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2-Erlina Puspitasari-Sample Analysis and Characterization of Results Using XRD
2-Erlina Puspitasari-Sample Analysis and Characterization of Results Using XRD
PRACTICAL REPORT
INSTRUMENTAL CHEMISTRY
EXPERIMENT 1
SAMPLE ANALYSIS AND CHARACTERIZATION OF RESULTS USING X-RAY
DIFRACTION (XRD)
I. Experimental Goal
Students are able to understand the working principles of XRD instrument and are able to
characterize various materials through a diffractogram interpretation.
II. Introduction
X-ray diffraction (XRD) is a powerful nondestructive technique for characterizing crystalline
materials. It provides information on structures, phases, preferred crystal orientations (texture),
and other structural parameters, such as average grainsize, crystallinity, strain, and crystal defects.
X-ray diffraction peaks are produced by constructive interference of a monochromatic beam of X-
rays scattered at specific angles from each set of lattice planes in a sample. The peak intensities
are determined by the distribution of atoms within the lattice. Consequently, the X-ray diffraction
pattern is the fingerprint of periodic atomic arrangements in a given material. This review
summarizes the scientific trends associated with the rapid development of the technique of X-ray
diffraction over the past five years pertaining to the fields of pharmaceuticals, forensic science,
geological applications, microelectronics, and glass manufacturing, as well as in corrosion analysis.
2.1 Principle of XRD
Materials are made up of atoms arranged in crystal microstructures. Minerals are crystalline
inorganic solids possessing well-defined chemical composition and are formed through natural
processes. Minerals are usually classified and characterized based on their physical properties
including hardness, color, crystallinity, flammability, and density. For example, calcite and
magnesite possess high utility owing to their wide variety of applications in several industries
including, paint, resin, ink, cosmetic, rubber, explosive, detergent, pharmaceutical, and
construction industries. Minerals are crystalline and external factors such as temperature, cooling
rate during solidification, and pressure strongly influence the periodic arrangement of atoms.
Elements and their compounds in solid-state can be categorized in amorphous, single crystalline,
and polycrystalline materials. The nature of amorphous materials is isotropic owing to the
irregular arrangement of atoms, which results in similar properties in all directions. Contrarily, the
atoms in crystalline materials are arranged in a repeated and regular pattern, which exhibits
changes in properties with direction (anisotropy). Various crystals of different sizes and shapes
combine to form polycrystalline materials. The distribution of crystal shapes, orientations, and
sizes in a
polycrystalline material strongly affects its properties. The nature of about 95% of the solid
materials is crystalline, and International Center Diffraction Data (ICDD) has maintained about
25,000 organic and 50,000 inorganic single component and crystalline databases.
Arrays of atoms are arranged in a repeated and regular pattern in crystalline structures. The
smallest recurring element of crystal is known as a unit cell, while size and shape of the unit cell
(Figure 2.1) can be explained by the angle between axes (α, β, γ) and length of three axes (a, b, c)
in a three-dimensional system. Atoms in an array are arranged in order, based on the position of
atoms (translation or transformation) while no change is found in terms of orientation or rotation.
The type of translation may be one-, two-, or three-dimensional. A regular arrangement of points
in a crystal is a lattice. A set of translational vectors in both two- and three-dimensions can be
used for representing these lattices, as shown in Figure 1a and 1b, respectively.
Figure 2.1 (a) Two-dimensional lattice with translation vector (b) Three-dimensional lattice with
translation vector
When the X-rays impinge on solid materials, they get scattered by the electrons revolving around
the nucleus of atoms. These scattered waves, emitted in multiple directions, interfere with each
other. The nature of interference can be constructive or destructive, based on the direction and
type of interaction of waves. Diffraction is the constructive interference of scattered X-rays. It is
worthy to note here that the orderly arrangement (periodicity) of atomic structures in solids,
causes constructive interference. It is, therefore, relatively easier to interpret the XRD graphs of
crystalline substances as compared to amorphous ones. A strong correlation exists between
periodicity and diffraction i.e., higher diffraction angles are observed with shorter periodicity and
vice versa. Lamas et al. demonstrated XRD graphs of amorphous and crystalline solids, as shown in
Figures 2.2a and 2.2b respectively. Due to the absence of a periodic arrangement in amorphous
materials, the XRD graph only indicates the maximum average peak at a certain diffraction angle,
while crystalline materials show several distinct XRD peaks owing to the periodic arrangement of
atoms. XRD is also a powerful technique for estimating the treatment effects on the crystallinity of
materials. For example, a recent study used XRD for understanding the effects of various
treatments on the
crystallinity of their sample material. XRD allowed them to identify that the combustion treatment
of their sample would enhance the material’s crystallinity to a relatively greater extent, as shown
in Figure 2.3.
Figure 2.2 XRD qualitative graphs representing (a) an amorphous material [21] and (b) a crystalline
material
Figure 2.3 XRD was used for understanding the role of various treatments on the crystallinity of
peat (a mixture of organic matter and minerals): (a; blue) sample material without treatment; (b;
green) H2O2 chemical oxidation treatment; (c; red) combustion treatment.
Knowledge about the atomic number and atomic position within the cell is determined by
diffraction peak intensity, while diffraction peak position provides information about the size and
shape of the unit cell.
Figure 2.4 (a) An illustration of X-ray diffraction pattern [26] (b) Pythagoras theorem applied for
deriving diffraction equations
Pythagoras theorem (Figure 2.4b) was used for deriving the following equations till eq. (5). As per
Bragg’s law, the condition for constructive interference is,
AB + BC = nλ (1)
From schematic of XRD (Figure 6a), it can be inferred that AB = BC,
2AB = nλ (2)
The Pythagoras theorem is applied on ∆ABZ as follows,
sin 𝜃 = 𝐴𝐵 𝑑 (3)
𝑑 sin 𝜃 = 𝐴𝐵 (4)
Inserting AB in eq. (2) yields,
nλ = 2𝑑 sin 𝜃 (5)
where n indicates the order of reflection (diffraction), λ denotes X-ray wavelength, 𝑑
characterizes spacing between atomic planes, and 𝜃 represents diffraction beam angle. The set of
lattice planes (hkl) with spacing (𝑑ℎ𝑘𝑙) can be related with the order of diffraction (n) as follows:
𝑑 = 𝑑ℎ𝑘𝑙 𝑛 (6)
With the substitution of Eq. (6) into Eq. (5), the following relation is found:
λ = 2𝑑ℎ𝑘𝑙 sin 𝜃ℎ𝑘𝑙 (7) The vector notation of Bragg’s law can be illustrated with the directions of
incident and scattered beams, as schemed in Figure 2.5. Moreover, Bragg’s law in vector form can
be expressed as follows [27]:
(𝑺−𝑺𝒐)/ λ = 𝒅ℎ𝑘𝑙 ∗ = ℎ𝒂𝟏 +𝑘𝒂𝟐 + 𝑙𝒂𝟑 (8)
where 𝑆 represents the unit vector with the direction of diffracted beam and 𝑆𝑜 indicates unit
vector in direction of the incident beam.
This law relates the wavelength of electromagnetic radiation to the diffraction angle and the
lattice spacing in a crystalline sample. These diffracted X-rays are then detected, processed, and
counted. By scanning the sample through a range of 2u angles, all possible diffraction directions of
the lattice should be attained due to the random orientation of the powdered material.
Conversion of the diffraction peaks to d-spacings allows identification of the compound because
each compound has a set of unique d-spacings. Typically, this is achieved by comparison of d-
spacings with standard reference patterns. 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. When electrons have sufficient
energy to dislodge inner shell electrons of the target material, characteristic X-ray spectra are
produced. These spectra consist of several components, the most common being Ka and Kb.
where λ the wavelength, 2 is the Bragg angle of reflection, and β is the integral breadth in radian.
And also calculate the strain from the equation:
β = 4ε tan θ (10)
2.4 Index Miller
Miller Indices form a notation system in crystallography for planes in crystal (Bravais) lattices.
There are two equivalent ways to define the meaning of the Miller Indices: via a point in the
reciprocal lattice, or as the inverse intercepts along the lattice vectors. Both definitions are given
below. In either case, one needs to choose the three lattice vectors a 1, a2, a3 that define the unit
cell (note that the conventional unit cell may be larger than the primitive cell of the Bravais
lattice). Given these, the three primitive reciprocal lattice vectors are also determined (denoted b 1,
b2, b3). Then, given the Miller Indices h,k,l denotes plane orthogonal to the reciprocal lattice
vector:
That is (hkl) simply indicates a normal to the planes in the basis of the primitive reciprocal lattice
vectors. Because the coordinates are integers, this normal is itself always a reciprocal lattice
vector. The requirement of lowest terms means that is the shortest reciprocal lattice vector in the
given direction.
Equivalent (hkl) denotes a plane that intercepts the three points a1/h, a2/h and a3/h or some
multiple thereof. That is the Miller Indices are proportional to the inverses of the intercepts of the
plane, in the basis of the lattice vectors. If one of the indices is zero, it means that the planes do
not intersect the axis (the intercept is at infinity). Considering only (hkl) planes intersecting one or
more lattice points, the perpendicular distance d between adjacent lattice planes is related to the
(shorter) reciprocal lattice vector orthogonal to the planes by the formula:
d = 2π / ghkl (12)
(14)
(15)
Similarly from EON and FON we get:
(16)
Combining equations (15) and (16) gives
h3: k3: l3 = a cos α: b cos β: c cos γ (17)
For a cubic system we have a = b = c, then equation (17) reduces to
h3: k3: l3 = cos α: cosβ: cos γ (18)
That is, the ratio of Miller indices is the ratio of the directional cosines.
Based on the diffractogram results in the figure above, it shows that the sample differences
between AgSiO2 and SiO2 powders. all the characteristic peaks appear at their corresponding 2θ,
o
and no novel peak comes out, which demonstrates that only Ag is produced on 38.174 (2θ).
Angle 2θ that appears there are 5 peaks, namely 38.174 o, 44.348 o, 64.522 o, 77.477 o, and 81.552
o
. characteristic of SiO2 and AgSiO2 samples located at an angle of 2θ are 22.129 o and 38.174 o.
In the equation, y is the intensity of the data point, y0 is the initial intensity of the data point, A is
the area of each peak with arbitrary unit (a.u.), w is the width of half the height of each peak
(FWHM) with units of degrees (°), x is the 2θ value of the data point, and xc is the the location of
the formed
peak and is the value of 2θ which has units of degrees (°). A value in the SiO2 sample is 0.031 and
0.036 for the AgSiO2 sample.
If Bragg's law is applied to the 2θ value which is the diffraction angle, then the the value of the
distance between layers. The equation of Bragg's Law with the value n is the order of reflection
which can be any integer (1, 2, 3, ...) consistent with sin θ does not exceed one, λ is the X-ray
wavelength, d is the distance between layers, and θ is the angle between the plane and the
incident ray. In the SiO2 sample, a wavelength (λ) of 1.54060 was obtained with an A value of
0.031, while in the AgSiO2 sample, a wavelength of 1.54060 was obtained with an A value of
0.036.
Based on Miller Indices with the notation (h,k,l) which determines the orientation of a crystal.
SiO2 sample shows one peak at angle 2 theta 20.356 degrees obtaining an hkl value of 100 which
indicates a simple cubic crystal form. The AgSiO2 sample shows five peaks at 2 theta angles of
38.174 o, 44.348 o, 64.522 o, 77.477 o, and 81.552 o obtained hkl values of 111, 200, 220, 311 and
222 which indicate a cubic crystal form with the possibility of simple cubic, face-centered, body-
centered and diamond shapes. Of the two samples have a crystalline form with a diffractogram
that also has an amorphous form.
The results obtained with JCPDS (Ag: 2𝜃= 38.14; 44.77; 64.57; 77.37 and 81.69° corresponding to
reflections (111), (200), (220), (311) and (222) on the sample of AgSiO2 with the results of this
study show the same 2𝜃 angle and reflection. This indicates that the diffractogram that appears is
a sample of AgSiO2 (Ag: 2𝜃=38.174 o, 44.348 o, 64.522 o, 77.477 o, and 81.552 o).
Determining the crystal size with the Debye Scherrer equation shows the relationship between
FWHM and 2𝜃 angle where the smaller the FWHM value, the greater the 2𝜃 angle value.
VI. Conclusion
Based on this research on sample analysis using XRD which is an accelerated analysis technique
mainly used to identify the phase of crystalline materials and can provide information about unit
dimensions. The diffractogram results show that the AgSiO2 powder is identical to the JCPDS with
an angle value of 2𝜃=38.174 o, 44.348 o, 64.522 o, 77.477 o, and 81.552 o
corresponding to
reflections (111), (200), (220), (311) and (222) on the sample of AgSiO2.
VII. Reference
1. C J Gilmore, J A Kaduk, H Schenk. International Tables for Crystallography, Volume H, Powder
Diffraction 2019.
2. R M Cuéllar-Franca and A Azapagic. Carbon capture, storage and utilisation technologies: a
critical analysis and comparison of their life cycle environmental impacts. Journal of CO2
Utilization 2015.
3. J Gao, L Chun, L Weizao, et al. Process simulation and energy integration in the mineral
carbonation of blast furnace slag. Chinese Journal of Chemical Engineering 2018.
4. M Razeghi. Fundamentals of solid states engineering. Kluwer Academic, New York 2002: 5-6
5. J F Shackelford. Introduction to materials science for engineers. Pearson Education
International, London UK, 6th Edition 2005:6.
6. R Sharma, D P Bisen, U Shukla, B G Sharma. X-Rays diffraction: a powerful method of
characterizing nanomaterials. Recent Research in Science and Technology 2012; 4(8): 77-9.
7. C D Putnam, M Hammel, G L Hura, J A Tainer. X-ray solution scattering (saxs) combined with
crystallography and computation: defining accurate macromolecular structures,
conformations and assembling in solution. Quarterly Reviews of Biophysics 2007; 40 (3): 191-
285.
8. Asif, A.; Yi, W. C; Rafael, M.S. X-Ray Diffraction Techniques for Mineral Characterization: A
Review for engineers of the fundamentals, applications and research directions. Preprints.
2021: 0438.v1.
9. B Fultz, J Howe. Transmission electron microscopy and diffractometry of materials. Springer,
Berlin 2013: 2.
10. D G Lamas, M O Neto, G Kellermann, A F Craievich. X-ray Diffraction and Scattering by
Nanomaterials. Nano characterization Techniques Chapter 5 2017.
11. J K Sjöström, R Bindler, T Granberg, M E Keylander. Procedure for Organic Matter Removal
from Peat Samples for XRD Mineral Analysis. Wetlands 2019; 39(3): 473-81.
12. I F Macías-Quiroga, G I Giraldo-Gómez, N R Sanabria-González. Characterization of Colombian
Clay and Its Potential Use as Adsorbent. The Scientific World Journal 2018; 5969178.
13. Andrei, A. Bunaciu; Elena, G. Udristioiu; Hassan, Y. A. X-Ray Diffraction: Instrumentation and
Applications. Critical Reviews in Analytical Chemistry, 2015.45:4, 289-299.
14. Bragg, W. H. Concerning the Nature of Things, Lecture IV, one of six lectures presented at the
Royal Institution. 1925 republished by Dover Phoenix Editions 2004: ISBN 0-486-49574-4.
15. Connolly, J. R. Introduction to X-Ray Powder Diffraction; Spring, 2007.
16. T. C. Huang and W. Parrish, Appl. Phys. Lett. 27, 123.
17. P. scherrer, Gottinger Nachrichten. Gesell 2. 1918. 98-100.
18. Anitha, S. N; Jayakumar, I. Journal of Nanoscience and Technology (1). 2015. 26-31.
19. Eric J. Mittemeijer and Udo Welzel, Max Planck Institute for Metals Research,
Heisenbergstrae 3, 70569 Stuttgart, Germany. Z. Kristallogr. 223 (2008) 552–560
20. Neil W. A; N. David. Mermin. Solid State Physics. Harcourt. New York. 1976
21. Chia, O. U. On the Miller Indices Determination of Si{1 0 0} Convex Corner Undercut Planes.
2005. J.Micromechanics and Microengineering. 15 833
VIII. Attachment
8.1 Interim Report
OBSERVATION AND DATA
ANALYSIS
1.
SiO2 22.129 11.065 6.688 0.117 1.1664
b.
Sample of Ag/SiO2
Peak 2θ θ Sin θ Sin2θ h2 + k2 + l2 hkl d hkl a
1 38.168 19.084 0.327 0.107 3 111 1 4
2 44.354 22.177 0.377 0.142 4 200 2 4
(Coupled TwoTheta/Theta)
AgSiO2_KELOMPOK 2.raw, 11/11/2023 2:05:53 PM
Peak List #1
Visible Icon Color Index Name Parent Caption (display) Scan Angle
Yes 1 Peak #1 Peak List #1 14.947 ° AgSiO2_KELOMPOK 2.raw #1 14.947 °
Yes 2 Peak #2 Peak List #1 38.168 ° AgSiO2_KELOMPOK 2.raw #1 38.168 °
Yes 3 Peak #3 Peak List #1 44.354 ° AgSiO2_KELOMPOK 2.raw #1 44.354 °
Yes 4 Peak #4 Peak List #1 64.478 ° AgSiO2_KELOMPOK 2.raw #1 64.478 °
Yes 5 Peak #5 Peak List #1 77.410 ° AgSiO2_KELOMPOK 2.raw #1 77.410 °
Yes 6 Peak #6 Peak List #1 81.527 ° AgSiO2_KELOMPOK 2.raw #1 81.527 °
(Coupled TwoTheta/Theta)
AgSiO2_KELOMPOK 2.raw, 11/11/2023 2:07:57 PM
Area List #1
Visible Icon Color Index Name Parent Scan Left Angle
Yes 1 [36.737 ° - 39.124 °] Area List #1 AgSiO2_KELOMPOK 2.raw #1 36.737 °
Yes 2 [43.136 ° - 45.421 °] Area List #1 AgSiO2_KELOMPOK 2.raw #1 43.136 °
Yes 3 [63.500 ° - 65.328 °] Area List #1 AgSiO2_KELOMPOK 2.raw #1 63.500 °
Yes 4 [76.348 ° - 78.278 °] Area List #1 AgSiO2_KELOMPOK 2.raw #1 76.348 °
Yes 5 [81.121 ° - 82.086 °] Area List #1 AgSiO2_KELOMPOK 2.raw #1 81.121 °
Right Angle Left Int. Right Int. Obs. Max d (Obs. Max) Gross Int. Net Height FWHM
39.124 ° 3.51 4.20 38.169 ° 2.35595 Å 97.0 93.1 0.240
45.421 ° 3.41 3.06 44.354 ° 2.04071 Å 31.7 28.5 0.319
65.328 ° 2.29 2.42 64.478 ° 1.44398 Å 20.0 17.7 0.332
78.278 ° 1.94 2.05 77.410 ° 1.23186 Å 16.0 14.0 0.407
82.086 ° 1.75 1.60 81.527 ° 1.17975 Å 5.08 3.39 0.327
Chord Mid. d (Chord Mid.) I. Breadth Gravity C. d (Gravity C.) Raw Area
38.174 ° 2.35565 Å 0.305 38.159 ° 2.35651 Å 37.58
44.348 ° 2.04094 Å 0.423 44.333 ° 2.04162 Å 19.45
64.522 ° 1.44311 Å 0.390 64.501 ° 1.44353 Å 11.19
77.477 ° 1.23097 Å 0.439 77.446 ° 1.23138 Å 9.988
81.552 ° 1.17944 Å 0.379 81.590 ° 1.17898 Å 2.901
(Coupled TwoTheta/Theta)