Advanced Characterization Tools I

Summer semester 2024

Submitted to

Sindy Fuhrmann

Submitted by

Gülay Gürsoy

[email protected]

Hamidagha Hasanov

[email protected]

Shamil Abdullayev

[email protected]
 X-ray Diffraction and Phase Analysis
1. Abstract

In this study, four samples including NaCl, two unknown samples, and silica glasses were analyzed using
X-Ray Diffraction (XRD) spectroscopy. The aim was to investigate the crystalline structure and phase
composition of the samples. XRD patterns were obtained and analyzed to identify the crystalline phases
present in each sample. The results reveal the crystallographic properties of the materials, aiding in the
determination of their structural characteristics. The analysis provides insights into the composition and
arrangement of atoms within the samples, shedding light on their physical properties and potential
applications.

2. Introduction and Theory

X-ray diffraction (XRD) is a vital analytical technique used to characterize the crystalline structure of
materials.

2.1 Working Principle of XRD

XRD techniques are based on the elastic scattering of X-rays from structures that have long range order.
The X-rays get diffracted by a crystal because the wavelength of X-rays is like the inter-atomic spacing in
the crystals. [1]

Figure 1. Working Principle of XRD [2]

X-ray diffractometers consist of three basic elements: an X-ray tube, a sample holder, and an X-ray
detector. X-rays are generated in a cathode ray tube by heating a filament to produce electrons,
accelerating the electrons toward a target by applying a voltage, and bombarding the target material with
electrons.[3]

2.2 Scherrer Equation

Next to instrumental effects, the width, β, of an X‐ray reflection (Full Width at Half Maximum,
FWHM) depends on the size of the coherent scattered regions, i.e. the size of the crystallites. The
smaller the scattering regions, the broader and less intense the reflections are. This can be used to
determine the crystal size, however, only for very small, sub-micrometer-sized crystals.
A simple line width analysis needs the preliminary determination of the instrumental broadening,
Binstr, by measuring an ideal reference sample (infinitely sized, stress‐free crystallites). The
physical line width (Bphys) from a sample, under the same measurement condition,
is then extracted from the experimental line width Bexp using

Bphys 2=Bexp2-Binstr2
Accordingto SCHERRER the mean crystal size, D, of the coherent scattered regions of a powder
sample for a distinct group of lattice planes {h k l} is determined by,

K.
D{hkl}=
B phys . cos ⁡(θ)
Scherrer´s equation can only give a rough estimate. [4]

3. Experimantel Procedure
First, a piece of Sample 1(NaCL), Sample 2 (unknown-I), sample 3 (unknown-II), and Kalk-Natron-Glass
were taken from small tubes, respectively.

Then we put it on the silicone material (See Figure 2) and crushed it until it became powder. We
carefully cleaned the remaining scattered dust. We repeated this process for each sample.(See Figure 3)

Figure 2: Silicon Material [5] Figure 3. Powdered Samples [5]

Then, we placed these 4 different samples on the X-ray device in places that allowed them to be easily
held because they were magnetic.(See Figure 4)

Figure 4. Samples on X-Ray [5]

Then we closed the lid of the device and gave names to each sample from the computer.(See Figure 5)

Figure 5.Names of each sample [5]

Finally, we started the experiment and waited for about 30 minutes to finish. (See Figure 6 )

Figure 6. When the experiment starts [5]

4. Result and Discussion

4.1 Sample 1- NaCl

NaCl crystallizes in a face-centered cubic (FCC) crystal structure, meaning that the sodium (Na+) and
chloride (Cl-) ions are arranged in a cubic lattice with chloride ions at the corners and a sodium ion at the
center of each face. The XRD pattern we got for sodium chloride showed clear peaks that match the
structure of NaCl. We identified these peaks using Miller indices, which help describe how the crystal
planes are positioned for diffraction.
 Figure 7. XRD Pattern of NaCI

We can calculate the length of the cubic unit cell for the two peaks with the highest intensity.

We used following the formula :

2
4a
sin2(θ)  K = (h2 + k2 + l2 ) with K 2
❑
The values of 2θ were obtained using Origin, and the corresponding {h k l} planes were identified. These
values were then used in the formula to determine the lattice constant. Table 1 presents all the
obtained values, with lattice constants calculated as 5.60 and 5.61 for two peaks, respectively.

Table 1.Values of two peaks

λ (Å） Bragg's angle for NaCl NaCl plane s Lattice constant (Å)
2 2 2
2θ θ sinθ h k l h +k +l sin2θ/s a=(λ2/4(sin2θ/s))1/2
1.5406 31.92 15.96 0.2750 2 0 0 4 0.0189 5.6029
1.5406 45.63 22.815 0.3878 2 2 0 8 0.0188 5.6188

Crystalite size was obtained using the Scherrer equation,

K 0.94∗1.5406 Å 1 . 448164 Å
D= = =
βcosθ θ 0
radian() cos( )
2

4.1.Sample 2- Unknown I

The XRD pattern of the unknown substance exhibited distinct diffraction peaks at specific 2θ angles.
These peaks were analyzed to determine their positions, intensities, and widths, providing information
about the crystallographic structure of the substance. Comparison of the experimental XRD pattern with
reference databases or known patterns was used to identify potential matches and infer the
composition of the unknown substance.
 Figure 8. XRD Pattern of CaCO3

The peak with the highest intensity corresponds to the (104) {h k l} index. The unknown compound was
identified as CaCO3 using the HANAWALT-Index method. We can calculate the parameters a and b of
the hexagonal unit cell for the two peaks with the highest intensity.

The following formula for determining the unit cell parameter for a hexagonal unit cell:

4.2.Sample 3- Unknown II

The XRD profile of the unidentified material displayed clear diffraction peaks at precise 2θ angles. These
peaks were examined to ascertain their positions, strengths, and widths, offering insights into the
substance's crystal structure. Comparing the XRD data with established databases or known patterns
aided in identifying possible matches and deducing the composition of the unidentified material. (See
Figure 9)

Figure 9. XRD Pattern of (KNO3) and Al2O3

Software analysis revealed that the compound is likely potassium nitrate (KNO 3) and aluminum oxide
(corundum, Al2O3).

4.3. Sample 4 Kalk-Natron-Glass

The XRD pattern of Kalk-Natron-Glass exhibited a broad, featureless background typical of amorphous
materials. No distinct diffraction peaks corresponding to crystalline phases were observed within the
detection limits of the instrument. The absence of crystalline peaks indicates that the glass is primarily
amorphous, with no significant crystalline impurities present. (See Figure 10)

Figure 10. XRD Pattern of Kalk-Natron-Glass

 3. References

[1] IOWA State Unıversity,Diffraction Basis ,from https://www.cif.iastate.edu/services/acide/xrd-

tutorial/xrd#:~:text=XRD%20techniques%20are%20based%20on,atomic%20spacing%20in%20the
%20crystals.

[2] Wubet,W. “Green Synthesis of CuO Nanoparticles for the Application of DyeSensitized Solar
Cell“.Seminar II. School Of Applied Natural Science. Adama Science And Technology
University.January,2018.

[3]Physics Feed,XRD Working and Application,https://physicsfeed.com/post/xrd-working-and-

application/

[4] X‐Ray Diffraction and Phase Analysis ,Material Science Lab Manual, 2024 SoSe, Friedrich Schiller
University of Jena, MSc. Chemistry of Materials.

[5] The picture was taken by group members.