A complex technological investigation of 14th-18th centuries Venetian paintings from the collection of the National Museum in Warsaw has been performed in connection with the “Serenissima- Light of Venice” exhibition. After analysis of the X-ray radiographs of the autoradiography to obtain indisputable information about over-painting (Tintoretto) or either confirmation or contradiction of their authenticity (Marieschi, Bellotto).

All the paintings under analysis were irradiated in a specially designed station at the research reactor MARIA in Swierk near Warsaw. Beta-rays emerging from the painting surface irradiated by thermal neutrons and recorded on a X-ray film displayed the distribution of elements in pigments used for creating individual layers of the painting. It allows for tracing the particular phases of the painting structure invisible to the naked eye.

The report presents results obtained for the following paintings: J. Tintoretto – Portrait of a Venetian Admiral, M. Marieschi – The palace of Doges in Venice, B. Bellotto called Canaletto – Fantasy architecture with self-portrait of the artist.

Among ceramics found at early historic sites in the Kalahandi district of India are a great variety of terracotta smoking pipes or hukka. The pipes are fashioned from fine, iron-rich clay with extensive surface decoration. Their intricacy makes them the most distinctive art form of the area. Found at the majority of sites in the region, they are of special interest, both due to the care used in their execution and as they predate the introduction of tobacco to the area, leaving the plant being smoked a question. To determine their method of manufacture, and investigate the possibility of local manufacture, an initial study was conducted of a small number of pipes from the site of Budhigarh. The pipes, along with clay from the site (used extensively by modern potters), were studied using x-ray radiography, petrography, and inductively coupled plasma spectroscopy (ICP).

The applicability of a broad spectrum of laboratory analytical methods to the study of remnant structures still observable in the corrosion products of ancient iron objects is discussed. These methods range from examination by light optical microscopy and SEM to direct microanalysis using x-ray mapping in EPMA. Samples ranging from low carbon iron to steels to cast iron have been examined and it has been found possible to observe remnant structures and infer fabrication information from the large majority of objects studied. The author thanks the Nathan Rubin-Ida Ladd Foundation for its support.

The art and technique of bloomery smelting, man's original method for winning metalliciron from its ore, has been largely lost in recent centuries. Many reconstructions of this technique have been attempted by archaeologists in the last 30 years. These experimental smelts have tended to be rather disappointing in terms of the production of usable iron; nonetheless, many conclusions have been drawn from this work.

The main goal of our work with bloomery smelting is the production of iron for the creation of forged sculpture. Our focus on producing a usable product has led us to a somewhat different view of the technology from what has been published in the archaeological literature.

In this paper, we will briefly summarize our work through the spring of 2000, which has been published elsewhere. We'll then report our recent findings from the 2000-2001 smelting season, describing a typical smelt of the most efficient smelting regimen we have yet discovered. We will pay particular attention to methods that differ from those of other experimenters, especially in regards to blowing rate, slag management, and the recycling of furnace products. Finally, we'll point toward areas of upcoming research.

Enamels from European Renaissance enameled gold jewelry and other objects dating from the sixteenth and seventeenth centuries, and Renaissance style and other objects from the eighteenth and nineteenth centuries were quantitatively analyzed using energy dispersive X-ray spectrometry. Differences were observed in the overall compositions, as well as the colorants and opacifiers used, of the Renaissance period and most of the later enamels. Some enamels from as late as the early nineteenth century, however, appeared to be essentially the same as those used during the Renaissance. The differences found in the enamel compositions can provide a set of objective compositional criteria to help distinguish between authentic Renaissance period enameled objects and some later enamels done in the style of the Renaissance.

Nineteenth century negatives and positives in the collections of the National Museums of Scotland (NMS) and the National Galleries of Scotland (NGS) were analysed non-destructively to identify the techniques used in their manufacture. Modern positive and negative images prepared using known nineteenth century processes were also analysed for comparison. Air-path energy dispersive x-ray fluorescence analysis and controlled pressure scanning electron microscopy with energy dispersive microanalysis enabled the images to be divided into groups based on the levels of bromine, iodine and silver, and the likely processes used inferred. An early group of positives were probably sensitised with either silver chloride or silver bromide and fixed with potassium bromide. However, most positives were probably sensitised with silver chloride and fixed with sodium thiosulphate. Most negatives were probably sensitized with silver iodide and fixed with potassium bromide (predominant), sodium thiosulphate or potassium iodide. Cobalt and arsenic are present due to the use of smalt in the production of white paper. Copper and zinc are attributed to incorporation of fragments of brass buttons left on the rags used in paper production, observed as small blue spots. The presence of iron, sometimes visible as orange spots, may be from rust off the paper making machines.

The technique and painting used in the earlier wall paintings from the characteristic Christian church in Drustar - close to the river Danube - in Bulgaria, are studied. The fragments of wall paintings used in this study are examined mainly by Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray Analysis (EDS). It is concluded that the technique used was fresco and that the pigments used are common to those used in the Byzantine era.

Drying oils used to formulate oil paints consist primarily of polyunsaturated triglycerides, along with smaller amounts of mono- and diglycerides, free fatty acids, and other compounds such as sterols. The drying of oils occurs through an oxidative crosslinking process that also produces smaller scission products such as short chain fatty acids and diacids. Compounds that are not attached to the crosslinked oil matrix include glycerin, the unreactive free saturated fatty acids and their glycerides, soaps of fatty acids produced by reaction with metal ions from the pigment, and scission products. As the oil ages, additional soluble material is produced by hydrolysis of glyceride esters. These relatively low molecular weight compounds can be extracted by exposure to solvents, as occurs during the cleaning of paintings. Excessive extraction of material canembrittle the paint film and affect the appearance of the paint. This paper examines the types and amounts of compounds extracted from oil paint films as a function of solvent, exposure time, pigment, and age of the paint. The results indicate that solvents vary more in the speed that they extract material than in their selectivity. The composition of the extracts is consistent with predictions based on the mechanisms of the drying and aging processes. These results confirm the importance of using the least polar solvent possible to clean paintings and to formulate varnishes.

Improving the characterisation of archaeological artifacts brings a need to understand better the relationships between composition, structure and properties. With archaeological material there is also a requirement to consider the effects of ageing and environmental interactions in altering the original structure and composition, both in the bulk and at the surface. However, curatorial constraints and, frequently, the condition of the objects preclude the sampling methods required for the most powerful means of structural analysis of materials, the high resolution transmission electron microscope. The samples normally available are small bulk samples and we must find other means of maximising spatial resolution in microchemical and microstructural analysis of both bulk and surface regions of the samples. This paper describes ways in which this is being achieved using the scanning proton microprobe (SPM) with both particle induced X-ray emission (PIXE) and Rutherford back scattered proton (RBS) spectra at resolutions down to ca. 1:m, electron probe microanalysis (EPMA) at 250-300nm, and scanning Auger microscopy (SAM) at resolutions of 10-20nm, but only from the surface layers of atoms in a sample. Examples will be given which demonstrate the contribution that each instrument can make, and that new and useful information is obtained each time resolution is increased. They will also show that structural features can be identified which are invisible to other microscopies. It will also be shown how modern PC-based software has greatly enhanced the mapping capability of all instruments.

The Qionglai kiln site is a famous folk kiln site in Sichuan province, China, of the Tang dynasty (618-907 A.D.). The wares from Qionglai kiln site bear a unique national style and striking local features. A series of opaque green-glazed shards with mild gloss and jade-like feel, excavated from Shifangtang kiln site were selected as test samples. The glaze and body compositions and microstructures of the shards were studied by means of EDXRF, FESEM and DTEM/SAD/EDS. The study has demonstrated that the opaque green glazes from Qionglai kiln site are high-temperature calcia-magnesia-silicate glazes and that typical phase-separated glazes of the droplet structure. The isolated droplets are rich in SiO2 and the matrix is rich in oxides of Ca, Mg, P, Ti and Fe. We have shown that Al2O3 suppresses phase separation. The droplet diameter falls in the range of 0.1-0.4 –m, causing intensive light scattering, and resulting in good opacification and jade-like texture. The green Glaze from Qionglai Kiln Site is one of the earliest phase-separated opaque glazes in China. The study also shows that there is a close relationship of compositions between Qionglai kiln and Changsha kiln.

The unusual appearance of a dark patina on a select group of Egyptian copper alloy objects in the Royal Ontario Museum (ROM) collection has raised the question of both its composition and formation and therefore, its authenticity. The purpose of this project was to determine both the constitution of the patina and the process by which it was formed. A cross section sample from one artifact was analysed using optical, metallurgical and scanning electron microscopy in order to clarify the relationship between the patina layer and the body metal. In addition, energy dispersive spectroscopy was employed to establish the chemical composition of the body metal. Surface samples were removed from all the objects and subjected to x-ray diffraction in order to identify the crystalline compounds present. Fourier transform infra-red spectroscopy was used to establish the presence of any organic compounds in the surface samples. Although further analysis is required, the results of the research suggest that the patina may have been formed as a result of a modern cleaning treatment possibly followed by an artificial re-patination treatment.

Finds of metallic copper from various primary smelting sites in the Sia valley in Cyprus have been analysed by ICP-OES for their composition and by optical and electron microscopy for metallography. Results show a characteristic pattern of impurities for each of the sites examined which allow an assignment to specific types of ore body and geological matrix. Different zones of the Cyprus Ophiolite Complex were exploited in different periods in antiquity, but these results show different types could be exploited contemporaneously within a specific period, especially during the first millennium BC. One location in this area, Agia Varvara-Almyras, an Iron Age copper smelting site with the only complete chain of operation recorded in ancient Cypriote metallurgy, is used to show how analytical work can guide future field surveys to find ancient furnaces, slag heaps and mines. The ultimate goal of the project is to extend it to reconstruct the complete history of copper production in a well-defined mining district over the last 4000 years.

This paper examines artifact distributions and chemical analysis of anthropogenic sediments by ICP-AES spectroscopy from the main civic-ceremonial plaza at the Late Classic (ca. AD 700-900) site of El Coyote in northwestern Honduras. Based on ethnoarchaeological comparisons drawn from a phosphate study of plaza soils in the nearby modern-day town of Petoa, spatial aspects of the organization of communal feasting are inferred for El Coyote.

In this work, pilot cleaning interventions applied by a wet micro-blasting method on architectural surfaces of three historic buildings in marble and porous stone were evaluated in situ and in the laboratory. The investigation was performed on characteristic stone surfaces (marbles and porous stone) of the following historic buildings: Athens Academy and National Library of Greece in Athens center polluted urban environment and Bank of Greece in Piraeus marine environment. The materials of the facades were characterized, and the mechanism of decay was diagnosed. In addition, the cleaning method's efficiency was evaluated based on the acceptability of the alteration of the cleaned architectural surfaces. Criteria were both aesthetic and physico-chemical. In particular, the architectural surfaces were examined in situ by the means of fiber optic microscopy, infrared thermography and colorimetry. In the laboratory, methods of investigation were optical microscopy, X-ray diffraction, scanning electron microscopy with energy dispersion by X-ray analysis, mercury intrusion porosimetry, Fourier transform infrared spectroscopy, conductivity and pH measurements. The majority of measurements and analyses were applied before and after the pilot cleaning interventions. Finally, the results of this study contribute to the development of an integrated methodology for the assessment of cleaning interventions applied on architectural surfaces.

Ethyl silicate-based consolidants are used to restore strength to degraded stones. One of the limitations of strength development using these products is their reported cracking behavior during drying. Particle Modified Consolidants (PMC) consist of a silicate matrix plus colloidal oxide particles. The presence of particles physically limits the silicate network from shrinking under capillary pressures, and thereby reduces strength loss during drying. In addition, the network maintains a higher permeability, because the dried consolidants remains porous. When the particles used are pigments, it is also conceivable to adjust the consolidant color. Moreover, a careful choice of particles should allow matching the thermal dilatation of the consolidant to that of the stone. An important limitation to further development of PMC has been the ability to avoid particle agglomeration in the dispersion. When agglomerates are present, not only do they increase the viscosity but they also can block pore entrances, preventing consolidant fromentering the stone. In this work we demonstrate the feasibility of adsorbing nano-silica particlesonto pigment particles to create a steric barrier to agglomeration. Rheology and density measurements confirm that the resulting dispersion is fluid and stable against settling. The consolidant readily penetrates Ohio Massilian sandstone, providing improved strength, stiffness, and salt resistance, compared to a commercial silicate consolidant.

Cement based mortars used for historic masonry restoration presented unsatisfactory results, due to their chemical and physico-mechanical incompatibility to original buildings. In the present research, several syntheses of restoration mortars are produced using traditional techniques and materials such as binders (aerial and natural hydraulic lime), pozzolanicadditives (natural and artificial pozzolanas) and aggregates (sand and crushed brick). The technical characteristics of the mortars were determined using mechanical tests (compressive and flexural) and mercury intrusion porosimetry measurements at the time of 1, 3, 9, 15 months of curing. Water absorption measurements were performed at the time of 9 and 15 months curing, in order to evaluate mortars microstructural characteristics, their rate of water absorption and the total percentage of absorbed water. The aerial lime - artificial pozzolana mortar presented the best mechanical and microstructural performance. Hydraulic mortars acquired the maximum of the mechanical strength in 1 month, lime - pozzolana mortars in 3 months while aerial lime mortars continue to gain mechanical strength even in 15 months curing. Furthermore, the use of ceramic aggregates produces lightweight and elastic mortars, compatible to historicones.

Roman Coinage suffered from severe debasement during the 3rd century AD. By 250 AD., the production of complex copper alloy (Cu-Sn-Pb-Ag) coins with a silvered surface, became common practice. The same method continued to be applied during the 4th century AD for the production of a new denomination introduced by Diocletian in 293/4 AD. Previous analyses of these coins did not solve key technological issues and in particular, the silvering process. The British Museum kindly allowed further research at Bradford to examine coins from Cope's Archive in more detail, utilizing XRF, SEM-EDS metallography, LA-ICP-MS and EPMA. Metallographic and SEM examination of 128 coins, revealed that the silver layer was very difficult to trace because its thickness was a few microns and in some cases it was present under the corrosion layer. Results derived from the LA-ICP-MS and EPMA analyses have demonstrated, for the first time, the presence of Hg in the surface layers of these coins. A review of ancient sources and historic literature indicated possible methods which might have been used for the production of the plating. A programme of plating experiments was undertaken to examine a number of variables in the process, such as amalgam preparation, and heating cycles. Results from the experimental work are presented.

The composition and microstructure of Cizhou monochrome overglaze enamels, the first known form of overglazed enamels in China, and green lead glazes from Guantai kiln were determined. Although microstructure and thickness of the enamels were very similar to those found for the single layer lead glazes, lead contents were lower. Enamels from the later part of the twelfth century formed a narrower compositional grouping than the lead glazes, indicating that increased control of the technology was attained. The monochrome enamels are thicker and have a composition distinct from that published for later painted enamels from sites other than Guantai. Increased viscosity and decreased values of thermal expansion coefficients were calculated for Guantai enamels relative to the glazes. An attempt to promote adhesion and reduce crawling may have caused the use of lower lead in the enamels relative to the single layer lead glazes.

The two most frequently mentioned mechanisms used to explain the severe damage that occurs when a porous material, containing the anhydride phase of sodium sulfate, is exposed to either water or rising humidity are critically reviewed. Both derivations are presented along with their underlying hypotheses. Critical differences are discussed and it is concluded that crystallization pressure is the relevant mechanism. In effect however, it is shown that the expressions obtained both for crystallization pressure and hydration pressure are quite similar.

A museum fire in 1958 severely damaged a Monet “Water Lilies” (1916-1926) painting that was on display. The surface of the painting is very dark with areas of blistering and charring. Over the years, traditional techniques have been found to be ineffective at removal of the soot and char from the surface. The painting, which is now in the care of the New York University (NYU) Conservation Center of the Institute of Fine Arts, was the subject of a study to determine if atomic oxygen treatment could remove the soot and char without damaging the fragile painting underneath. For test purposes, a small chip of paint was removed from the edge of the painting by a conservator at NYU and supplied to NASA Glenn Research Center for atomic oxygen treatment and analysis. The diffuse spectral reflectance, at three locations on the paint chip, was monitored at intervals during the atomic oxygen treatment process. Photo documentation of the chip during treatment was also performed. The color contrast was calculated from the spectral reflectance data as a function of treatment duration. Results of the testing indicated that the contrast improved as a result of the treatment, and the differentiation of colors on the surface was significantly improved. Soot and char could be removed without visibly affecting the gross surface features such as impasto areas. These results indicate the feasibility for the treatment of the “Water Lilies” painting.