Tamás G. Weiszburg

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.

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.