Stability and Equation of State of a Nanocrystalline Ga-Ge Mullite in a Vitroceramic Composite: A Synchrotron X-ray Iffraction Study

Synchrotron x-ray diffraction and diamond anvil cell techniques were used to characterize the phase transformations and to evaluate the structural stability at elevated pressures of a developed nanocrystalline composite. The optically transparent material was built of a germanium oxide-based amorphous host matrix with homogeneously dispersed 13±3 nm Ga-Ge mullite-type nanocrystals, which had a structure similar to the conventional Al2O3-SiO2 mullite. The equation of state of the nanocrystals and the overall structural integrity of the nanocomposite were investigated in quasihydrostatic conditions on compression to 36 GPa and on the following decompression to ambient conditions. The overall pressure-induced changes of x-ray diffraction patterns evidenced that the structural integrity of the material is well preserved up to about 14–16 GPa. The nanocomposite decompressed from 36 GPa to ambient pressure showed a very limited reversibility of the pressure-driven changes. A Birch-Murnaghan fit of the unit cell volume as a function of pressure yielded a zero-pressure bulk modulus, K0, for the nanocrystalline phase of 229(15) GPa which makes this material potentially interesting for structural applications at elevated pressures

Structural and spectroscopic characterization of A nanosized sulfated TiO2 filler and of nanocomposite nafion membranes

A large number of nano-sized oxides have been studied in the literature as fillers for polymeric membranes, such as Nafion®. Superacidic sulfated oxides have been proposed and characterized. Once incorporated into polymer matrices, their beneficial effect on peculiar membrane properties has been demonstrated. The alteration of physical-chemical properties of composite membranes has roots in the intermolecular interaction between the inorganic filler surface groups and the polymer chains. In the attempt to tackle this fundamental issue, here we discuss, by a multi-technique approach, the properties of a nanosized sulfated titania material as a candidate filler for Nafion membranes. The results of a systematic study carried out by synchrotron X-ray diffraction, transmission electron microscopy, thermogravimetry, Raman and infrared spectroscopies are presented and discussed to get novel insights about the structural features, molecular properties, and morphological characteristics of sulphated TiO2 nanopowders and composite Nafion membranes containing different amount of sulfated TiO2 nanoparticles (2%, 5%, 7% w/w

Estimating the viscosity of volcanic melts from the vibrational properties of their parental glasses

Abstract The numerical modelling of magma transport and volcanic eruptions requires accurate knowledge of the viscosity of magmatic liquids as a function of temperature and melt composition. However, there is growing evidence that volcanic melts can be prone to nanoscale modification and crystallization before and during viscosity measurements. This challenges the possibility of being able to quantify the crystal-free melt phase contribution to the measured viscosity. In an effort to establish an alternative route to derive the viscosity of volcanic melts based on the vibrational properties of their parental glasses, we have subjected volcanologically relevant anhydrous glasses to Brillouin and Raman spectroscopic analyses at ambient conditions. Here, we find that the ratio between bulk and shear moduli and the boson peak position embed the melt fragility. We show that these quantities allow an accurate estimation of volcanic melts at eruptive conditions, without the need for viscosity measurements. An extensive review of the literature data confirms that our result also holds for hydrous systems; this study thus provides fertile ground on which to develop new studies of the nanoscale dynamics of natural melts and its impact on the style of volcanic eruptions

Vibrational dynamics of rutile-type GeO2 from micro-Raman spectroscopy experiments and first-principles calculations

The vibrational dynamics of germanium dioxide in the rutile structure has been investigated by using polarized micro-Raman scattering spectroscopy coupled with first-principles calculations. Raman spectra were carried out in backscattering geometry at room temperature from micro-crystalline samples either unoriented or oriented by means of a micromanipulator, which enabled successful detection and identification of all the Raman active modes expected on the basis of the group theory. In particular, the Eg mode, incorrectly assigned or not detected in the literature, has been definitively observed by us and unambiguously identified at 525 cm − 1 under excitation by certain laser lines, thus revealing an unusual resonance phenomenon. First principles calculations within the framework of the density functional theory allow quantifying both wave number and intensity of the Raman vibrational spectra. The excellent agreement between calculated and experimental data corroborates the reliability of our findings

Viscosity, Boson Peak and Elastic Moduli in the Na2O-SiO2 System

The temperature and chemical dependence of the melt viscosity are ubiquitous in the model development of the volcanic dynamics, as well as in the glass production and design. We focussed on the yet-explored relationship between the bulk and shear moduli ratio and boson peak with the melt fragility of their parental glasses. Here, we explored the extension of the observed trend by testing the conventional binary system Na2O-SiO2, thus providing new evidence supporting the link between the flow of melts and supercooled liquids and the vibrational dynamics of their parental glasses. This was accomplished by integrating new low-frequency Raman measurements and integrating data from the literature on Brillouin light scattering and viscometry. This approach allows us to feed the MYEGA equation with reliable input parameters to quantitatively predict the viscosity of the Na2O-SiO2 system from the liquid up to the glass transition

Different spectroscopic behavior of coupled and freestanding monolayer graphene deposited by CVD on Cu foil

The growth of graphene on copper foil has been performed, following the well-known low-pressure chemical vapor (LP-CVD) procedure. The as-deposited monolayer graphene clearly exhibits two different coupling behaviors with the metal substrate, as demonstrated by visual microscopic investigation and by other experimental techniques, like Scanning Electron Microscopy (SEM) and micro-Raman spectroscopy. The single graphene sheet shows both large areas where it is coupled to the metal substrate and others where it exhibits freestanding-like characteristics. This phenomenology appears to be related to oxidation of the copper surface. In addition, we demonstrate the possibility to induce a variation of the coupling state by visible-light irradiation above a proper power threshold. The resulting change of the coupling with the metal substrate is associated to a local variation of the work function. Applications in high-performance electronic devices can be suitably tailored by optical methods and, in principle, by any local probe producing "hot spots" such as Scanning Tunneling Microscopy (STM) tips and electron beams.</p

Effect of Mn doping on the growth and properties of enstatite single crystals

Millimetric Mn-doped enstatite (MgSiO3) crystals have been grown by slow cooling in MoO3, V2O5, and Li2CO3 flux. Six starting mixture with different amount of manganese were slowly cooled from 1350 °C, 1050 °C and 950 °C down to 750 °C, 650 °C and 600 °C respectively. The enstatite crystals were characterized by X-ray powder diffraction (XRPD) and scanning electron microscopy with energy-dispersive spectrometry (SEM/EDS). Mn-doped enstatite crystals were reddish in color, euhedral and elongate parallel to c-axis. The largest enstatite crystal obtained is 8.5 mm in length. The effects of growth parameters on yield and size of crystals were studied. Variations observed in crystal size were attributed to the amount of Mn doping. Further characterizations by μ-Raman spectroscopy (μ-R) and cathodoluminescence (CL) allowed to study the effect of Mn doping on some chemical/physical characteristics of the enstatite and to assess its potential in advanced technological applications

Lanthanide doped upconverting colloidal CaF2 nanoparticles prepared by a single-step hydrothermal method: toward efficient materials with near infrared-to-near infrared upconversion emission

Colloidal Er3+/Yb3+, Tm3+/Yb3+ and Ho3+/Yb3+ doped CaF2 nanoparticles have been prepared by a one-pot hydrothermal procedure and their upconversion properties have been investigated