CRYSTAL STRUCTURES

The Chemistry of Engineering Materials

Lecture Notes 04
Chemistry for Engineers
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SOLIDS: are characterized by their definite shape and considerable mechanical

strength and rigidity

CLASSIFICATIONS OF SOLIDS:

1. Crystalline: the constituent atoms are arranged in a repeating or periodic array

over large atomic distances which give rise to its definite geometrical configuration

one in which the atoms are situated in a repeating or periodic array over a large
atomic distances.

2. Amorphous: the constituent atoms do not have a long range of atomic order
which results to its absence of definite geometrical shape

*The properties of solids are highly dependent on its crystal structures.

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LATTICE: a three dimensional network of imaginary lines connecting points in space

BASIS: an atom or group of atoms attached to every lattice point

CRYSTAL STRUCTURE: the manner in which atoms, ions or molecules are spatially
arranged.

Crystal Structure = Lattice + Basis

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METALLIC CRYSTAL STRUCTURES:

1. SIMPLE: atoms are only positioned at the corners

2. BODY-CENTERED: an additional atom is positioned at the center of the unit cell

3. FACE-CENTERED: atoms are positioned at the corners, as well at the faces of

the unit cell

4. BASE-CENTERED: atoms are positioned at the corners, as well at the opposite

faces of the cube (usually at the top and bottom faces)
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UNIT CELL (PRIMITIVE CELL): the smallest group of

atoms possessing the symmetry of the crystal which,
when repeated in all directions, will develop the crystal
lattice

PARAMETERS USED TO DESCRIBE A UNIT CELL

1. Lattice constants/parameter edge lengths along the

major axes (a, b, c)

2. Interaxial angles: angles between axes (α, β, γ)

CRYSTAL SYSTEM: a scheme by which crystal

structures are classified according to the unit cell
geometry
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BRAVAIS LATTICES: mathematical derivation of the possible number of ways of

arranging atoms in space; arrived at by combining one of the seven crystal systems
with the basic types of unit cells
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BRAVAIS LATTICES: mathematical derivation of the possible number of ways of

arranging atoms in space; arrived at by combining one of the seven crystal systems
with the basic types of unit cells
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FACE-CENTERED CUBIC
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BODY-CENTERED CUBIC
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HEXAGONAL CLOSED-PACK
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POLYMORPHISM: a phenomenon wherein a material has more than one crystal

structure.

ALLOTROPY: polymorphism occurring in elemental solids

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POINT COORDINATES:
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CRYSTALLOGRAPHIC DIRECTION: defined as a line between two points

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DETERMINATION OF THREE DIRECTIONAL INDECES IN A UNIT CELL

1. A vector of convenient length is positioned such that it passes through the

origin of the coordinate system. Any vector may be translated throughout the
crystal lattice without alteration, if parallelism is maintained.

2. The length of the vector projection on each of the three axes is determined;
these are measured in terms of the unit cell dimensions a, b, and c.

3. These three numbers are multiplied or divided by a common factor to reduce

them to the smallest integer values.

4. The three indices, not separated by commas, are enclosed in square brackets,
thus: [uvw]. The u, v, and w integers correspond to the reduced projections
along the x, y, and z axes, respectively.
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CRYSTALLOGRAPHIC PLANES: identified by Miller indeces (hkl)

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.

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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CRYSTALLOGRAPHIC PLANES:
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ATOMIC ARRANGEMENTS:
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ATOMIC ARRANGEMENTS:
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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 {100}. For example, in cubic crystals
the (111), (ῙῙῙ), (Ῑ11), (1ῙῙ), (11Ῑ ), (ῙῙ1), (Ῑ1Ῑ), and (1Ῑ1) planes all belong to the {111}.
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LINEAR DENSITY

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
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PLANAR DENSITY

Planar density(PD) is taken as the number of atoms per unit area that are centered
on a particular crystallographic plane.
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CLOSE-PACKED CRYSTAL STRUCTURES
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CLOSE-PACKED CRYSTAL STRUCTURES

For the HCP, the third close-packed layer is positioned in a way that the centers of
this layer are aligned directly above the original A position called the ABABAB….
stacking. ACACACAC… stacking is its equivalent.
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CLOSE-PACKED CRYSTAL STRUCTURES

For the FCC, the third close-packed layer is positioned in a way that the centers of
this layer are aligned directly above the original C position called the ABCABC….
stacking.
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SINGLE CRYSTAL: a crystalline solid with a periodic and repeated arrangement of
atoms is perfect or extends throughout the entirety of the specimen without
interruption.
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POLYCRYSTALLINE MATERIALS are

composed of a collection of many small
crystals called grains

Grain boundary: the area where two

grains meet
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ANISOTROPY: the dependence of the crystal physical properties with the
crystallographic direction in which measurements are taken.

ISOTROPIC: substances in which measured properties are independent

of the direction of measurement. The degree of anisotropy increases with decreasing
structural symmetry.
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X-RAY DIFFRACTION: DETERMINATION OF CRYSTAL STRUCTURES

Diffraction occurs when a wave encounters a series of regularly spaced obstacles

that

(1) are capable of scattering the wave, and

(2) have spacings that are comparable in magnitude to the wavelength.

Furthermore, diffraction is a consequence of specific phase relationships established

between two or more waves that have been scattered by the obstacles.
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X-RAY DIFFRACTION: DETERMINATION OF CRYSTAL STRUCTURES
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X-RAY DIFFRACTION and BRAGGS’ LAW
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X-RAY DIFFRACTION and BRAGG’S LAW:

BRAGG’S LAW: shows the relationship among x-ray wavelength, interatomic

spacing, and angle of diffraction for constructive interference

If Bragg’s law is not satisfied, then the interference will be nonconstructive in nature
so as to yield a very low-intensity diffracted beam.
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X-RAY DIFFRACTION and BRAGG’S LAW:

The magnitude of the distance between two adjacent and parallel planes of atoms
(i.e., as the lattice parameter(s). the interplanar spacing dhkl ) is a function of the
Miller indices (h, k, and l) as well
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X-RAY DIFFRACTION: DETERMINATION OF CRYSTAL STRUCTURES
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SAMPLE PROBLEMS:

1. Show for the body-centered cubic crystal structure that the unit cell edge length a
and the atomic radius R are related through a = 4R/√3.

2. Show that the atomic packing factor for BCC is 0.68

3. If the atomic radius of lead is 0.175 nm, calculate the volume of its unit cell in
cubic meters. [Ans: 1.21 x10-28m3]

4. Molybdenum has a BCC crystal structure, an atomic radius of 0.1363 nm, and an
atomic weight of 95.94 g/mol. Compute its theoretical density. [Ans: 10.22 g/cm3]

5. Niobium has an atomic radius of 0.1430 nm and a density of 8.57 g/cm3.

Determine whether it has an FCC or BCC crystal structure. Atomic weight of niobium
is 92.90 g/mol.
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SAMPLE PROBLEMS:

6. Magnesium has an HCP crystal structure, a ratio of c/a 1.624, and a density of
1.74 g/cm3. Atomic weight of magnesium is 24.31 g/mol. Compute the atomic radius
for magnesium. [Ans: 0.1604 nm]

7. The unit cell for uranium has orthorhombic symmetry, with a, b, and c lattice
parameters of 0.286 nm, 0.587 nm, and 0.495 nm, respectively. If its density, atomic
weight, and atomic radius are 19.05 g/cm3, 238.03 g/mol, and 0.1385 nm,
respectively, compute for the atomic packing factor. [Ans: 0.536]

8. List the point coordinates for all atoms that are associated with the FCC unit cell.

9. Sketch a tetragonal unit cell and within that cell indicate locations of the 11½ and
½ ¼ ½ point coordinates.
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SAMPLE PROBLEMS:

10. Determine the indices for the directions shown in the following cubic unit cell:

11. Draw an orthorhombic unit cell and within that cell a [2Ῑ1] direction.
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SAMPLE PROBLEMS:

12. Determine the Miller indices for the planes shown in the following unit cell:

13. Draw an orthorhombic unit cell and within that cell a (02Ῑ) and (021) planes.
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SAMPLE PROBLEMS:

14. Derive linear density expressions for FCC [100] and [111] directions in terms of
the atomic radius R.

15. Derive planar density expressions for FCC (100) and (111) planes in terms of the
atomic radius R.

16. Using the data for aluminum (FCC, atomic radius = 0.1431 nm), compute the
interplanar spacing for the (110) set of planes.

17. The metal rhodium has an FCC crystal structure. If the angle of diffraction for the
(311) set of planes occurs at (first-order reflection) is 26.13° when monochromatic x-
radiation having a wavelength of 0.0711 nm is used, compute (a) the interplanar
spacing for this set of planes, and (b) the atomic radius for a rhodium atom.