In this work, we present the role of vanadium ions (V+5 and V+3), oxygen vacancies (VO), and interstitial zinc (Zni) to the contribution of specific magnetization for a mixture of ZnO-V2O5 nanoparticles (NPs). Samples were obtained by mechanical milling of dry powders and ethanol-assisted milling for 1 h with a fixed atomic ratio V/Zn?=?5% at. For comparison, pure ZnO samples were also prepared. All samples exhibit a room temperature magnetization ranging from 1.18?×?10−3 to 3.5?×?10−3 emu/gr. Pure ZnO powders (1.34?×?10−3 emu/gr) milled with ethanol exhibit slight increase in magnetization attributed to formation of Zni, while dry milled ZnO powders exhibit a decrease of magnetization due to a reduction of VO concentration. For the ZnO-V2O5 system, dry milled and thermally treated samples under reducing atmosphere exhibit a large paramagnetic component associated to the formation of V2O3 and secondary phases containing V+3 ions; at the same time, an increase of VO is observed with an abrupt fall of magnetization to σ?~?0.7?×?10−3 emu/gr due to segregation of V oxides and formation of secondary phases. As mechanical milling is an aggressive synthesis method, high disorder is induced at the surface of the ZnO NPs, including VO and Zni depending on the chemical environment. Thermal treatment restores partially structural order at the surface of the NPs, thus reducing the amount of Zni at the same time that V2O5 NPs segregate reducing the direct contact with the surface of ZnO NPs. Additional samples were milled for longer time up to 24 h to study the effect of milling on the magnetization; 1-h milled samples have the highest magnetizations. Structural characterization was carried out using X-ray diffraction and transmission electron microscopy. Identification of VO and Zni was carried out with Raman spectra, and energy-dispersive X-ray spectroscopy was used to verify that V did not diffuse into ZnO NPs as well to quantify O/Zn ratios.

Results from the analysis of the variation of structural defects, such as oxygen vacancies indicate that by adjusting the thickness of the WO₃ films, fabricated by DC reactive sputtering, it is possible to modulate the oxygen vacancies concentration. This has a tremendous influence on the applications of these semiconductor materials. The thicknesses analyzed here are 42, 66, and 131 nm. After the annealing process at 500 °C, films were directly transformed to a stable γ-monoclinic crystal structure with P2₁/n space group, with a preferential orientation in the (200) plane. Atomic force microscopy exhibits nanometer range particle size with the highest roughness and higher surface area for the thinner film. FTIR analysis shows the presence of characteristic bands of the double bond stretching vibrational modes (W=O) and stretching vibrations of the γ(W-O-W) bonds corresponding to the monoclinic WO₃. Raman bands located at 345, and 435 cm⁻¹ are ascribed to the presence of W⁵⁺ species that induces the formation of oxygen vacancies VO. The thinner film shows a decrease in the optical indirect band gap attributed to the formation of oxygen vacancies in combination with W⁵⁺ species that induce the formation of energy states within the forbidden band gap range.

Though tungsten trioxide (WO3) in bulk, nanosphere, and thin film samples has been extensively studied, few studies have been dedicated to the crystallographic structure of WO3 thin films. In this work, the evolution from amorphous WO3 thin films to crystalline WO3 thin films is discussed. WO3 thin films were fabricated on silicon substrates (Si/SiO2) by RF reactive magnetron sputtering. Once a thin film was deposited, two successive annealing treatments were made: an initial annealing at 400 °C for 6 h was followed by a second annealing at 350 °C for 1 h. Film characterization was carried out by X-ray diffraction (XRD), high-resolution electron transmission microscopy (HRTEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM) techniques. The β-WO3 final phase grew in form of columnar crystals and its growth plane was determined by HRTEM.

Manganites of the family La_0.7Ca_0.3−xSr_xMnO₃ were fabricated by four preparation methods: (a) the microwave-assisted sol-gel Pechini method; (b) sol-gel Pechini chemical synthesis; (c) solid-state reaction with a planetary mill; and (d) solid-state reaction with an attritor mill, in order to study the effect of the preparation route used on its magnetocaloric and magnetic properties. In addition, the manganites manufactured by the Pechini sol-gel method were compacted using Spark Plasma Sintering (SPS) to determine how the consolidation process influences its magnetocaloric properties. The Curie temperatures of manganites prepared by the different methods were determined in ~295 K, with the exception of those prepared by a solid-state reaction with an attritor mill which was 301 K, so there is no correlation between the particle size and the Curie temperature. All samples gave a positive slope in the Arrot plots, which implies that the samples underwent a second order Ferromagnetic (FM)–Paramagnetic (PM) phase transition. Pechini sol-gel manganite presents higher values of Relative Cooling Power (RCP) than the solid-state reaction manganite, because its entropy change curves are smaller, but wider, associated to the particle size obtained by the preparation method. The SPS technique proved to be easier and faster in producing consolidated solids for applications in active magnetic regenerative refrigeration compared with other compaction methods.