Strain and Grain Size Determination of CeO2 and TiO2 Nanoparticles: Comparing Integral Breadth Methods versus Rietveld, μ-Raman, and TEM
Abstract
:1. Introduction
2. Materials and Methods
2.1. X-ray and TEM Experimental Details
2.2. μ-Raman Experimental Details
3. Results and Discussion
3.1. PXRD Analysis
3.2. Scherrer Method
3.3. Monshi Method
3.4. W–H Method
3.4.1. UDM Method
3.4.2. USDM Method
3.4.3. UDEDM Method
3.5. SSP Method
3.6. H–W Method
3.7. Rietveld Refinement and Spherical Harmonic Approach
3.8. μ-Raman Analysis
3.9. TEM Analysis and Comparison
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
- Punia, P.; Bharti, M.K.; Chalia, S.; Dhar, R.; Ravelo, B.; Thakur, P.; Thakur, A. Recent advances in synthesis, characterization, and applications of nanoparticles for contaminated water treatment—A review. Ceram. Int. 2021, 47, 1526–1550. [Google Scholar] [CrossRef]
- Rajender, G.; Giri, P.K. Strain induced phase formation, microstructural evolution and bandgap narrowing in strained TiO2 nanocrystals grown by ball milling. J. Alloy. Compd. 2016, 676, 591–600. [Google Scholar] [CrossRef]
- Henao, C.P.B.; Montes, V.H.; Sierra, R.B. Nanopartículas para materiales antibacterianos y aplicaciones del dióxido de titanio. Rev. Cuba Investig. Biomed. 2016, 35, 387–402. [Google Scholar]
- Raez, J.M.; Arencibia, A.; Segura, Y.; Arsuaga, J.M.; López-Muñoz, M.J. Combination of inmobilized TiO2 and zero valent iron for efficient arsenic removal in aqueous solutions. Sep. Purif. Technol. 2021, 258, 118016. [Google Scholar] [CrossRef]
- Falsafi, S.R.; Rostamabadi, H.; Assadpour, E.; Jafari, S.M. Morphology and microstructural analysis of bioactive-loaded micro/nanocarriers via microscopy techniques; CLSM/SEM/TEM/AFM. Adv. Colloid Interface Sci. 2020, 280, 102166. [Google Scholar] [CrossRef]
- Kunka, C.; Boyce, B.L.; Foiles, S.; Dingreville, R. Revealing inconsistencies in X-ray width methods for nanomaterials. Nanoscale 2019, 11, 1–24. [Google Scholar] [CrossRef] [PubMed]
- Monshi, A.; Foroughi, M.R.; Monshi, M.R. Modified Scherrer Equation to Estimate More Accurately Nano-Crystallite Size Using XRD. World J. Nano Sci. Eng. 2012, 2, 154–160. [Google Scholar] [CrossRef] [Green Version]
- Williamson, G.K.; Hall, W.H. X-ray line broadening from filed aluminium and wolfram. Acta Metall. 1953, 1, 22–31. [Google Scholar] [CrossRef]
- Scardi, P.; Leoni, M.; Delhez, R. Line broadening analysis using integral breadth methods: A critical review. J. Appl. Cryst. 2004, 37, 381–390. [Google Scholar] [CrossRef]
- Kumar, B.R.; Hymavathi, B. X-ray peak profile analysis of solid-state sintered alumina doped zinc oxide ceramics by Williamson–Hall and size-strain plot methods. J. Asian Ceram. Soc. 2017, 5, 94–103. [Google Scholar] [CrossRef] [Green Version]
- Himabindu, B.; Devi, N.L.; Kanth, B.R. Microstructural parameters from X-ray peak profile analysis by Williamson-Hall models—A review. Mater. Today Proc. 2021. [Google Scholar] [CrossRef]
- Tagliente, M.A.; Massaro, M. Strain-driven (0 0 2) preferred orientation of ZnO nanoparticles in ion-implanted silica. Nucl Instrum. Methods 2008, 266, 1055–1061. [Google Scholar] [CrossRef]
- Young, R.A. The Rietveld Method; International Union of Crystallography Oxford University: New York, NY, USA, 1993. [Google Scholar]
- Blanco, R.C.; Casagrande, S.P. Método de Rietveld para el estudio de estructuras cristalinas. Rev. Fac. Defic. UNI 2004, 2, 1–5. [Google Scholar]
- Raquejo, D.J. Desarrollo de un Protocolo para la Aplicación del Método de Rietveld y del Estándar Interno en la Caracterización de Materiales Cerámicos con Contenido de Amorfos. Bachelor’s Thesis, Universidad EAFIT, Medellín, Colombia, 2015. [Google Scholar]
- Pecharsky, V.J.; Zavalij, P.Y. Fundamentals of Powder Diffraction and Structural Characterization of Materials, 2nd ed.; Springer Science+Business Media, LLC: Berlin/Heidelberg, Germany, 2009; pp. 269–292. ISBN 978-0-387-09578-3. [Google Scholar]
- Ramos-Guivar, J.A.; Taipe, K.; Schettino, J.M.A.; Silva, E.; Torres, M.A.M.; Passamani, E.C.; Litterst, F.J. Improved removal capacity and equilibrium time of maghemite nanoparticles growth in zeolite type 5A for Pb(II) adsorption. Nanomaterials 2020, 10, 1668. [Google Scholar] [CrossRef] [PubMed]
- Paillard, V.; Puech, P.; Laguna, M.A.; Carles, R.; Kohn, B.; Huisken, F. Improved one-phonon confinement model for an accurate size determination of silicon nanocrystals. J. Appl. Phys. 1999, 86, 1921–1924. [Google Scholar] [CrossRef]
- Grujić-Brojčin, M.; Šćepanović, M.J.; Dohcević-Mitrovic, Z.D.; Popović, Z.V. Use of phonon confinement model in simulation of Raman spectra of nanostructured materials. Acta Phys. Pol. A 2009, 116, 51–54. [Google Scholar] [CrossRef]
- Guivar, J.A.R.; Bustamante, D.A.; Gonzalez, J.; Sanches, E.A.; Morales, M.; Raez, J.M.; López-Muñoz, M.-J.; Arencibia, A. Adsorption of arsenite and arsenate on binary and ternary magnetic nanocomposites with high iron oxide content. Appl. Surf. Sci. 2018, 454, 87–100. [Google Scholar] [CrossRef]
- Holzwarth, U.; Gibson, N. The Scherrer equation versus the “Debye-Scherrer equation”. Nat. Nanotechnol. 2011, 6, 534. [Google Scholar] [CrossRef]
- Nath, D.; Singh, F.; Das, R. X-ray diffraction analysis by Williamson-Hall, Halder-Wagner and size-strain plot methods of CdSe nanoparticles- a comparative study. Mater. Chem. Phys. 2020, 239, 122021. [Google Scholar] [CrossRef]
- Rabiei, M.; Palevicius, A.; Monshi, A.; Nasiri, S.; Vilkauskas, A.; Janusas, G. Comparing methods for calculating nano crystal size of natural hydroxyapatite using X-ray diffraction. Nanomaterials 2020, 10, 1627. [Google Scholar] [CrossRef] [PubMed]
- Khandan, A.; Ozada, N.; Karamian, E. Novel Microstructure Mechanical Activated Nano Composites for Tissue Engineering Applications. J. Bioeng. Biomed. Sci. 2015, 5, 1–4. [Google Scholar]
- Hall, W.H. X-ray line broadening in metals. Proc. Phys. Soc. A 1949, 62, 741–743. [Google Scholar] [CrossRef]
- Scardi, P.; Leoni, M. Whole powder pattern modelling. Acta Cryst. 2002, A58, 190–200. [Google Scholar] [CrossRef] [PubMed]
- Jamal, M.; Asadabadi, S.J.; Ahmad, I.; Aliabad, H.A.R. Elastic constants of cubic crystals. Comput. Mater. Sci. 2014, 95, 592–599. [Google Scholar] [CrossRef]
- Goldsby, J.C. Basic Elastic Properties Predictions of Cubic Cerium Oxide Using First-Principles Methods. J. Ceram. 2012, 2013, 1–4. [Google Scholar] [CrossRef]
- Borgese, L.; Bontempi, E.; Gelfi, M.; Depero, L.; Goudeau, P.; Geandier, G.; Thiaudière, D. Microstructure and elastic properties of atomic layer deposited TiO2 anatase thin films. Acta Mater. 2011, 59, 2891–2900. [Google Scholar] [CrossRef]
- Zak, A.K.; Majid, W.H.A.; Abrishami, M.E.; Yousefi, R.; Parvizi, R. Synthesis, magnetic properties and X-ray analysis of Zn0.97 X0.03O nanoparticles (X = Mn, Ni, and Co) using Scherrer and size-strain plot methods. Solid State Sci. 2012, 14, 488–494. [Google Scholar]
- Al-Tabbakh, A.A.; Karatepe, N.; Al-Zubaidi, A.B.; Benchaabane, A.; Mahmood, N.B. Crystallite size and lattice strain of lithiated spinel material for rechargeable battery by X-ray diffraction peak-broadening analysis. Int. J. Energy Res. 2019, 43, 1903–1911. [Google Scholar] [CrossRef]
- Gholizadeh, A. X-Ray Peak Broadening Analysis in LaMnO3+δ Nano-Particles with RhombohedralCrystal Structure. J. Adv. Mater. Process. 2015, 3, 71–83. [Google Scholar]
- Scardi, P.; Leoni, M. Line profile analysis: Pattern modelling versus profile fitting. J. Appl. Cryst. 2006, 39, 24–31. [Google Scholar] [CrossRef] [Green Version]
- Scardi, P. Diffraction Line Profiles in the Rietveld Method. Cryst. Growth Des. 2020, 20, 6903–6916. [Google Scholar] [CrossRef]
- Rodríguez-Carvajal, J. Introduction to the Program FULLPROF: Refinement of Crystal and Magnetic Structures from Powder and Single Crystal Data; Laboratoire Léon Brillouin (CEA-CNRS): Saclay, France, 2001. [Google Scholar]
- Popa, N.C. The (hkl) Dependence of Diffraction-Line Broadening Caused by Strain and Size for all Laue Groups in Rietveld Refinement. J. Appl. Cryst. 1998, 31, 176–180. [Google Scholar] [CrossRef]
- Casas-Cabanas, M.; Palacín, M.R.; Rodríguez-Carbajal, J. Microstructural analysis of nickel hydroxide: Anisotropic size versus stacking faults. Powder Diffr. 2005, 20, 334–344. [Google Scholar] [CrossRef]
- Jensen, G.V.; Bremholm, M.; Lock, N.; Deen, G.R.; Jensen, T.R.; Iversen, B.B.; Niederberger, M.; Pedersen, J.S.; Birkedal, H. Anisotropic Crystal Growth Kinetics of Anatase TiO2 Nanoparticles Synthesized in a Nonaqueous Medium. Chem. Mater. 2010, 22, 6044–6055. [Google Scholar] [CrossRef]
- Mi, J.L.; Clausen, C.; Bremholm, M.; Lock, N.; Jensen, K.M.O.; Christensen, M.; Iversen, B.B. Rapid Hydrothermal Preparation of Rutile TiO2 Nanoparticles by Simultaneous Transformation of Primary Brookite and Anatase: An in Situ Synchrotron PXRD Study. Cryst. Growth Des. 2012, 12, 6092–6097. [Google Scholar] [CrossRef]
- Wang, Y.; Chan, S.L.I.; Amal, R.; Shen, Y.R.; Kiatkittipong, K. XRD Anisotropic broadening of nano-crystallites. Powder Diffr. 2010, 25, 217. [Google Scholar] [CrossRef]
- Spanier, J.E.; Robinson, R.D.; Zhang, F.; Chan, S.W.; Herman, I.P. Size-dependent properties of CeO2-y nanoparticles as studied by Raman scattering. Phys. Rev. B 2001, 64, 245407. [Google Scholar] [CrossRef] [Green Version]
- Richter, H.; Wang, Z.P.; Ley, L. The one phonon Raman spectrum in microcrystalline silicon. Solid State Commun. 1981, 39, 625–629. [Google Scholar] [CrossRef]
- Campbell, I.H.; Fauchet, P.M. The Effects of Microcrystal Size and Shape on the One Phonon Raman Spectra of crystalline Semiconductors. Solid State Commun. 1986, 58, 739–741. [Google Scholar] [CrossRef]
- Danei, M.; Dehghankhold, M.; Ataei, S.; Davarani, F.H.; Javanmard, R.; Dokhani, A.; Khorasani, S.; Mozafari, M.R. Impact of particle size and polydispersity index on the clinical applications of lipidic nanocarrier systems. Pharmaceutics 2018, 10, 57. [Google Scholar] [CrossRef] [Green Version]
- Kibasomba, P.M.; Dhlamini, S.; Maaza, M.; Liu, C.P.; Rashad, M.M.; Rayan, D.A.; Mwakikunga, B.W. Strain and grain size of TiO2 nanoparticles from TEM, Raman spectroscopy and XRD: The revisiting of the Williamson-Hall plot method. Results Phys. 2018, 9, 628–635. [Google Scholar] [CrossRef]
Samples | CeO2 | TiO2 | ||
---|---|---|---|---|
Scherrer method | D (nm) | 19.6 (2) | 12.7 (2) | |
R2 | 0.99 | 0.26 | ||
Modified Scherrer method | D (nm) | 21.6 (3) | 14.6 (2) | |
R2 | 0.99 | 0.27 | ||
Williamson–Hall method | UDM | D (nm) | 24 (9) | 17.9 (8) |
ε × 10−3 | 0.75 (1) | 2.30 (2) | ||
R2 | 0.86 | 0.02 | ||
USDM | D (nm) | 22.8 (1) | 17 (6) | |
ε × 10−3 | 0.56 (1) | 1.95(1) | ||
σ (TPa) × 10−4 | 1.51(5) | 2.48(2) | ||
R2 | 0.56 | 0.08 | ||
UDEDM | D (nm) | 23.6 (1) | 18.5(8) | |
ε× 10−7 | 1.26 (1) | 7.42(1) | ||
σ (TPa) × 10−4 | 1.85 (4) | 3.1 (2) | ||
U (TJm−3) × 10−7 | 0.63 (3) | 3.71(1) | ||
R2 | 0.75 | 0.08 | ||
Size–strain plot method | D (nm) | 17.4 (5) | 9.7 (2) | |
ε× 10−3 | 0.77 (1) | 4.83 (1) | ||
R2 | 0.999 | 0.81 | ||
Halder–Wagner method | D (nm) | 10.3 (8) | 5.6 (2) | |
R2 | 0.999 | 0.992 | ||
ε × 10−3 | 97.2 (7) | 17.1 (5) | ||
Rietveld Refinement (SHP) | D (nm) | 15.4 (1) | 10.1 (2) | |
ε | 32.9 (2) | 110.7 (5) | ||
μ-Raman | D (nm) | 14.5 (1) | 11.5 (1) | |
TEM | D (nm) | 14.5 (5) | 17.9 (5) |
Refinement Parameters | nanoCeO2 | nanoTiO2 |
---|---|---|
Profile | TCH | TCH |
5.4106 | 3.7839 | |
5.4106 | 3.7839 | |
5.4106 | 9.5017 | |
90 | 90 | |
90 | 90 | |
90 | 90 | |
158.396 | 136.045 | |
0.087 (2) | 0.000 (2) | |
0.098 (3) | 0.535 (2) | |
0.000 (2) | 0.387 (5) | |
−1.119 (8) | −0.967 (2) | |
−0.091 (3) | −0.167 (3) | |
- | 0.473 (2) | |
FWHM parameters | ||
U | 0.085 | 4.384 |
V | −0.41 | −2.610 |
W | 0.014 | 0.921 |
Global average size (nm) | 15.4 (1) | 10.1 (2) |
6.08 | 5.46 | |
5.79 | 5.55 | |
χ2 | 2.99 | 1.69 |
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. |
© 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
Share and Cite
Canchanya-Huaman, Y.; Mayta-Armas, A.F.; Pomalaya-Velasco, J.; Bendezú-Roca, Y.; Guerra, J.A.; Ramos-Guivar, J.A. Strain and Grain Size Determination of CeO2 and TiO2 Nanoparticles: Comparing Integral Breadth Methods versus Rietveld, μ-Raman, and TEM. Nanomaterials 2021, 11, 2311. https://doi.org/10.3390/nano11092311
Canchanya-Huaman Y, Mayta-Armas AF, Pomalaya-Velasco J, Bendezú-Roca Y, Guerra JA, Ramos-Guivar JA. Strain and Grain Size Determination of CeO2 and TiO2 Nanoparticles: Comparing Integral Breadth Methods versus Rietveld, μ-Raman, and TEM. Nanomaterials. 2021; 11(9):2311. https://doi.org/10.3390/nano11092311
Chicago/Turabian StyleCanchanya-Huaman, Yamerson, Angie F. Mayta-Armas, Jemina Pomalaya-Velasco, Yéssica Bendezú-Roca, Jorge Andres Guerra, and Juan A. Ramos-Guivar. 2021. "Strain and Grain Size Determination of CeO2 and TiO2 Nanoparticles: Comparing Integral Breadth Methods versus Rietveld, μ-Raman, and TEM" Nanomaterials 11, no. 9: 2311. https://doi.org/10.3390/nano11092311