Gothic green glazed tile from Malbork Castle: multi-analytical study
Looking at the façade of a historical building, it is often difficult to distinguish between the original decoration and later additions. One such building is the Holy Virgin Mary Church at the Malbork Castle (Northern Poland), built between 1276 and 1406. During the latest restoration works, ceramic tiles with some remnants of the green glaze, decorating the Holy Virgin Mary Church façade, were studied in situ using portable X-ray fluorescence spectrometry. Micro-samples were analyzed in laboratory by scanning electron microscopy with energy dispersive X-ray spectrometry (SEM–EDS) and wavelength-dispersive X-ray spectrometry (SEM–WDS), micro-Raman spectroscopy and powder X-ray micro-diffraction. We found that what was originally thought to be a paint layer was in fact a heavily deteriorated SiO2–PbO glaze. White, yellow and black pigments were found to have been added into the glaze as opacifiers and colorants. Copper and iron were used as glaze colorants. The originally added pigments were transformed into new phases, such as antimony-doped tin oxide. The technology used to produce the glazed tiles was identified. All the results collectively confirmed the medieval origin of the green glazed tiles.Graphical abstractGothic green glazed tile from Malbork Castle: multi-analytical study.
Painted plaster and glazed brick fragments from Achaemenid Pasargadae and Persepolis, Iran
BackgroundArchitectural fragments of decorated walls, floors, and columns excavated by Ernst Herzfeld (1879–1948) at the archaeological sites of Persepolis and Pasargadae in Iran are housed in the Freer Study Collection at the Freer Gallery of Art and Arthur M. Sackler Gallery (FSG), Smithsonian Institution in Washington, DC. Technical studies of these painted earthen plasters and glazed brick fragments were undertaken to enhance our knowledge of materials and technology of Achaemenid Persia between the late sixth and fourth centuries BCE. Initial analysis was done on the surface of the fragments using non-invasive X-ray fluorescence with a portable instrument. Polished cross-sections were used to examine the layering stratigraphy of paints and glazes, and to undertake compositional analysis using scanning electron microscopy with energy-dispersive X-ray spectroscopy.ResultsUp to five layers of paint are present on the Pasargadae plaster, constituting the remnants of a geometric design. The plasters were bound with clay tempered with an organic material that has long since degraded, leaving small voids throughout. Pigments identified include Egyptian blue, malachite green, red ocher, and cinnabar red. The floor fragments from Persepolis were finished with a lime plaster and two layers of hematite-rich paint. The brick fragments from Persepolis were found to be composed of high-silica material similar to faience, which were decorated with alkaline glazes, including a yellow glazed colored with lead antimonate, gray glaze colored with magnesium and iron, and green glazed colored with copper.ConclusionsWhile the exact ages of the finishes are unknown, a similar technology was employed to decorate Achaemenid architecture in its principle Iranian cities. The variety of materials excavated by Herzfeld demonstrates the ability of Achaemenid artisans to work with multiple mediums to create a polychromatic finish including that of glazed tiles, earthen plaster tempered with gravel, earthen plaster tempered with organic matter, colored earths, pigmented paints and lime plasters. The layering of these materials can be seen and analyzed in cross-section although surface deterioration is often quite severe. The analysis of the compositional data on the architectural fragments inform their long-term preservation at the FSG as well as at the sites themselves.
Hygroscopic Expansion of some Casting Investments
CREDIT is generally given to Taggart1 for introducing the cast gold inlay to the dental profession. Although he realized that gold shrinks when cooled from molten state to solid state of room temperature, the investment available to him did not supply sufficient compensation. In 1910, Van Horn2 published a paper dealing with a method by which he obtained the compensation by means of wax expansion. The next major research in connection with this problem was the work of Coleman3 at the National Bureau of Standards. He determined the gold shrinkage to be 1.25 per cent and presented a casting technic with compensation values of quantitative nature. The total compensation for the gold shrinkage was obtained by the combination of the setting and thermal expansion of the mold. This procedure is the general practice followed at the present time for compensation. There are some disadvantages to this method. Skinner has indicated the difficulty of obtaining smooth castings and the improper compensation for the casting shrinkage.4 It has been found by Hollenback5 and Scheu6a that castings made at a high temperature are rougher than those made at a low temperature (450° C.), depending upon the great difference in thermal expansion between plaster of Paris and silica, which causes a poor union of the fine particles. This may also result in friability and there may be some warpage due to the differential expansion. A method which provides sufficient compensation at a low mold temperature is the hygroscopic casting technic.b Wilson7 showed that certain plasters expand as much as 0.0044 inch to the inch by taking up moisture from the air. With this information at hand, Scheula, b tested some commercial investment to determine what results the addition of moisture would have. He found6b: (1) All of the casting investments that were tested expanded. (2) The thicker the mix, the greater the expansion. (3) A mix with hot water expanded more than one with cold water. (4) The time at which the mix is placed in the water is of great importance. It was found that if the mix is placed in the water early, it would not expand so much as when placed in a little later. It was also found that if the mix was placed in the water after a certain time, it could not expand to the maximal amount. (5) The temperature of the water in which the mix is placed is important, for two reasons; (a) the temperature of the water controls slightly the expansion of the investment, and (b) water at a temperature of 1000 F. slightly softens the wax pattern so that the fine margins are not marred while expansion is taking place. The mix should remain in the water at least 20 minutes to obtain the full expansion, after which time no further expansion is obtained.