Structure and magnetic phase transitions in (Ni1−xCox)Cr2O4 spinel nanoparticles

Abstract

NiCr2O4 and CoCr2O4 are two distinct members of the chromite family (ACr2O4) having unique structural and magnetic properties. This paper is a continuation of previous work [Mohanty et al., J. Magn. Magn. Mater.451(2018)20] and is focused on the modification of ferrimagnetic properties in NiCr2O4 by substituting Co ions at Ni sites. In order to do so (Ni1−xCox)Cr2O4 (x = 0, 0.50, 0.75, 1.00) powder samples were synthesized using chemical co-precipitation techniques. Interest is primarily on (Ni0.5Co0.5)Cr2O4 and (Ni0.25Co0.75)Cr2O4 as characterization results on the end members have been reported. It was determined with in-situ temperature dependent X-ray diffraction measurements that these compositions become fully crystallized cubic spinels with space group Fd3-m above 700 °C. All samples were subsequently calcined at 900 °C to ensure phase purity and uniform crystallinity. Transmission electron microscopy showed non-uniform distribution of particle sizes with the majority of the particles having bi-pyramidal structures with flat tops for both samples. A comparative account of different ferrimagnetic Curie temperature, θf or TC, estimations are presented as determined from measured temperature dependences of the following techniques: Fits of the magnetic susceptibility data indicated a minimum value for the (Ni0.5Co0.5)Cr2O4 sample at 56.1 ± 0.9 K, followed by an increase to 76.8 ± 0.4 K for the (Ni0.25Co0.75)Cr2O4 sample; Neutron diffraction measurements gave values of 80 ± 1 K and 87 ± 1 K; Their paramagnetic Curie points, θp, were determined to be 73.3 and 84.9 K, respectively. The magnetic frustration index f = ΘCW/TC was found to decrease continuously over the series from 11.9 for NiCr2O4 to 7.1 and 6.5 for x = 0.5 and 0.75 respectively with (Ni0.5Co0.5)Cr2O4 being more frustrated than (Ni0.25Co0.75)Cr2O4. Magnetization as a function of applied magnetic field measured at 3 K demonstrates unusually high coercivity for (Ni0.5Co0.5)Cr2O4, supporting the notion for the higher degree of magnetic frustration in this sample. No exchange bias was observed for M (μ0H) in the (Ni0.25Co0.75)Cr2O4 sample measured at 3 K, but did however show a significant anomaly in its hysteresis loop at this temperature. The anomaly in hysteresis behaviour disappeared when measured at 1.7 K and also at higher temperatures. Frequency dependent ac-susceptibility measurements revealed no shift in the peak position with frequency refuting the existence of spin-glass like behavior in both these samples.