INTRODUCTION:

In the present decade or the past two-decades scientist were focused in this spinel ferrite because of its multi dimension application in various field such as industrial as well as bio medical application, there are so many applications such as data storage devices hyperthermia etc. Since people were taken more interest to do the research work in the field of ferrite materials. The present research module is depend on Spinel type ferrite¹. In the spinel ferrite there are 56 atoms and 32 cations. The Spinel ferrites are formulated as AFe₂O₄, where A is metallic elements of P-blocks consist of one of the most important groups of magnetic materials, due to their interesting characteristics. There is a loop hole for researchers to do work on electronic, recording industries and medical areas depends essentially on the shape, size, purity and magnetic stability of the nanoparticles^1-3. In the present research module, we were attempt to synthesized the Cu- spinel ferrite and try to doped with Ce ³⁺ion, we doped Ce ion with the concentration of very small quantity such as 0.02 to 0.10 with replacement of Fe^3+.Later we focus on effect of substitution of Ce ion in Cu type spinel ferrite in the context of Structural and magnetic properties. The present research work is also focus on to ionic radius and its occupancy in tetrahedral and octahedral sites preferences Such that we should understand that the effect of ionic radius is also key parameter for changing the materials physical, electrical and chemical properties etc^4-5.

EXPERIMENTAL TECHNIQUES:

For synthesis of Cu-spinel ferrite we took the chemicals in nitrate form such as Cu- Nitrate, Fe- Nitrate Urea, Ce- Nitrate, distilled water etc. all the chemical ware measured in stoichiometric ration and put it in 200ml beaker and finally add the 100ml of distilled water such that the chemicals is properly dissolved in a distilled water. After dissolving the chemical, we get the transparent solution in beaker then we put this beaker in magnetic hot plate and starring continuously at temperature 80 degree Celsius, slowly we got the gel like liquid there after we put this gel inside the microwave oven and fired it in 600 watts. After fired we get the floppy ash powder⁵. This ash powder is grinded in mortal pestle at least 4hrs such we get the fine powder. After getting the fine powder the sample was put into furnace for sintering at 800˚c for 4hr. Latter after sintering the material is aging crush in mortal pestle finally, we got fine nano- powder named as CuFe₂O₄

RESULT AND DISCUSSION:

Structural analysis (XRD):

Peak Positions:

a. The peak positions in the XRD patterns correspond to the crystal planes of the spinel structure, typically represented by their Miller indices (h k l).

b. The peak positions remain relatively consistent across the different compositions (x = 0.2, 0.4, 0.6, 0.8, 1.0), indicating that the overall crystal structure is maintained.

Peak intensity variations:

a). As the Ce substitution concentration (x) increases, the relative intensities of the peaks change.

This suggests that the substitution of Ce for Fe in the spinel structure alters the atomic arrangement and the relative abundances of the different crystal planes.

Figure 1: Shows the X-ray diffraction (XRD) patterns of the CuFe_(2-x) Ce_(x)O₄ spinel ferrite system, where x represents the substitution concentration of cerium (Ce) in place of iron (Fe). The key observations and interpretations from the provided XRD patterns are as follows:

Peak Broadening

a) Some of the peaks-exhibit broadening as the Ce substitution concentration (x) increases.

b) This peak broadening can be attributed to the introduction of structural defects or distortions in the spinel lattice due to the substitution of larger Ce ions for smaller Fe ions.

Identification of Miller indices (h k l):

The major peaks in the XRD patterns can be assigned to the following Miller indices:

1. The peak around 2θ = 18˚-20˚ corresponds to the (111) plane.

2. The peak around 2θ = 30˚- 32˚ corresponds to the (220) plane.

3. The peak around 2θ = 35˚- 37˚ corresponds to the (311) plane.

4. The peak around 2θ = 43˚- 45˚ corresponds to the (400) plane.

5. The peak around 2θ = 53˚- 55˚ corresponds to the (422) plane.

6. The peak around 2θ = 57˚- 59˚ corresponds to the (511) plane.

7. The peak around 2θ = 63˚- 65˚ corresponds to the (440) plane.

Effect of Ce substitution

As the Ce substitution concentration (x) increases, the following trends are observed:

· The peak intensities for the (111), (220), and (400) planes decrease, suggesting a reduction in the abundance of these crystal planes.

· The peak intensities for the (311), (422), (511), and (440) planes increase, indicating an enhancement in the abundance of these crystal planes.

a). These changes in the relative peak intensities reflect the structural modifications induced by the substitution of Ce for Fe in the spinel lattice.

b). The XRD patterns provide insights into the structural changes in the CuFe_(2-x) Ce_(x)O₄ spinel ferrite system as a function of Ce substitution concentration (x). The peak positions, intensities, and broadening reveal the evolution of the crystal structure and the preferred orientation of the crystal planes due to the incorporation of Ce into the spinel lattice⁶.

Fig 2: Shows the X-ray diffraction (XRD) patterns of the Cu Fe(2-x) Ce(x) O4 spinel ferrite system, where x represents the substitution concentration of cerium (Ce) in place of iron (Fe).

Effect of Ce substitution:

· As the Ce substitution concentration (x) increases, significant changes are observed in the XRD patterns:

· The peak positions shift towards lower 2θ angles, indicating an increase in the interplanar spacing (d-spacing) of the crystal planes.

· The peak intensities and relative intensities between the peaks also change, reflecting the structural modifications in the spinel lattice⁷.

Ionic radius effect:

The ionic radius of the cations present in the spinel structure plays a crucial role in the observed changes:

· Fe3+ has an ionic radius of 0.645 Å.

· Ce3+ has a larger ionic radius of 1.14 Å.

· The substitution of the larger Ce³⁺ ions for the smaller Fe³⁺ ions in the spinel lattice leads to an expansion of the unit cell, causing the observed shift in the peak positions towards lower 2θ angles.

Peak position shifts:

· The peak positions shift towards lower 2θ angles as the Ce substitution concentration (x) increases from 0.2 to 1.0.

· This gradual shift in the peak positions is a direct consequence of the expanding unit cell due to the incorporation of the larger Ce³⁺ ions into the spinel structure⁸.

Peak intensity changes:

· The relative intensities of the peaks change as the Ce substitution concentration (x) increases.

· This can be attributed to the structural distortions and changes in the atomic arrangement within the spinel lattice caused by the substitution of Fe³⁺ by Ce³⁺ ions. The changes in the peak intensities suggest a preference for the formation of certain crystal planes over others, reflecting the structural evolution of the spinel ferrite with increasing Ce content⁸.

Structural modifications:

· The substitution of Ce3+ for Fe3+ in the spinel structure leads to lattice distortions and changes in the cation distribution between the tetrahedral and octahedral sites⁹.

· These structural modifications can result in the observed peak shifts, peak broadening, and changes in the relative peak intensities¹⁰.

In summary, the XRD patterns demonstrate the significant impact of Ce substitution on the structural properties of the Cu Fe_(2-x) Ce_(x)O₄ spinel ferrite system. The shift in peak positions and the changes in peak intensities are directly related to the difference in ionic radii between the substituting Ce³⁺ and the replaced Fe³⁺ions, which results in the expansion of the spinel unit cell and the subsequent structural rearrangements within the lattice^11,12.

Magnetic structure:

Fig 3. Shows the hysteresis loops for CuFe_(2-x) Ce_(x)O₄ spinel ferrite samples with varying Ce concentrations (x = 0.02, 0.04, 0.06, 0.08, and 0.1)

These magnetization curves provide insights into the magnetic properties of the samples, which can be correlated with the XRD results discussed earlier. Let's analyze the B-H curves and relate them to the structural changes observed in XRD¹³.

a). Saturation Magnetization (Ms):

· As the Ce concentration increases from 0.02 to 0.1, the saturation magnetization (maximum B value) generally increases.

· This trend correlates with the XRD results, where Ce³⁺ substitution for Fe³⁺ leads to structural modifications. The larger Ce³⁺ ions may enhance the overall magnetic moment of the spinel structure¹⁴.

b). Coercivity (Hc):

· The coercivity, represented by the width of the hysteresis loop, appears to change with Ce³⁺ concentration.

· This can be related to the XRD peak broadening observed with increasing Ce³⁺ content, which indicates changes in crystallite size and lattice strain.

c). Remanence (Br):

· The remanent magnetization (B value at H = 0) also shows variations with Ce concentration.

· This property is influenced by the cation distribution and crystal structure, which were shown to change in the XRD analysis¹⁵.

d). Loop Shape:

· The shape of the hysteresis loops evolves with increasing Ce³⁺ content, becoming wider and more pronounced¹⁶.

· This change in magnetic behavior correlates with the structural modifications observed in XRD, such as peak shifts and intensity changes.

e). Magnetic Anisotropy:

· The slope of the curves near saturation provides information about magnetic anisotropy.

· Changes in this slope across samples can be linked to the lattice distortions and cation redistribution indicated by XRD peak shifts and intensity changes¹⁷.

Correlation with XRD results:

a). Structural Expansion:

The XRD results showed a shift in peak positions towards lower angles with increasing Ce³⁺ content, indicating lattice expansion. This expansion can lead to changes in magnetic interactions, reflected in the evolving shapes of the B-H curves¹⁸.

b). Cation Distribution:

The substitution of Ce³⁺ for Fe³⁺ alters the cation distribution in tetrahedral and octahedral sites of the spinel structure. This redistribution, evident from XRD peak intensity changes, directly impacts the magnetic properties observed in the B-H curves¹⁹.

c). Crystallite Size and Strain:

XRD peak broadening with increasing Ce³⁺ content suggested changes in crystallite size and lattice strain. These structural modifications influence magnetic domain behavior, which is reflected in the coercivity and shape of the hysteresis loops²⁰.

d). Phase Purity:

The XRD patterns indicated the maintenance of the spinel structure across all compositions. This phase purity is consistent with the systematic changes observed in the magnetic properties across the Ce³⁺ concentration range²¹.

The B-H curve analysis from VSM measurements shows a clear evolution of magnetic properties with increasing Ce³⁺ substitution in the CuFe_(2-x) Ce_(x)O₄ spinel ferrite system^{22, 23}. These changes in magnetic behavior correlate well with the structural modifications observed in the XRD analysis, demonstrating the strong interplay between crystal structure and magnetic properties in these materials²⁴.

Morphological Evolution:

SEM (scanning electron microscope)

Fig 4: Scanning electron microscope for CuFe_(2-x) Ce_(x)O₄ spinel ferrite samples with varying Ce³⁺ concentrations (x = 0.02, 0.04, 0.06, 0.08, and 0.1).

Morphological Evolution:

The particles exhibit a hierarchical structure consisting of primary particles that aggregate into larger secondary structures. As the Ce³⁺ content increases from x=0.02 to x=0.10, there's a noticeable evolution in the particle morphology and size distribution.

Particle Size Analysis:

· At x=0.02 (Image 1, 500X): Shows a relatively uniform distribution of agglomerated particles

· At x=0.04 (Image 2, 1,500X): Reveals more detailed surface features of the agglomerates

· At x=0.06 (Image 3, 3,500X): Demonstrates clearer boundaries between individual particles

· At x=0.08 (Image 4, 7,000X): Shows enhanced surface roughness and porosity

· At x=0.10 (Image 5, 10,000X): Exhibits the finest detail of particle morphology and surface texture

Agglomeration Characteristics: The particles show a strong tendency to form agglomerates across all compositions. These agglomerates appear to be composed of smaller primary particles with sizes in the submicron range. The interconnected nature of these particles suggests significant surface interaction and possible sintering during the synthesis process²⁵

Surface Texture: The particles display a rough surface texture with numerous small features, indicating a high surface area. This characteristic could be beneficial for applications requiring high surface activity, such as catalysis or sensing^26-28

Structural Features:

· The particles show a somewhat spherical to irregular morphology

· There's evidence of neck formation between particles, suggesting partial sintering

· The presence of both larger and smaller particles indicates a broad size distribution

· Visible porosity exists between the agglomerates, which could be important for specific applications

Impact of Cerium Doping: As the cerium content increases from x=0.02 to x=0.10, there appears to be a subtle influence on the particle morphology and agglomeration behavior. The higher magnification images (especially at x=0.08 and x=0.10) reveal more detailed surface features and potentially finer particle sizes.

CONCLUSION:

Based on the comprehensive analysis of both X-ray diffraction (XRD) patterns and magnetic hysteresis (B-H) curves for the CuFe_(2-x) Ce_(x)O₄ spinel ferrite system, we can draw the following conclusions.

a). Structural Modifications:

The substitution of Ce³⁺ for Fe³⁺ in the spinel structure leads to significant changes in the crystal lattice. XRD results show peak shifts towards lower 2θ angles, indicating lattice expansion due to the larger ionic radius of Ce³⁺ (1.14 Å) compared to Fe³⁺ (0.645 Å). This expansion is accompanied by changes in peak intensities and broadening, suggesting alterations in cation distribution and crystallite size.

b). Magnetic Property Evolution:

The B-H curves demonstrate a systematic change in magnetic properties with increasing Ce³⁺ content. The saturation magnetization generally increases, while coercivity and remanence show composition-dependent variations. These changes correlate directly with the structural modifications observed in XRD analysis.

c). Structure-Property Relationship:

There is a clear interplay between the crystal structure and magnetic properties. The lattice expansion and cation redistribution evidenced by XRD directly influence the magnetic interactions, domain behavior, and anisotropy observed in the B-H curves. This relationship underscores the importance of atomic-level structure in determining macroscopic magnetic properties The CuFe_(2-x) Ce_(x)O₄ spinel ferrite system exhibits a rich interplay between composition, crystal structure, and magnetic properties. The ability to systematically modify these properties through Ce³⁺ substitution offers exciting possibilities for tailoring this material system for various applications in magnetic devices, sensors, and other technologies where controlled magnetic behavior is crucial. Further studies could explore the effects of higher Ce³⁺ concentrations and investigate other substituting elements to expand the range of achievable properties in this versatile spinel ferrite system.

REFERENCE:

1. Naresh N. Sarkar, Kishor G. Rewatkar, Vivek M. Nanoti, Nishant T. Tayade. Structural, Magnetic-Electrical Behavior of Zr substituted Ni–Zn Spinel Ferrite. Research J. Science and Tech. 2018; 10 (1):2349-2988 doi. org /0.5958/2349-2988.2018.00003.7

2. Kebede Keterew Kefeni, Bhekie Brilliance Mamba “Photocatalytic application of spinel ferrite nanoparticles and nanocomposites in wastewater treatment,” Sustainable Materials and Technologies. 2018; https://doi.org/10.1016/ j.susmat. 2019.e00140.

3. Saumya Giri, Devendra K Sahu, N. N. sarkar and K. G. Rewatkar, “Study of structural and magnetic properties of aluminium substituted nanosized barium hexaferrite prepared by sol–gel auto-combustion technique” Bull. Mater. Sci. Indian Academy of Sciences. 2021; (44):124 https://doi.org/10.1007/s12034-021-02433-2.

4. Thomas Abo Atia, Pietro Altimari, Emanuela Moscardini, Ida Pettiti, Luigi Toro Francesca Pagnanelli “Synthesis and Characterization of Copper Ferrite Magnetic Nanoparticles by Hydrothermal Route.” The Italian Association of Chemical Engineering 2016;(47): doi: 10.3303/CET1647026.

5. Pendaranahalli Nadikeraiah Anantharamaiah, Hadonahalli Munegowda Shashanka, Srikari Srinivasan, Debabrata Das, Ahmed A. El-Gendy, and C. V. Ramana, Structural, “Magnetic, and Magnetostriction Properties of Flexible,Nanocrystalline CoFe2O4 Films Made by Chemical Processing” ACS Omega 2022; 7: 43813−43819.http://pubs.acs.org/journal/acsodf.

6. D. L. Chaudhari, D. S. Choudhary, K. G. Rewatkar “Spinel Ferrite Nanoparticles: Synthesis, Characterization and Applications,” International Journal of Trend in Scientific Research and Development (IJTSRD), April 2020;(4) Issue 3 April 2003

7. Mahnaz Amiri, Khalil Eskandari, Masoud Salavati-Niasari. Magnetically retrievable ferrite nanoparticles in the catalysis application. Published by Elsevier B.V. 0001-8686/© 2019; https://doi.org/10.1016/j.cis.2019.07.003.

8. T. Giannakopoulou, L. Kompotiatis, A. Kontogeorgakos, G. Kordas. Microwave behavior of ferrites prepared via Sol–Gel method. Journal of Magnetism and Magnetic Materials. 2002; 246: 360–365.

9. Y. Ichiyanagi, M. Kubota, S. Moritake, Y. Kanazawa, T. Yamada, T. Uehashi. Magnetic properties of Mg-ferrite nanoparticles. Journal of Magnetism and Magnetic Materials. 2007; 310: 2378–2380. doi:10.1016/j. jmmm. 2006.10.737.

10. Kebede K. Kefeni, Bhekie B. Mamba, Titus A.M. Msagati. Application of spinel ferrite nanoparticles in water and wastewater treatmen. Separation and Purification Technology. 2017 doi: http://dx.doi.org/10.1016/j.seppur.2017.07.015.

11. K. Maaz, S. Karim, A. Mumtaz, S.K. Hasanain, J. Liu c, J.L. Duan. Synthesis and magnetic characterization of nickel ferrite nanoparticles prepared by co-precipitation route. Journal of Magnetism and Magnetic Materials. 2009; 321:1838-1842 doi:10.1016/j. jmmm.2008.11.09.

12. Rifat Shaheen, Hafeez-ullah, Muhammad Ijaz, Hafiz Muhammad Tahir. Influence of Tb Substitute Strontium based Spinal Ferrite and their Structural, Dielectric and Magnetic properties. Journal of Magnetism and Magnetic Materials. MAGMA-D-23-01419.

13. Traian Florin Marincaa, Ionel Chicinas, Olivier Isnardb. Structural and magnetic properties of the copper ferrite obtained by reactive milling and heat treatment. Eramics International. 2013; 39: 4179–4186. http://dx.doi.org/10.1016/j. ceramint.2012;(10).274.

14. D.R. Patil, B.K. Chougule. Effect of copper substitution on electrical and magnetic properties of NiFe2O4 ferrite. Materials Chemistry and Physics. 2009; 117: 35 40. doi:10.1016/j. matchemphys.2008.12.034.

15. S.A. Seyyed Ebrahimi, J. Azadmanjir. Evaluation of NiFe2O4 ferrite nanocrystalline powder synthesized by a Sol–Gel auto-combustion method. Journal of Non-Crystalline Solids. 2007; 353: 802-804. doi:10.1016/j. jnoncrysol.2006.12.044.

16. B. S. Satone, K. G. Rewatkar, Sandeep B. Satone. Structural, Electrical and Magnetic Properties of La/Al Substituted Nano Calcium Hexaferrites prepared by Sol–Gel Auto-Combustion Method. International Journal of Science and Research. 2017; 6(2).

17. Gullipilli Sandhya, R. Ravichandra Babu1. Synthesis and Characterization Co and Mg Co-doped TiO2 Nanoparticles. Asian J. Research Chem. 2018; 11(3): DOI: 10.5958/09744150.2018.00115.3.

18. Naresh Kumar and Richa Kanwar. Study of Structural and Electrical Properties of R0.67Sr0.33MnO3, (R = Nd, Pr). Research J. Engineering and Tech. 2015; 6(1)

19. Satyanarayana Thodeti, S. Sudhakar Reddy, Srikanth Vemu. Synthesis and characterization of Copper nanoparticles by chemical reduction method. Research J. Science and Tech. 2018; 10(1): DOI: 10.5958/2349-2988.2018.00007.4.

20. K. K. Pathak, Mimi Akash Pateria, Kusumanjali Deshmukh. Comparative Study of Optical and Electrical Properties of CdSe:Sm and CdSe:Nd Nanocrystalline Thin Film. Research Journal of Engineering and Technology. 2018; 9(1) DOI: 10.5958/2321-581X.2018.00010.

21. Bhavisha Patel, Anuraag Rai, Himanshu Raut, Akshay Khandhar, Nirav Khunt. Synthesis of Zinc Nanoparticle by Using Peppermint Leaves and Evaluation of Zinc Nanoparticle by UV, SEM and XRDS. Research Journal of Pharmacognosy and Phytochemistry. 2022; 14(4):247-1. doi:10.52711/0975-4385.2022.00043

22. P.K. Upadhyay, Vikas Kumar Jain, Kavita Sharma, Ravi Sharma. Synthesis and Applications of ZnO Nanoparticles in Biomedicine. Research J. Pharm. and Tech. 2020;13(4):1636-1644. doi: 10.5958/0974-360X.2020.00297.8.

23. Dinesh Sirohi, Pratibha Singh, K. N. Pandey, Vishal Verma, Vijai Kumar, A. K. Saxena. Thermal and morphological behavior of PEEK/PEI blends with polyphosphazene coated carbon nanotube. Asian J. Research Chem. 2012; 5(5) DOI: 10.5958/0974-4150.

24. Raj Mani, Ravindra Kumar Gautam, Sushmita Banerjee, Anoop K. Srivastava, Amita Jaiswal, M. C. Chattopadhyaya. A Study on La 0.6 Sr 0.4 Co 0.3 Fe 0.8 O 3 (LSCF) Cathode Material Prepared by Gel Combustion Method for IT-SOFCs: Spectroscopic, Electrochemical and Microstructural Analysis. Asian J. Research Chem. 2015; 8(6): 389-393doi: 10.5958/0974-4150.2015.00062.0.

25. Preeti Soni, Shweta Vyas. Studies on X-Ray Diffraction (XRD) patterns of Soya-hulls for Interpretation of Crystallinity Index. Asian Journal of Research in Chemistry (AJRC). DOI: 10.52711/0974-4150.2022.00040

26. K. Santhosh Kumar, Narlagiri Priyanka. Synthesis and Enhancement of mechanical properties of TiO2 Nano particles on Mild steel. Research Journal of Engineering and Technology. DOI: 10.5958/2321-581X.2019.00024.2.

27. M A Wani and R M Belekar. Structural Behavior and Photoluminescence Properties of Ytterbium (III) Doped Lithium Aluminates Prepared via Microwave Assisted Solution Combustion Method. Journal of Scientific Research. 2020; 64(2) DOI: 10.37398/JSR.2020.640245,

28. M.A. Wani a, R.M. Belekar. Energy transfer mechanism of Eu2+, Mn2+ Doped lithium aluminate phosphor: Synthesis, Hirshfeld surface analysis and optical study. Materials Chemistry and Physics. 2022; 292.

Received on 05.10.2024 Revised on 18.11.2024

Accepted on 19.12.2024 Published on 10.03.2025

Available online from March 21, 2025

Research J. Science and Tech. 2025; 17(1):13-20.

DOI: 10.52711/2349-2988.2025.00002

This work is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License. Creative Commons License.