X-Ray Powder Diffraction:

Basics, Rietveld Refinement, and Applications

Bipina T V CE20D700
RS Meeting
07th Sep’2022

BIPINA T V (CE20D700)
Research Advisor: Dr. Piyush Chaunsali
What are X-Rays ?

• X-rays were discovered by

German physicist Röntgen (1895)

• X rays (1-10 Å) have more

penetrating energy than light
(400-700 nm)

2 Image sourced from internet

What is diffraction?
• Crystals – repeating arrangement of atoms form distinct planes separated by well-
defined distances (d)

• When the atomic planes are exposed to an X-ray beam, X-rays are scattered by
regularly spaced atoms

• Strong amplification of the emitted signal occurs at specific angles, where the
scattered waves constructively interfere - Diffraction
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Bragg’s law
Proposed by Lawrence Bragg and his father, William Henry Bragg, in 1913

Constructive interference
when,
sin θ = (λ/2) / d
or
n λ = 2d sin θ

Cubic

Tetragonal

Hexagonal

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XRD Pattern – A fingerprint

Content same (SiO2), but pattern different 

specific chemistry and atomic arrangement of
each phase
5 http://prism.mit.edu/xray/
Components of X- ray diffractometer

3 basic elements:
1. X-ray tube: X-rays are generated by a
cathode ray tube, filtered to produce
monochromatic radiation, collimated to
concentrate, and directed toward the
sample
2. Sample holder
3. X-ray detector: intensity of the reflected
X-rays is recorded

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Sample preparation

• Appropriate sample preparation – Most critical !!

• 0.5-1g of sample is sufficient
• Powder should be ground to particle size ideally < 5 μm
• Reducing the particle size helps in reducing microabsorption and extinction
• But grinding should be done w/o sample fractionation, phase transformation,
decomposition, and amorphization
• Heat generated during grinding can be avoided using liquid medium (IPA,
acetone, ethanol etc. for cements and clinkers)

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Rietveld Refinement

Minimization function

8 H M Rietveld, 1969
Analysis of X-Ray diffractogram

Typical X-ray
diffractogram

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Analysis of X-Ray diffractogram

Qualitative Analysis
Step 1:
Removal of background

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Analysis of X-Ray diffractogram

Qualitative Analysis
Step 2:
Search peaks

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Analysis of X-Ray diffractogram

Qualitative Analysis
Step 3:
Search match
i. Edit restrictions

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Analysis of X-Ray diffractogram

Qualitative Analysis
Step 3:
Search match
i. Edit restrictions

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Analysis of X-Ray diffractogram

Qualitative Analysis
Step 3:
Search match
i. Edit restrictions
ii. Load the files
iii. Select suitable file

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Analysis of X-Ray diffractogram

Select suitable file

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Analysis of X-Ray diffractogram

ICSD file of
Ye’elimite
(Orthorhombic)

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Analysis of X-Ray diffractogram

ICSD file of
Ye’elimite
(Orthorhombic)

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Analysis of X-Ray diffractogram

Quantitative Analysis
Step 4:
i. Convert pattern to phase

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Analysis of X-Ray diffractogram

Quantitative Analysis
Step 5:
i. Change automatic
mode to semi-
automatic mode
ii. Refine scale and cells
iii. Set global parameters

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Analysis of X-Ray diffractogram

Obtained phase composition

with Goodness of Fit (GoF)

GoF = 3.14

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 Practical Applications in Building Materials

• Determination crystalline phases in a mixture (clinker, cement, hydrates, etc.)

• How much of each crystalline phase is in the mixture (quantitative analysis)

• Hydration kinetics and mechanisms can be studied

• For identifying degradation mechanisms (sulfate attack, DEF, etc.)

• To find if amorphous phases are present in the mixture

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Thank You
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