The Effect of Small Deficiency in Calcium Ion on Structural and Magnetic Properties in La0.7Ca0.15□0.05Sr0.1MnO3 with Various Synthesis Methods
DOI:
https://doi.org/10.48048/tis.2026.11410Keywords:
Magnetic Materials, Perovskite Manganite, Solid-State, Sol-Gel, Wet-Mixing, Magnetic materials, Perovskite manganite, Solid-state, Sol-gel, Wet-mixingAbstract
We have investigated the effect of a small calcium ion deficiency and different synthesis methods on the structural and magnetic properties of the La0.7Ca0.15□0.05Sr0.1MnO3 compound. The samples were synthesized using solid-state, sol-gel, and wet-mixing methods. Structural analysis revealed that all samples exhibited a single-phase orthorhombic crystal structure with the Pnma space group. The lattice parameters and the MnO6 octahedral structure changed based on the synthesis method and slight deficiency, leading to structural distortion and a mixed-valence state of Mn ions. The average crystallite sizes were 75.79, 113.98, and 107.23 nm, while the average grain sizes were 3.41, 2.06, and 1.29 μm for solid-state, sol-gel, and wet-mixing samples, respectively. FTIR confirmed the primary MnO6 octahedral structure through Mn-O and Mn-O-Mn bonds at wavenumbers of 513 - 539 and 590 - 591 cm−1. Magnetic measurements revealed the highest magnetization values of 29.50, 42.58, and 33.37 emu/g at room temperature under a 1 T magnetic field. In the meantime, the values of saturation magnetization were 37.11, 46.49, and 40.09 emu/g, as determined by the Law of Approach to Saturation method. Based on the structural and magnetic results, the sol-gel method produced the largest crystallite size and the lowest material defect level (smallest microstrain), resulting in the highest magnetization at room temperature under a 1 T magnetic field. These findings demonstrate a strong correlation between synthesis method, structural parameters, and magnetic properties.
HIGHLIGHTS
- Effect of Ca deficiency and synthesis methods on structural & magnetic properties.
- Crystallite size 75 - 114 nm and grain size 1.3 - 3.4 µm depending on method.
- All samples have soft magnetic properties.
- Crytallite size, grain size, and defect on material influencing magnetic properties.
GRAPHICAL ABSTRACT
Downloads
References
AD Souza, S Rayaprol, A Sagdeo, AK Sinha and M Daivajna. Magnetic phase transformation in La0.7-xBixSr0.3MnO3 (0.25 ≤ x ≤ 0.40). Journal of Magnetism and Magnetic Materials 2020; 511, 166966.
M Wali, A Hajji, R Dhahri, E Dhahri and F Sahnoune. Enhancement of the magnetocaloric effect by deficit in A site at room temperature and correlation with transport properties. Solid State Communications 2024; 391, 115630.
PZZ Nehan, O Vitayaya, DR Munazat, MTE Manawan, D Darminto and B Kurniawan. The magnetocaloric effect properties for potential applications of magnetic refrigerator technology: A review. Physical Chemistry Chemical Physics 2024; 26(20), 14476-14504.
H Gu, X Zhang, H Wei, Y Huang, S Wei and Z Guo. An overview of the magnetoresistance phenomenon in molecular systems. Chemical Society Reviews 2013; 42(13), 5907-5943.
O Vitayaya, PZZ Nehan, DR Munazat, MTE Manawan and B Kurniawan. Magnetoresistance (MR) properties of magnetic materials. RSC Advances 2024; 14(26), 18617-18645.
A Kitanovski. Energy applications of magnetocaloric materials. Advanced Energy Materials 2020; 10(10), 1903741.
A Ezaami, E Sellami-Jmal, I Chaaba, W Cheikhrouhou-Koubaa, A Cheikhrouhou and EK Hlil. Effect of elaborating method on magnetocaloric properties of La0.7Ca0.2Ba0.1MnO3 manganite. Journal of Alloys and Compounds 2016; 685, 710-719.
S Hcini, N Kouki, A Omri, A Dhahri and ML Bouazizi. Effect of sintering temperature on structural, magnetic, magnetocaloric and critical behaviors of Ni-Cd-Zn ferrites prepared using sol-gel method. Journal of Magnetism and Magnetic Materials 2018; 464, 91-102.
PZZ Nehan, O Vitayaya, DR Munazat, M Naibaho, M Manawan, D Darminto and B Kurniawan. A comparison study on structural properties in La0.7Ca0.2Sr0.1MnO3 compound synthesized by solid-state, sol-gel, and wet-mixing methods. Materials Science Forum 2025; 1152, 45-54.
A Ezaami, NO Nasser, W Cheikhrouhou-Koubaa, M Koubaa, A Cheikhrouhou and EK Hlil. Physical properties of La0.7Ca0.2Sr0.1MnO3 manganite: A comparison between sol-gel and solid state process. Journal of Materials Science: Materials in Electronics 2017; 28(4), 3648-3658.
S Mahjoub, M Baazaoui, EK Hlil and M Oumezzine. Effect of synthesis techniques on structural, magnetocaloric and critical behavior of Pr0.6Ca0.1Sr0.3Mn0.975Fe0.025O3 manganites. Ceramics International 2015; 41(9), 12407-12416.
KY Pan, SA Halim, KP Lim, W Daud, SK Chen and M Navasery. Microstructure, electrical and magnetic properties of polycrystalline La0.85K0.15MnO3 manganites prepared by different synthesis routes. Journal of Materials Science: Materials in Electronics 2013; 24(6), 1869-1874.
P Suresh and S Srinath. Effect of synthesis route on the multiferroic properties of BiFeO3: A comparative study between solid state and sol-gel methods. Journal of Alloys and Compounds 2015; 649, 843-850.
MMB Rejeb, Y Regaieg, A Marzouki-Ajmi, W Cheikhrouhou-Koubaa, S Ammar-Merah, A Cheikhrouhou and T Mhiri. A comparative study of La0.65Ca0.2(Na0.5K0.5)0.15MnO3 compound synthesized by solid-state and sol-gel process. Journal of Alloys and Compounds 2017; 695, 2597-2604.
DR Munazat, B Kurniawan, DS Razaq, K Watanabe and H Tanaka. Crossover critical behavior and magnetic entropy change of La0.7Ba0.1Ca0.1Sr0.1MnO3: A comparison between wet-mixing and sol-gel synthesis methods. Physica B: Condensed Matter 2020; 592, 412227.
VE Salazar-Muñoz, AL Guerrero and SA Palomares-Sánchez. Review of magnetocaloric properties in lanthanum manganites. Journal of Magnetism and Magnetic Materials 2022; 562, 169787.
O Vitayaya, B Kurniawan, PZZ Nehan, DR Munazat, T Sudiro, A Imaduddin, H Nugraha, SD Yudanto and MTE Manawan. Enhanced magnetoresistance properties of K-site deficient La0.85K0.1□0.05MnO3 manganites synthesized via sol-gel, wet-mixing, and solid-state reaction methods. RSC Advances 2024; 14(52), 38615-38633.
CA Taboada-Moreno, F Sánchez-De Jesús, F Pedro-García, CA Cortés-Escobedo, JA Betancourt-Cantera, M Ramírez-Cardona and AM Bolarín-Miró. Large magnetocaloric effect near to room temperature in Sr doped La0.7Ca0.3MnO3. Journal of Magnetism and Magnetic Materials 2020; 496, 165887.
T Sun, S Zhao, F Ji and X Liu. Enhanced room-temperature MR and TCR in polycrystalline La0.67(Ca0.33−xSrx)MnO3 ceramics by oxygen assisted sintering. Ceramics International 2018; 44(2), 2400-2406.
J Makni-Chakroun, W Cheikhrouhou-Koubaa, M Koubaa and A Cheikhrouhou. Impact of a small amount of vacancy in both lanthanum and calcium on the physical properties of nanocrystalline La0.7Ca0.3MnO3 manganite. Journal of Alloys and Compounds 2015; 650, 421-429.
B Arun, VR Akshay and M Vasundhara. Observation of enhanced magnetocaloric properties with A-site deficiency in La0.67Sr0.33MnO3 manganite. Dalton Transactions 2018; 43, 15512-15522.
PZZ Nehan, B Kurniawan, DR Munazat, O Vitayaya, M Naibaho, T Sudiro, MTE Manawan, D Darminto and H Nojiri. Calcium ion deficiency and its influence on structure, critical behavior, magnetic and magnetocaloric effect properties in La0.7Ca0.2-x□xSr0.1MnO3 (x = 0.00, 0.05, and 0.10) manganites. Journal of Alloys and Compounds 2025; 1020, 179467.
X Lu, W Chen, S Tang, J Xu, Y Zeng, X Wang, X Peng, J Li and B Hong. Tuning the microstructure and magnetocaloric properties of Na+-substituted La0.67Ca0.33−xNaxMnO3 porous nanospheres. Journal of Alloys and Compounds 2024; 976, 173016.
K Laajimi, M Khlifi, EK Hlil, K Taibi, MH Gazzah and J Dhahri. Room temperature magnetocaloric effect and critical behavior in La0.67Ca0.23Sr0.1Mn0.98Ni0.02O3 oxide. Journal of Materials Science: Materials in Electronics 2019; 30(13), 11868-11877.
MZ Kurt, S Kılıç Çetin, A Kandemir, G Akça, F Karadağ and A Ekicibil. Enhancement of magnetocaloric effect by partial substitution of Bi in La0.60Dy0.10Sr0.30Mn(1−x)BixO3 manganites (x = 0, 0.01, 0.03, and 0.10). Journal of Materials Science: Materials in Electronics 2024; 35(8), 565.
DR Munazat, B Kurniawan, N Kurita, X Wang, M Manawan, T Sudiro and H Nojiri. Investigation of A-site cation disorder on structure, magnetic properties, and magnetic entropy change of trisubstituted divalent ion in La0.7(Ba,Ca,Sr)0.3MnO3 manganite. Physical Chemistry Chemical Physics 2024; 26(14), 111-114.
M Debnath, E Bose, D Biswas and S Pal. Effects on magnetocaloric and magnetoresistive properties due to nonmagnetic Zn2+ substitution at Mn-site in charge-ordered Pr0.5Ca0.5MnO3 manganite. Journal of Alloys and Compounds 2024; 1004, 175704.
R Kumar and M Kar. Correlation between lattice strain and magnetic behavior in non-magnetic Ca substituted nano-crystalline cobalt ferrite. Ceramics International 2016; 42(6), 6640-6647.
G Singh, A Gaur, P Bisht and RN Mahato. Effect of bismuth doping on structural, morphological, Griffiths-like phase, and magnetocaloric properties in La0.9−xBixBa0.1MnO3 (x = 0, 0.05, and 0.1). Journal of Magnetism and Magnetic Materials 2024; 591, 171731.
RD Shannon and CT Prewitt. Revised values of effective ionic radii. Structural Science 1970; 26(7), 1046-1048.
A Sakka, R M’nassri, MM Nofal, S Mahjoub, W Cheikhrouhou-Koubaa, N Chniba-Boudjada, M Oumezzine and A Cheikhrouhou. Structure, magnetic and field dependence of magnetocaloric properties of Pr0.5RE0.1Sr0.4MnO3 (RE = Eu and Er). Journal of Magnetism and Magnetic Materials 2020; 514, 167158.
AM Zhang, WC Zhang, XS Wu and JG Lin. Abnormal enhancement of ferromagnetism for LaMnO3+δ thin films with decreasing oxygen pressure. AIP Advances 2017; 7(5), 055837.
B Sudakshina, KD Chandrasekhar, HD Yang and M Vasundhara. Observation of complex magnetic behaviour in calcium doped neodymium manganites. Journal of Physics D: Applied Physics 2017; 50(6), 065004.
MS Hossain and S Ahmed. Easy and green synthesis of TiO2 (Anatase and Rutile): Estimation of crystallite size using Scherrer equation, Williamson-Hall plot, Monshi-Scherrer Model, size-strain plot, Halder- Wagner Model. Results in Materials 2023; 20, 100492.
D Nath, F Singh and R Das. X-ray diffraction analysis by Williamson-Hall, Halder-Wagner and size-strain plot methods of CdSe nanoparticles - a comparative study. Materials Chemistry and Physics 2020; 239, 122021.
T Ungár. Microstructural parameters from X-ray diffraction peak broadening. Scripta Materialia 2004; 51(8), 777-781.
AK Zak, WHA Majid, ME Abrishami and R Yousefi. X-ray analysis of ZnO nanoparticles by Williamson-Hall and size-strain plot methods. Solid State Sciences 2011; 13(1), 251-256.
C Henchiri, R Hamdi, T Mnasri, MA Valente, PR Prezas and E Dhahri. Structural and magnetic properties of La1-x⎕xMnO3 (x = 0.1; 0.2 and 0.3) manganites. Applied Physics A 2019; 125(10), 725.
B He, Z Zou, W Zhang, X Jiang and Z Mao. Physical explanation of magnetic and magnetocaloric effects of La0.7Sr0.3Mn0.95Ni0.05O3 in different synthesis methods. Journal of Electronic Materials 2023; 52(4), 2665-2675.
TM Al-Shahumi, IA Al-Omari, SH Al-Harthi and MTZ Myint. Synthesis, structure, morphology, magnetism, and magnetocaloric-effect studies of (La1−xPrx)0.7Sr0.3MnO3 nanocrystalline perovskites. SN Applied Sciences 2023; 5(4), 121.
TM Al-Shahumi, IA Al-Omari, SH Al-Harthi, MTZ Myint, P Kharel, S Lamichhane and SH Liou. Synthesis, structure, morphology, magnetism, and magnetocaloric-effect studies of La0.7Sr0.3Mn1−xFexO3 perovskite nanoparticles. Journal of Alloys and Compounds 2023; 958, 170454.
M Khosrozadeh, K Mabhouti, P Norouzzadeh and R Naderali. Complex impedance spectroscopy, dielectric response, and magnetic properties of the La0.7Sr0.3BO3 (B = Mn, Fe, Co, or Ni) perovskite oxides. Ceramics International 2024; 50(1), 315-328.
IO Faniyi, O Fasakin, B Olofinjana, AS Adekunle, TV Oluwasusi, MA Eleruja and EOB Ajayi. The comparative analyses of reduced graphene oxide (RGO) prepared via green, mild and chemical approaches. SN Applied Sciences 2019; 1(10), 1181.
PZZ Nehan, AA Akbar, MIN Karim, RA Fahriza and M Zainuri. Synthesis of silica from rice husk waste for hydrophobic material as an anti-water coating for eyeglasses. Jurnal Fisika Dan Aplikasinya 2023; 19(2), 44-48.
B Uthaman, VR Akshay and MR Varma. Investigation on the structural, magnetic, magnetocaloric and magnetotransport behaviour of La0.7Sr0.3MnO3 manganites synthesised by different routes. Physical Chemistry Chemical Physics 2024; 26(18), 13773-13789.
M Houshiar, F Zebhi, ZJ Razi, A Alidoust and Z Askari. Synthesis of cobalt ferrite (CoFe2O4) nanoparticles using combustion, coprecipitation, and precipitation methods: A comparison study of size, structural, and magnetic properties. Journal of Magnetism and Magnetic Materials 2014; 371, 43-48.
PA Yadav, AV Deshmukh, KP Adhi, BB Kale, N Basavaih and SI Patil. Role of grain size on the magnetic properties of La0.7Sr0.3MnO3. Journal of Magnetism and Magnetic Materials 2013; 328, 86-90
B Arun, VR Akshay and M Vasundhara. Observation of enhanced magnetic entropy change near room temperature in Sr-site deficient La0.67Sr0.33MnO3 manganite. RSC Advances 2019; 9(41), 23598-23606.
G Channagoudra, S Gupta and V Dayal. Study of structural, transport and magneto-crystalline anisotropy in La1-xSrxMnO3 (0.30 ≤ x ≤ 0.40) perovskite manganites. AIP Advances 2021; 11(2), 025305.
MSI Sarker, U Salma, MNI Khan, MM Rahman and MKR Khan. Impact of annealing temperature on the structural, magnetic and dielectric properties of BaFe12-xYxO19 (x = 0.0, 0.2, 0.4, 0.6) nanocrystalline samples. Ceramics International 2024; 50(22), 45868-45879.
H Zhang, D Zeng and Z Liu. The law of approach to saturation in ferromagnets originating from the magnetocrystalline anisotropy. Journal of Magnetism and Magnetic Materials 2010; 322(16), 2375-2380.
R Topkaya. Effect of composition and temperature on the magnetic properties of BaBixLaxFe(12-2x)O19 (0.0 ≤ x ≤ 0.2) hexaferrites. Applied Physics A 2017; 123(7), 488.
G Dong, Y Liu, S Zhang, K Chu, H Li, X Pu, T Sun, F Ji and X Liu. Room-temperature TCR and low-field MR of La0.7Ca0.3-xSrxMnO3 (0.06 ≤ x ≤ 0.1) polycrystalline ceramics. Ceramics International 2019; 45(17), 21448-21456.
S Zhao, XJ Yue and X Liu. Influence of Sr doping on structural, electrical and magnetic properties of La0.7Ca0.3MnO3 nanoparticles. Ceramics International 2017; 43(16), 13240-13246.
PV Jithin, Y Bitla, MM Patidar, V Ganesan, KJ Sankaran and J Kurian. Structural, magnetic and electrical transport properties of the sol-gel derived La1-xCaxMnO3 (0≤x≤0.3) nanoparticles. Materials Chemistry and Physics 2023; 301, 127651.
SK Yadav, DP Pabba, A Soosairaj, K Divya, LR Asirvatham, VS Manikandan, M Navaneethan and A Thirumurugan. Study on the structural, magnetic, and magnetodielectric properties of M-type BaFe12O19 and SrFe12O19 hexaferrite nanoparticles. Surfaces and Interfaces 2024; 52, 104956.
R Dhahri, M Bejar, M Hajlaoui, N Sdiri, MA Valente and E Dhahri. Structural properties and electrical behaviour in the polycrystalline lanthanum-deficiency La1-x□xMnO3 manganites. Journal of Magnetism and Magnetic Materials 2009; 321(11), 1735-1738.
Downloads
Published
Issue
Section
License
Copyright (c) 2025 Walailak University
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
