diameter of the octahedral sites located
between the 3-cm diameter balls. Figure 3.30 shows the
arrangement of the balls on a plane containing an octahedral site.

This is consistent with Table 3-6. Since r = R = 0.414, the radius of

the small lead balls is

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Quasicrystals
 Quasicrystals (QCs) have a structure that is ordered but not periodic.
 They show a locally rotational repeating periodicity in the atomic
structure.
 Aluminum alloys with such metals as iron,
cobalt, or nickel are the most common structures
that have quasicrystal structures
 Compounds contain quasicrystal are the
candidate materials for the aerospace application,
surgical instrument, ınsulator, coating etc.
 Quasicrystals have a long-range
quasiperiodic order but no three-dimensional
translational periodicity.

 The 2011 Nobel Prize in chemistry

was awarded to an Israeli scientist Dan
Shechtman discovered quasicrystal.
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Ionic Crystals
Factors need to be considered in order to understand structures of
ionic crystals
 Ionic Radii
The crystal structures of ionically bonded compounds often can be described
by placing the anions at the normal lattice points of a unit cell, with the
cations then located at one or more of the interstitial sites
 Electrical Neutrality
If the charges on the anion and the cation are identical and the coordination
number for each ion is identical to ensure a proper balance of charge, then
the compound will have a formula AX. If the valence of the cation is +2 and
that of the anion is -1, then twice as many anions must be present, and the
formula is AX2.
 Cesium Chloride Structure (radius ratio=rcs/rcl=1.67/1.81=0.92)
 Sodium Chloride Structure (rna/rcl=0.97/1.81=0.536)
 Zinc Blende Structure (rzn/rs=0.74/1.84=0.402)
 Fluorite Structure (rca/rf=0.99/1.36=0.728)
 Wurtzite Structure (rBe/rO=0.35/1.32=0.265) 78
Ionic Crystals

Factors need to be considered in order to understand structures of ionic

crystals
 Connection between Anion Polyhedra
As a rule, the coordination polyhedra (formed by the close packing of anions) will
share corners, as opposed to faces or edges. This is because in corner sharing
polyhedra, electrostatic repulsion between cations is reduced considerably and this
leads to the formation of a more stable crystal structure.
A number of common structures in ceramic materials are described in the following
discussions. Compared to metals, ceramic structures are more complex. The lattice
constants of ceramic materials tend to be larger than those for metallic materials
because electrostatic repulsion between ions prevents close packing of both anions
and cations.
 CsCl

CaF2 ZnS

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Cesium Chloride (CsCl) Structure

 Simple cubic
 Cubic interstitial site filled by Cl anion
 rCs / rCl = 1.67 / 1.81 = 0.92  CN = 8

Cl-
81
Sodium Chloride (NaCl) Structure

 FCC structure, with Na cations at the four octahedral sites and

Cl anions at FCC positions .

 rNa / rCl = 0.97 / 1.81 = 0.536  CN = 6

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Zinc Blende (ZnS) Structure

 Sulfide ions enter tetrahedral sites in a unit cell.

 rZn / rS = 0.74 / 1.84 = 0.402  CN = 4

83
Zn
Fluorite (CaF2) Structure
 FCC structure
 Anions locate at all eight of the tetrahedral positions
 Four cations and eight anions per cell and the formula is AX2
 CN = 8 for calcium and CN = 4 for fluoride

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Wurtzite (ZnS) Structure

 Ions are placed in the interstitial locations of HCP structure.

 Half of the tetrahedral sites filled with anions

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 86
CaTiO3
SrTiO3
Calcium Titanate
(c) 2003 Brooks/Cole Publishing /
Thomson Learning
Example - 14
Radius Ratio for KCl
For potassium chloride (KCl), (a) verify that the compound has the
cesium chloride structure and (b) calculate the packing factor for
the compound.
SOLUTION

87
SOLUTION (Continued)

88
Example - 15

Illustrating a Crystal Structure and Calculating Density

Show that MgO has the sodium chloride crystal structure and
calculate the density of MgO.

SOLUTION

From Appendix B, rMg+2 = 0.066 nm and rO-2 = 0.132 nm, so:

rMg+2 /rO-2 = 0.066/0.132 = 0.50
Since 0.414 < 0.50 < 0.732, the coordination number for
each ion is six, and the sodium chloride structure is possible.

89
 SOLUTION (Continued)

The atomic masses are 24.312 and 16 g/mol for magnesium and
oxygen, respectively. The ions touch along the edge of the cube, so:
a0 = 2 rMg+2 + 2rO-2 = 2(0.066) + 2(0.132) = 0.396 nm = 3.96  10-8 cm

2
(4Mg )(24.312)  (4O )(16)
-2
  8
 4.31g / cm
3

(3.96  10 cm) (6.02  10 )

3 23

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 (c) 2003 Brooks/Cole Publishing / Thomson Learning™

(a) The zinc blende unit cell, (b) plan view.

91
Example - 16

Calculating the Theoretical Density of GaAs

The lattice constant of gallium arsenide (GaAs) is 5.65 Å. Show that

the theoretical density of GaAs is 5.33 g/cm3.

SOLUTION
For the ‘‘zinc blende’’ GaAs unit cell, there are four Ga and four As
atoms per unit cell.
From the periodic table (Chapter 2):
Each mole (6.023  1023 atoms) of Ga has a mass of 69.7 g.
Therefore, the mass of four Ga atoms will be (4 * 69.7/6.023 
1023) g.

92
SOLUTION (Continued)

Each mole (6.023  1023 atoms) of As has a mass of 74.9 g.

Therefore, the mass of four As atoms will be (4 * 74.9/6.023
 1023) g. These atoms occupy a volume of (5.65  10-8)3 cm3.

4(69.7  74.9) / 6.023  10

23
mass
density   8
(5.65  10 cm)
3
volume

Therefore, the theoretical density of GaAs will be 5.33 g/cm3.

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 94

(c) 2003 Brooks/Cole Publishing / Thomson Learning

Corundum
Crystal structure of a new high Tc ceramic superconductor based on
a yttrium barium copper oxide. These materials are unusual in that
they are ceramics, yet at low temperatures their electrical resistance
vanishes. (Source: ill.fr/dif/3D-crystals/superconductor.html; © M.
Hewat 1998.)

95
Covalent Structures

 Covalently bonded materials frequently have complex

structures in order to satisfy the directional restraints
imposed by the bonding.

 Diamond cubic (DC) - A special type of face-centered cubic

(FCC) crystal structure found in carbon, silicon, and other
covalently bonded materials.
 The atoms at the corners of the tetrahedral cubes provide atoms at the
regular FCC lattice points. Four additional atoms are present within the DC
unit cell from the atoms at the center of the tetrahedral cubes. We can
describe the DC crystal structure as an FCC lattice with two atoms
associated with each lattice point.

96
Diamond Cubic Structure
 Covalently bonded materials frequently must have complex structures
in order to satisfy the directional restraints imposed by the bonding.

 Elements such as silicon, germanium, and carbon in its diamond form

are bonded by four covalent bonds and produce a tetrahedron.
This large cube contains eight
smaller cubes that are the size
of the tetrahedral cube;
however, only four of the cubes
contain tetrahedra.

Tetrahedron Diamond cubic (DC) unit cell

97
 (c) 2003 Brooks/Cole Publishing / Thomson Learning
(a) Tetrahedron and (b) the diamond cubic (DC) unit cell. This open
structure is produced because of the requirements of covalent
bonding.

98
Crystalline Silica

 Silica has a crystalline

ceramic structure that is
partly covalent and partly
ionic.
 This figure shows the
crystal structure of one of
the forms of silica, β-
cristobalite, which is a
complicated FCC structure.
 rSi/rO = 0.0.42/0.132=
0.318 so the coordination
number is 4.
99
 (c) 2003 Brooks/Cole Publishing / Thomson
Learning™

Connection between anion polyhedra. Different possible

connections include sharing of corners, edges, or faces. In this
figure, examples of connections between tetrahedra are
shown.
100
Example - 17

Determining the Packing Factor for Diamond Cubic Silicon

Determine the packing factor for diamond cubic silicon.
Thomson Learning
(c) 2003 Brooks/Cole Publishing /

Determining the relationship between

lattice parameter and atomic radius in a
diamond cubic cell. 101
 SOLUTION
We find that atoms touch along the body diagonal of the cell.
Although atoms are not present at all locations along the body
diagonal, there are voids that have the same diameter as atoms.
Consequently:

Compared to close packed structures this is a relatively open structure.

102
Example - 18

Calculating the Radius, Density, and Atomic Mass of Silicon

The lattice constant of Si is 5.43 Å . What will be the radius of a

silicon atom? Calculate the theoretical density of silicon. The
atomic mass of Si is 28.1 gm/mol.

SOLUTION

103
 Learning
(c) 2003 Brooks/Cole Publishing / Thomson
The silicon-oxygen tetrahedron and the resultant β-cristobalite form
of silica. 104
 105
The unit cell of crystalline polyethylene.
(c) 2003 Brooks/Cole Publishing / Thomson Learning
Example - 19
Calculating the Number of Carbon and Hydrogen Atoms in
Crystalline Polyethylene
How many carbon and hydrogen atoms are in each unit cell of
crystalline polyethylene? There are twice as many hydrogen atoms
as carbon atoms in the chain. The density of polyethylene is about
0.9972 g/cm3.
SOLUTION
If we let x be the number of carbon atoms, then 2x is the number of
hydrogen atoms. From the lattice parameters shown in previous
slide:
( x)(12g / mol )  (2 x)(1g / mol )
  8 8 8
(7.41  10 cm )(4.94  10 cm )(2.55  10 cm )(6.02  10 )
23

x = 4 carbon atoms per cell and 2x = 8 hydrogen atoms per cell

106
Diffraction Techniques for Crystal Structure Analysis

 Diffraction - The constructive interference, or reinforcement, of

a beam of x-rays or electrons interacting with a material. The
diffracted beam provides useful information concerning the
structure of the material.
 Bragg’s law - The relationship describing the angle at which a
beam of x-rays of a particular wavelength diffracts from
crystallographic planes of a given interplanar spacing.
 In a diffractometer a moving x-ray detector records the 2θ
angles at which the beam is diffracted, giving a characteristic
diffraction pattern

107
 (a) Destructive and (b) reinforcing
interactions between x-rays and the
(c) 2003 Brooks/Cole Publishing / Thomson Learning

crystalline material. Reinforcement

occurs at angles that satisfy Bragg’s
law.

108
Photograph of a XRD diffractometer. (Courtesy of H&M Analytical
Services.) 109
(a) Diagram of a diffractometer, showing powder sample, incident and
diffracted beams. (b) The diffraction pattern obtained from a sample
of gold powder. 110
Example - 20

Examining X-ray Diffraction

The results of a x-ray diffraction experiment using x-rays with λ =
0.7107 Å (a radiation obtained from molybdenum (Mo) target) show
that diffracted peaks occur at the following 2θ angles:

Determine the crystal structure, the indices of the plane producing

each peak, and the lattice parameter of the material.
111
SOLUTION

We can first determine the sin2 θ value for each peak, then
divide through by the lowest denominator, 0.0308.

112
SOLUTION (Continued)

We could then use 2θ values for any of the peaks to calculate the
interplanar spacing and thus the lattice parameter. Picking peak 8:
2θ = 59.42 or θ = 29.71

This is the lattice parameter for body-centered cubic iron.

113
Photograph of a transmission electron microscope (TEM) used for
analysis of the microstructure of materials. (Courtesy of JEOL USA, Inc.)

114
A TEM micrograph of an aluminum alloy (Al-7055) sample. The
diffraction pattern at the right shows large bright spots that
represent diffraction from the main aluminum matrix grains. The
smaller spots originate from the nano-scale crystals of another
compound that is present in the aluminum alloy. (Courtesy of Dr.
JÖrg M.K. Wiezorek, University of Pittsburgh.)
115