https://doi.org/10.30799/jnst.225.19050205 J. Nanosci. Tech. - Volume 5 Issue 2 (2019) 666–668 ISSN: 2455-0191 Share Your Innovations through JACS Directory Journal of Nanoscience and Technology Visit Journal at http://www.jacsdirectory.com/jnst Analysis of Mechanical Parameters of Zinc Oxide Nanoparticles using Williamson–Hall Method Nidhi1,*, Shalini Dubey1, Arpit Swarup Mathur1, B.P. Singh1, Devendra Kumar2 1Department 2Department ARTICLE of Physics, Institute of Basic Sciences, Khandari, Agra – 282 002, Uttar Pradesh, India. of Chemistry, Institute of Basic Sciences, Khandari, Agra- 282 002, Uttar Pradesh, India. DETAILS Article history: Received 27 March 2019 Accepted 18 April 2019 Available online 06 May 2019 Keywords: Green Synthesis ZnO Nanoparticles Williamson–Hall Method ABSTRACT In this paper, green synthesis has been used for synthesis of ZnO nanoparticles (NPs). Zinc oxide NPs have been synthesized with the aid of lemon juice extract. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results make known that the ZnO sample is hexagonal in shape with an average particles size of nanometer range. As the particle size is of nanometer range, we have evaluated mechanical parameters such as stress, strain and energy density using the X-ray peaks obtained in X- ray diffraction (XRD) reports. The crystalline size, strain and energy density in the lattice of ZnO nanoparticles are estimated by means of Williamson-Hall (W-H) method. 1. Introduction Green synthesis of metal oxide nanoparticles was designed to reduce the eco-friendly toxicity or reduce the environmental pollution. ZnO nanoparticles have been synthesized using various conventional like hydrothermal, direct precipitation, chemical method. However green methods are always sustainable and attractive [1]. The functional groups present in the biological extracts play an important role in chemical conversions. The ZnO plays a dynamic part in the everyday life of the third uppermost universal production volume between the harmless metal to use. ZnO has distinctive characteristics like direct band gap, extraordinary electrochemical permanence, poisonous absorbance and amply in environment. These nanoparticles can be used for sensors, catalysts, as solar selective materials, for hydrogen storage, for thermal heating materials in electronic and electro-optical devices. A perfect crystal would spread substantially in every direction hence no crystals are faultless because of fixed size. This variation from perfect crystallinity indicates extending of diffraction peaks. Two chief characteristics excerpted from peak width investigation are crystalline size and strain in lattice [2-4]. Deviations from regular crystallinity spread substantially in every direction that results to widening of diffraction peaks. Crystalline size and lattice strain are the chief characteristics that could be abstracted from the peak width investigation. Because of synthesis of polycrystalline collections, the crystalline size of particles is not identical as size of the particle [5]. The defectiveness of crystal can be extended from allocations of lattice coefficients. The source of strain similarly comprises sinter stress, triple junction, grain margin, and stress. In diverse modes, Bragg’s peak is marked through crystalline size and strain in lattice that increases the peak breadth and intensity instable. Here crystalline size diverges with 1/cosθ and strain diverges with tanθ as peak breadth [6-7]. As Williamson Hall study is an important method, in this paper we have estimated crystalline size, strain, stress and energy density using this method. 2. Experimental Methods The P-XRD analysis was carried out on XPERT-PRO X-ray diffractometer operated at a voltage of 45 kV and a current of 40 mA with CuKα radiation in a θ-2θ configuration. The high-resolution transmission *Corresponding Author:kmnidhish@gmail.com(Nidhi) https://doi.org/10.30799/jnst.225.19050205 electron microscope studies were carried out on model Jeol/JEM 2100, operated at accelerating voltage of 200 kV with the resolution-point 0.23 nm and lattice 0.14 nm. The FESEM has been carried out on The JEOL Model JSM-6100 operating at resolution of 4 nm at 8 mm at an accelerating voltage 0.3 to 30 kV and magnification 10X to 300,000X. 2.1 Synthesis of Zinc Oxide Nanoparticles 1.09 g zinc acetate dihydrate was dissolved in 20 mL deionised water in a 100 mL round bottom flask and 40 mL lemon juice was added drop wise to the solution under vigorous stirring by magnetic stirrer. The resultant solution was irradiated at 110 W for 20 min by maintaining the temperature 65 °C in a microwave synthesizer. The resultant white precipitate of zinc oxide nanoparticles was centrifuged, washed by distilled water and dried at room temperature. Finally, the powder was dried in a vacuum desiccator over anhydrous CaCl2. 3. Results and Discussion 3.1 X-Ray Diffraction Spectral Studies X-ray diffraction studies can be utilized to assess peak broadening through crystalline size and strain in lattice because of dislocations. The XRD spectra (Fig. 1) of nanoparticles showed that particles were crystalline in nature. Full width at half maximum (β) has been utilized to compute the size distribution of particles [8-10]. It has been perceived that the wider is the peak, wider is the size distribution of nanoparticles. The crystalline size of nanoparticles was evaluated using the width of X-ray peaks supposing they are unrestricted from non-uniform strains through Debye-Scherrer’s formula. The average nano crystalline size was evaluated by means of Debye-Scherrer formula as [9,10]: D= K Cos (1) where K = shape factor = 0.9, D = Crystalline size, and  = Wavelength of Cukα line =1.54060 Å. From the calculations, the average crystalline size of zinc oxide nanoparticles was found 28.82 nm and cell parameters are mentioned in Table 1. Table 1 Cell parameters for ZnO nanoparticles Unit Cell Parameter Å(a) 3.205 Unit Cell Parameter Å(c) 5.173 c/a Ratio 1.614 Cell Volume (Å3) 46.0398 2455-0191 / JACS Directory©2019. All Rights Reserved Cite this Article as: Nidhi, Shalini Dubey, Arpit Swarup Mathur, B.P. Singh, Devendra Kumar, Analysis of mechanical parameters of zinc oxide nanoparticles using Williamson–Hall method, J. Nanosci. Tech. 5(2) (2019) 666–668. 667 Nidhi, et al. / Journal of Nanoscience and Technology 5(2) (2019) 666–668 correspondingly. Now an Eq.(4) stance for UDM wherever it is considered that strain is constant in every crystallographic direction. It was perceived from the lattice parameter calculations that such strain might be because of the lattice contraction. Fig. 1 P-XRD graph of ZnO nanoparticles 3.2 TEM Analysis TEM results Fig. 2 revealed size of zinc oxide nanoparticles. Image divulges that particles size of synthesized zinc oxide nanoparticles lies in the range of 1.17 to 45.67 nm. Fig. 4 The Williamson-Hall study using UDM Strain is calculated through uniform stress deformation model (USDM)by means of Hooke’s law represented by σ = Yε where σ = Stress, Y= Young’s modulus. Such law sustains the linear proportionality. Hooke’s law is effective intended for considerably minor strain. Considering that a minor strain is existing in ZnO, then Hooke’s law can be utilized. Relating Hooke’s law estimation to Eq.(4), Cos = Fig. 2 TEM images of ZnO nanoparticles 3.3 FESEM Analysis The surface morphological characteristics of the nanoparticles were evaluated by means of FESEM analysis, shown in Fig. 3. SEM micrographs evidently indicate zinc oxide nanoparticles are almost hexagonal symmetry. K 4Sin + D Y (5) For the hexagonal structure, Young’s modulus (Y) is specified through subsequent equation, in which S11= 7.858 × 10−12 m2N−1, S13=−2. 206 × 10−12 m2N−1, S33=6.940 × 10−12 m2N−1, S44 = 23.57 × 10−12 m2N−1 are elastic constant [14] for zinc oxide. Young’s modulus (Y) of zinc oxide was evaluated ≈ 127 GPa. 4sinθ/Y and βcosθ were plotted on X and Y-axis correspondingly. The USDM plot meant for zinc oxide is as presented in Fig. 5. The stress is evaluated from slope as shown in Table 2. 2      (h + 2k ) 2 (al )2  h 2 +  +   c 3     Y =  4 2 2     2 (h + 2k ) 2  ( 2 ) h k + ( ) al  al   + + S 33   + (2S13 + S 44 ) h 2 +  S11  h +    3 3 c  c       (6) Fig. 3 FESEM images of ZnO nanoparticles 3.4 Williamson Hall Method In Williamson-Hall method, crystalline size D and micro strain ε are related. The slope of the plot among 4sinθ and βcosθ gives the micro strain and the crystalline size value [11-13]. The resultant strain prompted in powder because of crystal deficiency and distortion was evaluated by means of,  =  4Tan (2) It was analysed from Eqs.(1) and (2) that peak breadth from crystalline size diverges as 1/cosθ, strain diverges as tanθ. Considering that strain and particle size are not dependent to one another and the perceived line breadth is basically summation of Eqs.(1) and (2). = K + 4Tan DCos (3) By readjusting the above equations K + 4Sin Cos = D Fig. 5 The W-H study using USDM Another model is utilized to compute the energy density of synthesized ZnO which is known as Uniform Deformation Energy Density Model (UDEDM). In Eq.(5), the crystals are considered to have a regular, isotropic nature. Though, in many cases, the assumption of homogeneity and isotropy is not reasonable. Furthermore, the constants of proportionality associated with the stress strain relation are no longer independent when the strain energy density u is considered. For an elastic system that follows Hooke’s law, the energy density u can be computed from u = σ2/2Y then Eq.(5) can be rewritten according to the energy and strain relation, 1/ 2 Cos = (4) The beyond equations are Williamson-Hall equations. A graph is plotted through 4sinθ and βcosθ along X and Y-axis respectively for synthesized zinc oxide nanoparticles as presented in Fig. 4. Particle size is evaluated from Y-intercept and strain is evaluated as of slope of the fitted line K  2u  + (4Sin   D Y  ) (7) 1/ 2  2u  4Sin   Y  Plots of βcosθ versus were plotted and the data fitted to lines. The anisotropic energy density u was calculated by the slope of line, and the crystalline size from the y-intercept and given in Table 3. https://doi.org/10.30799/jnst.225.19050205 Cite this Article as: Nidhi, Shalini Dubey, Arpit Swarup Mathur, B.P. Singh, Devendra Kumar, Analysis of mechanical parameters of zinc oxide nanoparticles using Williamson–Hall method, J. Nanosci. Tech. 5(2) (2019) 666–668. Nidhi, et al. / Journal of Nanoscience and Technology 5(2) (2019) 666–668 0.012 Acknowledgements 0.01 Authors are thankful to Head Department of Physics and Head Department of Chemistry of Dr. Bhim Rao Ambedkar University, Agra for providing necessary facilities regarding experimental work. The authors would like to thank SAIF, Punjab University, Chandigarh for XRD and SEM analysis, SAIF, Cochin for TEM analysis. y = -0.0006x + 0.0068 R² = 0.0042 0.008 β Cos θ 668 0.006 0.004 0.002 0 References 0 0.5 1 1.5 2 4 Sin θ(2/Y)1/2 [1] Fig. 6 The W-H study using UDEDM [2] Table 2 Strain and size by UDM & USDM (UDM) D (nm) 20.3 ε ×10-3 0.04 (USDM) D (nm) 20.3 [3] ε 0.038 σ (GPa) 4.9 Table 3 Energy density, strain & size by UDEDM D (nm) 20.3 u (KJm-3) 3.6×104 ε ×10-3 0.75 [4] [5] σ (MPa) 95.6 Nano crystalline zinc oxide have been synthesized effectively using green synthesis method. Average particle size of crystalline material is 28.82 nm which is in good agreement with TEM records. It has been concluded that micro strain arises due to crystal imperfections or dislocations. Peak broadening has been observed in XRD results. This broadening was due to strain in lattice. Crystalline size, strain, stress and energy density has been estimated using Scherrer formula and Williamson Hall analysis. The TEM records were in noble agreement by means of the corresponding results of Williamson Hall method. [6] [7] [8] [9] [10] 4. Conclusion The zinc oxide nanoparticles have been successfully synthesized by using lemon juice extract. Hence green synthesis minimizes the impact of harmful chemicals. So, such a synthesis is eco-friendly. Prepared ZnO material was characterized using several analytical tools like XRD, SEM and TEM. XRD result reveals the peak broadening and morphology of the samples were characterized by SEM which proved the hexagonal shape. 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