Structure of Crystalline Solids

Fundamental concepts
• Solid materials may be classified according to the regularity with which atoms or ions are
arranged with respect to one another
• A crystalline material is one in which the atoms are situated in a repeating or periodic array over
large atomic distances
• Long range order exists, 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
• For those which do not crystallize, this long range atomic order is absent
• These are termed noncrystalline or amorphous
• Some of the properties of crystalline solids depend on the crystal structure of the material, the
manner in which atoms, ions, or molecules are spatially arranged
• There is an extremely large number of different crystal structures all having long range atomic
order
• These vary from relatively simple structures for metals to exceedingly complex ones, as
displayed by some of the ceramic and polymeric materials
Fundamental concepts (continued…)
• When describing crystalline structures, atoms (or
ions) are thought of as being solid spheres having
well defined diameters
• This is termed the atomic hard sphere model in
which spheres representing nearest neighbor atoms
touch one another (as shown in the following figure)
• An example of the hard sphere model for the
atomic arrangement found in some of the common
elemental metals is shown in the figure
• In this particular case, all the atoms are identical
• Sometimes, the term lattice is used in the context
of crystal structures
• In this sense lattice means a three dimensional
array of points coinciding with atom positions (or
sphere centers)
Unit cells
• The atomic order in crystalline solids indicates that
small groups of atoms form a repetitive pattern
• Thus, in describing crystal structures, it is often
convenient to subdivide the structure into small
repeat entities called unit cells
• Unit cells for most crystal structures are
parallelepipeds or prisms having three sets of
parallel faces
• One is drawn within the aggregate of spheres (as
shown in the figure), which in this case happens to
be a cube
• A unit cell is chosen to represent the symmetry of
the crystal structure, wherein all the atom positions
in the crystal may be generated by translations of
the unit cell integral distances along each of its
edges
Unit cells (continued…)
• Thus, the unit cell is the basic structural unit or building block of the crystal structure and
defines the crystal structure by virtue of its geometry and the atom positions within
• Convenience usually dictates that parallelepiped corners coincide with centers of the hard
sphere atoms
• Furthermore, more than a single unit cell may be chosen for a particular crystal structure
• However, we generally use the unit cell having the highest level of geometrical symmetry

Metallic crystal structure

• The atomic bonding in this group of materials is metallic and thus non-directional 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
• Also, for metals, using the hard sphere model for the crystal structure, each sphere represents
an ion core
Metallic crystal structure (continued…)
• The following table presents the atomic radii for a number of metals
• Three relatively simple crystal structures are found for most of the common metals:
face-centered cubic, body-centered cubic and hexagonal close-packed
The face-centered cubic crystal structure
• The crystal structure found for many metals has a
unit cell of cubic geometry, with atoms located at
each of the corners and the centers of all the cube
faces
• It is aptly called the face-centered cubic (FCC)
crystal structure
• Some of the familiar metals having this crystal
structure are copper, aluminum, silver, and gold
• Figure (a) shows a hard sphere model for the FCC
unit cell
• In Figure (b), the atom centers are represented by
small circles to provide a better perspective of atom
positions
• The aggregate of atoms in Figure (c) represents a
section of crystal consisting of many FCC unit cells
The face-centered cubic crystal structure (continued…)
• These spheres or ion cores touch one another across a face diagonal
• The cube edge length, a, and the atomic radius, R, are related through

a  2R 2

• For the FCC crystal structure, each corner atom is shared among eight unit cells,
whereas a face- centered atom belongs to only two
• Therefore, 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 may be assigned to a given unit cell
• The cell comprises the volume of the cube, which is generated from the centers of
the corner atoms
• Corner and face positions are really equivalent; that is, translation of the cube
corner from an original corner atom to the center of a face atom will not alter the cell
structure
The face-centered cubic crystal structure (continued…)
• Two other important characteristics of a crystal structure are the coordination number and the
atomic packing factor (APF)
• For metals, each atom has the same number of nearest-neighbor or touching atoms, which is
the coordination number
• For face-centered cubics, the coordination number is 12
• This may be confirmed by examination of Figure (a)
• The front face atom has four corner nearest-neighbor atoms surrounding it, four face atoms
that are in contact from behind, and four other equivalent face atoms residing in the next unit
cell to the front, which is not shown
• The APF is the sum of the sphere volumes of all atoms within a unit cell (assuming the atomic
hard sphere model) divided by the unit cell volume  that is

Volume of atoms in a unit cell

APF 
Total unit cell volume

• For the FCC structure, the APF is 0.74, which is the maximum packing possible for spheres all
having the same diameter
• Metals typically have relatively large atomic packing factors to maximize the shielding provided
by the free electron cloud
The body-centered cubic crystal structure
• Another common metallic crystal structure also has a cubic unit cell with atoms
located at all eight corners and a single atom at the cube center
• This is called a body-centered cubic (BCC) crystal structure
• A collection of spheres depicting this crystal structure is shown in the following
figure (c), whereas Figures (a) and (b) are diagrams of BCC unit cells with the atoms
represented by hard sphere and reduce-sphere models, respectively
The body-centered cubic crystal structure (continued…)
• Center and corner atoms touch one another along cube diagonals, and each unit cell length, a,
and atomic radius, R, are related through

4R
a
3

• Chromium, iron, tungsten, as well as several other metals exhibit a BCC structure
• Two atoms are associated with each BCC unit cell: the equivalent of one atom from the eight
corners, each of which is shared among eight unit cells, and the single center atom, which is
wholly contained within its cell
• In addition, corner and center atom positions are equivalent
• The coordination number for the BCC crystal structure is 8: each center atom has as nearest
neighbors its eight corner atoms
• Since the coordination number is less for BCC than FCC, so also is the atomic packing factor
for BCC lower 0.68 versus 0.74
The hexagonal close-packed crystal structure
• Not all metals have unit cells with cubic symmetry
• Figure (a) shows a reduced-sphere unit cell for this structure, which is termed hexagonal
close-packed (HCP)
• An assemblage of several HCP unit cells is presented in Figure (b)
• The top and bottom faces of the unit cell consist of six atoms that form regular hexagons and
surround a single atom in the center
• Another plane that provides three additional atoms to the unit cell is situated between the top
and bottom planes
The hexagonal close-packed crystal structure (continued…)
• The atoms in this mid-plane have as nearest neighbors atoms in both of the
adjacent two planes
• The equivalent of six atoms contained in each unit cell: one- sixth of each of the 12
top and bottom face corner atoms, one-half of each of the 2 center face atoms, and
all 3 mid-plane interior atoms
• If a and c represents, respectively, the short and long unit cell dimensions, the c/a
ratio should be 1.633
• However, for some HCP metals this ratio deviates from the ideal value
• The coordination number and the atomic packing factor for the HCP crystal
structure are the same as for FCC; 12 and 0.74, respectively
• The HCP crystal structures are the same as for FCC; 12 and 0.74, respectively
• The HCP metals include cadmium, magnesium, titanium, and zinc
Density computations
• Knowledge of the crystal structure of a metallic solid permits computation of its theoretical density, ,
through the relationship
nA

Vc N A

n = number of atoms associated with each unit cell

A = atomic weight
Vc = volume of the unit cell

NA = Avogadro’s number

Polymorphism and allotropy

• Some metals as well as non-metals, may have more than one crystal structure, a phenomenon known as
polymorphism
• When found in elemental solids, the condition is often termed allotropy
• The prevailing crystal structure depends on both the temperature and the external pressure
• One familiar example is found in carbon: graphite is the stable polymorph at ambient conditions, whereas,
diamond is formed at extremely high pressures
• Pure iron has a BCC crystal structure at room temperature, which changes to FCC iron at 912 oC
• Most often a modification of the density and other physical properties accompanies a polymorphic
transformation
Allotropic transformation in tin
• White (or ) tin, having a body-centered tetragonal crystal structure at room temperature,
transforms, at 13.2oC, to gray (or ) tin, which has a crystal structure similar to diamond
• The rate at which this change takes place is extremely slow
• However, below 13.2oC, the rate of transformation is faster
• Accompanying this white-to-gray transformation is an increase in volume (27%), and,
accordingly, a decrease in density (from 7.3 to 5.77 g/cm 3)
• Consequently, this volume expansion results in the disintegration of the white tin metal into a
coarse powder of the gray allotrope
Allotropic transformation in tin (continued…)
• For normal sub-ambient temperatures, there is no need to worry about this
disintegration process for tin products because of the very slow rate at which the
transformation occurs
• This white-to-gray-tin transition produced some rather dramatic results in 1850 in
Russia
• The winter that year was particularly cold and record low temperatures persisted for
extended periods of time
• The uniforms of some Russian soldiers had tin buttons, many of which crumbled
because of these extreme cold conditions, as did also many of the tin church pipes
• The problem came to be known as the “tin disease”
Crystal systems
• Because there are many different possible crystal
structures, it is sometimes convenient to divide them into
groups according to unit cell configurations and/or atomic
arrangements
• One such scheme is based on the unit cell geometry, that
is, the shape of the appropriate unit cell parallelepiped
without regard to the atomic positions in the cell
• Within this framework, an xyz coordinate system is
established with its origin at one of the unit cell corners
• Each of the x, y, and z axes coincides with one of the three
parallelepiped edges that extend from this corner, as shown
the figure
• 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 , , and 
• These are termed the lattice parameters of a crystal
structure
Crystal systems (continued…)
• On this basis, there are seven different possible combinations of a, b, and c, and , , and 
• Each of these represents a distinct crystal system
• These seven crystal systems are cubic, tetragonal, hexagonal, orthorhombic, rhombohedral,
monoclinic and triclinic
• The cubic system, for which a = b= c and  =  =  = 90o, has the greatest degree of
symmetry
• The least symmetry is displayed by the triclinic system because a  b  c and     
• From the discussion of metallic crystal structures, it is apparent that both FCC and BCC
structures belong to the cubic crystal system, whereas HCP falls within the hexagonal system
• The conventional hexagonal unit cell really consists of three parallelepipeds
• 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
Crystallographic points, directions, and planes
• When dealing with crystalline materials, it often becomes necessary to specify a
particular point within a unit cell, a crystallographic direction, or some crystallographic
plane of atoms
• Labeling conventions have been established in which three numbers or indices are
used to designate point locations, directions, and planes
• The basis for determining index values is the unit cell, with a right-handed
coordinate system consisting of three (x, y, and z) axes situated at one of the corners
and coinciding with the unit cell edges
• For some crystal systems, viz. hexagonal, rhombohedral, monoclinic, and triclinic –
the three axes are not mutually perpendicular, as in the familiar Cartesian coordinate
scheme
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 the figure
• Let us specify the position of P in terms of the
generalized coordinates 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
Example Problem: For the unit cell shown in the following figure, locate the point
having coordinates 1/4 1 1/2.
Example Problem: Specify point coordinates for all atom positions for a cubic unit
cell with atoms at cube corners and cube center, i.e., a BCC unit cell.
Thank You

Next Class:
Crystallographic directions