Dissolution and phosphate-induced transformation of ZnO nanoparticles in synthetic saliva probed by AGNES without previous solid-liquid separation. Comparison with UF-ICP-MS

The variation over time of free Zn2+ ion concentration in stirred dispersions of ZnO nanoparticles (ZnO NPs) prepared in synthetic saliva at pH 6.80 and 37 degrees C was followed in situ (without solid liquid separation step) with the electroanalytical technique AGNES (Absence of Gradients and Nernstian Equilibrium Stripping). Under these conditions, ZnO NPs are chemically unstable due to their reaction with phosphates. The initial stage of transformation (around 5-10 h) involves the formation of a metastable solid (presumably ZnHPO4), which later evolves into the more stable hopeite phase. The overall decay rate of ZnO NPs is significantly reduced in comparison with phosphate-free background solutions of the same ionic strength and pH. The effective equilibrium solubilities of ZnO (0.29-0.47 mg.L-1), as well as conditional excess-ligand stability constants and fractional distributions of soluble Zn species, were determined in the absence and presence of organic components. The results were compared with the conventional ultrafiltration and inductively coupled plasma-mass spectrometry (UF-ICP-MS) methodology. AGNES proves to be advantageous in terms of speed, reproducibility, and access to speciation information. KeywordsThis work was supported by the Spanish Ministry MINECOunder Grant No. CTM2016-78798 and European UnionSeventh Framework Programme FP7-NMP.2012.1.3-3 underGrant No. 310584 (NANoREG). FQ gratefully acknowledgesa grant from AGAUR

Magnetic hardening induced by ferromagnetic-antiferromagnetic coupling

Consultable des del TDXTítol obtingut de la portada digitalitzadaEs bien sabido que las interacciones de canje inducidas entre materiales ferromagnéticos (FM) y antiferromagnéticos (AFM) cuando son enfriados desde una temperatura superior a la temperatura de Néel, TN, del AFM, hacen aumentar la coercividad, HC, del componente FM. Nosotros hemos analizado los efectos de hacer una molienda mecánica de polvos FM (Co o SmCo5) con AFM (con TN, ya sea por encima de temperatura ambiente, por ejemplo el NiO, o por debajo, por ejemplo el CoO). Se han estudiado varias combinaciones (Co + NiO, SmCo5 + NiO y SmCo5 + CoO), dando especial énfasis a los sistemas FM + NiO. Los distintos comportamientos estructurales y magnéticos del Co y del SmCo5 durante la molienda y los tratamientos térmicos hacen necesario adaptar la ruta de procesado adecuadamente para cada caso. Así, en los sistemas Co + AFM los efectos de las interacciones FM-AFM se inducen mayoritariamente después de un enfriado en campo de los polvos molidos desde T > TN. Contrariamente, en polvos SmCo5 + AFM, los tratamientos térmicos deterioran enormemente las propiedades magnéticas duras del SmCo5. De todas formas, un análisis comparativo de las propiedades del SmCo5 molido con NiO o con CoO parece indicar que, en cierto grado, las interacciones de canje pueden, de hecho, inducirse en el SmCo5 + NiO durante la molienda. Las interacciones de canje FM-AFM se manifiestan en un desplazamiento del ciclo de histéresis y unos aumentos de HC y de la razón de cuadratura, MR/MS. Estos efectos se observan a temperatura ambiente siempre que TN sea mayor que la temperatura ambiente (por ejemplo, con NiO). Además, si se optimizan las proporciones de FM a AFM, así como las condiciones de molienda, también es posible aumentar, hasta cierto punto, el producto de energía, (BH)Max. Por un lado, el aumento del contenido de AFM hace aumentar las interacciones FM-AFM (induciendo un aumento de HC y MR/MS). Sin embargo, como la imanación de un AFM es prácticamente nula, la imanación de saturación del material compuesto FM-AFM se ve también reducida proporcionalmente al porcentaje de AFM. Como consecuencia de estos dos efectos competitivos, se obtiene que las composiciones que maximizan HC no son las óptimas para aumentar (BH)Max. Por tanto, tanto el tiempo de molienda como las proporciones FM:AFM deben optimizarse adecuadamente dependiendo de las propiedades magnéticas deseadas para los productos finales.Ferromagnetic (FM) - antiferromagnetic (AFM) exchange interactions induced after field cooling FM-AFM composites through the Néel temperature of the AFM are known to increase the coercivity, HC, of the FM component. We have studied the effect of milling different FM (Co or SmCo5) with AFM powders (with TN, either above room temperature, e.g. NiO, or below room temperature, e.g. CoO). Several combinations (i.e. Co + NiO, SmCo5 + NiO and SmCo5 + CoO) have been studied, with special focus on FM + NiO composites. The different structural and magnetic behaviors of Co and SmCo5 during ball milling or heat treatments make it necessary to properly adapt the processing route for each case. Thus, in Co + AFM composites the effects of FM-AFM exchange interactions are mainly induced after field cooling the as-milled powders from above TN. Contrarily, in SmCo5 + AFM powders, heating results in deterioration of the hard magnetic properties. However, comparison of the magnetic properties of SmCo5 milled with NiO or with CoO indicates that for SmCo5 + NiO some exchange interactions can be actually induced during the milling. FM-AFM exchange interactions result in a shift of the hysteresis loop and in enhancements of HC and the squareness ratio, MR/MS. These effects are observed at room temperature, provided that TN is above room temperature (i.e. for NiO). In addition, an enhancement of the energy product, (BH)Max, can also be accomplished, to a certain extent, after optimization of the FM:AFM ratio and milling conditions. On the one hand, an increase of the AFM content brings about an increase of FM-AFM exchange interactions (i.e. an increase of HC and MR/MS). Nevertheless, on the other hand, since the AFM has a zero net magnetization, the overall saturation magnetization, MS, of the FM-AFM composites decreases proportionally to the amount of AFM. As a consequence of these competing effects, it has been found that the compositions resulting in maximum coercivities are not the optimum ones to enhance (BH)Max. Therefore, both the milling time and the FM-AFM ratio need to be optimized depending on the desired properties for the final materials