CE 207 MATERIAL SCIENCE AND

ENVIRONMENTAL SUSTAINABILITY

Lecture #03-07
The Structure of Crystalline Solids

Moriom Akter
Lecturer
CRYSTALLINE MATERIAL
A crystalline material is one in which the atoms are situated in a repeating or
periodic array over large atomic distances 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.

CRYSTAL STRUCTURE
The manner in which atoms, ions, or molecules are spatially arranged is
called the crystal structure of the crystalline solid. Metals have relatively
simple crystal structures whereas the ceramic and polymeric materials show
complex crystal structures.

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ATOMIC HARD SPHERE MODEL VS LATTICE
In atomic hard sphere model, atoms (or ions) are thought of as being
identical solid spheres having well-defined diameters and in which nearest-
neighbor atoms touch one another.
In lattice, atoms (or ions) are thought of as being points, positioned at the
center of the spheres of atomic hard spheres, thus a three-dimensional array
of points.

Atomic hard sphere model Lattice structure

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COORDINATION NUMBER
For metals, the coordination number is the total number of nearest-neighbor
or touching atoms that each atom has.

ATOMIC PACKING FACTOR (APF)

The APF is the sum of the sphere volumes of all atoms (equivalent atoms)
within a unit cell (assuming the atomic hard sphere model) divided by the
unit cell volume.

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UNIT CELL
The small group of atoms which form crystalline solids by repeating over
large range is called unit cell. Unit cells for most crystal structures are
parallelepipeds or prisms having three sets of parallel faces .
METALLIC CRYSTAL STRUCTURES
The atomic bonding in metals is metallic and thus nondirectional in nature.
Consequently, there are minimal restrictions as to the number and position of
nearest-neighbor atoms; this leads to relatively large numbers of nearest
neighbors and dense atomic packings for most metallic 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.

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THE FACE-CENTERED CUBIC CRYSTAL STRUCTURE
The crystal structure where the unit cell has cubic # Relation between
geometry, with atoms located at each of the corners cube edge a and
and the centers of all the cube faces is called the atoms’ radius R,
face-centered cubic (FCC) crystal structure.
Example: copper, aluminum, silver, gold etc.
# Number of
associated whole
atom = 4
# Coordination
number = 12
# Atomic packing
factor (APF) = 0.74
Atomic hard sphere model Lattice model https://www.youtube.com/watch?v=GSPVC34ijIA

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THE BODY-CENTERED CUBIC CRYSTAL STRUCTURE
The crystal structure where the unit cell has cubic # Relation between
geometry, with atoms located at all eight corners cube edge a and
and a single atom at the cube center is called the atoms’ radius R,
body-centered cubic (BCC) crystal structure.
Example: chromium, iron (α), Molybdenum etc.
# Number of
associated whole
atom = 2
# Coordination
number = 8
# Atomic packing
factor (APF) = 0.68
Atomic hard sphere model Lattice model https://www.youtube.com/watch?v=_9RnbGqtkd4
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THE HEXAGONAL CLOSE-PACKED CRYSTAL STRUCTURE
In HCP structure, the top and bottom faces of the # Relation between
unit cell consist of six atoms that form regular hexagon’s edge a,
hexagons and surround a single atom in the center. height c and atoms’
Another plane that provides three additional atoms radius R, a=2R;
to the unit cell is situated between the top and 2
𝑐 = 4𝑅 ; c/a= 1.633
bottom planes totally inside the unit cell. 3

Example: cadmium, cobalt, zinc etc. # Number of

associated whole
atom = 6
# Coordination
number = 12
# Atomic packing
Atomic hard sphere model Lattice model factor (APF) = 0.74
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https://www.youtube.com/watch?v=_OhQv5gsoSQ
CRYSTAL STRUCTURE IN DIFFERENT METALS

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EXAMPLE PROBLEM 3.1
Determination of FCC Unit Cell Volume: Calculate the volume of an FCC
unit cell in terms of the atomic radius R.
Solution:

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EXAMPLE PROBLEM 3.2
Computation of
the Atomic
Packing Factor
for FCC: Show
that the atomic
packing factor
for the FCC
crystal structure
is 0.74.
Solution:

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DENSITY COMPUTATIONS
Theoretical density ρ can be n = number of atoms associated
calculated from the knowledge of with each unit cell
crystal structure. A = atomic weight
𝑉𝑐 = volume of the unit cell
𝑁𝐴 = Avogadro’s number
(6.023 × 1023 atoms/mol)
EXAMPLE PROBLEM 3.3
Theoretical Density Computation for Copper: 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 the answer with its
measured density.
Solution:
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POLYMORPHISM AND ALLOTROPY
Polymorphism is the ability of an elemental solid material to exist in more
than one crystal structure.
Allotropy is the ability of chemical elements to exist in two or more
different forms in the same physical state.
In the case of crystal solids, allotropy is a particular case of polymorphism.

# carbon: graphite is the stable # pure iron: has a BCC crystal

polymorph at ambient conditions, structure at room temperature,
whereas diamond is formed at which changes to FCC iron at
extremely high pressures. 912˚C. https://sciencedemonstrations.fas.harvard.edu/presentations/bcc-fcc
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CRYSTAL STRUCTURE VS CRYSTAL SYSTEMS
A crystal structure is described by both the geometry of, and atomic
arrangements within, the unit cell, whereas a crystal system is described only
in terms of the unit cell geometry. For example, face-centered cubic and
body-centered cubic are crystal structures that belong to the cubic crystal
system.

LATTICE PARAMETERS
The unit cell geometry is completely defined in terms of
six parameters: the three edge lengths a, b, and c, and
the three interaxial angles α, β and γ. These are indicated
in figure and termed as the lattice parameters of a
crystal structure.

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SEVEN CRYSTAL SYSTEM

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POINT COORDINATES
The position of any point located Example: Determine the point
within a unit cell may be specified coordinate of point P.
in terms of its coordinates as Step 1: 0.6a, 0.5b, 0.7c
fractional multiples of the unit cell Step 2:
0.6𝑎 0.5𝑏 0.7𝑐
, , = 0.6, 0.5, 0.7
edge lengths (i.e., in terms of a, b, 𝑎 𝑏 𝑐
and c). Steps of point coordinate Step 3: 0.6 0.5 0.7 (Ans)
determination.
Step 1: Find the x, y, z coordinate
Step 2: Divide the x value with a,
y value with b and z value with c. 0.7c

Step 3: State the found results 0.6a

separating by a space.
0.5b 16
EXAMPLE PROBLEM 3.4
Location of Point Having Specified Coordinates: For the unit cell shown
1 1
in the accompanying sketch (a), locate the point having coordinates 1 .
4 2
Solution:

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EXAMPLE PROBLEM 3.5
Specification of Point Coordinates: Specify point coordinates for all atom
positions for a BCC unit cell.
Solution:

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CRYSTALLOGRAPHIC DIRECTIONS
A crystallographic direction is defined as a line between two points, or a
vector. The following steps are utilized in the determination of the three
directional indices:
Step 1: Identify the starting point of arrow as origin.
Step 2: Determine x, y, z coordinate using origin found at step 1.
Step 3: Divide the x value with a, y value with b and z value with c.
Step 4: Reduce the found results to lowest integer by multiplication or
division and represent negative sign above as bar.
Step 5: State the found results separating by a space and enclosed by a third
( [] )bracket.

Indices found in this procedure is called Miller indices.

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CRYSTALLOGRAPHIC DIRECTIONS (Cont.)
Example: Determine the given crystallographic direction.
a Step 1: O’ is the new origin.
Step 2: (x, y, z) = ( -a, 0.5b, c)
−𝑎 0.5𝑏 𝑐
Step 3: , , = -1, 0.5, 1
𝑎 𝑏 𝑐
c b Step 4: multiplying by 2, (͞2, 1, 2)
Step 5: [ ͞2 1 2 ]
O’
When the spacing of atoms along each direction is the same for several
nonparallel directions with different indices, they are called equivalent
directions. These equivalent directions are grouped together into a family,
which are enclosed in angle brackets. For example, in cubic crystals, [1 0 0],
[͞1 0 0 ], [0 1 0], [0 ͞1 0 ], [0 0 1], and [ 0 0 ͞1] are equivalent, thus: <100>.
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EXAMPLE PROBLEM 3.6
Determination of Directional
Indices: Determine the indices for
the direction shown in the
accompanying figure.

Solution:

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EXAMPLE PROBLEM 3.7
Construction of Specified Crystallographic Direction
Draw a [1 ͞1 0 ] direction within a cubic unit cell.
Solution:

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CRYSTALLOGRAPHIC DIRECTIONS: HEXAGONAL CRYSTALS
In case of hexagonal crystal system, directions are determined using four-
axis coordinate system. The three axes are all contained within a single plane
(basal plane) and are at 120˚ angles to one another. The z axis is
perpendicular to this basal plane. Steps of determination:
Step 1: Determine the Miller indices [u’ v’ w’].
Step 2: Convert [u’ v’ w’] into [u v t w] using the following relations:
1 1
𝑢 = 2𝑢 − 𝑣 ; 𝑣 = 2𝑣 ′ − 𝑢′ ; 𝑡 = − 𝑢 + 𝑣 ; 𝑤 = 𝑤′
′ ′
3 3
Step 3: Reduce the found results to lowest integer by multiplication or
division and represent negative sign above as bar.
Step 4: State the found results separating by a space and enclosed by a third
bracket.
Indices found in this procedure is called Miller–Bravais indices.
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CRYSTALLOGRAPHIC DIRECTIONS: HEXAGONAL CRYSTALS

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EXAMPLE PROBLEM 3.8
Determination of Directional Indices for a Hexagonal Unit Cell:
Determine the indices for the direction shown in the hexagonal unit cell of
sketch below.
Solution: Step 1: Miller indices [u’ v’ w’] = [ 1 1 1]
1 1 2
Step 2: [u v t w] = [ -1] using the following
3 3 3
relations:
1 ′ ′
1 1 ′
1
𝑢 = 2𝑢 − 𝑣 = ; 𝑣 = 2𝑣 − 𝑢′ = ;
3 3 3 3
2
𝑡 = − 𝑢 + 𝑣 = − ; 𝑤 = 𝑤′ = 1
3
Step 3: Multiplying by 3; [1 1 2ത 3]
Step 4: [1 1 2ത 3] (Ans)
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EXAMPLE
Draw a 2 1ഥ 1ഥ 3 direction within a Hexagonal unit cell.
Solution: Method 1
Step 1: Miller-Bravais indices [u v t w] = 2 1ഥ 1ഥ 3 .
2 1 1
Step 2: [u v t w] = [ - - 1] dividing by 3.
3 3 3
Step 3: Using following relations determined [u’ v’ w’] = [ 1 0 1]
1 1
𝑢 = 2𝑢 − 𝑣 ; 𝑣 = 2𝑣 ′ − 𝑢′ ; 𝑤 = 𝑤 ′
′ ′ x
3 3
y
Step 4: Taking x, y and z axis crystallographic direction is shown.(Ans)
Method 2
Step 1: Miller-Bravais indices [u v t w] = 2 1ഥ 1ഥ 3 .
2 1 1
Step 2: [u v t w] = [ - - 1] dividing by 3.
3 3 3
Step 3: Establish 4 axes system marking 𝑎1 , 𝑎2 , 𝑎3 & 𝑧.
Step 4: Tracing the coordinate crystallographic direction is shown. 26
EXAMPLE (Cont.)
2 1 1
[u v t w] = [ - - 1]
3 3 3

𝑎3

𝑎1

𝑎2
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CRYSTALLOGRAPHIC PLANES
The orientations of planes for a crystal structure are represented by
crystallographic plane. The following steps are utilized in the determination
of the plane indices:
Step 1: If the plane passes through the selected origin, select a new origin by
an appropriate translation.
Step 2: Determine the length of the planar intercept for each axis in terms of
the lattice parameters a, b, and c. A plane that parallel to an axis is
considered to have an infinite intercept.
Step 3: Divide the x value with a, y value with b and z value with c.
Step 4: Take the reciprocals of these numbers.
Step 5: Reduce the found results to lowest integer by multiplication or
division and represent negative sign above as bar.
Step 6: State the found results separating by a space and enclosed by a first
bracket. 28
EXAMPLE PROBLEM 3.9
Determination of Planar (Miller) Indices: Determine the Miller indices for
the plane shown in the accompanying sketch.

Step 1: New origin O’ selected.

Step 2: (x, y, z) intercept =
ꝏa, -b, c/2
Step 3: after division = ꝏ, -1, 1/2
Step 4: Reciprocal = 0, -1, 2
Step 5: Putting bar above = 0, 1̅ , 2
Step 6: ( 0 ̅1 2 )

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EXAMPLE PROBLEM 3.10
Construction of Specified Crystallographic Plane: Construct a ( 0 ̅1 1 )
plane within a cubic unit cell.
Solution:

Step 1: Select an origin O’. Step 4: any plane going through the
Step 2: inverse given indices: intercept is accepted as ( 0 ̅1 1 )
1 1 1 plane.
, , = ꝏ, -1, 1 or, ꝏa, -1b, 1c
0 −1 1
Step 3: mark the intercepts. 30
FAMILY OF PLANES
A “family” of planes contains all those planes that are crystallographically
equivalent—that is, having the same atomic packing; and a family is
designated by indices that are enclosed in braces—such as {1 1 1}. For
example, in cubic crystals the (1 1 1), (̅̅ 1 1̅ 1̅ ), ( 1̅ 1 1), (1 1̅ ̅1), (1 1 1̅ ),
( ̅1 ̅1 1 ), ( ̅1 1 1̅ ), and (1 ̅1 1 ) planes all belong to the {1 1 1} family.

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CRYSTALLOGRAPHIC PLANES: HEXAGONAL CRYSTALS
For crystals having hexagonal symmetry, it is desirable that
equivalent planes have the same indices; as with directions,
this is accomplished by the Miller–Bravais system. Steps of
plane determination:
Step 1: Determine the Miller indices (h k l).
Step 2: Convert (h k l) into (h k i l) using the following relation:
i=-(h+k)
Step 3: Reduce the found results to lowest integer by multiplication or
division and represent negative sign above as bar.
Step 4: State the found results separating by a space and enclosed by a
second bracket.
Indices found in this procedure is called Miller–Bravais indices.
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EXAMPLE PROBLEM 3.11
Determination of Miller–Bravais Indices for a Plane Within a
Hexagonal Unit Cell: Determine the Miller–Bravais indices for the plane
shown in the hexagonal unit cell.

Solution:

Step 1: Miller indices (h k l) = ( 1 ̅1 1)

Step 1: New origin O’ selection not required.
Step 2: (x, y, z) intercept = a, -a, c
Step 3: after division = 1, -1, 1
Step 4: Reciprocal = 1, -1, 1 x
Step 5: Putting bar above = 1, ̅1, 1
Step 6: ( 1 ̅1 1 )
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EXAMPLE PROBLEM 3.11
Determination of Miller–Bravais Indices for a Plane Within a
Hexagonal Unit Cell: Determine the Miller–Bravais indices for the plane
shown in the hexagonal unit cell.

Solution:

Step 1: Miller indices (h k l) = ( 1 ̅1 1)

Step 2: Convert (h k l) into (h k i l),
i = - ( h + k ) = - (1-1) = 0
Therefore, 1 ̅1 0 1
Step 3: Reduction or multiplication not required here.
Step 4: ( 1 1̅ 0 1) (Ans)

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LINEAR DENSITIES
Linear density (LD) is defined as the number of atoms per unit length
whose centers lie on the direction vector for a specific crystallographic
direction. The units of linear density are reciprocal length (e.g., 𝑛𝑚−1 , 𝑚−1 ).

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PLANAR DENSITIES
Planar density (PD) is taken as the number of atoms per unit area that are
centered on a particular crystallographic plane. The units for planar density
are reciprocal area (e.g., 𝑛𝑚−2 , 𝑚−2 ).

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LINEAR AND PLANAR DENSITIES: EXAMPLE
Question: Determine the linear density in [1 1 0] direction and planer
density in (1 1 0) plane in an FCC unit cell.
z

x
Solution:

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STACKING SEQUENCE: HCP VS FCC
Both FCC and HCP crystal structures show same atomic packing factors of
0.74 yet have different crystal structure due to the difference that exist in
their stacking sequence.

A first layer (marked ‘A’) of closely packed atoms can fit a second layer in
two alternate position marked as ‘B’ and ‘C’ in the figure. Let’s say, second
layer is placed in position ‘B’. If the third layer is placed so that its atoms are
directly above ‘A’, the stacking will be ABA — this is the HCP structure,
and it continues ABABABAB. If the third layer is placed directly above ‘C’
the stacking will be ABCA — this is the FCC structure, and it continues
ABCABCABCABC.
https://www.youtube.com/watch?v=anl7ZIUA97I

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STACKING SEQUENCE: HCP VS FCC (Cont.)

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STACKING SEQUENCE: HCP VS FCC (Cont.)

Stacking Sequence of
HCP 40
STACKING SEQUENCE: HCP VS FCC (Cont.)

Stacking Sequence of FCC

https://www.youtube.com/watch?v=LO9ya-x5DaU 41
STACKING SEQUENCE: HCP VS FCC (Cont.)

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SINGLE CRYSTALS
For a crystalline solid, when the periodic and
repeated arrangement of atoms is perfect or extends
throughout the entirety of the specimen without
interruption, the result is a single crystal. All unit
cells interlock in the same way and have the same
orientation. Single crystals exist in nature, but they
may also be produced artificially.
POLYCRYSTALLINE MATERIALS
Most crystalline solids are composed of a collection of many small crystals or
grains; such materials are termed polycrystalline. The crystallographic
orientation varies from grain to grain. Also, there exists some atomic
mismatch within the region where two grains meet; this area, called a grain
boundary. 43
FORMATION OF POLYCRYSTALLINE MATERIALS
a. Small single b. Growth of
crystal starts single crystals
forming through or grains by
formation of unit addition of
cells more unit cells

c. Solidification d. appearance
is almost under the
complete; grains microscope;
starts meeting dark lines are
neighboring grain the grain
boundaries
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ANISOTROPY VS ISOTROPY
Anisotropy is defined as the property of a substance to show variations in
physical properties along different molecular axes.
Substances in which measured properties are independent of the direction of
measurement are considered to have isotropy.

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ANISOTROPY VS ISOTROPY (Cont.)
z z

[111] [111]

y y
[100] [100]
[110] [110]
x x
Copper Tungsten

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X-RAY DIFFRACTION: CRYSTAL STRUCTURE DETERMINATION

X-RAY DIFFRACTION

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X-RAY DIFFRACTION AND BRAGG’S LAW

n = order of diffraction
λ = wavelength
2θ = diffraction angle
𝑑ℎ𝑘𝑙 = the interplanar spacing
h, k, l = Miller indices
a = lattice parameter (unit cell edge length)

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EXAMPLE PROBLEM 3.12
Interplanar Spacing and Diffraction Angle Computations: For BCC iron,
compute (a) the interplanar spacing, and (b) the diffraction angle for the
(220) set of planes. The lattice parameter for Fe is 0.2866 nm. Also, assume
that monochromatic radiation having a wavelength of 0.1790 nm is used, and
the order of diffraction is 1.
Solution: n λ = 2𝑑ℎ𝑘𝑙 𝑠𝑖𝑛θ

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NONCRYSTALLINE SOLIDS
Noncrystalline solids lack a systematic and regular arrangement of atoms
over relatively large atomic distances. Sometimes such materials are also
called amorphous.

(a) crystalline 𝑆𝑖𝑂2 (b) noncrystalline 𝑆𝑖𝑂2

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REFFERENCES
• Materials Science and Engineering An Introduction by William D.
Callister, Jr. (seventh edition) Chapter 3

ANY QUESTION?

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