The thermal and chemical stability of micelle-synthesized size-selected Pt nanoparticles (NPs) supported on thin SiO2 (20 nm) films was monitored in situ via transmission electron microscopy (TEM) under pure hydrogen and pure oxygen environments. The coarsening treatment was performed for 30 min at each temperature (1 Torr of either O2 or H2), while the TEM measurements were carried out at 1 Torr of H2 and 0.5 Torr of O2. Surprisingly, the NPs were found to be stable against sintering under both gaseous atmospheres up to 650 °C. Nevertheless, drastic sintering via diffusion-coalescence was observed upon annealing in H2 at 800 °C. In contrast, an identically prepared sample demonstrated lack of agglomeration at the same temperature under O2. The latter observation is ascribed to a strengthened chemical bond at the NP/support interface due to the formation of PtOx species at low temperature. Subsequently, oxidative NP redispersion - associated with some loss of Pt due to the formation of volatile PtOx species - is inferred from the behavior in O2 at/above 650 °C. In contrast, SiO2 reduction catalyzed by the presence of the Pt NPs and Pt silicide formation was found in H2 at 800 °C, which might play a role in the enhanced coarsening observed. Subsequent exposure of the PtSi NPs to oxygen led to the formation of Pt-SiO2 core-shell structures. Our findings highlight the dynamic structural transformations that nanoscale materials experience under different environments and the important role played by their initial size, size distribution and dispersion on their stability against sintering.

Strict control of composition is of paramount importance for the reproducible fabrication of advanced ceramics. In particular, the preparation of high-grade transparent ceramics of definite line-compounds requires that the ratio of major constitutive elements be quantified with a precision better than a fraction of a mole percent to prevent the precipitation of secondary phases and the scattering of light. Such a requirement poses difficult challenges to most analytical methods, especially when applied to nearly-stoichiometric insulating phases. In this work, we show that laser-induced breakdown spectroscopy (LIBS) is a wellsuited technique for the assessment of non-stoichiometry in yttrium aluminum garnet (YAG) ceramics and that the aluminum to yttrium ratio can be determined with a resolution of 0.3 mol %, well within the phase boundaries of YAG.

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Transparent ceramics are important optical materials with applications in street lighting, high-strength windows, electro-and magneto-optical isolators, high-power laser gain media and radiation detectors. Their fabrication most often relies on powder densification techniques carried out at high temperatures, sometimes promoted by sintering additives. Here, we describe the application of laser-induced breakdown spectroscopy (LIBS) for following the concentration levels of silica used as a sintering agent in the fabrication of yttrium aluminum garnet (YAG) transparent ceramics. The sensitivity limit of our protocol reaches a few tens of ppm of silica in YAG ceramic samples, showing that LIBS can be implemented reliably for the rapid assessment of sintering additives in advanced ceramic processing.