Low-temperature investigation of natural iron-rich oxoborates vonsenite and hulsite: thermal deformations of crystal structure, strong negative thermal expansion and cascades of magnetic transitions

This work is devoted to an investigation of the magnetic properties and thermal behaviour of the natural oxoborates vonsenite and hulsite in the temperature range 5–500 K. The local environment, the oxidation states of the Fe and Sn atoms, and the charge distribution were determined using Mössbauer spectroscopy and are in accordance with a refinement of the crystal structure of hulsite from single-crystal X-ray diffraction data (SCXRD) in anisotropic approximation for the first time. The magnetic properties were studied by vibrating sample magnetometry (VSM) (5 ≤ T ≤ 400 K) and are reported for the first time for iron-rich hulsite. Both oxoborates show a very complex magnetic behaviour. Cascades of magnetic transitions are revealed and the critical temperatures were determined. The sequences of magnetic transitions in both vonsenite and hulsite with increasing temperature were found to be as follows: magnetically ordered state → partial magnetic ordering → paramagnetic state. According to X-ray diffraction data (93 ≤ T ≤ 500 K), these processes are accompanied by anomalies in the unit-cell parameters and thermal expansion of the oxoborates at critical temperatures. A strong negative volume thermal expansion is observed for both oxoborates at temperatures below ∼120 K.

Antisites driven magnetic transition study in La2NiMnO6

La2NiMnO6 is a unique compound of multiferroics that exhibits two magnetic transitions of Curie points TC1 and TC2 below room temperature on a partial conversion of charge carriers, Ni2+ → Ni3+ and Mn4+→ Mn3+, stabilized with O2- vacancies in distorted octagons in a double perovskite of a spin cluster (glass), wherein the spins freezing at a critical Tg point at lower temperatures. The peak temperature and irreversibility temperature shifted to the lower temperature. The dc magnetization M (T) measurements indicate random ferromagnetic and antiferromagnetic interactions and multiple magnetic transitions. The critical slowing properties signify the spin-glass nature proved by the thermomagnetic relaxation measure.