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This paper presents evidence supported by scientific analyses and historical documents that medieval plasters used for wall paintings in Denmark were, with high probability, produced by mixing quicklime, aggregate and water in an exothermic process, resulting in a mortar referred to as hot-mixed. This process enables the production of plaster with a very high binder content. Previous thin-section analyses were supplemented by recent analyses of samples collected from three medieval wall paintings in Danish churches. Also included in the analyses were plaster samples produced from hot-mixed mortar and samples produced from lime putty mortar. The analyses of the medieval plasters showed an average binder content in the range of two parts lime to one part aggregate. Moreover, lime inclusions, a characteristic of hot-mix, were found in all samples. SEM analyses showed a similar microstructure in the medieval plasters and the samples produced by hot-mixed mortar, while significant differences were found between the medieval plaster and lime putty samples.

In this article we present the fragments of a crucible and a possible tuyère that provide evidence of early copper metallurgy in Scandinavia at least 1500 years earlier than previously thought. The technical ceramics were found in a cultural layer containing Early Neolithic Funnel Beaker pottery dating to around 3800–3500bcbeneath a long barrow dating to 3300–3100bc. The presence of a copper alloy in the crucible is confirmed by three independent X-ray fluorescence analyses using both a hand-held and a stationary instrument, SEM-EDS analysis of a cross-section, as well as a Bruker Tornado μ-X-Ray-fluorescence scanner (μ-XRF). The transmission of metallurgy to southern Scandinavia coincided with the introduction of long barrows, causewayed enclosures, two-aisled houses, and certain types of artefacts. Thus, metallurgy seems to be part of the new networks that enabled the establishment of a fully Neolithic society.

Whetstones of the Viking Age can have a conspicuous design, but not much is understood about the specific use of more unusual specimens, or their place in rituals. This article proposes a new interpretation of whetstones, based on novel studies of a well-known whetstone from Lejre, and miniature pendants from Tissø. Our examination of the prominent whetstone from the Lejre hoard with an x-ray fluorescence (XRF) scan, did not reveal any metal traces, which suggests that it was unused. At Tissø, the find distribution of so-called stafflike pendants – made of iron, bronze, or silver – links them to a metal-working area, and since their morphology resembles full-scale whetstones we suggest that they may be symbolic, miniature whetstones. Finally, we argue that the overarching meaning of the ritual use of whetstones is more related to the authority over – and control of – metallurgical processes, as well as the trade of metal goods, and only by proxy to the smith himself.

Samples of conserved archaeological wood of different ages, origins, and conservation histories were aged in a climate chamber for seven months, while the humidity alternated between 30% RH for 12 hours and 80% RH for 12 hours at a constant temperature of 30°C. Photographs were taken once every hour, which enabled the creation of a time-lapse movie. Some samples degraded visibly, whereas others were unaffected. Most of the samples were robust and would be able to survive well even in a very poor museum climate. Among the sensitive samples, three types of degradation were identified, namely disintegration, pyrite oxidation, and efflorescence of white crystals. Disintegration was ascribed to dimensional changes caused by the RH alternations in very fragile wood. The white efflorescence was interpreted as the recrystallization of an alum-associated substance, possibly mercallite (KHSO4). The pyrite oxidation was observed as the efflorescence of a thick yellow, grey, and green powder. Characterization of selected samples was performed using X-ray fluorescence spectrometry, X-ray diffraction spectrometry, scanning electron microscopy with energy dispersive X-ray spectroscopy, inductively coupled plasma – optical emission spectroscopy, Fourier transform infrared spectroscopy, ionic conductivity – liquid chromatography, and pyrolysis-gas chromatography-mass spectrometry with in situ silylation using hexamethyldisilazane.

Characterisations of ancient sheep breeds and wool types and theories about wool fibre processing are integral parts of textile archaeology. The studies build on statistical calculations of measurements of wool fibre diameters and reveal characteristics of the yarns that are attributed to the available raw wool and to the production methods of the time. Different microscope types have been used for data collection. Presently digital images from either scanning electron microscopy (SEM) or transmitted light microscopy (TLM) are the preferred methods. The advantage of SEM is the good depth of field at high magnification, while TLM is simpler to use and more readily available. Several classification systems have been developed to facilitate the interpretation of the results. In this article, the comparability of the results from these two methods and from the use of different magnifications in general is examined based on the analyses of a large number of the Danish prehistoric textiles. The results ...

This paper describes a cleaning method for removing ingrained carbonaceous dirt from lime-based wall paintings by utilizing hydrogels in combination with aqueous cleaning liquids. Nanorestore Gel® ...

A system for continuous monitoring of atmospheric corrosivity has been developed. An electronic unit measures and records changes in the electrical resistance of a thin metal track applied on an insulating substrate. If the metal corrodes, the effective cross sectional area of the track decreases and the electrical resistance increases. Sensors made of silver, copper, iron/steel, zinc, lead, tin, aluminium, bronze, and brass at thicknesses from 50 nm to 250 m were tailored for environments with different corrosivities. The developed technology proved capable of providing high sensitivity, allowing for real-time corrosion monitoring even in low-corrosive indoor cultural heritage facilities. Laboratory tests showed good reproducibility with the standard deviation of parallel measurements at less than ±20% for metals which corrode uniformly in the tested environments. Several examples selected from a broad testing programme in partner museums, libraries, and other institut ions show successful applications of the logger system for characterization of air quality control in indoor locations, during transport and in temporary exhibitions; assessment of new buildings and storage facilities; and fundamental studies of optimal conservation and storage procedures. A first outline of a classification system for lead, which is particularly sensitive to the presence of carboxylic acids, is given. The technique has a large potential as an independent method for monitoring air quality in facilities displaying and storing valuable objects of cultural heritage.

Establishing the age at which prehistoric individuals move away from their childhood residential location holds crucial information about the socio dynamics and mobility patterns in ancient societies. We present a novel combination of strontium isotope analyses performed on the over 3000 year old "Skrydstrup Woman" from Denmark, for whom we compiled a highly detailed month-scale model of her migration timeline. When combined with physical anthropological analyses this timeline can be related to the chronological age at which the residential location changed. We conducted a series of high-resolution strontium isotope analyses of hard and soft human tissues and combined these with anthropological investigations including CT-scanning and 3D visualizations. The Skrydstrup Woman lived during a pan-European period characterized by technical innovation and great social transformations stimulated by long-distance connections; consequently she represents an important part of both Danish and European prehistory. Our multidisciplinary study involves complementary biochemical, biomolecular and microscopy analyses of her scalp hair. Our results reveal that the Skrydstrup Woman was between 17-18 years old when she died, and that she moved from her place of origin -outside present day Denmark- to the Skrydstrup area in Denmark 47 to 42 months before she died. Hence, she was between 13 to 14 years old when she migrated to and resided in the area around Skrydstrup for the rest of her life. From an archaeological standpoint, this one-time and one-way movement of an elite female during the possible "age of marriageability" might suggest that she migrated with the aim of establishing an alliance between chiefdoms. Consequently, this detailed multidisciplinary investigation provides a novel tool to reconstruct high resolution chronology of individual mobility with the perspective of studying complex patterns of social and economic interaction in prehistory.

The corrosion rate of copper and bronze Cu-8 wt.%Sn increased rapidly when the concentration of formic or acetic acid in air reached about 300 ppb at 80% relative humidity (RH) and a temperature of 20 °C. It decreased slowly during the several days after pollutant removal due to the slow rate of pollutant desorption from the metal surfaces. Corrosion of these metals was barely affected by the acids at RH up to 60%. For iron, the critical concentration of formic acid in air which led to surface activation at 80% RH was between 1000 and 1590 ppb.

Many ancient Chinese bronze mirrors have survived with a patina that leaves the delicate surface decorations intact. The microstructure of these mirrors is two-phase: Cu-rich α and Sn-rich δ. Although the mirrors have been labeled ‘corrosion-resistant’, the smooth surface includes a corroded layer up to 100 µm thick. In this ‘altered’ layer, there is selective attack of the α phase; the α-phase regions are replaced by tin oxide with the δ phase remaining metallic. Here, electrochemical polarization has been used to drive the dealloying process in modern, cast bronze duplicating the microstructure on ancient bronzes. Timed experiments were performed to investigate the growth of the ‘altered’ region on the model samples. The altered layer forms quickly but the rate of growth slows over time. Theoretical calculations show that dissolution of copper from the α phase leaves a large volume for the tin oxide corrosion product permitting retention of the smooth surface.

Ancient Chinese bronze vessels from the Shang to Zhou dynasties (c. 1500 - 221 BCE) were cast using piece molds. Several large vessel shapes, especially those with legs, have been found to be made in several steps with the vessel body cast onto previously-made legs or other appendages. In this situation the molten metal contacts and must attach to the solid pieces from the first casting. Similar interfaces are found at solid metal mold spacers or chaplets used in the casting process. Previous researchers showed that the casting can exhibit concentration gradients and evidence of slip in the regions around these interfaces. In this work, we studied the thermal expansion of the bronze at cast-on joints in ancient Chinese bronzes using thermomechanical analysis (TMA). The results are compared with those from reference lead-tin bronze alloys.

Many ancient Chinese bronze mirrors have a smooth patina. An ingress of corrosion to a depth of approximately 100 μm is found beneath the patina. The corrosion selectively replaces the Cu-rich α phase leaving the Sn-rich σ phase intact. Previous work by x-ray diffraction has shown that the a-phase replacement product is poorly crystallized or nanocrystalline SnO2. Transmission electron microscopy was employed to further characterize the replacement product in both ancient mirror and replication samples. Nanocrystalline SnO, in the form of small spheroids has been found. Remnants of an original alloy phase appear to be interspersed with the tin oxide.

Many ancient Chinese bronze mirrors have survived with a patina that leaves the delicate relief surface decorations intact. The microstructure of these ancient mirrors is two-phase and consists of acicular α-phase (Cu-rich) regions encased in a δ-phase (Sn-rich) matrix. At the surface, there is evidence of selective dissolution of the α-phase; the α-phase regions are replaced pseudomorphically by a mineral product with the δ -phase remaining metallic. Electrochemical polarization has been used to drive the copper dealloying process in modern, cast bronze. Synchrotron x-ray diffraction was employed to compare the ancient samples with those that were prepared potentiostatically. Poorly crystallized tin oxide (SnO2) was found in the α - replacement products of both sample types. The corrosion-resistance of the potentiostatically-treated bronze samples was tested by atmospheric exposure. Comparison with exposed, untreated samples indicated that the treatment was protective.

Many ancient Chinese bronze mirrors have survived with their original surface decorationsintact, particularly those with “glassy” black surface coatings. The microstructures and compositions of cross-sectional samples from ancient mirrors have been analyzed with optical and electron microscopy and synchrotron x-ray fluorescence. The core has a two-phase metal structure while the surface shows evidence of selective dissolution of copper from the α (Curich) phase. The ci phase regions are replaced pseudomorphically by a mineral product with the δ (Sn-rich) phase remaining metallic. A fundamental study of the electrochemistry of the copper-tin system has given information on theconditions under which selective dissolution of copper takes place. Electrochemical polarization has been used to drive the copper dealloying process in cast high-tin bronze. Theresulting microstructure is similar to the dealloyed microstructure observed in the ancient samples.

The effectiveness of in situ multielement X-ray absorption near edge spectroscopy for studying the passivation of alloys is demonstrated. By simultaneously windowing the appropriate K{sub a} fluorescence lines with a 13-element energy-dispersive germanium detector it is possible to measure concurrently the behavior of different alloying elements during electrochemical polarization. A thin film of stainless steel was stepped between {minus}1.5 and +0.4 V (MSE) (the transpassive region of chromium) in a pH 8.4 borate buffer. On the first oxidation, no metal was lost and Fe and Ni showed some oxidation. On reduction, significant Fe and a barely detectable quantity of Ni dissolved. During the second oxidation, some Cr and a smaller fraction of Ni dissolved.