X-ray Diffraction Methods

Distortions of Diffraction Spectra

Preferential Orientation

The standard spectrum has been collected from a pure powder sample with fine powder size,
usually several micrometers in diameter.

We would expect to match both peak locations and relative peak intensities between the
acquired spectrum and the standard if the sample is the same substance as the standard.
Matching relative intensities, however, is not always possible even when
the examined specimen has the same crystalline structure as the standard.

One reason for this discrepancy might be the existence of preferential crystal orientation
in the sample. This often happens when we examine coarse powder or nonpowder
samples. The preferential orientation of crystals (grains in solid) may even make
certain peaks invisible.

Crystallite Size

Lecture 7.1
Residual stress
Peak shifts in spectra occur when residual stress in a sample
 Tensile stress increasing the spacing shifts to lower 2
 Compression stress of decreasing the spacing shifts a peak to higher 2
Crystalline and amorphous samples
Instrumentation
 The divergent slit is placed between x-ray
tube and sample

 The monochromatic filter is placed in the

diffracted beam path instead of the incident
beam path

 The incident beam is directed to the

specimen at a small glancing angle
(usually < 1◦) and the glancing angle is
fixed during operation and only the detector
rotates to obtain the diffraction signals

 Thin-film XRD requires a parallel incident

beam, not a divergent beam
 A monochromator is placed in the optical
path between the X-ray tube and the
specimen, not between the specimen and the
detector
System Aberrations
In ideal conditions, an X-ray beam focuses on a specimen and the intensity of
diffraction from the specimen is detected accurately at the 2θ angle.

Errors due to parafocussing :

 Axial divergence error
 Flat-specimen error; and
 Specimen transparency error

Recent years high resolution X-ray diffractometry (HRXRD) was developed