Chapter 1

Structures of Solids

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 Introduction to Solid-State Chemistry

Solid state chemistry is concerned mainly

with crystalline inorganic materials, their
synthesis, structures, properties and
applications.

Materials chemistry

Synthesis – structure determination –

physical properties – new materials
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 Materials Science
Processing and fabrication – characterization –
optimization of properties and testing –
improved/new materials for engineering
applications in products or devices.

Materials science focuses on materials that are

already known to be useful or have the potential
to be developed for applications, either by
compositional control to optimize properties or
by fabrication into desired forms, shapes or
products.
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 Materials science therefore includes whatever
aspects of chemistry, physics and engineering that
are necessary to achieve the desired aims.

Materials chemistry is much more than just a

subset of materials science, however, since it is
freed from the constraint of a focus on specific
applications;

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 Materials chemists love to synthesize new
materials and measure their properties, some of
which may turn out to be useful and contribute to
the development of new industries, but they do
this within an overarching interest in new
chemistry, new structures and improved
understanding of structure – composition –
property relationships.

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 Crystalline and amorphous are two basic sub-
types of solids, which may look similar on the
outside, but are actually vastly different from the
inside.

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 Origins
The word crystal is derived from the ancient Greek
word krustallos, which means both ice and crystal.

The word amorphous too has originated from Greek

words a (without) and morphé (shape), which
together mean shapeless.

We all are aware that solids are one of the three

basic forms of matter.

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 Crystalline and Amorphous Solids

But how many of us know that there are actually

sub-forms of solids as well?

For instance, just try comparing the properties of a

diamond with those of rubber, and the difference
between the two would become so very obvious.
In the world of chemistry, diamonds and rubber
are known as crystalline and amorphous solids
respectively.

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 Crystalline and Amorphous Solids
Even though both of them are solids physically,
chemically, they are vastly different from each other.

Studying these different types of solids is essential

for understanding what the world around us is made
up of.

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 Crystalline and Amorphous Solids
Crystalline Solids
By definition, a crystalline solid, also simply known
as a crystal, is a solid material whose basic
constituents such as atoms, ions, and molecules are
arranged in a highly ordered and well-defined
microscopic structure, known as a crystal lattice.

These solids are formed in a process known as

crystallization, wherein, the lattice structure gets
extended in all directions.

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 Macroscopic single crystal structures too are
found in nature having the characteristic
crystalline shape, comprising flat faces and
characteristic orientations.

These include snowflakes, diamonds, table salt,

etc.

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 Amorphous Solids
Amorphous solids are basically the exact opposite
of crystalline solids.

While an amorphous solid may display some finite

order in terms of the arrangement of its atoms,
ions, and molecules, it will clearly lack the long-
range ordered structure that a crystalline solid
exhibits.

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 The arrangement of elements in amorphous solids
is mostly random and disorderly.

Because of this, when amorphous solids are cut,

they break into uneven pieces.

Examples include window glass, various

polymers, rubber, etc.

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 Crystalline vs. Amorphous Solids
Characteristic Geometry

The atoms, ions, and molecules in a crystalline

solid are arranged in such a way that they have a
definite shape and structure, known as
characteristic geometry.

In amorphous solids, such a characteristic

geometry isn’t present

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 Crystalline vs. Amorphous Solids
X-ray Diffraction

The elemental components of crystalline solids are

arranged in regular arrays.

Hence, when they are exposed to X-rays, each solid

produces a unique diffraction pattern, which can be
used for its identification.

Different amorphous solids don’t show very

distinctive diffraction patterns, as their elemental
components aren’t arranged in regular arrays.
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 Crystalline vs. Amorphous Solids
Melting Point

Crystalline solids have sharp melting points, that

is, they change into liquids at definite temperatures.

Amorphous solids, on the other hand, are thought

to be liquids at all temperatures.

This is because, on being heated, they do not

abruptly change into liquids, but instead soften and
start flowing in a semisolid form.

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 Crystalline vs. Amorphous Solids
Cooling Characteristics

The graphical representation of the cooling

characteristics of an amorphous solid gives a smooth
curve, while that of a crystalline solid has two break
points along the curve.

These break points indicate the beginning and end of

the crystallization process, during which, the
temperature remains constant.

This happens because, in the crystallization process,

energy is released, which goes on to compensate for
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 Crystalline vs. Amorphous Solids
Isotropy and Anisotropy

Amorphous solids display several of the

characteristics of a liquid.

Just like in liquids, in amorphous solids, properties

such as electrical conductivity, thermal conductivity,
mechanical strength, refractive index, etc., remain
the same in all directions.

Hence, they are known as isotropic materials.

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 Crystalline vs. Amorphous Solids
Crystalline solids, on the other hand, have these
characteristics in varying amounts in different
directions.

For example, light traveling through a crystal

travels at different speeds in different directions
within it.

That is why crystalline solids are known as

anisotropic.

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 Crystalline vs. Amorphous Solids
Cutting

A crystalline solid, when cut using the right cutting

tool, cleanly splits into two parts.

An amorphous solid, on the other hand, give

irregular cuts, because of its uneven composition.

Thus, crystalline and amorphous, both are solids that

may exhibit similarities in terms of their
appearances, but are actually vastly different from
each other in terms of their elemental makeup and
properties.
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 Difference between Crystalline and Amorphous
CRYSTALLINE SOLIDS AMORPHOUS SOLIDS
Atoms are arranged in They do not have regular
regular 3 dimension arrangement
Sharp melting point No particular melting point
Anisotropic Isotropic
True solid Pseudo solid
Symmetrical Unsymmetrical
More rigid Less rigid
Long range order Short range order
Example: Potassium nitrate, Example: Cellophane,
copper polyvinyl chloride
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 Crystalline Solids

 A Crystalline Solid is the solid form of a

substance in which the atoms or molecules are
arranged in a definite, repeating pattern in three
dimensions.

 Single Crystals, ideally have a high degree of

order, or regular geometric periodicity,
throughout the entire volume of the material.

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 A material is a crystal if it has essentially a sharp
diffraction pattern

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 Crystallography
Crystallography ≡ The branch of science that
deals with the geometric description of crystals &
their internal arrangements.

It is the science of crystals & the math used to

describe them.

It is a VERY OLD field which pre-dates Solid

State Physics by about a century! So much of the
terminology (& theory notation) of Solid State
Physics originated in crystallography.
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 Single Crystal has an atomic structure that repeats
periodically across its whole volume.

Even at infinite length scales, each atom is related to

every other equivalent atom in the structure by
translational symmetry.

Single Crystals
Single Pyrite
Amorphous
Crystal
Solid
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 Polycrystalline Solids

A Polycrystalline Solid is made up of an aggregate

of many small single crystals(crystallites or grains).

Polycrystalline materials have a high degree of

order over many atomic or molecular
dimensions.

These ordered regions, or single crystal regions,

vary in size & orientation with respect to one
another.
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 These regions are called grains(or domains)& are
separated from one another by grain boundaries.

The atomic order can vary from one domain to the

next.

The grains are usually 100 nm -100 microns in

diameter.

Polycrystals with grains that are < 10 nm in diameter

are called nanocrystallites.

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 Polycrystalline
Pyrite
Grain

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 CRYSTAL LATTICE AND UNIT CELL
Crystal lattice:

The regular arrangement of an infinite set of points

which describes the three dimensional arrangement
of constituent particles ( atom, ions, molecules) in
space is called a crystal lattice or space lattice

The space lattice may be one, two or three

dimensional depending upon the number of
parameters required to define it.

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 There are only 14 possible three dimensional
lattices. They are called Bravais Lattice

Following are the characteristics of a crystal lattice

(i) Each point in a lattice is called lattice point or
lattice site
(ii) Each point in a crystal lattice represents one
constituent particle which may be atom, ion or
molecule
(ii) Lattice points are joined by straight line to
bring out the geometry of the lattice

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 The smallest repeating units of space lattice which
when repeated over and over again in three
dimensions, result into whole of the space lattice
of crystal is called unit cell.

The crystal may, therefore be considered to

consists of infinite number of unit cells.

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 A unit cell is characterized by :
(i) its dimensions along the three edges a, b, c.
These edges may or may not be perpendicular to
each other
(ii) angle between edges α ( between b and c ) ; β (
between a and c ) and γ ( between a and b).
Thus unit cell is characterized by six parameters

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 POINT COORDINATES

The position of any point located within a unit cell

may be specified in terms of its coordinates as
fractional multiples of the unit cell edge lengths
(i.e., in terms of a, b, and c).

To illustrate, consider the

unit cell and the point P
situated therein as shown
in Figure
We specify the position of
P in terms of the
generalized coordinates

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 q, r, and s
where q is some fractional length of a along the x
axis,
r is some fractional length of b along the y axis, and
similarly for s.

Thus, the position of P is designated using

coordinates q r s with values that are less than or
equal to unity.
Furthermore, we have chosen not to separate these
coordinates by commas or any other punctuation
marks (which is the normal convention).
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 EXAMPLE PROBLEM

Location of Point Having Specified Coordinates

For the unit cell shown in the accompanying sketch
(a), locate the point having coordinates ¼ 1 ½ .

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 Solution
From sketch (a), edge lengths for this unit cell are
as follows: a 0.48 nm, b 0.46 nm, and c 0.40 nm.
Furthermore, in light of the preceding discussion,
fractional lengths are q = 1/4 , r = 1, and s = 1/2 .
Therefore, first we move from the origin of the unit
cell (point M) qa = 1/4(0.48 nm) = 0.12 nm units
along the x axis (to point N), as shown in the (b)
sketch. Similarly, we proceed rb = (1)(0.46 nm) =
0.46 nm parallel to the y axis, from point N to point
O.
Finally, we move from this position, sc = 1/2(0.40
nm) 0.20 nm units parallel to the z axis to point P
as noted again in sketch (b). This point P then
corresponds to the 1 point coordinates.

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 CRYSTALLOGRAPHIC PLANES

unit cell is the basis, with the three-axis coordinate

system as represented

In all but the hexagonal crystal system, crystallographic

planes are specified by three Miller indices as (hkl).

Any two planes parallel to each other are equivalent and

have identical indices. The procedure used to determine
the h, k, and l index numbers is as follows:

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 1. If the plane passes through the selected origin,
either another parallel plane must be constructed
within the unit cell by an appropriate translation, or a
new origin must be established at the corner of another
unit cell.
2. At this point the crystallographic plane either
intersects or parallels each of the three axes; the length
of the planar intercept for each axis is determined
in terms of the lattice parameters a, b, and c.

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 3. The reciprocals of these numbers are taken. A plane
that parallels an axis may be considered to have an
infinite intercept, and, therefore, a zero index.
4. If necessary, these three numbers are changed to the
set of smallest integers by multiplication or division
by a common factor.
5. Finally, the integer indices, not separated by
commas, are enclosed within parentheses, thus: (hkl).

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 An intercept on the negative side of the origin is
indicated by a bar or minus sign positioned over
the appropriate index.

Furthermore, reversing the directions of all

indices specifies another plane parallel to, on the
opposite side of, and equidistant from the origin.

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 Figure: Representations of a series each of the (a) (001), (b) (110), and
(c) (111) crystallographic planes.
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 Determination of Planar (Miller) Indices
Determine the Miller indices for the plane shown in the
accompanying sketch (a).

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 Solution
Because the plane passes through the
selected origin O, a new origin must be
chosen at the corner of an adjacent unit cell,
taken as O' and shown in sketch (b).This
plane is parallel to the x axis, and the
intercept may be taken as ∞a.The y and z
axes’ intersections, referenced to the new
origin O', are -b and c/2 , respectively. Thus,
in terms of the lattice parameters a, b, and c,
these intersections are ∞, -1, and 1/2 . The
reciprocals of these numbers are 0, -1, and
2; because all are integers, no further
reduction is necessary. Finally, enclosure in
parentheses yields (0 -12).
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 These steps are briefly summarized here:

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 Importance of Miller Indices

In Materials Science it is important to

have a notation system for atomic
planes since these planes influence
• Optical properties
• Reactivity
• Surface tension
• Dislocations

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 Coordination of Ions

Coordination number, C.N. depends on the relative

size of the ions.

If all of the atoms in a crystal are the same size,

then there are two ways to pack the atoms to form a
crystal structure.

In this case, the maximum number of atoms that be

coordinated around any individual is 12.

We call this 12-fold coordination. There are two

ways that atoms can be packed in 12-fold
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 First, examine a single layer
of atoms of equal size.

Note that there are two kinds

of voids between the atoms,
those that have a sort of
triangular shape with the
triangles pointing up we'll call
B voids, and those with the
triangles pointing down we'll
call C voids.

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 If we add the next layer of atoms so that they occupy the
space above the B voids, and then add the next layer
above the A atoms, this will result in a stacking sequence
that runs AB AB AB ....etc.

This type of closest packing is referred to as hexagonal

closest packing.

It results in a hexagonal lattice with the c-axis oriented

perpendicular to the AB AB layers.

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 If after adding the layer of B atoms we place the
next layer so that the atoms occupy positions over
the C voids in the A layer, and continue the process
upward, we get a stacking sequence that runs ABC
ABC ABC.... etc.

This type of packing is referred to as cubic closest

packing.

It results in a cubic or isometric lattice with

the axis perpendicular to the layers.

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 To see what happens when one of the involved ions or
atoms becomes smaller, we need to examine the
relative sizes of the atoms.

The relative sizes are indicated by the radius ratio of

the coordinating atoms or ions.

In crystal structures we usually look at cations

surrounded by anions, so the radius ratio is defined as
Rx/Rz, where Rx is the radius of the cation, and Rz is
the radius of the surrounding anions.

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 Since the anions are usually the larger ions, this
results in decreasing values of Rx/Rz as the size of
the cation decreases.

If we decrease the size of the cation in such an

arrangement, still allowing for the surrounding
anions to touch each other and touch the cation, with
decreasing size of the cation, the coordination will
first result in 8 anions surrounding the cation.

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 This is called 8-fold coordination or cubic
coordination because the shape of the object
constructed by drawing lines through the centers of
the larger ions is a cube.

If the size of the coordinated cation becomes smaller,

it will become too small to touch the surrounding
anions.

Thus, there is limiting radius ratio that will occur

when the Rx/Rz becomes too small.

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 To see what this limit is, we
must look at the vertical plane
running through the centers
anions labeled A and B.

In this construction we can determine the radius

ratio for the limiting condition, often called the "no
rattle limit" because if the radius ratio becomes
smaller than this the cation will "rattle" in its
site. Using the Pythagorean theorem we can write:

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 (2Rz +2Rx)2 = (2Rz)2 + (22Rz)2
2Rz +2Rx = (4Rz2 + 8Rz2)
2Rz +2Rx = (12Rz2)
2Rz +2Rx = 3.464Rz
2Rx = 1.464Rz
Giving Rx/Rz = 0.732

Thus, for Rx/Rz < 0.732 the

cation will be too small or will
rattle in its site and the
structure will have to change
to 6-fold coordination.

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 Six-fold coordination is also
called octahedral coordination
because the shape defined by
drawing planes through the
center of the larger ions is an
octahedron.
Octahedral coordination is stable when Rx/Rz ,
0.732, but decreasing the radius of cation,
Rx, will eventually reach a limit where again the
smaller ion will rattle in its site.

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 The no rattle limit can be determined by
looking at the horizontal plane running
through the ions labeled C and D. In this
case we can write:
2Rz + 2Rx)2 = (2Rz)2 + (2Rz)2 = 2(4Rz2)
2Rz +2Rx = 2√2Rz
Rz + Rx = √2Rz
Rx = (√2 - 1)Rz
Rx/Rz = 0.414

For Rx/Rz < 0.414 the structure goes into 4-

fold coordination.
Planes through the centers of the larger atoms
in this case will form a tetrahedron, so 4-fold
coordination is also called tetrahedral
coordination.
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 The calculation to determine the "no rattle" limit
for tetrahedral coordination is complex (Reading
Assignment).

The result shows that the limit is reached when

Rx/Rz = 0.225.

As the radius ratio becomes smaller than this,

triangular coordination becomes the stable
configuration.

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 For triangular coordination, the
coordination number is three, that
is 3 anions surround the smaller
cation.
The "no rattle" limit is reached for
triangular coordination when
Rx/Rz becomes less than 0.155.

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 At values of Rx/Rz < 0.155 the
only way the smaller ion can be
coordinated by the larger ions is
to have 2 of the larger ions on
either side.

This 2-fold coordination is

termed linear coordination.

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 Rx/Rz C.N. Type
The table here
summarizes the Hexagonal or
cation to anion radius 1.0 12 Cubic
ratios, Rx/Rz, for Closest Packing
various coordination
numbers and gives 1.0 - 0.732 8 Cubic
the name of the 0.732 - 0.414 6 Octahedral
coordination
polyhedron for each 0.414 - 0.225 4 Tetrahedral
coordination
number. 0.225 - 0.155 3 Triangular
<0.155 2 Linear

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 Simple Cubic (SC) structure
• Rare due to poor packing (only Po has this structure)
• Close-packed directions are cube edges.

• Coordination # = 6
(# nearest neighbors)
 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
a 4
unit cell 1  (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. 3.19,
Callister 6e.
 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
a 4
unit cell 1  (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. 3.19,
Callister 6e.
 Body Centered Cubic (BCC) structure
• 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.
 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
71
 Face Centered Cubic (FCC) structure
• 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.

72
 Atomic Packing Factor: FCC
• APF for a body-centered cubic structure = 0.74
Close-packed directions:
length = 4R
= 2a
Unit cell c ontains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister 6e. atoms volume
4
unit cell 4  ( 2a/4 )3
3 atom
APF =
volume
a3
unit cell
73
 FCC stacking sequence
• ABCABC... Stacking Sequence
• 2D Projection
A
B B
C
A
A sites B C B B
C
B sites B B
C sites

A
• FCC Unit Cell B
C

74
 Hexagonal Close-Packed (HCP)
structure
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection

A sites Top layer

B sites Middle layer

A sites Bottom layer

Adapted from Fig. 3.3,
Callister 6e.

• Coordination # = 12
• APF = 0.74

75
 Theoretical density, 
# atoms/unit cell Atomic weight (g/mol)
 nA
Volume/unit cell Vc NA Avogadro's number
(cm 3 /unitcell) (6.023 x 10 23 atoms/mol)

Example: Copper
Data from Table inside front cover of Callister (see next slide):
• crystal structure = FCC: 4 atoms/unit cell
• atomic weight = 63.55 g/mol (1 amu = 1 g/mol)
• atomic radius R = 0.128 nm (1 nm = 10 c-7m)
Vc = a 3 ; For FCC, a = 4R/ 2 ; Vc = 4.75 x 10 -23 cm 3
Result: theoretical Cu = 8.89 g/cm 3
Compare to actual: Cu = 8.94 g/cm 3
14
 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
metals ceramic polymer
Graphite/
Metals/ Composites/
s s Alloys
Ceramics/ Polymers
fibers
Semicond
30
Why? Based on data in Table B1, Callister
Platinum *GFRE, CFRE, & AFRE are Glass,
Metals have... 20 Gold, W
Tantalum 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).

• large atomic mass

3)
Steels
Tin, Zinc
Zirconia
Ceramics have... 5
• less dense  (g/cm 4
3
Titanium
Al oxide
Diamond
Si nitride
packing (covalent Aluminum Glass -soda
Concrete
Glass fibers
Silicon PTFE GFRE*
bonding) 2
Magnesium Graphite Carbon fibers
CFRE *
• often lighter elements Silicone
PVC Aramid fibers
AFRE *
PET
Polymers have... 1 PC
HDPE, PS
• poor packing PP, LDPE

(often amorphous) 0.5

Wood
• lighter elements (C,H,O) 0.4
0.3
Composites have... Data from Table B1, Callister 6e.
• intermediate values 16
 Polycrystals
• Most engineering materials are polycrystals.

Adapted from Fig. K,

color inset pages of
Callister 6e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
1 mm

• Nb-Hf-W plate with an electron beam weld.

• Each "grain" is a single crystal.
• If crystals are randomly oriented,
overall component properties are not directional.
• Crystal sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
18
 Single vs polycrystals
• Single Crystals E (diagonal) = 273
GPa Data from Table 3.3,
-Properties vary with Callister 6e.
(Source of data is R.W.
direction: anisotropic. Hertzberg, Deformation
and Fracture Mechanics
-Example: the modulus of Engineering
Materials, 3rd ed., John
of elasticity (E) in BCC iron: Wiley and Sons, 1989.)

E (edge) = 125
• Polycrystals GPa
-Properties may/may not 200 m Adapted from Fig.
4.12(b), Callister 6e.
vary with direction. (Fig. 4.12(b) is courtesy
of L.C. Smith and C.
-If grains are randomly Brady, the National
Bureau of Standards,
oriented: isotropic. Washington, DC [now
the National Institute of
(Epoly iron = 210 GPa) Standards and
-If grains are textured, Technology,
Gaithersburg, MD].)
anisotropic.

19
Anisotropy
 Demo: Heating and cooling of iron wire

The same atoms can

• Demonstrates "polymorphism" have more than one
crystal structure.
Temperature, C
Liquid
1536
BCC Stable
1391
longer
heat up
FCC Stable
shorter!
914 longer!
BCC Stable
cool down
Tc 768 magnet falls off
shorter
 Ionic bonding & structure
• Charge Neutrality:
--Net charge in the F-
structure should CaF2: Ca2+ + anions
be zero.
cation
F-

--General form: AmXp

m, p determined by charge neutrality
• Stable structures:
--maximize the # of nearest oppositely charged neighbors.
- - - - - -
+ + +
Adapted from Fig. 12.1,
Callister 6e.
- - - - - -
unstable stable stable 3
 Coordination # and ionic radii
r cation
• Coordination # increases with ranion
Issue: How many anions can you
arrange around a cation?

r cation ZnS
Coord #
ranion (zincblende)
Adapted from Fig. 12.4,
< .155 2 Callister 6e.

.155-.225 3 NaCl
(sodium
.225-.414 4 chloride)
Adapted from Fig. 12.2, Callister
6e.
.414-.732 6
CsCl
(cesium
.732-1.0 8 chloride)
Adapted from Fig. 12.3, Callister
Adapted from Table 12.2, 6e.
Callister 6e.
4
 Sample calculations of radii ratios
CN = 6 – Octahedral site CN = 4 – tetrahedral site

2rA
rC rC h 6
rA 3
rA

rC  rA  rA 2 h rC 6
rC  rA  1 
rC 2 rA 3
1 2
rA rC

6
1  0.225
rA rC  rA  6
rC 3 rA 3
 2  1  0.414
rA
 Structure of compounds: NaCl
• Compounds: Often have similar close-packed structures.
• Structure of NaCl • Close-packed directions
--along cube edges.
CN = 6

(Courtesy P.M. Anderson) (Courtesy P.M. Anderson)

13
Example: Predicting structure of FeO
• On the basis of ionic radii, what crystal structure
would you predict for FeO?
Cation Ionic radius (nm) • Answer:
Al 3+ 0.053
rcation 0.077
Fe 2+ 0.077 
ranion 0.140
Fe3+ 0.069
 0.550
Ca2+ 0.100

Anion
O2- 0.140
Cl- 0.181
Data from Table 12.3,
F- 0.133 Callister 6e.
5
Example: Predicting structure of FeO
• On the basis of ionic radii, what crystal structure
would you predict for FeO?
Cation Ionic radius (nm) • Answer:
Al 3+ 0.053
rcation 0.077
Fe 2+ 0.077 
ranion 0.140
Fe3+ 0.069
 0.550
Ca2+ 0.100
based on this ratio,
--coord # = 6
Anion --structure = NaCl
O2- 0.140
Cl- 0.181
Data from Table 12.3,
F- 0.133 Callister 6e.
5
 AmXp structures
rcation 0.100
• Consider CaF2 :   0.8
ranion 0.133
• Based on this ratio, coord # = 8 and structure = CsCl.
• Result: CsCl structure w/only half the cation sites
occupied.
• Only half the cation
sites are occupied
since
#Ca2+ ions = 1/2 # F- ions.

Adapted from Fig. 12.5, Callister

6e.

6
 AmBnXp structures

BaTiO3 MgAl2O4

Perovskite Spinels
Ti4+ Ba2+ O2- Mg2+ Al3+ O2-

CN=6 CN=12 CN=4 CN=6

 Summary
• Atoms may assemble into crystalline or
amorphous structures
• We can predict the density of a material,
provided we know the atomic weight, atomic
radius, and crystal geometry (e.g., FCC,
BCC, HCP)
• Different structures of the same material are
called polymorphs; the material is said to display
polymorphism
• Material properties generally vary with single
crystal orientation (i.e., they are anisotropic),
but properties are generally non-directional
(i.e., they are isotropic) in polycrystals with
randomly oriented grains
23
 X-RAYS TO CONFIRM CRYSTAL STRUCTURE
• Incoming X-rays diffract from crystal planes.

reflections
must be in
phase to detect
extra
 signal
Adapted from Fig. 3.2W,
 
distance
Callister 6e.
travelled
by wave “2” spacing
d

betwee
n
• Measurement x-ray planes
of: Critical intensity d=n /2sin c
angles, c, for X- (from
detector)
rays provide

atomic spacing, d.
c
20
 Crystallographic directions and planes
Objectives
•To be able to sketch directions
corresponding to indices or vice
versa in a cubic crystal system

•Specify Miller indices for planes

drawn into a unit cell

•Compute planar and linear

densities
 Crystal systems
Cubic system
•3 mutually axes;      = 90
•3 equal edges; a = b = c (lattice constants)
Cubic system is only one of
seven crystal systems!
(3) Cubic a = b =c All angles = 90
(2) Tetragonal a = b ≠c All angles = 90
(4) Orthorhombic a ≠ b ≠c All angles = 90
(2) Monoclinic a≠b≠c 2 angles = 90; one ≠ 90
(1) Triclinic a≠b≠c All angles ≠; none = 90
(1) Hexagonal a=b≠c 2 Angles = 90; one = 120
(1) Rhombohedral a=b=c All angles equal ≠ 90

Seven crystal systems are results from the arrangement

of 14 different ways of arranging equivalent points in
space – Bravais lattices
 Crystal directions
• Crystal Directions – a vector - can be z
identified in a xyz coordinate system
– 1. Choose an origin so that vector passes
through it
– 2. Write the coordinate of the end of the
direction vector
– 3. Write the coordinate of the origin of the A
direction vector B
– 4. Subtract the coordinate of the end from
the coordinate from the origin F
– 5. Multiply all numbers by a common y
integer, as necessary, to reduce fractions C
– 6. Write the crystal direction enclosed by
brackets without commas E
D
• Generally designated by [uvw]
x
• Negatives are represented with a bar
above the number
 Miller Indices (crystal planes)
• Crystal Planes can also be defined z
within a cell.
– 1. Select a convenient origin for the B
coordinate system so that the plane
does not pass through it A
– 2. Find the coordinate of the points
where the plane intersects the 3 C
major axes. (If the plane does not
intersect a particular axis, the
intercept is infinity!) y
– 3. Take the reciprocal (inverse) of D
the intercepts
– 4. The plane indices are the final
numbers obtained
x
• Generally designated as (h k l) also
called Miller indices
 Family of directions

Directions in cubic system [100], [010], [001],

[100], etc. are equivalent
The family is represented by <100>
All combinations of [123] directions
regardless of signs are also equivalent –
they are part of the <123> family
All combinations of (111) planes,
regardless of signs are equivalents
The family is represented by {111}
Not true in non-cubic systems!!!
 Planes and direction relationships
Make a note, we will be using this later

Planes and directions that share the

indices are perpendicular
[hkl] is perpendicular to (hkl)

(h.u+kv+l.w)
Cosine  =
(h2+k2+l2)1/2.(u2+v2+w2)1/2

Not true in non-cubic systems!!! 

 Linear density

• We saw that many properties depended

on crystal directions
Number of atoms centered on a segment
Linear density =
Length of segment

2 atoms ;(m)-1
LD110 =
4R
 Planar density
Properties of crystals can be dependent on the specific
plane (chemical, mechanical, magnetic etc.)
Number of atoms centered on a plane
Planar density =
• Area of plane
• Example: Find FCC (lead)
4R/√2
with Pb radius of 1.750 Å
• –PD110 = 2atoms/8R2√2; (m)-2
• –PD111 = 2atoms/4R2√2; (m)-2
• Both directions and planes
4R/2√3 4R (their densities) are important
to the mechanism of slip. It is
the mechanism of metal
deformation!!!
 Use of interplanar spacing

reflections
must be in
phase to detect
extra
 signal

 
distance
travelled
by wave “2” spacing a
d =
betwee (hkl)
planes (h2+k2+l2)1/2
n
Parallel planes of atoms
Bragg’s Law: n = 2d sin 
Allows the determination of
• Crystal structure
• Crystal orientation
• Lattice parameter
• Compound identification
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