CHE241 Spring 2015

Lesson 3: Crystalline structure of materials, unit cell, crystal lattices, crystallinity in

metals, ceramics, polymers and semiconductors, crystal directions, crystal planes,
Miller indices, X-ray diffraction

Learning Objectives: What are fundamental crystal structures for various materials?
What are the basic rules for describing crystalline structures?
How do determine the crystal structures?
Contents:
3.0 Amorphous and crystalline arrangements
3.1 Fundamental crystal structures
3.2 Crystal structures of various materials
3.2.1Metal Structures
3.2.1.1 Simple Cubic Structure (sc)
3.2.1.2 Body Centered Cubic Structure (bcc)
3.2.1.3 Face Centered Cubic Structure (fcc)
3.2.1.4 Hexagonal Close-Packed (hcp) Structure
3.2.1.5 Calculation of Theoretical Density
3.2.2 Ceramic Structures
3.2.2.1 MX: NaCl Type (fcc) (or halite structure)
3.2.2.2 MX: CsCl Type (simple cubic)
3.2.2.3 MX2: Fluorite-CaF2(fcc)
3.2.2.4 Kaolinite Unit Cell
3.2.2.5 Density Computations for Ceramics
3.2.3 Polymeric Structures
3.2.4 Semiconductor Structures
3.2.4.1 Diamond Cubic Structure
3.2.4.2 Zinc Blende Structure
3.2.5 Summary of Characteristics of Crystal Systems
3.3 Description of Crystal Structures
3.3.1 Lattice Positions
3.3.2 Lattice Directions
3.3.3 Lattice Planes
3.3.4 Linear and Planar Density
3.4 Determination of crystal structures: X-Ray Diffraction
3.4.1 Braggs Law
3.4.2 X-ray Detection
3.4.3 The relationship between d-spacing and the unit cell dimensions
3.4.4 Prediction of XRD patterns

Page 1 of 35
CHE241 Spring 2015

3.0 Amorphous and crystalline arrangements

Noncrystalline materials: atoms Crystalline materials: Atoms pack

have no periodic packing. in periodic, 3-dimensional arrays
Amorphous = Noncrystalline Most metals
Ceramics
Glasses Some polymers
Many polymers

Page 2 of 35
CHE241 Spring 2015

3.1 Fundamental crystal structures

How materials can be classified based on atomic order?

Page 3 of 35
CHE241 Spring 2015

Page 4 of 35
CHE241 Spring 2015

a, b, and c are the lattice constants

Lattice Points: A lattice is a regular collection of points in euclidean space.

Instead of actual atoms, lattice points are used in crystal lattices.

One lattice point can be associated with more than one atom.
The lattice points may not be the centers of atoms.

The simple cubic lattice becomes the simple cubic crystal structure when an atom is placed
on each lattice point.

Page 5 of 35
CHE241 Spring 2015

Crystal structures: there are 7 crystal systems (basic unit cell geometries)

Page 6 of 35
CHE241 Spring 2015

Crystal structures: there are 14 crystal lattices

7 lattice systems:
cubic
tetragonal
orthorhombic
rhombohedral
hexagonal
monoclinic
triclinic

Page 7 of 35
CHE241 Spring 2015

3.2 Crystal structures of various materials

3.2.1 Metal Structures
3.2.1.1 Simple Cubic Structure (sc)

Only sc metal: Po

Example 3.1 Calculate the APF for a simple cubic (sc) structure.

Page 8 of 35
CHE241 Spring 2015

3.2.1.2 Body Centered Cubic Structure (bcc)

3.2.1.3 Face Centered Cubic Structure (fcc)

Page 9 of 35
CHE241 Spring 2015

3.2.1.4 Hexagonal Close-Packed (hcp) Structure

Page 10 of 35
CHE241 Spring 2015

3.2.1.5 Calculation of Theoretical Density

where n = number of atoms/unit cell

A = atomic weight
Vcell = Volume of unit cell
NA = Avogadros number
= 6.022 x 1023 atoms/mol

Example 3.5 Calculate the theoretical density of Cr.

Page 11 of 35
CHE241 Spring 2015

3.2.2 Ceramic Structures

3.2.2.1 MX: NaCl Type (fcc) (or halite structure)

Figure 3.9 Sodium chloride (NaCl) structure showing (a) ion positions in a unit cell,
(b) full-size ions, and (c) many adjacent unit cells. [Parts (b) and (c) courtesy of
Accelrys, Inc.]
Examples: NaCl, MgO, CaO, FeO, and NiO.

Page 12 of 35
CHE241 Spring 2015

Ionic Packing Factor (IPF)

Similar to the Atomic Packing Factor (APF), the Ionic Packing Factor (IPF) is the fraction
of the unit cell volume occupied by the ions.

Example 3.6 Calculate the IPF of NaCl.

3.2.2.2 MX: CsCl Type (simple cubic)

NaCl: rNa+/rCl- = 0.541 CsCl: rCs+/rCl- = 0.912

Example ceramics: No important commercial ceramics have this type of structure.

Example 3.7 (1) Calculate the IPF of CsCl and (2) determine if Cl- anions are in touch.

Page 13 of 35
CHE241 Spring 2015

3.2.2.3 MX2: Fluorite-CaF2(fcc)

Example 3.8 (1) Calculate the IPF of CaF2 and (2) determine if the central cube of the
unit cell can accommodate a helium atom.

Page 14 of 35
CHE241 Spring 2015

3.2.2.4 Kaolinite Unit Cell

Exploded view of Kaolinite unit cell, 2(OH) 4 Al 2 Si 2 O 5

Page 15 of 35
CHE241 Spring 2015

3.2.2.5 Density Computations for Ceramics

mcell: mass of unit cell

Vcell: volume of unit cell
: mass of cation, I, g.
: mass of anion, j, g.
: atomic weight of cation, i, g/mol
: atomic weight of anion, j, g/mol
: number of cation, i, per unit cell
: number of anion, j, per unit cell
NA: Avogadros number, 6.022 x 1023 atoms/mol

Example 3.9 On the base of the crystal structure, compute the theoretical density for
sodium chloride (NaCl). How does this compare with its measured density?

Page 16 of 35
CHE241 Spring 2015

3.2.3 Polymeric Structures

Polyethylene has an orthorhombic unit cell structure:

Example 3.10 Calculate the number of C and H atoms in the polyethylene unit cell (Figure
3.18), given a density of 0.9979 g/cm3.

Page 17 of 35
CHE241 Spring 2015

3.2.4 Semiconductor Structures

3.2.4.1 Diamond Cubic Structure

Figure 3.20 Diamond cubic unit cell showing (a) atom positions. There are two atoms per
lattice point (note the outlined example). Each atom is tetrahedrally coordinated. (b) The
actual packing of full-size atoms associated with the unit cell. [Part (b) courtesy of Accelrys,
Inc.]

3.2.4.2 Zinc Blende Structure

Page 18 of 35
CHE241 Spring 2015

3.2.5 Summary of Characteristics of Crystal Systems

Page 19 of 35
CHE241 Spring 2015

3.3 Description of Crystal Structures

3.3.1 Lattice Positions

Example 3.13 For the unit cell shown below, locate the point having coordinates 1 .

Page 20 of 35
CHE241 Spring 2015

3.3.2 Lattice Directions

The direction of any line in a crystal lattice can be specified by drawing a line
starting from the unit cell origin parallel to the given line and then taking the coordinates
(u, v, w).
However, by convention, the coordinates of the smallest integer position, u, v, w
are used. The lattice direction is then described as [u v w].

Example: for all the lines that are parallel to the line drawn from the origin, 000, of
the unit cell to the lattice point, , has the same lattice direction, which is
described as [111] instead of [1/2 1/2 1/2].

Page 21 of 35
CHE241 Spring 2015

Figure 3.24 Notation for lattice directions. Note that parallel [uvw] directions (e.g., [111])
share the same notation because only the origin is shifted.

Determination of Directions
Determine the coordinate of two points
Subtract the coordinates of the tail point from the coordinates of the head point to
obtain the number of lattice parameters travelled in the direction of each axis of the
coordinate system
Clear fractions or reduce to obtain the lowest integers
Enclose the number in square brackets

Ex.
Two points are 0,0,2 and 1,1,3

1,1,3 - 0,0,2 = 1,1,1 no fractions to clear, [111] direction

Page 22 of 35
CHE241 Spring 2015

Family of Directions: A set of directions, which are structurally identical, differing

only in their orientations in space, which can be described as <uvw>.

In the cubic system:

Family of directions, 111, representing all body diagonals for adjacent unit cells in the
cubic system

For a non-cubic system: it may not be the same.

Page 23 of 35
CHE241 Spring 2015

The Angle between Two Directions (For cubic system only)

Example 3.15 What is the angle between the [110] and [111] directions in the cubic system?

Page 24 of 35
CHE241 Spring 2015

3.3.3 Lattice Planes

Lattice places are expressed as a set of integers, e.g., Miller indices, (hkl)
The integers are the inverse of axial intercepts
Like lattice directions, a set of Miller indices represent not only one, but many parallel
planes.

Figure 3.26 Notation for lattice planes. (a) The (210) plane illustrates Miller indices
(hkl). (b) Additional examples.

Page 25 of 35
CHE241 Spring 2015

Miller-Bravais Indices (for hexagonal systems)

Four axes: (hkil)

Figure 3.27MillerBravais indices (hkil) for the hexagonal system

Page 26 of 35
CHE241 Spring 2015

Family of Planes
Structurally equivalent planes, {hkl} or {hkil} In the cubic system:

Figure 3.28 Family of planes, {100}, representing all faces of unit cells in the cubic system.

Page 27 of 35
CHE241 Spring 2015

Planes for a crystal structure are represented by Miller indices (h k l).

Any two planes parallel to each other are equivalent and have identical indices.

Procedure to determine h, k and l

1. Make sure that the selected plane does not passes through the origin 0,0,0; it can be
parallel to a plane passing at the origin.
2. Take the length of the directions in terms of lattice parameters a,b,c.
3. Take the reciprocal (inverse) of these distances; a parallel plane that would have an
infinite intercept has index zero.
4. These indices can be divided by a common factor to represent the smallest integers.
5. Finally, the integer indices, not separated by commas, are enclosed within parentheses
(h k l). An intercept at negative side of origin is indicated by a bar positioned over the
appropriate index.

Example 3.16 Describe the following lattice planes.

Page 28 of 35
CHE241 Spring 2015

3.3.4 Linear and Planar Density

Linear Density
Number of atoms per length whose centers lie on the direction of interest
The line must goes through the center of the atom

Planar Density
Number of atoms per unit area
Only those atoms centered on a plane of interest are counted.

Example 3.17
(1) Calculate the linear density of Al in the [110] direction.

(2) Iron foil can be used as a catalyst. The atomic packing of the exposed planes is important.
a) Draw (100) and (111) lattice planes for Fe with a bcc structure .
b) Calculate the planar density for each of these planes.

[110]

Page 29 of 35
CHE241 Spring 2015

3.4 Determination of crystal structures: X-Ray Diffraction

How the size of the crystalline structures can be measured?

X-ray diffraction is used for crystal structure determination and interplanar spacing
determination.

A bean of X-rays directed on a crystalline material may experience diffraction

(constructive interference) as a result of its interaction with a series of parallel atomic
planes.

Page 30 of 35
CHE241 Spring 2015

3.4.1 Braggs Law: the diffraction angle depends on the wavelength of the X-rays and
the distance d between the planes.

Braggs Equation:

: Braggs angle
2: Diffraction angle
d: Interplanar spacing
: Radiation wavelength (e.g, Cu K , =1.5418 )

Page 31 of 35
CHE241 Spring 2015

n: The order of reflection, which may be any integer (1,2,3,) consistent with sin not
exceeding unity (one). When n = 1, the reflection peak is called the primary peak.

3.4.2 X-ray Detection

When the Braggs equation is satisfied, constructive x-ray beams will be reflected,
which could be recorded by films.

3.4.3 The relationship between d-spacing and the unit cell dimensions

For a cubic system:

The relationship between d-spacing distance of two planes and the unit cell edge.

Page 32 of 35
CHE241 Spring 2015

Example 3.18 Figure 3.33 shows the XRD pattern of aluminum (Al). Al is known to
have an fcc structure. Estimate the unit cell edge length and the atomic radius of Al.

Figure 3.33 Diffraction pattern of aluminum powder. Each peak (in the plot of x-ray
intensity versus diffraction angle, 2) represents diffraction of the x-ray beam by a set of
parallel crystal planes (hkl) in various powder particles.

Page 33 of 35
CHE241 Spring 2015

3.4.4 Prediction of XRD patterns

Primitive unit cells: with lattice points only at unit-cell corners. Braggs law applies.
Nonprimitive unit cells: with lattice points along a unit-cell edge, within a unit-cell face,
or in the interior of the unit cell, which cause out-of-phase scattering at certain Bragg
angles. Therefore, some diffraction predicted by Braggs law does not occur.

Reflection Rules

Example 3.19 Predict the first three peaks on the XRD diagram for simple cubic (sc), body-
centered cubic (bcc), and face-centered cubic (fcc) structures.

Page 34 of 35
CHE241 Spring 2015

Homework:
a) Reading, Chapter 3, Shackelford

b) Explore the link to Web Mineral

Use the following links to visualize the crystalline structure of materials on Web Mineral

a) Load the crystalline unit (choose Large Pop-Up and maximize the window on your computer screen);
b) Using the Menu on the Pop-Up screen, use Display On/Off to remove bonds, it will facilitate the visualization
of atoms;
c) Rotate the crystalline unit around the x, y and z axis looking for planes of symmetry and the relative position of
atoms on the unit cell;
d) Using the Menu on the Pop-Up screen, use Display On/Off to add and remove the Polyedra option to identify
the coordination number;
e) Count the number of atoms associated with the unit cell.

Aluminum, Face Centered Cubic

http://webmineral.com/jpowd/JPX/jpowd.php?target_file=Aluminum.jpx

Chromium, Body Centered Cubic

http://webmineral.com/data/Chromium.shtml

Zinc, Hexagonal Closed Packed

http://webmineral.com/data/Zinc.shtml

Halite (NaCl), Cubic Closed Packed

http://webmineral.com/jpowd/JPX/jpowd.php?target_file=Halite.jpx

Kaolinite, triclinic (modified)

http://webmineral.com/jpowd/JPX/jpowd.php?target_file=Kaolinite.jpx

Diamond
http://webmineral.com/jpowd/JPX/jpowd.php?target_file=Diamond.jpx

Database of Parameters for Crystal Structures

http://www.kayelaby.npl.co.uk/chemistry/3_7/3_7_7.html

Page 35 of 35