X-Ray Diffraction Studies Some Crystal Systems

Dr. Mohd Hamdi Bin Ali Buraidah

Learning Outcomes

In the end of this experiment, students should know about crystal systems, able to determine
planar spacing from Bragg equation and lattice parameters.

Theory

Introduction

A crystal consists of atoms or molecules arranged in a pattern that repeats periodically in three
dimensions. A crystal structure is a highly organized structure that results from the nature of
molecules to form a pattern. Figure 1 shows the example of the sodium chloride structure. The
sodium chloride crystal contains many positive ions and negative ions which are bound together
due to electrostatic attraction. This arrangement is dependent on the repulsion and attraction
that involves both the electrostatic and ionic size. A crystal structure can be regarded as
infinitely repetition of the unit cell. The unit cell is the simplest repeating unit in a crystal
structure. Each unit cell is defined in terms of lattice points.

Figure 1: Portion of the sodium chloride structure

The unit cell is a small box containing one or more atoms arranged in 3-dimensions. The size
and shape of unit cell may be specified by means of the lengths a, b and c of the three
independent edges and the three angles α, β and γ between these edges as shown in Figure
2. The volume, V of a unit cell is given by


V  abc 1  cos2 α  cos2 β  cos2 γ  2 cos α cos β cos γ 
1 2
………………..(1)

For the cubic system ( a  b  c and α  β  γ  90 ), the equation (1) becomes V  a .

o 3

Seven crystal system, fourteen Bravais lattice and their unit cell volume are given in Table 1.

β
c
α
γ b
a
Figure 2: Lattice parameters of unit cell
 Table 1: The seven crystal systems and fourteen Bravais lattice.

Crystal Lattice Parameter Bravais lattices Unit cell volume

System Restrictions
Cubic a = b = c Simple V = a3
α = β = γ = 90˚ Body-centered
Face-centered
Tetragonal a = b ≠ c Simple V = a2c
α = β = γ = 90˚ Body-centered
Orthorhombic a ≠ b ≠ c Simple V = abc
α = β = γ = 90˚ Body-centered
Base-centered
Face-centered
Monoclinic a ≠ b ≠ c Simple V = abc sin β
α = γ = 90˚; β ≠ 90˚ Base-centered
Triclinic a ≠ b ≠ c Simple V = abc (1- cos2 α - cos2 β - cos2
α ≠ β ≠ γ ≠ 90˚ γ + 2cos α cos β
cos γ)½

Hexagonal a = b ≠ c Simple V = a2c sin (60°)

α = β = 90˚; γ = 120˚
Trigonal a = b ≠ c Simple V = a2c sin (60°)
α = β = 90˚; γ = 120˚

Vectors and atomic planes in a crystal lattice can be described by Miller indices notation (hkl).
There are several related notations:
 (h,k,l) represents a point
 [hkl] represents a direction
 <hkl> represents a family of directions
 (hkl) represents a plane
 {hkl} represents a family of planes

The Miller indices are related to the peak position or interplanar spacing, d and the unit cell
dimensions (lattice parameters). Generally, the relationship of the interplanar spacing, d and
lattice parameters for cubic, orthorhombic and tetragonal structure can be expressed as

1 2
1  h2 k 2 l 2 
    ....................(2)
d  a 2 b 2 c 2 

In fact, the formula to calculate values of the interplanar spacing (dhkl) for different crystal
structure are show as table below.

Table 2: Values of the interplanar spacing (dhkl)

Crystal System Interplanar spacing, dhkl

Cubic 1
1 2
 2 

2

 a 2 h  k  l 
2

Tetragonal 1
 h2  k 2 l 2  2

 2
 2
 a c 
Orthorhombic 1
 h2 k 2 l 2  2

 2  2  2
a b c 
 Monoclinic 1
 1  h 2 l 2 2hl cos β  k 2  2

 2  2  2    2 
 sin β  a c a c  b 
Triclinic 1
 h2 k2 l2  2

 2 sin 2
α  2
sin 2
  2
sin 2  
2hk
cos α cos β  cos γ 
a b c ab 
 2kl  
  bc cos  cos   cos    ca cos  cos   cos  
2lh

 
 1  cos α  cos β  cos γ  2 cos α cos β cos γ
2 2 2

 
 
 
 
Hexagonal 1
 4 l2 
 
2

 2 h 2
 hk  k 2
 
 3a c2 

The following formula applies to the most general case:

d  V[h 2 b 2 c 2 sin2 α  k 2 a 2 c 2 sin2 β  l 2 a 2 b 2 sin2 γ  2hlab 2 c(cos α cos γ  cos β)

1
 2hkabc 2 (cos α cos β  cos γ)  2kla 2 bc(cos β cos γ  cos α)] 2

....................(3)

X-ray diffraction spectroscopy (XRD) is a powerful experimental technique used to determine

the
 Crystal structure and its lattice parameters
 Interplanar spacing (dhkl) - spacing between lattice planes

Bragg diffraction


}d


d
}

d sin  d sin 
}

For constructive
interference,
2(d sin ) = n 

From the data collected from XRD, the Scherrer equation can be utilized in determination of
the size of particles of crystals in the form of powder.
The Scherrer equation can be written as:
𝐾𝜆
𝜏=
𝛽 𝑐𝑜𝑠𝜃

where

 τ is the mean size of the ordered (crystalline) domains, which may be smaller or equal
to the grain size
 K is a dimensionless shape factor, with a value close to unity. The shape factor has a
typical value of about 0.9, but varies with the actual shape of the crystallite
 λ is the X-ray wavelength
 β is the line broadening at half the maximum intensity (FWHM)in radians.
 θ is the Bragg angle (in degrees).

Experiment 1

In this experiment you are required to identify the materials that will be provided to you.

Procedure:
Collect the X-ray powder diffraction data for the given materials. In this experiment, X’Pert
HighScore program will be used to identify the materials.

Step 1
 Start the X’Pert HighScore program
 Load the data file
− In the File menu, go to Open, choose the data desired data you want to analysis.
Step 2

 If the data are not flat, it can be adjusted by using background subtract function.
− Right click the mouse on the graph, choose Determine Background.
 − Click More button to adjust the background intensity.

− Choose the Min. intensity from scan as background intensity. Then click Subtract and
followed by Replace.

Step 3
 You can start to search the material that match with your data.
− Clicks tab Treatment, then choose Insert Peak.
 − After inserted all the peak appeared in the data, right click the mouse and choose
Search-Match.

− Then a small window will pop out, remain all the setting unchange, click Search
followed by OK, a series of the candidates will show in right bottom side of the
software.

− When you match the peak with standard pattern, you can refer the screen on left
bottom.

Candidate
pattern

Peak
pattern
 − After you found a suitable candidate, you can drag the standard pattern from
Candidates frame into List Pane and this can be repeat few times to find a most
suitable material.

 Explain why the data have a background where the data scan are not starting from zero
intensity.

Experiment 2

Step 1
 Assign Miller indices (hkl) to each peak in your diffraction pattern by comparing your data
to the JCPDS database.
− Right click your desired Pattern List which match with the data, then click Show
Pattern.

− Then, one windows with all the standard peak and value of that materials will pop
out.
− Assign all the hkl planes for each peak.

Step 2
 Calculate lattice parameters (a,b and c) and volume of the unit cell by using the formula
shown in Table 2 in introduction.
Step 3
 Then, find the unit cell volume according formula state in Table 1.

Step 4
 After that, calculate crystallite size by using Scherrer equation.
− The FWHM of each peak can be find from the X’pert HighScore.
− Clicks tab Treatment, then choose Insert Peak.

− After insert the peak, choose Peak List to search the FWHM of each peak.

− Finally, the particles size can be found by substitute all the value into the Scherrer
equation.

Step 5

 Tabulate the data for Step 1 to Step 4 into four different table and the data should include
every calculation value, theoretical value and error percentage for each value.