Chapter Two: The Structure of Crystalline Solids

2.1. Crystal Structures

• Solid materials are classified according to the regularity with which atoms or ions are arranged with respect
to one another. Upon the solidification of solid materials, the constituent atoms or ions arrange themselves in
two manners:
▪ Crystalline solid (Fig. 1a). Repetitions of a regular three-dimensional structure (over large
atomic distances).
▪ Amorphous, shapeless, or noncrystalline solid (Fig. 1b). Irregular Aggregations or disordered
repetitions (over large atomic distances).
• Crystal structure is the spatial arrangement of atoms in solid material, and it judges their properties.
• Under normal solidification conditions, all metals, many ceramic materials, and certain polymers form
crystalline structures.

Each atom is bonded to its nearest-neighbor atoms, and form Each atom is bonded to its nearest-neighbor atoms, and form
regular patterns over a large atomic distance. irregular patterns over a large atomic distance.
a b
Figure 1: (a) Crystalline structure. (b) Amorphous or noncrystalline structure.

• In the atomic hard-sphere model (Fig. 2a), atoms are considered to be solid spheres having well-defined
diameters. As well, spheres representing nearest-neighbor atoms touch one another.
• The term lattice is used in the context of crystal structures. Lattice is a three-dimensional array of points
coinciding with atom positions, or sphere centers (Fig. 2b).
• Crystal or lattice structure can be subdivided into small repetitive patterns of atoms called unit cells (Fig. 2):
▪ Unit cells are the basic unit (or building block) of the crystal structure.
▪ For most crystal structures, unit cells are parallelepipeds or prisms having three sets of parallel faces.
▪ The unit cell defines the crystal structure by virtue of its geometry and the atom positions within.

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 ▪ For a particular crystal structure, there are more than a single unit cell may be chosen; however, the
unit cell having the highest level of geometrical symmetry is used.
▪ The repetition of a unit cell, for integral distances along each of its edges, generates the crystal and
defines the positions of atoms within it.

a b
Figure 2: Unit cell in (a) the atomic hard-sphere model and (b) the crystal lattice.

2.1.1. Crystal Systems and Crystal Structures

• Crystal structures are classified according to the geometrical configuration (shape) of the unit cell without
regard to the atomic positions within it, which is defined as the crystal system.
• The crystal system is defined by using a three dimensional Cartesian coordinate system xyz (Fig. 3):
▪ Crystal structures are defined by six parameters, lattice parameters.
▪ Lattice parameters are three edge lengths (lattice constants) a, b, and c, and three inter-axial angles
(lattice angles) α, β, and γ.
▪ There are seven different possible combinations of a, b, and c, and α, β, and γ, each of them represents
a distinct crystal system (Fig. 3).
▪ The cubic system has the highest degree of symmetry, while the triclinic one has the lowest.
• The crystal structure is defined by the unit cell geometry and the atomic arrangement within it, while the
crystal system is defined according to the unit cell geometry (regardless to the atomic arrangement).
• Atomic arrangement in the crystal system may be primitive (constituent atoms are positioned only at the
corners of the unit cell) or centered (constituent atoms are positioned at other positions along with corners).
• There are three types of the centered crystal structures:
i. Face-centered, constituent atoms are located at the centers of cube faces along with corners.
ii. Body-centered, constituent atoms are located at the center of the body along with corners.
iii. End-centered, constituent atoms are located at the centers of any two opposite faces along with corners.

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 Figure 3: Lattice parameter relationships and unit cell geometries for the seven crystal systems.

2.1.2. Metallic Crystal Structures

• Metallic bonding is nondirectional. Consequently, most metallic crystal structures have relatively large
numbers of nearest-neighbor atoms (ion cores) and dense atomic packings.
• Each atom has the same number of nearest-neighbor, known as the coordination number (Nc).
• Atomic packing factor (APF) is the volume of atoms in a unit cell divided by the unit cell volume.
• Four types of crystal structures are found for most of the common metals: simple cubic, face-centered cubic,
body-centered cubic, and hexagonal close-packed structures.

I. Primitive or simple cubic crystal structure

• Atoms are located only at the eight corners of the cube (Fig. 4).
• Each cell has one-eighth of the eight corner atoms, or a total of one whole atom.
• Each corner atom is shared among eight unit cells.
• Spheres (ion cores) touch one another along the cube edges.
• Coordination number Nc = 6
• Unit cell volume = 𝑎3 = (2𝑅)3 = 8𝑅3 , (a = 2R)
4
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑎 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 1∗ ∗𝜋∗𝑅 3
• APF = = 3
= 0.52
𝑇𝑜𝑡𝑎𝑙 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 8𝑅 3

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 • Only polonium has this type of crystal structures.

Figure 4: Primitive or simple cubic crystal structure.

II. Face-centered cubic (FCC) crystal structure

• Atoms are located at all eight corners of the cube and a single atom at the center of each face (Fig. 5).
• Each unit cell has one-eighth of each of the eight corner atoms and one-half of each of the six face atoms, or
a total of four whole atoms.
• Each corner atom is shared among eight unit cells, whereas the face-centered atom belongs to only two.
• Spheres (ion cores) touch one another across the diagonal of each face.
• Coordination number Nc = 12
• Unit cell volume = 𝑎3 = (2√2 R)3 = 16√2 R3 , (4R)2 = a2 + a2 , a = 2√2 R).
4
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑎 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 4∗ ∗𝜋∗𝑅 3
• APF = = 3
= 0.74
𝑇𝑜𝑡𝑎𝑙 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 16√2𝑅 3

Figure 5: Face-centered cubic (FCC) crystal structure.

III. Body-centered cubic (BCC) crystal structure

• Atoms are located at all eight corners of the cube and a single atom at its center (Fig. 6).
• Each unit cell has one-eighth of each of the eight corner atoms and entire one atom at its center, or a total of
two whole atoms.
• Each corner atom is shared among eight unit cells, whereas the body-centered atom is entirely contained
within its cell.
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 • Spheres (ion cores) touch one another along the cube diagonals.
• Coordination number Nc = 8
4𝑅 3 64𝑅3 4𝑅
• Unit cell volume = 𝑎3 = ( ) = , (AB2 = 2a2 ; AC2 = (4R)2 = AB2 + BC2 = 2a2 + a2 = 3a2 ; a = ).
√3 3√3 √3
4
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑎 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 2∗ ∗𝜋∗𝑅 3
• APF = = 3
= 0.68
𝑇𝑜𝑡𝑎𝑙 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 (64𝑅 3 )/3√3

Figure 6: Body-centered cubic (BCC) crystal structure.

IV. Hexagonal close-packed (HCP) crystal structure.

• Atoms are located at the corners and the center of two paralleled hexagonal planes and three more atoms in
the midplane, between the two hexagons (Fig. 7).
• Each unit cell has one-sixth of each of the 12 top and bottom face corner atoms, one-half of each of the two
center face atoms, and the entire three midplane atoms, or a total of six whole atoms.
• Each corner atom is shared among six unit cells, whereas the midplane atoms are entirely contained within
the cell. Additionally, each of the face-centered atoms belongs to only two.
• Coordination number Nc = 12
• The ideal c/a ratio should be 1.633 (Fig. 8). For some HCP metals this ratio deviates from the ideal value:
▪ a: length of the hexagon’s edge.
▪ c: height of the unit cell.
√3 √3
• Unit cell volume = 6 * * a2 * c = 6 * * (2R)2 * (1.633*2R) = 12√3 (1.633)R3 , (a = 2R ; c = 1.633a).
4 4
4
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑎 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 6∗ ∗𝜋∗𝑅 3
• APF = = 3
= 0.74
𝑇𝑜𝑡𝑎𝑙 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 12√3 (1.633)𝑅3

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 Figure 8: Hexagonal close-packed (HCP) crystal structure.

Figure 8: Determination of the c/a ratio

❖ Atomic radii and crystal structures for some metals are presented in (Table 1):

Table 1: Atomic radii and crystal structures for some metals

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2.1.3. Density Computations

• Theoretical density of a metal (based on its crystal structure) can be determined as follows:
𝒏∗𝑨
ρ=
𝑽𝑪 ∗ 𝑵𝑨

Where:
▪ n = number of atoms associated with each unit cell.
▪ A = atomic weight.
▪ VC = volume of the unit cell.
▪ NA = Avogadro’s number = 6.022 × 1023 atoms/mol.

Example 1: 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 (8.94 g/cm3).

The theoretical (calculated) density is very close to the measured one.

2.1.4. Polymorphism and Allotropy

• Polymorphism is the phenomenon of a substance (metals or nonmetals) exhibiting different crystal structures.
• Allotropy is the property of some chemical elements to have more than one crystal structure, in the solid state,
known as allotropes of these elements. And it’s a special case of polymorphism.
• The prevailing crystal structure depends on both the temperature and the external pressure:
▪ Carbon: graphite is the stable allotrope at ambient conditions, whereas diamond is formed at extremely
high pressures.
▪ Pure Iron: At room temperature the stable form, called ferrite, or α-iron, has a BCC crystal structure.
Ferrite experiences a polymorphic transformation to FCC austenite, or γ-iron, at 912°C. This austenite
persists to 1394°C, at which temperature the FCC austenite reverts back to a BCC phase known as δ-
ferrite, which finally melts at 1538°C.
• Changes of physical properties accompany this phenomenon, such as the density.
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 2.2. Crystallographic Points, Directions, and Planes.

• Metallic crystal structures can be well investigated by specifying particular points, directions, and planes
within their unit cells.
• Points, directions, and planes are designated by three indices on the right-handed coordinate system (xyz).

2.2.1. Point Coordinates

• Points are specified as fractional multiples of the unit cell edge lengths. As for point P (Fig. 9a):
▪ a, b, and c are the lengths of the unit cell edges along the three axes x, y, and z, respectively.
▪ q, r, and s are fractional multiples of the unit cell edges lengths a, b, and c, respectively.
▪ The point location is designated using coordinates q r s with values that are less than or equal to unity
(a, b, and c).
▪ q, r, and s coordinates are documented without separation by commas or any other punctuation marks.
• Point coordinates for ion cores in the tungsten (BCC) and aluminum (FCC), (Fig. 9b&c):
111
▪ Tungsten: 000, 100, 110, 010, 001, 101, 111, 011,
222
11 11 11 11 1 1 1 1
▪ Aluminum: 000, 100, 110, 010, 001, 101, 111, 011, 0, 1, 1 , 0 , 0 , 1 .
22 22 22 22 2 2 2 2

a b c
Figure 9: (a) Specification of point coordinates. (b) Ion cores coordinates for tungsten. (c) Ion cores coordinates for aluminum.

2.2.2. Crystallographic Directions

I. Cubic Crystal
• A crystallographic direction is a vector, between two points in the lattice.
• Any vector may be translated throughout the crystal lattice without alteration, if parallelism is maintained.

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 • The following steps are used to determine the three directional indices:
1. The vector is positioned such that it passes through the origin of the coordinate system.
2. Determine the lengths of the vector projections on the three axes (x, y, and z).
3. Reduce them to the smallest integer values.
4. Enclose them in square brackets, [uvw].
• The u, v, and w integers correspond to the reduced projections along the x, y, and z axes, respectively.
• Negative indices are also possible, which are represented by a bar over the appropriate index, e.g. the [u𝑣̅ w]
direction would have a component in the –y direction.
• Changing the signs of all indices produces an antiparallel direction, e.g. [𝑢̅𝑣𝑤
̅] is directly opposite to [u𝑣̅ 𝑤].
• For some crystal structures, several nonparallel directions with different indices are crystallographically
equivalent (the spacing of atoms along each direction is the same):
▪ In cubic crystals, the directions [100], [1̅00], [010], [01̅0], [001], and [001̅] are equivalent.
▪ Equivalent directions are grouped together into a family, which are enclosed in angle brackets 〈100〉.
▪ In cubic crystals, directions having the same indices without regard to order or sign are equivalent.
e.g. [132] and [32̅1̅] are equivalent.
▪ In tetragonal crystals, [100] and [010] directions are equivalent, whereas [100] and [001] are not.

Example 2: Find the indices for each direction in the accompanying figure.
For direction A:
x y z
2 1 0
Projections −
3 2
Reduction -4 3 0
Enclosure ̅𝟑𝟎]
[𝟒

❖ Direction B: [23̅2], Direction C: [13̅3̅], Direction D: [136̅].

II. Hexagonal Crystals

• For the hexagonal crystal structure, there are three axes (a1, a2, and a3) contained within a single plane, basal
plane, and are at 120˚ angles to one another. The fourth axis, z, is perpendicular to the basal plane (Fig. 10).
• The four-axis (Miller–Bravais) coordinate system is used to specify directions and planes in the HCP structure.
• Directional indices are denoted by four integer-indices, [uvtw], the u, v, t, and w integers correspond to the
reduced projections along the a1, a2, a3, and z, respectively.

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• A direction within the HCP structure can be determined through the following steps:
1. Determine the lengths of the vector projections on the three axes a1, a2, and z.
2. Reduce them to the smallest integer values, and denote them by [u′v′w′].
3. Convert the three-index system [u′v′w′] to the fourth index system [uvtw].
1 1
u = (2uʹ - vʹ) v = (2vʹ - uʹ) t = - (u + v) w = wʹ
3 3
4. Reduce them to the smallest integer values.
5. Enclose them in square brackets, as [uvtw].
▪ In order to specify directions within the HCP structure, a reduced-scale coordinate system is established:
▪ A grid has been constructed on the basal plane
that consists of sets of lines parallel to each of
the a1, a2, and a3 axes. The intersections of two
sets of parallel lines (e.g., those for a2, and a3)
lie on and trisect the other axis (e.g., divide a1
into thirds) within the hexagonal unit cell. In
addition, the z axis is also apportioned into three
equal lengths (at trisection points m and n).

Figure 10: Four-axis coordinate system for HCP crystal system.

Example 3: Find the directional indices (four Miller indices) for each direction in the accompanying figure.

a1 a2 z

0 -1 1
Projections
2

Reduction 0 -2 1

Enclosure [uʹvʹwʹ] ̅𝟏]

[0𝟐

1 2 1 −4 2 −4 2
u = (2*0 - -2) = , v = (2*-2 - 0) = ,t=-( + )= ,w=1
3 3 3 3 3 3 3

u v t w

Reduction 2 -4 2 3

Enclosure ̅𝟐𝟑]
[2𝟒

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 Example 4: Convert the [111] direction into the four-index system for hexagonal crystals and draw this
direction within a reduced-scale coordinate system.

̅𝟑]
Reduction and enclosure: [11𝟐

2.2.3 Crystallographic Planes

I. Cubic Crystals
• Crystallographic planes are specified by three Miller indices as (hkl).
• h, k, and l index numbers can be determined as follows:
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. The length of the planar intercept for each axis is determined in terms of the lattice constants.
3. Take the reciprocals of these numbers.
4. Reduce them to the smallest integer values.
5. Enclose them in parentheses, as (hkl).

Example 5: Determine the Miller indices for the plane shown in the accompanying sketch.
❖ A new origin must be chosen at the corner of an adjacent unit cell (Oʹ) instead of the original one (O).
x y z
Intercepts ∞ -1 1
2
Reciprocals 0 -1 2
Reduction 0 -1 2
Enclosure ̅𝟐)
(0𝟏

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 Example 6: Determine the Miller indices for the planes shown in the accompanying sketch.
❖ Plane B:
x y z
Intercepts -1 -1 1
2
Reciprocals -1 -1 2
Reduction -1 -1 2
Enclosure ̅𝟏
(𝟏 ̅𝟐)

❖ Plane A: (403)

Example 7: Draw within a cubic unit cell the following planes: (12̅2̅), (1̅11̅), (13̅1), and (112̅).

• The atomic arrangement and the atomic packing for a crystallographic plane depend on the type of crystal
structures, e.g. the (110) atomic planes for FCC and BCC crystal structures (Fig. 11).
• Parallel planes are equivalent, as they have identical atomic arrangement and indices (Fig. 12).
• A family of planes contains all of crystallographic planes that are crystallographically equivalent, and have
the same atomic packing. And it is designated by indices that are enclosed in braces, as {hkl}.
▪ In cubic crystals, the (111), (1̅1̅1̅ ), (1̅11), (11̅1̅), (111̅), (1̅1̅1), (1̅11̅), and (11̅1) planes all belong
to the {111} family.
▪ In cubic crystals, planes having the same indices, irrespective of order and sign, are equivalent
(e.g. both (12̅3) and (31̅2) belong to the {123} family.
▪ In tetragonal crystals, the {100} family would contain only the (100), (1̅00), (010), and (01̅0)
because the (001) and (001̅) planes are not crystallographically equivalent.
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 a b
Figure 11: Atomic packing of the plane (110) in the (a) FCC and (b) BCC crystal systems.

a b c
Figure 12: Representations of a series each of the (a) (001), (b) (110), and (c) (111) crystallographic planes.

II. Hexagonal Crystals

• For the HCP structure, a plane can be clearly identified by using four-index (hkil), Miller–Bravais indices.
• h, k, i, and l index numbers can be determined as follows:
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. Determine the lengths of the planar intercept on the three axes a1, a2, and z, and they are related to h,
k, and l, respectively.
3. Take the reciprocals of these numbers.
4. Compute the fourth index (i); in which i = - (h + k).
5. Reduce them to the smallest integer values.
6. Enclose them in parentheses, as (hkil).
• Equivalent planes have the same indices.

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 Example 8: Determine the Miller indices for the plane shown in the accompanying sketch.
❖ A new origin must be chosen.
a1 a2 z
Intercepts 1 ∞ ∞
Reciprocals 1 0 0
Reduction 1 0 0
i = - (h + k) - (1 + 0) = -1

Enclosure ̅𝟎)
(10𝟏

Example 9: Determine the Miller indices for the plane shown in the accompanying sketch.

a1 a2 z
Intercepts -1 1 1
Reciprocals -1 1 1
Reduction -1 1 1
i = - (h + k) - (1 + 1) = 0
Enclosure ̅𝟏𝟎𝟏)
(𝟏

Example 10: Draw within a HCP unit cell the following planes: (11̅01), (112̅0).

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2.2.4. Linear and Planar Densities.

• Linear density (LD) is the number of atoms per unit length whose centers lie on the direction vector for a
specific crystallographic direction, and it is measured by nm-1, m-1, etc.
• Planar density (PD) is the number of atoms per unit area that are centered on a particular crystallographic
plane, and it is measured by nm-2, m-2, etc.
• Equivalent directions have identical linear densities.
• Planes having the same planar density values are equivalent.

Example 11: For the FCC crystal, determine the linear and planar densities for the [110] direction and the
(110) plane, respectively.

2.2.5. Close-Packed Crystal Structures

• Close-packed planes are the planes having a maximum atom packing density.
• Both FCC and HCP crystal structures may be generated by the stacking of close-packed planes on top of one
another; the difference between the two structures lies in the stacking sequence.
• Let the centers of all the atoms in one close-packed plane be labeled A (Fig. 13a).
▪ There are two sets of equivalent triangular depressions formed by three adjacent atoms.
▪ Depressions with up vertices are arbitrarily designated as B positions.
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 ▪ Depressions with down vertices are arbitrarily designated as C positions.
▪ A second close-packed plane may be positioned with the centers of its atoms over either B, the stacking
sequence is termed AB (Fig. 13b), or C sites, the stacking sequence is termed AC; at this point both
FCC and HCP are equivalent.
▪ For HCP, the centers of the third plane are aligned directly above the original A positions. This stacking
sequence, ABABAB ..., is repeated over and over (Fig. 13c). The ACACAC ... arrangement would be
equivalent.
▪ For FCC, the centers of the third plane are situated over the C sites of the first plane. This yields an
ABCABCABC ... stacking sequence; the atomic alignment repeats every third plane (Fig. 13d). The
ACBACB ... arrangement would be equivalent.
• The real distinction between FCC and HCP lies in where the third close-packed layer is positioned.

a b

c d
Figure 13: (a) A portion of a close-packed plane of atoms. (b) The AB stacking sequence for close-packed atomic planes. (c) Close-
packed plane stacking sequence (ABABAB …) for HCP. (d) Close-packed stacking sequence (ABCABC …) for FCC.

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2.3. Crystalline and Noncrystalline Materials

2.3.1. Single Crystals

• The arrangement of atoms is perfectly repeated throughout the entirety of the specimen without interruption.
• If there are no external constrains on the growth of the single-crystal extremities, the crystal will assume a
regular geometric shape having flat faces.
• Single crystals exist in nature as in case of garnet, but they may also be produced artificially such as the
single crystals of silicon and other semiconductors (used in particular electronic microcircuits).

2.3.2. Polycrystalline Materials

• A Polycrystalline, multicrystalline, or polycrystals solid material is composed of many crystals (grains) of

varying size and orientation.
• Crystals, grains, are formed during the Solidification process, and it passes through several stages, as follows:
1. Nucleation stage. This stage starts at the solidification temperature, in which atoms of a liquid begin
to bond together at the nucleation points (sites or seeds) and start to form crystals with random
crystallographic orientations (Fig. 141). The final sizes of individual crystals depend on the number
of nucleation points.
2. Grain growth stage. The small grains grow by the successive addition from the surrounding liquid of
atoms to the structure of each (Fig. 14b).
3. Grain formation. The crystals increase in size by the progressive addition of atoms and grow until they
impinge upon adjacent growing crystal (Fig. 14c).
• A grain boundary is the interface between two grains. In which, some atomic mismatch exists within the region
where two grains meet (Fig. 14d).

2.3.3. Noncrystalline Materials

• A noncrystalline, supercooled liquids, or amorphous solid is a material in which the arrangement of atoms is
interrupted and irregular over relatively large atomic distances throughout the entirety of the specimen.
• Formation of crystalline or amorphous structures depends on the ease with which a random atomic structure
in the liquid to transform to an ordered state during solidification.
• Rapid cooling of molten materials favors the formation of a noncrystalline solid, because little time is allowed
for the ordering process.

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• Metals normally are crystalline, some ceramic materials are crystalline, and the inorganic glasses are
amorphous. Polymers having various degrees of crystallinity.

a b

c d
Figure 14: Schematic diagrams of the various stages in the solidification of a polycrystalline material; the square grids depict unit
cells. (a) Nucleation. (b) Grain growth. (c) Grain formation. (d) Grain boundaries (dark lines).

2.3.4. Anisotropy

• Anisotropy is the directionality of properties;

▪ The properties of single crystals of some substances depend on the crystallographic direction in which
measurements are taken.
▪ For example, the elastic modulus, the electrical conductivity, and the index of refraction may have
different values in the [100] and [111] directions.
▪ The extent and magnitude of anisotropic effects in crystalline materials are functions of the symmetry
of the crystal structure; triclinic structures normally are highly anisotropic.
• Isotropy is the independency of the measured physical properties from their directions.
• For many polycrystalline materials:
▪ Each grain is considered as a single crystal that has a particular orientation; thus, it will be anisotropic.
▪ A specimen composed of the grain aggregate, with fully-random crystallographic orientations,
behaves isotropically, and the magnitude of a measured property represents some average of the
directional values.
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• If the crystallographic orientations are not random, and there is a preferential orientation, the material is
said to have a texture that effects its properties.
• Texture is the distribution of crystallographic orientations of a polycrystalline sample;
▪ The texture of a sample may be weak, strong, or moderate depending on the percentage of crystals
that have the preferred orientation.
▪ Electron Backscatter Diffraction (EBSD) technique is used to reveal the texture of polycrystalline
materials (Fig. 15).

Figure 15: Crystallographic texture of polycrystalline material using EBSD.

2.4. X-Ray Diffraction

• Used to determine the atomic and molecular arrangement, interplanar spacing, and the crystal structure.
• The diffraction phenomenon occurs when a wave encounters a series of regularly spaced obstacles that are
capable of scattering the wave, and have spacings that are comparable in magnitude to the wavelength.
• Diffraction is a consequence of specific phase relationships established between two or more waves that have
been scattered by the obstacles.
• Diffraction phenomenon can be described as follows:
▪ Two waves have the same wave length and are in phase.
▪ Assume that both waves are scattered in such a way that they traverse different paths.
▪ The phase relationship between the scattered waves depends on the difference in path length:
1. Constructive (Fig. 16a). If the path length difference is an integral number of wavelengths,
then the scattered waves are in phase and reinforce one another. A diffracted beam composed
of a large number of scattered waves that mutually reinforce one another.
2. Destructive (Fig. 16b). If the path length difference is an integral number of half-wavelengths,
then the scattered waves are out of phase and cancel one other. Corresponding amplitudes
cancel or annul one another, and the resultant wave has zero amplitude.

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 3. Intermediate phase relationships.

a b
Figure 16: interference between two diffracted waves. (a) Constructive interference. (b) Destructive interference.

2.4.1. X-Ray Diffraction and Bragg’s Law

• X-rays are electromagnetic radiation having high energies and short wavelengths (on the order of the atomic
spacings for solids).
• When a beam of x-rays impinges on a solid material, a portion of this beam will be scattered in all directions
by the electrons or ions that lie within the beam’s path.
• Consider the impingement of a parallel, monochromatic, and coherent beam of X-rays of wavelength λ on
two parallel and separated planes, A-A′ and B-B′ at an angle θ (Fig. 17);
▪ In order to detect the scattered rays, they must be in phase, the path length difference between them is
equal to a whole number, n, of wavelengths, which means that the phase relationship is constructive.
▪ The two planes have the same h, k, and l indices, and are separated by the interplanar spacing dhkl.
▪ Two rays in this beam are scattered by atoms P and Q.
▪ The path length difference = nλ = 𝑆𝑄 ̅̅̅̅ = dhkl sin θ + dhkl sin θ = 2 dhkl sin θ (Bragg’s Law).
̅̅̅̅ + 𝑄𝑇

▪ n: the order of reflection, n = 1, 2, 3, …….

• The interplanar spacing (dhkl) is a function of the Miller indices (h, k, and l) and the lattice parameters:
𝑎
➢ For the cubic crystal structure: dhkl = 2
√ℎ + 𝑘 2 + 𝑙 2

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 Figure 17: Diffraction of x-rays by planes of atoms (AAʹ– and BBʹ).

• Bragg’s law specifies when diffraction will occur for unit cells having atoms positioned only at cell corners.
• Atoms situated at other sites face and interior unit cell positions, act as extra scattering centers, which can
produce out-of-phase scattering at certain Bragg angles. Hence,
▪ Some of diffracted beams, should be present, will be absent (destruction phenomenon).
▪ Therefore, different crystal structures will only allow reflections of particular planes.
▪ For the BCC crystal structure, h + k + l must be even if diffraction is to occur.
▪ For FCC, h, k, and l must all be either odd or even.

Table 2: Allowed list of h2 + k2 + l2 for cubic crystals.

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2.4.2. X-Ray Diffractometer

• Commonly, a powdered or polycrystalline specimen consisting of many fine and randomly oriented particles
are exposed to monochromatic x-radiation.
• Each powder particle (or grain) is a crystal, and having a large number of them with random orientations
ensures that some particles are properly oriented such that every possible set of crystallographic planes will
be available for diffraction.
• The diffractometer is an apparatus used to determine the angles at which diffraction occurs (Fig. 18a).
• The diffraction angle equals two times of the incident angle, which ensures that the incident and reflection
angles are maintained equal to one another.
• High-intensity peaks result when the Bragg diffraction condition is satisfied by some set of crystallographic
planes (Fig. 18b).

(a) (b)
Figure 18: (a) Schematic diagram of an x-ray diffractometer; T: x-ray source, S: specimen, C: detector, and O: the axis around which
the specimen and detector rotate. (b) Diffraction pattern for polycrystalline α-iron.

Example 12: The figure below shows the first four peaks of the x-ray diffraction pattern for copper, which has
an FCC crystal structure; monochromatic x-radiation having a wavelength of 0.1542 nm was used.

a. Index each of these peaks.

b. Determine the interplanar spacing for each of
the peaks.
c. For each peak, determine the atomic radius for
Cu and compare them with the common value,
0.1278 nm.

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 a. Since Cu has an FCC crystal structure, only those peaks for which h, k, and l are all either odd or even will
appear. Therefore, the Miller indices for these peaks are: (111), (200), (220), and (311).

b. Interplanar spacing:
• d111 = 0.2067 nm. For (111) crystallographic plane:
• d200 = 0.1797 nm.
• d220 = 0.1275 nm.
• d311 = 0.1087 nm.

c. Atomic radius:
• (111), R = 0.1266 nm. For (111) crystallographic plane:
• (200), R = 0.1271 nm.
• (220), R = 0.1275 nm.
• (311), R = 0.1274 nm.
They are very close to the common
value.

Example 13: For which set of crystallographic planes will a first-order diffraction peak occur at a diffraction
angle of (2θ) = 46.21° for BCC iron (R = 0.1241 nm) when monochromatic radiation having a wavelength of
0.0711 nm is used?

❖ By trial and error, the only three integers having a

sum that is even, and the sum of the squares of
which equals 10.0 are 3, 1, and 0. Therefore, the
set of planes responsible for this diffraction peak
are the (310) ones.

References

i. Callister, W. and Rethwisch, D. (2009). Materials science and engineering. 8th ed. United States of America: John
Wiley & Sons, Inc.
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