Finite size and surface effects on the magnetic properties of cobalt ferrite nanoparticles
Source abstract
Abstract
Cobalt ferrite, CoFe2O4, nanoparticles in the size range 2–15 nm have been prepared using a non-aqueous solvothermal method. The magnetic studies indicate a superparamagnetic behavior, showing an increase in the blocking temperatures (ranging from 215 to more than 340 K) with the particle size, D TEM. Fitting M versus H isotherms to the saturation approach law, the anisotropy constant, K, and the saturation magnetization, M S, are obtained. For all the samples, it is observed that decreasing the temperature gives rise to an increase in both magnetic properties. These increases are enhanced at low temperatures (below ~160 K) and they are related to surface effects (disordered magnetic moments at the surface). The fit of the saturation magnetization to the T 2 law gives larger values of the Bloch constant than expected for the bulk, increasing with decreasing the particle size (larger specific surface area). The saturation magnetization shows a linear dependence with the reciprocal particle size, 1/D TEM, and a thickness of 3.7 to 5.1 A was obtained for the non-magnetic or disordered layer at the surface using the dead layer theory. The hysteresis loops show a complex behavior at low temperatures (T ≤ 160 K), observing a large hysteresis at magnetic fields H > ~1000 Oe compared to smaller ones (H ≤ ~1000 Oe). From the temperature dependence of the ac magnetic susceptibility, it can be concluded that the nanoparticles are in magnetic interaction with large values of the interaction parameter T 0, as deduced by assuming a Vogel–Fulcher dependence of the superparamagnetic relaxation time. Another evidence of the presence of magnetic interactions is the almost nearly constant value below certain temperatures, lower than the blocking temperature T b, observed in the FC magnetization curves.
Source: openaire · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Magnetic Properties and Synthesis of Ferrites · Magnetic properties of thin films · Iron oxide chemistry and applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (65)
Show source-provided references
1. Ahn Y, Choi EJ, Kim S, Ok HN (2001) Magnetization and Mössbauer study of cobalt ferrite particles from nanophase cobalt iron carbonate. Mater Lett 50:47–52. doi: 10.1016/S0167-577X(00)00412-210.1016/S0167-577X(00)00412-2 ↗
2. Aquino R, Depeyrot J, Sousa MH, Tourinho FA, Dubois E, Perzynski R (2005) Magnetization temperature dependence and freezing of surface spins in magnetic fluids based on ferrite nanoparticles. Phys Rev B72:184435. doi: 10.1103/PhysRevB.72.18443510.1103/PhysRevB.72.184435 ↗
3. Batlle X, Labarta A (2002) Finite-size effects in fine particles: magnetic and transport properties. J Phys D Appl Phys 35:R15–R42. doi: 10.1088/0022-3727/35/6/20110.1088/0022-3727/35/6/201 ↗
4. Berkowitz AE, Walter JL (1982) Amorphous particles produced by spark erosion. Mater Sci Eng 55:275–287. doi: 10.1016/0025-5416(82)90141-010.1016/0025-5416(82)90141-0 ↗
5. Berry CC (2005) Possible exploitation of magnetic nanoparticle–cell interaction for biomedical applications. J Mater Chem 15:543–547. doi: 10.1039/b409715g10.1039/B409715G ↗
6. Bødker F, Mørup S, Linderoth S (1994) Surface effects in metallic iron nanoparticles. Phys Rev Lett 72:282–285. doi: 10.1103/PhysRevLett.72.28210.1103/PhysRevLett.72.282 ↗
7. Brabers VAM (1995) Progress in spinel ferrite research. In: Buschow KHJ (ed) Handbook of magnetic materials, vol 8. Elsevier Science, Amsterdam, pp 189–324. doi: 10.1016/S1567-2719(05)80032-0
8. Cabañas A, Poliakoff M (2001) The continuous hydrothermal synthesis of nano-particulate ferrites in near critical and supercritical water. J Mater Chem 11:1408–1416. doi: 10.1039/b009428p10.1039/b009428p ↗
9. Caizer C (2003) T2 law for magnetite-based ferrofluids. J Phys Condens Matter 15:765–776. doi: 10.1088/0953-8984/15/6/30310.1088/0953-8984/15/6/303 ↗
10. Charles SW, Chandrasekhar R, O’Grady K, Walker M (1988) Remanence curves of cobalt ferrite powders obtained by fractionation of a suspension through a silica gel column. J Appl Phys 64:5482–5840. doi: 10.1063/1.342225
11. Chen JP, Sorensen CM, Klabunde KJ, Hadjipanayis GC, Devlin E, Kostikas A (1996) Size-dependent magnetic properties of MnFe2O4 fine particles synthesized by coprecipitation. Phys Rev B54:9288–9296. doi: 10.1103/PhysRevB.54.928810.1103/PhysRevB.54.9288 ↗
12. Chinnasamy CN, Senoue M, Jeyadevan B, Perales-Perez O, Shinoda K, Tohji K (2003) Synthesis of size-controlled cobalt ferrite particles with high coercivity and squareness ratio. J Colloid Interface Sci 263:80–83. doi: 10.1016/S0021-9797(03)00258-310.1016/S0021-9797(03)00258-3 ↗
13. Coey JMD (1971) Noncollinear spin arrangement in ultrafine ferrimagnetic crystallites. Phys Rev Lett 27:1140–1142. doi: 10.1103/PhysRevLett.27.114010.1103/PhysRevLett.27.1140 ↗
14. Davies KJ, Wells S, Upadhyay RV, Charles SW, O’Grady K, El Hilo M, Meaz T, Mørup S (1995) The observation of multi-axial anisotropy in ultrafine cobalt ferrite particles used in magnetic fluids. J Magn Magn Mater 149:14–18. doi: 10.1016/0304-8853(95)00319-310.1016/0304-8853(95)00319-3 ↗
15. De Toro JA, Lopez de la Torre MA, Riveiro JM, Saez-Puche R, Gomez-Herrero A, Otero-Diaz L (1999) Spin-glass-like behavior in mechanically alloyed nanocrystalline Fe-Al-Cu. Phys Rev B60:12918–12923. doi: 10.1103/PhysRevB.60.1291810.1103/PhysRevB.60.12918 ↗
16. Didukh P, Greneche JM, Slawska-Waniewska A, Fanin PC, Casas L (2002) Surface effects in CoFe2O4 magnetic fluids studied by Mössbauer spectrometry. J Magn Magn Mater 242–245:613–616. doi: 10.1016/S0304-8853(01)01044-710.1016/S0304-8853(01)01044-7 ↗
17. Ding J, McCormick PG, Street R (1995) Magnetic properties of mechanically alloyed CoFe2O4. Solid State Commun 95:31–33. doi: 10.1016/0038-1098(95)00223-510.1016/0038-1098(95)00223-5 ↗
18. Ding J, McCormick PG, Street R (1997) Formation of spinel Mn-ferrite during mechanical alloying. J Magn Magn Mater 171:309–314. doi: 10.1016/S0304-8853(97)00093-010.1016/S0304-8853(97)00093-0 ↗
19. Dormann JL, Fiorani D, Tronc E (1997) Magnetic Relaxation in Fine-Particle Systems. In: Prigogine I, Ricedoi SA (eds) Adv Chem Phys 98:283–494. doi: 10.1002/9780470141571.ch410.1002/9780470141571.ch4 ↗
20. García-Otero J, Porto M, Rivas J, Bunde A (1999) Influence of the cubic anisotropy constants on the hysteresis loops of single-domain particles: a Monte Carlo study. J Appl Phys 85:2287–2292. doi: 10.1063/1.36953910.1063/1.369539 ↗
21. Grigorova M, Blythe HJ, Blaskov V, Rusanov V, Petkov V, Masheva V, Nihtianova D, Martinez LM, Muñoz JS, Mikhov M (1998) Magnetic properties and Mössbauer spectra of nanosized CoFe2O4 powders. J Magn Magn Mater 183:163–172. doi: 10.1016/S0304-8853(97)01031-710.1016/S0304-8853(97)01031-7 ↗
22. Hamdeh HH, Hikal WM, Taher SM, Ho JC, Thuy NP, Quy OK, Hanh N (2005) Mössbauer evaluation of cobalt ferrite nanoparticles synthesized by forced hydrolysis. J Appl Phys 97:064310. doi: 10.1063/1.185621910.1063/1.1856219 ↗
23. Hanh N, Quy OK, Thuy NP, Tung LD, Spinu L (2003) Synthesis of cobalt ferrite nanocrystallites by the forced hydrolysis method and investigation of their magnetic properties. Physica B 327:382–384. doi: 10.1016/S0921-4526(02)01750-710.1016/S0921-4526(02)01750-7 ↗
24. Hendriksen PV, Linderoth S, Lindgård PA (1993a) Finite-size modifications of the magnetic properties of clusters. Phys Rev B 48:7259–7273. doi: 10.1103/PhysRevB.48.725910.1103/PhysRevB.48.7259 ↗
25. Hendriksen PV, Linderoth S, Lingard PA (1993b) Magnetic properties of Heisenberg clusters. J Phys Condens Matter 5:5675–5684. doi: 10.1088/0953-8984/5/31/02910.1088/0953-8984/5/31/029 ↗
26. Kodama RH (1999) Magnetic nanoparticles. J Magn Magn Mater 200:359–372. doi: 10.1016/S0304-8853(99)00347-910.1016/S0304-8853(99)00347-9 ↗
27. Kodama RH, Berkowitz AE, McNiff EJ Jr, Foner S (1996) Surface spin disorder in NiFe2O4 nanoparticles. Phys Rev Lett 77:394–397. doi: 10.1103/PhysRevLett.77.39410.1103/PhysRevLett.77.394 ↗
28. Kodama RH, Berkowitz AE, McNiff EJ Jr, Foner S (1997) Surface spin disorder in ferrite nanoparticles. J Appl Phys 81:5552–5557. doi: 10.1063/1.36465910.1063/1.364659 ↗
29. Laugier J, Bochu B (2004) LMGP suite—suite of programs for the interpretation of X-ray experiments. http://www.inpg.fr/LMGP and http://www.ccp14.ac.uk/tutorial/lmgp/
30. Lee JG, Park JY, Kim CS (1998) Growth of ultra-fine cobalt ferrite particles by a sol–gel method and their magnetic properties. J Mater Sci 33:3965–3968. doi: 10.1023/A:100469672967310.1023/A:1004696729673 ↗
31. Lee DC, Mikulec FV, Pelaez JM, Koo B, Korgel BA (2006) Synthesis and magnetic properties of silica-coated FePt nanocrystals. J Phys Chem B110:11160–11166. doi: 10.1021/jp060974z
32. Lin D, Nunes AC, Majkrzak CF, Berkowitz AE (1995) Polarized neutron study of the magnetization density distribution within a CoFe2O4 colloidal particle II. J Magn Magn Mater 145:343–348. doi: 10.1016/0304-8853(94)01627-510.1016/0304-8853(94)01627-5 ↗
33. Linderoth S, Balcells L, Labarta A, Tejada J, Hendriksen PV, Sethi SA (1993) Magnetization and Mössbauer studies of ultrafine Fe-C particles. J Magn Magn Mater 124:269–276. doi: 10.1016/0304-8853(93)90125-L10.1016/0304-8853(93)90125-L ↗
34. Liu C, Zou B, Rondinone AJ, Zhang ZJ (2000) Chemical control of superparamagnetic properties of magnesium and cobalt spinel ferrite nanoparticles through atomic level magnetic couplings. J Am Chem Soc 122:6263–6267. doi: 10.1021/ja000784g10.1021/ja000784g ↗
35. Liu Q, Sun J, Long H, Sun X, Zhong X, Xu Z (2008) Hydrothermal synthesis of CoFe2O4 nanoplatelets and nanoparticles. Mater Chem Phys 108:269–273. doi: 10.1016/j.matchemphys.2007.09.03510.1016/j.matchemphys.2007.09.035 ↗
36. López JL, Pfannes HD, Paniago R, Sinnecker JP, Novak MA (2008) Investigation of the static and dynamic magnetic properties of CoFe2O4 nanoparticles. J Magn Magn Mater 320:e327–e330. doi: 10.1016/j.jmmm.2008.02.06510.1016/j.jmmm.2008.02.065 ↗
37. Luders U, Barthelemy A, Bibes M, Bouzehouane K, Fusil S, Jacquet E, Contour JP, Bobo JF, Fontcuberta J, Fert A (2006) NiFe2O4: a versatile spinel material brings new opportunities for spintronics. Adv Mater 18:1733–1736. doi: 10.1002/adma.20050097210.1002/adma.200500972 ↗
38. Mandal K, Mitra S, Kumar PA (2006) Deviation from Bloch T3/2 law in ferrite nanoparticles. Europhys Lett 75:618–623. doi: 10.1209/epl/i2006-10148-y10.1209/epl/i2006-10148-y ↗
39. Masunaga SH, Jardim RF, Fichtner PFP, Rivas J (2009) Role of dipolar interactions in a system of Ni nanoparticles studied by magnetic susceptibility measurements. Phys Rev B80:184428. doi: 10.1103/PhysRevB.80.18442810.1103/PhysRevB.80.184428 ↗
40. Montemayor SM, García-Cerda LA, Torres-Lubián JR (2005) Preparation and characterization of cobalt ferrite by the polymerized complex method. Mater Lett 59:1056–1060. doi: 10.1016/j.matlet.2004.12.00410.1016/j.matlet.2004.12.004 ↗
41. Morais PC, Garg VK, Oliveira AC, Silva LP, Azevedo RB, Silva AML, Lima ECD (2001) Synthesis and characterization of size-controlled cobalt-ferrite-based ionic ferrofluids. J Magn Magn Mater 225:37–40. doi: 10.1016/S0304-8853(00)01225-710.1016/S0304-8853(00)01225-7 ↗
42. Morrish AH (1965) The physical principles of magnetism. Wiley, New York
43. Moumen N, Pileni MP (1996) New syntheses of cobalt ferrite particles in the range 2–5 nm: comparison of the magnetic properties of the nanosized particles in dispersed fluid or in powder form. Chem Mater 8:1128–1134. doi: 10.1021/cm950556z10.1021/cm950556z ↗
44. Moumen M, Veillet P, Pileni MP (1995) Controlled preparation of nanosize cobalt ferrite magnetic particles. J Magn Magn Mater 149:67–71. doi: 10.1016/0304-8853(95)00340-110.1016/0304-8853(95)00340-1 ↗
45. Mumtaz A, Maaz K, Janjua B, Hasanain SK, Bertino MF (2007) Exchange bias and vertical shift in CoFe2O4 nanoparticles. J Magn Magn Mater 313:266–272. doi: 10.1016/j.jmmm.2007.01.00710.1016/j.jmmm.2007.01.007 ↗
46. Nam JH, Park SJ, Kim WK (2003) Microstructure and magnetic properties of nanostructured NiZnCu ferrite powders synthesized by sol-gel process. IEEE Trans Magn 39:3139–3141. doi: 10.1109/TMAG.2003.81603210.1109/TMAG.2003.816032 ↗
47. Naughton BT, Clarke DR (2007) Lattice expansion and saturation magnetization of nickel–zinc ferrite nanoparticles prepared by aqueous precipitation. J Am Ceram Soc 90:3541–3546. doi: 10.1111/j.1551-2916.2007.01980.x10.1111/j.1551-2916.2007.01980.x ↗
48. Néel L (1949a) Théorie du trainage magnétique des ferromagnétiques en grains fins avec applications aux terres cuites. Ann Geophys (CNRS) 5:99–136
49. Néel L (1949b) Influence des fluctuations thermiques sur l’aimantation de grains ferromagnétiques très fins. CR Acad Sci 228:664–666
50. Niederberger M, Garnweitner G, Pinna N, Neri G (2005) Non-aqueous routes to crystalline metal oxide nanoparticles: formation mechanisms and applications. Progress Solid State Chem 33:59–70. doi: 10.1016/j.progsolidstchem.2005.11.03210.1016/j.progsolidstchem.2005.11.032 ↗
51. Nogues J, Sort J, Langlais V, Skumryev V, Suriñach S, Muñoz JS, Baro MD (2005) Exchange bias in nanostructures. Phys Rep 422:65–117. doi: 10.1016/j.physrep.2005.08.00410.1016/j.physrep.2005.08.004 ↗
52. Pankhurst QA, Connolly J, Jones SK, Dobson J (2003) Applications of magnetic nanoparticles in biomedicine. J Phys D Appl Phys 36:R167–R181. doi: 10.1088/0022-3727/36/13/20110.1088/0022-3727/36/13/201 ↗
53. Pauthenet R, Bochirol L (1951) Aimantation spontanée des ferrites. J Phys Radium 12:249–251. doi: 10.1051/jphysrad:0195100120302490010.1051/jphysrad:01951001203024900 ↗
54. Pfeiffer H (1990) Determination of anisotropy field distribution in particle assemblies taking into account thermal fluctuations. Phys Status Solidi A118:295–306. doi: 10.1002/pssa.221118013310.1002/pssa.2211180133 ↗
55. Pinna N, Grancharov S, Beato P, Bonville P, Antonietti M, Niederberger M (2005) Magnetite nanocrystals: nonaqueous synthesis, characterization, and solubility. Chem Mater 17:3044–3049. doi: 10.1021/cm050060+10.1021/cm050060+ ↗
56. Rosensweig RE (1985) Ferrohydrodynamics. Dover Publications, New York
57. Selvan RK, Kalaiselvi N, Augustin CO, Doh CH (2006) SnO2 pinning: an approach to enhance the electrochemical properties of nanocrystalline CuFe2O4 for lithium-ion batteries. Electrochem Solid State Lett 9:A390–A394. doi: 10.1149/1.220943510.1149/1.2209435 ↗
58. Shafi KVPM, Gedanken A, Prozorov R, Balogh J (1998) Sonochemical preparation and size-dependent properties of nanostructured CoFe2O4 particles. Chem Mater 10:3445–3450. doi: 10.1021/cm980182k10.1021/cm980182k ↗
59. Shi Y, Ding J, Yin H (2000) CoFe2O4 nanoparticles prepared by the mechanochemical method. J Alloys Compd 308:290–295. doi: 10.1016/S0925-8388(00)00921-X10.1016/S0925-8388(00)00921-X ↗
60. Song Q, Zhang ZJ (2004) Shape control and associated magnetic properties of spinel cobalt ferrite nanocrystals. J Am Chem Soc 126:6164–6168. doi: 10.1021/ja049931r10.1021/ja049931r ↗
61. Stoner EC, Wohlfarth EP (1948) A mechanism of magnetic hysteresis in heterogeneous alloys. Philos Trans R Soc Lond A240:599–642. doi: 10.1098/rsta.1948.0007 (reprinted in 1991 IEEE Trans Magn 27:3475–3518. doi: 10.1109/TMAG.1991.1183750 )10.1109/TMAG.1991.1183750 ↗
62. Tirosh E, Shemer G, Markovich G (2006) Optimizing cobalt ferrite nanocrystal synthesis using a magneto-optical probe. Chem Mater 18:465–470. doi: 10.1021/cm052401p10.1021/cm052401p ↗
63. Tung LD, Kolesnichenko V, Caruntu D, Chou NH, O’Connor CJ, Spiu L (2003) Magnetic properties of ultrafine cobalt ferrite particles. J Appl Phys 93:7486–7488. doi: 10.1063/1.154014510.1063/1.1540145 ↗
64. Vazquez-Vazquez C, Lovelle M, Mateo C, Lopez-Quintela MA, Bujan-Nuñez MC, Serantes D, Baldomir D, Rivas J (2008) Magnetocaloric effect and size-dependent study of the magnetic properties of cobalt ferrite nanoparticles prepared by solvothermal synthesis. Phys Status Solidi A205:1358–1362. doi: 10.1002/pssa.20077812810.1002/pssa.200778128 ↗
65. Zhao L, Zhang H, Xing Y, Song S, Yu S, Shi W, Guo X, Yang J, Lei Y, Cao F (2008) Studies on the magnetism of cobalt ferrite nanocrystals synthesized by hydrothermal method. J Solid State Chem 181:245–252. doi: 10.1016/j.jssc.2007.10.03410.1016/j.jssc.2007.10.034 ↗