Chapter 3

Crystal and Amorphous Structure in

Materials
Chapter Objectives
• Describe what crystalline and noncrystalline (amorphous) materials are.
• Learn how atoms and ions in solids are arranged in space and identify the
basic building blocks of solids.
• Describe the difference between atomic structure and crystal structure for
solid material.
• Distinguish between crystal structure and crystal system.
• Compute the densities for metals having body centered, and face-
centered cubic structures.
• Describe how to use the x-ray diffraction method for material
characterization.
• Write the designation for atom position, direction indices, and Miller
indices for cubic crystals.
• Determine Miller-Bravais indices for hexagonal-closed packed structure.
• Be able to draw directions and planes in cubic and hexagonal crystals.

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3.1 THE SPACE LATTICE AND UNIT CELLS
Crystalline Material and Amorphous (Noncrystalline) Material
• Solid materials can be classified according to the regularity of atom or
ion arrangement.
– Crystalline material: The atoms or ions of a solid are arranged in a
pattern that repeats itself in three dimensions, and the solid has long-
range order (LRO).
– Amorphous materials (Noncrystalline) : The atoms and ions are not
arranged in a long-range, periodic, and repeatable manner and
possess only short-range order (SRO). The order exists only in the
immediate neighborhood of an atom or a molecule.

Crystalline Amorphous
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Atomic hard-sphere model
• The atomic hard-sphere model is used to describe crystalline
structures.
• Atoms or ions are thought of as being solid spheres having well-
defined diameters.
• In the atomic hard-sphere model spheres representing nearest-
neighbor atoms touch one another.
• All the atoms are identical in this particular case.

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Space lattice
• A network of lines in three dimensions is used to describe the atomic
arrangements in crystalline solids. The atoms are placed on the points
of intersection. Such a network is called a space lattice.
• The space lattice can be described as an infinite three dimensional array
of points. Each point in the space lattice has identical surroundings.

Unit cell
• The unit cell is the smallest
structural unit. Repetition of the
unit cell can generate the entire
crystal.
• Generally choose parallelepiped unit
cell with highest level of symmetry.
Lattice constants
• The axial lengths a, b, and c，
• The interaxial angles α, β, and γ

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3.2 Crystal Systems and Bravais Lattices

Crystal Systems
• By assigning specific values for axial lengths and interaxial
angles, unit cells of different types can be constructed.

• Crystallographers have shown that only seven different

types of unit cells are necessary to create all space
lattices.

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Foundations of Materials Science YANG Yuansheng
Bravais Lattice

• According to Bravais (1811-1863),

fourteen standard unit cells can
describe all possible lattice networks.

• The four basic types of unit

cells
➢ Simple
➢ Body-centered
➢ Face-centered
➢ Base-centered

Fig. The 14 Bravais conventional unit cells

grouped according to crystal system.
The dots indicate lattice points that, when
located on faces or at corners, are shared by
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3.3 Principal Metallic Crystal Structures
• Three densely packed crystal structures in most elemental metals (about
90%) :
• body-centered cubic (BCC)
• Face-centered cubic (FCC)
• hexagonal close-packed (HCP).
• The densely packed structures are in lower and more stable energy
arrangements.
• The HCP structure is a denser modification of the simple hexagonal crystal
structure.

BCC FCC HCP

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 Body-Centered Cubic (BCC) Crystal Structure
• In the BCC unit cell, the central atom is surrounded by eight nearest
neighbors.
• coordination number: the number of nearest-neighbor or toughing
atoms for one atom. The coordination number of BCC structure is 8.
• Atoms per unit cell: Each of BCC cells has the equivalent of 2 atoms per
unit cell.
➢ One complete atom is
located at the center,
➢ an eighth of a sphere is
located at each corner of
the cell.
➢ 1 (at the center) + 8 × 1/
8 (at the corners) = 2
atoms per unit cell.

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lattice constant, a
• In the BCC unit cell, the atoms contact each other across the cube
diagonal.
• The relationship between the length of the cube side a and the atomic
radius R is

Atomic packing factor (APF)

• The APF is the fraction of solid sphere
volume in a unit cell, assuming the atomic
hard sphere model

• For the BCC structure, the APF is 0.68.

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Foundations of Materials Science YANG Yuansheng
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Face-Centered Cubic (FCC) Crystal Structure
• In FCC unit cell, there is one lattice point at each corner of the cube and one
at the center of each cube face.
• The atoms in the FCC crystal structure are packed as close together as
possible, and are called a close-packed structure.
• The coordination number: 12
• The lattice constant: a = 4R/ √2.
• Atoms per unit cell: 4
• The atomic packing factor (APF): 0.74.

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Foundations of Materials Science YANG Yuansheng
 Hexagonal Close-Packed (HCP) Crystal Structure
• The third common metallic crystal structure is the hexagonal close-packed (HCP)
structure. The HCP structure is a close-packed structure.
• The coordination number: 12
• The lattice constant: a = 2R. c/a = 1.633 ( ideal HCP ).

• In both the HCP and FCC

crystal structures, each atom
is surrounded by 12 other
atoms, and thus both
structures have same
coordination number.
• Note: The atomic packing in
FCC and HCP crystal
structures is different.

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• Large cell: The HCP unit cell is represented is called the “larger cell.”
• Primitive cell: The isolated HCP unit cell, also called the primitive cell.
– In one primitive cell, there are 2 atoms.
– In Large cell, there are 6 atoms per unit cell.
• The atomic packing factor (APF): 0.74
• It is convenient to use the larger cell for presenting the crystal directions and
planes.
The c/a ratio
• The ratio of the height c of the
hexagonal prism of the HCP crystal
structure to its basal side a is called the
c/a ratio.

• The c/a ratio for an ideal HCP crystal

structure consisting of uniform spheres
packed as tightly together as possible is
1.633.

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• For the HCP metals, there is a certain amount of deviation from the ideal
hard-sphere model.
• Cadmium and zinc have c/a ratios higher than the ideal ratio. The atoms
in these structures are slightly elongated along the c axis of the HCP unit
cell.
• The metals magnesium, cobalt, zirconium, titanium, and beryllium have
c/a ratios less than the ideal ratio. In these metals, the atoms are slightly
compressed in the direction along the c axis.
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 3.4 Atom Positions in Cubic Unit Cells
• Rectangular x, y, and z axes are used to locate atom positions in cubic unit cells.
• Atom positions in unit cells are located by using unit distances along the x, y,
and z axes.
• In crystallography, the positive x axis is usually the direction coming out of the
paper, the positive y axis is the direction to the right of the paper, and the
positive z axis is the direction to the top.
For BCC unit cell:
• The atom positions for the eight corner
atoms are
(0, 0, 0) (1, 0, 0) (0, 1, 0) (0, 0, 1)
(1, 1, 1) (1, 1, 0) (1, 0, 1) (0, 1, 1)
• The center atom has the position
coordinates (1/2, 1/2, 1/2).
• For simplicity, sometimes only two
atom positions in the BCC unit cell are
specified:
• (0, 0, 0) and (1 /2, 1 /2, 1 /2).

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3.5 Directions in Cubic Unit Cells
Direction indices
• The properties of metals and alloys vary with crystallographic
orientation.
• A crystallographic direction is defined as a line between two points, or
a vector.
• For cubic crystals, the crystallographic
direction indices are the vector components
of the direction resolved along each of the
coordinate axes and reduced to the smallest
integers.
• To diagrammatically indicate a direction in a
cubic unit cell, we draw a direction vector
from an origin, which is usually a corner of
the cubic cell, until it emerges from the
cube surface .
• The direction indices are enclosed by square brackets with no separating
commas, [uvw].
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Steps to determine direction indices

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• For example:
– the position coordinates of the direction vector OR are (1, 0, 0), and so
the direction indices for the direction vector OR are [100].
– The position coordinates of the direction vector OS (Fig. 3.10a) are (1,
1, 0), and so the direction indices for OS are [110].
– The position coordinates for the direction vector OT (Fig. 3.10b) are (1,
1, 1), and so the direction indices of OT are [111].

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Indices of a family (form)
• All parallel direction vectors have the same direction indices.
• If the atom spacing along each direction is the same, directions are
crystallographically equivalent.
• Equivalent directions are called indices of a family or form.
• Use angle brackets.
– For example, the following cubic edge directions are
crystallographic equivalent directions:

• The notation 〈100〉 is

used to indicate cubic
edge directions
collectively.

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• Other directions of a form:
– the cubic face diagonals 〈110〉
– the cubic body diagonals 〈111〉

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Angle between two crystal directions
• we can use the definitions of dot product to determine the
angles between any two direction vectors:

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3.6 Miller Indices for Crystallographic Planes
in Cubic Unit Cells
Miller indices
• The Miller notation system is used to identify crystal planes in cubic crystal
structures.
• The Miller indices of a crystal plane are defined as the reciprocals of the
fractional intercepts (with fractions cleared) with the crystallographic x, y,
and z axes of the three nonparallel edges of the cubic unit cell.

• The notation (hkl) is used to

indicate Miller indices
– h, k, and l are the Miller
indices of a cubic crystal
plane for the x, y, and z
axes, respectively.

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• The procedure for determining the Miller indices for a cubic crystal
plane:
– 1. Choose a plane that does not pass through the origin at (0, 0, 0);
– 2. Determine the intercepts of the plane in terms of the crystallographic
x, y, and z axes for a unit cube;
– 3. Form the reciprocals of these intercepts;
– 4. Clear fractions and determine the smallest set of whole numbers that
are in the same ratio as the intercepts.
– These whole numbers are the Miller indices of the crystallographic plane
and are enclosed in parentheses without the use of commas.

Example:

• the intercepts: 1/3, 2 /3, 1.

• The reciprocals of these intercepts are 3, 3/2, 1.
• Clear fractions: 6, 3, 2
• the Miller indices are (632).

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Foundations of Materials Science YANG Yuansheng
Planes of a family or form
• If sets of equivalent lattice planes are related by the symmetry of
the crystal system, they are called planes of a family or form.
• The indices of one plane of the family are enclosed in braces as {hkl}
to represent the indices of a family of symmetrical planes.
– For example, the Miller indices of the cubic surface planes (100),
(010), and (001) are designated collectively as a family or form
by the notation {100}.
– {111} family:

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Relationship between direction indices and Miller indices
• The direction indices of a direction perpendicular to a crystal plane
are same as the Miller indices of the plane.
• Note: only for the cubic system.
– For example, the [100] direction is perpendicular to the (100)
crystal plane.

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Interplanar spacing
• Interplanar spacing represents the distance
from a selected origin containing one plane
and another parallel plane with the same
indices that is closest to it.
• In cubic crystal structures, the interplanar
spacing between two closest parallel planes
with the same Miller indices is given by:

– For example, the

distance between
(110) planes 1 and 2,
d110, is AB.
– the distance between
(110) planes 2 and 3
is d110 and is length BC.
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3.7 Crystallographic Planes and Directions
in Hexagonal Crystal Structure

Indices for Crystal Planes in HCP Unit Cells

• Miller-Bravais indices:
• The HCP crystal plane indices, called Miller-Bravais indices, are
denoted by the letters h, k, i, and l and are enclosed in
parentheses as (hkil).
• Crystal planes in HCP unit cells are commonly identified by
using four indices instead of three.

• The a unit of measurement along the

a1, a2, and a3 axes is the distance
between the atoms along these axes.
• The unit of measurement along the c
axis is the height of the unit cell.
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Determining Miller-Bravais indices
• The reciprocals of the intercepts that a crystal plane makes with the
a1, a2, and a3 axes give the h, k, and i indices, while the reciprocal
of the intercept with the c axis gives the l index.
• Note: h + k = -i

• the intercepts are

– a1 intercept =∞,
– a2 intercept = +1,
– a3 intercept = −1,
– c intercept = ∞.

• the reciprocals
h = 1,
k = 0,
i = −1, and
l=0
• the (011ത 0) plane.
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 Prism Planes
• The Miller-Bravais indices of ABCD
prism plane are (101ത 0) . The ABEF
prism plane has the indices (11ത 00)
and the DCGH plane the indices
(011ത 0).
• All HCP prism planes can be
identified collectively as the {101ത 0}
family of planes.

• Sometimes HCP planes are identified only by three indices (hkl)

since h + k = −i.
• However, the (hkil) indices are used more commonly because they
reveal the hexagonal symmetry of the HCP unit cell.

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Basal Planes
• The basal plane in the unit cell is parallel to the a1, a2, and a3 axes. The
basal planes of the HCP unit cell are very important planes .
• Miller-Bravais indices for the HCP basal plane:
– The intercepts of the basal plane on the top of the HCP unit cell with
the a1, a2, and a3 axes will be at infinity.
• a1 intercept = ∞, a2 intercept = ∞, and a3 intercept = ∞.
• The c axis is unity since the top basal plane intersects the c axis
at unit distance, c intercept = 1.
– Taking the reciprocals of these
intercepts gives the Miller-Bravais
indices for the HCP basal plane.
• h = 0, k = 0, i = 0, and l = 1.
– The HCP basal plane is (0001)
plane.

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Direction Indices in HCP Unit Cells

• Directions in HCP unit cells are indicated by four indices u, v, t, and w

enclosed by square brackets as [uvtw].
• The u, v, and t indices are lattice vectors in the a1, a2, and a3 directions,
respectively , and the w index is a lattice vector in the c direction.
• To maintain uniformity for both HCP indices for planes and directions, it has
been agreed that u + v = −t for directions.

• Relationship between four indices uvtw and three indices u’v’w’

a1+a2+a3 = 0

u+v+t = 0

ua1+va2+ta3
= ua1+va2

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Determining Direction Indices in HCP Unit Cells
• To determine the direction indices of a1.
• [u v w] : u= 1, v= 0, w = 0 [100]
• [u v w]  [u v t w] by

• u = 2/3, v = -1/3, t = - 1/3

• u = 1, v = -1/2, t = - 1/2
• w=0
• [u v t w] : [21ത 10]
ത
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u + v = −t

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3.8 Comparison of FCC, HCP, and BCC Crystal Structures

FCC and HCP Crystal

Structures
• Both the HCP and FCC crystal
structures are close-packed
structures.
• atomic packing factor of 0.74
• The close-packed plane:
– FCC: (111) planes
– HCP: (0001) planes
• Same packing arrangement

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The difference in the stacking arrangement

• The three-dimensional
FCC and HCP crystal
structures are not
identical
• The stacking
arrangement of their
atomic planes is
different
• The stacking sequence:
– FCC: ABCABC …
– HCP: ABABAB …

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 HCP

FCC

stacking sequence

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BCC Crystal Structure
• The BCC structure is not a close-packed structure and has not close packed
planes like the {111} planes in the FCC structure and the {0001} planes in
the HCP structure.
• The most densely packed planes in the BCC structure are the {110} family
of planes.
• The 〈111〉 directions are close-packed directions in the BCC structure,
along the cube diagonals.

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3.9 Volume, Planar, and Linear Density Unit-Cell
Calculations

Volume Density
• Using the hard-sphere atomic model
• the atomic radius obtained from X-ray diffraction analysis
• a value for the volume density of a metal:

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Foundations of Materials Science YANG Yuansheng
Planar Atomic Density
• the atomic densities on various crystal planes.
• the planar atomic density is calculated by:

• In order for an atom area to

be counted in this calculation,
the plane of interest must
intersect the center of an
atom.

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Foundations of Materials Science YANG Yuansheng
Linear Atomic Density
• linear atomic density: the atomic densities in various directions in crystal
structures.
• linear atomic density is calculated by using the relationship

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Foundations of Materials Science YANG Yuansheng
3.10 Polymorphism or Allotropy
• Many elements and compounds exist in more than one crystalline form
under different conditions of temperature and pressure. This
phenomenon is termed polymorphism, or allotropy.
– iron, titanium, and cobalt undergo allotropic transformations at
elevated temperatures at atmospheric pressure.

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 3.11 Crystal Structure Analysis
X-Ray
• Information about crystal structure can be
obtained by using X-Rays.
• The X-rays used are about the same
wavelength (0.05-0.25 nm) as distance
between crystal lattice planes.
X-Ray Diffraction
• A monochromatic (single-wavelength)
beam of X-rays is incident on a crystal.
Crystal planes of target metal will reflect
X-ray beam.
• If rays leaving a set of planes are out of
phase, no reinforced beam is produced.
• If rays leaving are in phase, reinforced
beam is produced. Constructive
interference occurs.
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Bragg’s law
• For rays reflected from different planes to be in phase, the extra distance
traveled by a ray should be a integral multiple of wave length λ .
• consider incident X-rays 1 and 2. For these rays to be in phase, the extra
distance of travel of ray 2 is equal to MP + PN, which must be an integral
number of wavelengths λ.
Thus:
nλ = MP + PN (n = 1,2, …) • If dhkl is interplanar distance,
n is order of diffraction • Then MP = PN = dhklSinθ
• the condition for constructive
interference (the production of a
diffraction peak of intense radiation)
must be

• the first order of diffraction (n = 1),

Bragg’s law takes the form

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Foundations of Materials Science YANG Yuansheng
X-Ray Diffraction Analysis of Crystal Structures
• Modern X-ray crystal analysis uses an X-ray diffractometer that has a radiation
counter to detect the angle and intensity of the diffracted beam.
• A recorder automatically plots the intensity of the diffracted beam as the
counter moves on a goniometer circle that is in synchronization with the
specimen over a range of 2θ values.

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 X-ray diffraction recorder chart
• an X-ray diffraction recorder chart for the intensity of the diffracted beam
versus the diffraction angles 2θ.
• both the angles of the diffracted beams and their intensities can be
recorded at one time with the diffractometer.

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3.12 Amorphous Materials
• Materials with only short-range order are amorphous materials. Atoms in
amorphous materials occupy random spatial positions as opposed to
specific positions in crystalline solids.
• Most polymers, glasses, and some metals are members of the amorphous
class of materials.

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X-ray pattern of amorphous substance
• X-ray amorphous materials produce broad humps with low intensities
in XRD patterns.

• Schematic view of amorphous and crystalline solids. The right part

of the figure corresponds to the typical X-ray patterns of crystalline
and amorphous materials.
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Metallic glass
• Some metals and alloys also have the ability to form
amorphous structures (metallic glass).
• Alloys may form metallic glasses through rapid solidification at
high cooling rates.
• At high cooling rates, the atoms simply do not have enough
time to form a crystalline structure and instead form an
amorphous structure.

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Metallic Glass Products
3.13 Summary
• Crystalline materials, Amorphous Materials

• The Space Lattice and Unit Cells

• Crystal Systems and Bravais Lattices

• Principal Metallic Crystal Structures (FCC, BCC, and HCP)

• Crystal directions, Direction Indices

• Crystal planes, Miller Indices

• Volume, Planar, and Linear Density

• Polymorphism or Allotropy

• X-Ray Diffraction Analysis of Crystal Structures

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