Tamás Váczi

Interactions and chemical transformations of coronene inside and outside carbon nanotubes

By exposing flat and curved carbon surfaces to coronene, a variety of van der Waals hybrid heterostructures are prepared, including coronene encapsulated in carbon nanotubes, and coronene and dicoronylene adsorbed on nanotubes or graphite via π-π interactions. The structure of the final product is determined by the temperature of the experiment and the curvature of the carbon surface. While at temperatures below and close to the sublimation point of coronene, nanotubes with suitable diameters are filled with single coronene molecules, at higher temperatures additional dimerization and oligomerization of coronene occurs on the surface of carbon nanotubes. The fact that dicoronylene and possible higher oligomers are formed at lower temperatures than expected for vapor-phase polymerization indicates the active role of the carbon surface used primarily as template. Removal of adsorbed species from the nanotube surface is of utmost importance for reliable characterization of encapsulated molecules: it is demonstrated that the green fluorescence attributed previously to encapsulated coronene is instead caused by dicoronylene adsorbed on the surface which can be solubilized and removed using surfactants. After removing most of the adsorbed layer, a combination of Raman spectroscopy and transmission electron microscopy was employed to follow the transformation dynamics of coronene molecules inside nanotubes.

A new, simple approximation for the deconvolution of instrumental broadening in spectroscopic band profiles

A robust empirical correction formula has been developed for the approximation of Lorentzian widths, using a known spectrometer bandpass, in instrument-broadened Voigt bands in optical spectra. The relationship between analytically calculated [(WVoigt – WLorentz)/WGauss] and [WVoigt/wGauss – 1] values (where w is the full width at half-maximum [FWHM]) is analyzed to derive the formula for the approximation of the (WVoigt – WLorentz) difference. The precision of the method is demonstrated by comparing its performance to several previously published numerical correction approaches. The fraction of the Lorentzian contribution in Voigt FWHMs is evaluated in terms of the Gaussian FWHM to assess the conditions under which the deconvolution of instrumental broadening is necessary.

Pyrophanite pseudomorphs after perovskite in Perkupa serpentinites (Hungary): a microtextural study and geological implications

Pyrophanite in serpentinite at Perkupa (Hungary) is described in detail for the first time as a replacement product of perovskite. It occurs as a 20- to 30-μm-wide rim, mantling a remnant core composed of perovskite or its alteration products. The pyrophanite rim consists of an inner zone, representing a pseudomorph after perovskite, and an outer overgrowth zone. Raman mapping and electron backscatter diffraction data show that the pyrophanite rims typically represent single crystals rather than being composed of multiple domains in different crystallographic orientations. Perovskite occurs exclusively in the core of pyrophanite and was identified as the orthorhombic CaTiO3 phase, based on Raman spectra. Heterogeneous, polyphase mineral cores, consisting of calcite, anatase and/or brookite, kassite, and Mn-bearing kassite, in some cases in association with relict perovskite, are typical in the larger pyrophanite-rimmed grains. The crystallographically coherent pyrophanite rims could have formed through a process where the precursor perovskite crystal acted as a structural template for the newly forming phase, that is, by interface-coupled dissolution reprecipitation during serpentinization of the precursor rock. This alteration of perovskite to pyrophanite was not complete, resulting in the presence of perovskite fragments enclosed in pyrophanite. During the metamorphic evolution of the rock, some of the remnant perovskite cores further altered to TiO2 polymorphs (anatase and brookite) and calcite, via transitional alteration products.

Incremental growth and mineralogy of Pannonian (Late Miocene) sciaenid otoliths: paleoecological implications

Incremental growth and mineralogy of Pannonian (Late Miocene) sciaenid otoliths: paleoecological implications Ontogenetic age and body dimensions were studied on three extremely well-preserved sciaenid fish otoliths from sublittoral marls of Lake Pannon from Doba, Bakony Mts, Hungary. Macroscopic and microscopic observations offered clear evidence for the preservation of the genuine structural characteristics, for instance the bipartite incremental features. Ontogenetic ages were assigned for the three specimens as 16, 7 and 6 years by counting the annuli of the sagittae. Analytical results prove that the original aragonitic mineralogy has been preserved making them, and probably other Late Miocene teleost fossils, suitable for future microchemical analysis to reconstruct the past physicochemical environment.

Electron-beam-induced annealing of natural zircon: a Raman spectroscopic study

The annealing of radiation damage in zircon by low-energy electron irradiation was explored systematically. Natural zircon samples spanning a wide range of self-irradiation damage were irradiated with the focused electron beam of an electron probe microanalyser. The effects of beam current and irradiation time were tested systematically, and the changes in zircon were measured using Raman spectroscopy. Our results confirm the damage-annealing effect of an accelerated electron beam. We demonstrate that non-thermal annealing occurs through electron-enhanced defect reactions and that the extent of the annealing is a function of both the irradiation time and the beam current. The complete annealing of radiation damage in zircon by an accelerated electron beam was not possible under the conditions of our experiments. Our results indicate that Raman band broadening in ion-irradiated zircon can possibly be explained through phonon confinement, as the estimated domain sizes of the crystalline volume amid recoil clusters decrease with increasing α dose. The results underlay the importance of doing Raman spectroscopy before electron-beam and ion-beam analysis. To avoid unwanted beam-induced annealing of damage in zircon during EPMA analysis, the electron energy transferred per volume unit of sample should be minimised, for instance by keeping the integrated charge low and/or by defocusing the electron beam.

Medieval Gilding Technology of Historical Metal Threads Revealed by Electron Optical and Micro-Raman Spectroscopic Study of Focused Ion Beam-Milled Cross Sections

Although gilt silver threads were widely used for decorating historical textiles, their manufacturing techniques have been elusive for centuries. Contemporary written sources give only limited, sometimes ambiguous information, and detailed cross-sectional study of the microscale soft noble metal objects has been hindered by sample preparation. In this work, to give a thorough characterization of historical gilt silver threads, nano- and microscale textural, chemical, and structural data on cross sections, prepared by focused ion beam milling, were collected, using various electron-optical methods (high-resolution scanning electron microscopy (SEM), wavelength-dispersive electron probe microanalysis (EPMA), electron backscattered diffraction (EBSD) combined with energy-dispersive electron probe microanalysis (EDX), transmission electron microscopy (TEM) combined with EDX, and micro-Raman spectroscopy. The thickness of the gold coating varied between 70-400 nm. Data reveal nano- and microscale metallurgy-related, gilding-related and corrosion-related inhomogeneities in the silver base. These inhomogeneities account for the limitations of surface analysis when tracking gilding methods of historical metal threads, and explain why chemical information has to be connected to 3D texture on submicrometre scale. The geometry and chemical composition (lack of mercury, copper) of the gold/silver interface prove that the ancient gilding technology was diffusion bonding. The observed differences in the copper content of the silver base of the different thread types suggest intentional technological choice. Among the examined textiles of different ages (13th-17th centuries) and provenances narrow technological variation has been found.

The role of magmatic and hydrothermal processes in the evolution of Be-bearing pegmatites: Evidence from beryl and its breakdown products

Abstract Beryl and euclase crystals from the Mina do Santino and the Jacú pegmatites in the Borborema Pegmatite Province in northeastern Brazil contain several generations of melt and fluid inclusions, which allow interpretation of P-T-X conditions responsible for beryl crystallization and for alteration of a primary pegmatitic mineral assemblage to a mixture of hydrothermal minerals (euclase, bertrandite, kaolinite, and quartz). Primary melt and fluid inclusions hosted by beryl were trapped simultaneously. However, their homogenization temperatures are significantly higher (870-900 °C) than the values previously reported for pegmatitic systems (<712 °C) and should be treated with caution. An isobaric drop of temperature resulted in the exsolution of a fluid. A low-salinity CO2-enriched phase and a saline water-rich phase were trapped in pseudosecondary inclusions in beryl at a pressure of 2.1-2.7 kbar and temperature of 390-480 °C. Cooling of the country rocks below 400 °C caused a ductile-to-brittle transition and allowed infiltration of cold groundwater, which further decreased the temperature in the system to 190-240 °C. At the same time, the pressure dropped from a lithostatic (2.1-2.7 kbar) to a hydrostatic value (0.57-0.73 kbar). Consequently, minerals deposited under magmatic conditions (feldspars and beryl) became unstable and a newly formed hydrothermal mineral paragenesis (euclase, bertrandite, kaolinite, and quartz) overprinted the earlier one. The hydrothermal fluids responsible for the alteration differ from the earlier-exsolved fluids in having a lower salinity, lower homogenization temperature, the absence of CO2, and the presence of CH4.

Nothia ex gr. excelsa (Grzybowski, 1898), ‘flysch-type’ agglutinated foraminifera from the Karpatian (Early-Miocene) of Hungary

Abstract Nothia ex gr. excelsa (Grzybowski, 1898) branched, agglutinated, tubular foraminifera is documented for the first time from the Karpatian (latest Burdigalian) molasse sediments of the Paratethys. Excellently preserved specimens allowed the study of the macro- and microstructure of the test using reflected and polarized light microscopes, SEM and Raman spectroscopy. The mineralogical components of the agglutinated grains, the appearance of the protruded aperture with a scalloped-edge, the microstructure of the bilamellar wall, the presence of the calcite microgranular cement could all be described in detail. Based on autecology, the test morphology and the associated fauna indicate that Nothia ex gr. excelsa was a surface-dwelling detritivore with a seasonal-phytophagous mode of life.

Fusiform vateritic inclusions observed in European eel (Anguilla Anguilla L.) sagittae

Microscopic inclusions have been observed in 7 out of 106 European eel (Anguilla anguilla L.) sagittae using polarizing microscope and scanning electron microscope meanwhile the annual increments were studied to characterize the age structure of the population living in Lake Balaton. The presence of vaterite, a rare calcium carbonate polymorph was observed in these inclusions using Raman spectroscopy. Vateritic sagittae in wild fish are usually considered as symptom of physiological stress. The observed fusiform inclusions represent a new morphological type of vaterite inclusions in eel otolith. Two alternatives are hypothesized to explain their formation: 1) metabolic disorder, such as erroneous protein synthesis; 2) introduction of an alien protein into the eels inner ear. The origin and physiological significance of this new morphological type of vateritic inclusions is still an open question. Same as whether it can be found in other species or specific only to eel otoliths.