Unit 4 Characterization of

Nanomaterials
Generation of X-Rays
X-Ray Diffraction
XRD Patterns of Materials in Various Forms
XRD Patterns of a Few Nanomaterials
What’s the Common Feature?
Reasons for Line Broadening in Nanomaterials
• Limited no of diffracting planes in nanomaterials. Insufficient no of planes
cause destructive interference at all angles than Bragg angles. In other words,
some diffraction peaks with low intensity occur at lower and higher angles
than Bragg angles
• Microdeformations and randomly distributed dislocations: depend on order of
diffraction
• Substitutional or interstitial solid solutions/impurities: independent of order
of diffraction
• Randomly oriented crystals: due to absence of complete constructive and
destructive interference
• Instrumental Error: (a) Kα line having width of 0.001 Å (Kα1 = 1.54056 Å and
Kα2 = 1.54439 Å (b) X-ray beam containing convergent and divergent beams
along with parallel beams causing diffraction at angles other than Bragg
angles
Determination of Crystallite Size
t : crystallite size
K: Scherrer constant (ranging between 0.9-1.15)
λ : wavelength
2θ: Diffraction angle
βc: corrected FWHM
β0: determined from observed FWHM by convoluting Gaussian
profile of a nanomaterials
βi: measured on annealed and completely homogeneous
powder with particle size of 1-10 μm. Can also be measured
from standard samples like Si or quartz
ε: strain
Limitations of XRD
• Low intensity of diffracted X-Rays for low atomic number elements
• Relatively large amount of material required
• Solution: Use electron diffraction or neutron diffraction. Typical
intensities for electron beam diffraction are 108 times higher than
those for XRD.
• XRD is suitable if average grain size < 100 nm and grain size distribution
is narrow with instrument broadening becoming critical for grain sizes
more than 30 nm.
• If grain size distribution is inhomogeneous with some grains > 100 nm:
use TEM
Electron Microscopy
Sample Preparation for SEM and TEM
• Conducting surface requirement in SEM
• Role of sputtering
• TEM Sample preparation
- Powder suspension method
- Ultramicrotomy
- Mechanical polishing
- Electropolishing/electrolytic thinning
- Focused Ion Beam (FIB) milling
Characteristic X-Ray Generation and EDS
Particle Size Analysis
BET Surface Area Analysis

https://andyjconnelly.wordpress.com/2017/03/13/bet-surface-area/
S: Specific surface area
R: Particle radius
D: Equivalent particle diameter
ρ: Density

P and P0: Equilibrium and saturation pressure of adsorbate at the

temperature of adsorption
v: volume of adsorbed gas
vm: gas volume adsorbed at the surface in one monolayer
c: BET constant
E1: heat of adsorption for the first layer
El: heat of adsorption for second and higher layers
R: Universal gas constant
T: Absolute temperature

Ns: Number of gas molecules in a gas monolayer

Vm: Volume of 1 mole of gas measured at
standard and temperature conditions
NA: Avagadro number
as: area covered by one molecule
m: mass of solid sanmple
Dynamic Light Scattering
RH: Hydrodynamic radius
kB: Boltzmann constant
T: Absolute temperature
η: viscosity
D: Self-diffusion coefficient
Disadvantage
X-Ray Photoelectron Spectroscopy

Eb: Binding energy (The smallest amount of

energy required to remove a particle from system
of particles)
hν: Energy of X-rays
Ek: Kinetic energy of emitted electrons
φ: work function (minimum energy needed to
remove an electron from a solid to a point in the
vacuum immediately outside the solid surface

https://xpslibrary.com/xps-basics-2/
How is it Useful?
X-Ray Absorption Spectroscopy

https://www.bnl.gov/nsls2/userguide/lectures/lecture-4-ravel.pdf
https://www.bnl.gov/nsls2/userguide/lectures/lecture-4-ravel.pdf
https://www.bnl.gov/nsls2/userguide/lectures/lecture-4-ravel.pdf
https://www.bnl.gov/nsls2/userguide/lectures/lecture-4-ravel.pdf
https://www.bnl.gov/nsls2/userguide/lectures/lecture-4-ravel.pdf
References

Slide Number References

2-3 V. Raghavan, Materials Science and Engineering: A First Course, 5th Edition, 2011
4-5, 7-11, R.K. Goyal, Nanomaterials and Nanocomposites: Synthesis, Properties, Characterization Techniques and
13,15, 21-25, Applications, CRC Press, 1st Edition, 2018
27
6, 12,14 B.S. Murty, P. Shankar, B. Raj, B.B. Rath, J. Murday, Textbook of Nanoscience and Nanotechnology, Springer
University Press, 1st Edition, 2013
16-18 Dieter Vollath, Nanomaterials: An Introduction to Synthesis, Properties and Applications, Wiley-VCH, 2nd
Edition, 2013
20 https://andyjconnelly.wordpress.com/2017/03/13/bet-surface-area/
26 https://xpslibrary.com/xps-basics-2/
28-32 https://www.bnl.gov/nsls2/userguide/lectures/lecture-4-ravel.pdf