XRD Peak profile analysis 2012

Quick estimation for XRD Peak Profile Anatomy

Mahmoud.S.Soliman

Suez Canal University, Faculty of Education in El-Arish, Egypt

Mahmoud_einstien2@yahoo.com

Tel: +0201008076262

Using Braggs Law;

2 sin =

Where d is interplanar distance, is wavelength of incident x-ray beam and is Braggs

angle.

1- By differentiating respect to and we get;

2 cos =

By substituting n=1 for first order diffraction.

This means that when the incident wave length on the crystal is not monochromatic, the
peak position of the crystal planes shifted toward small angles. This occurs when the
characteristic , of x-ray spectrum not well filtered.

I I
Peak Position shifts toward
small angles

Fig (1)

And also, means there is an overlapping occur for the peaks (of the crystal planes) that
results due to each wavelength (because the near value of wavelength of , ) at the
small angles and the separation between the peaks increases at large angles, where;

= 2 cos
 XRD Peak profile analysis 2012

Separation between
overlapped peaks increases at
large angles

Fig (2)

2- By differentiating respect to and we get;

2 sin + 2 cos =0

= = tan

This means that when -value changes by increasing or decreasing due to lattice
strain there is a change in the broadening of the peak profile. When -value
increases so, a peak also moves toward small angles and vice versa, and the lattice
strain observed clearly at large angles that close to 90, where,

( ) =

.
= tan

= . tan

Strain may occur due to compress or relaxation of unit cell (because increasing
the concentration of fillers that enters the unit cell).
 XRD Peak profile analysis 2012

= cot .

Which means that the peak broadening is due to the lattice strain, if -value
increases uniformly, the peak shifts toward small angles and vice versa. But if -
value changes non-uniformly the peak broadening occurs.

3- By differentiating respect to and we get;

2 sin =

This means that if the incident beam is not monochromatic, the measured -value
is not true because there is a change in its value. And -value must be measured
at large angles, where;

=
So,

lim 0

4- Using Debye- Scherrer equation;

.
= .

Where is constant, is full width of the most intensive peak at the half
maximum (FWHM).
Where = .( ) and is Braggs angle of the most intensive peak divided
by 2.
This means that there is a broadening due to the reduction of crystallite size and
observed clearly at large angles. So, broadening inversely proportional with
crystallite size.
 XRD Peak profile analysis 2012

Fig (3)
From FWHM we can calculate the lattice strain as;

Where is Braggs angle of the most intensive peak, note that intensity usually
decreases at large angles.
5- For cubic crystal system;

And
=

(sin ) = ( + + )

(sin ) ( + + )

This means that reflections due to high , , planes occur at large angles.
 XRD Peak profile analysis 2012

Conclusion:

Before beginning in XRD measurements you must carefully be sure that:

1- The X-ray source is monochromatic.

2- The broadening of the XRD machine is eliminated.
3- The integral width is used instead of FWHM.

References:

[1] Elements of x-ray diffraction,Morris cohen,B.D.cullity,Wesley publications.

[2] X-Ray Diffraction Crystallography, Introduction, Examples and Solved

Problems, Yoshio Waseda , Eiichiro Matsubara,Kozo Shinoda.

[3]Egyptian Society of crystallography and its applications (ESCA) workshop, 2012