The problem of sampling on built heritage: a preliminary study of a new non-invasive method.

The relevance of a risk assessment of the built heritage was clearly justified due to the fact that it acts as a pollutant repository and hazardous pollutants have the capacity to penetrate into materials. However, the limitation of the sampling processes due to the high value of the built heritage makes a correct evaluation difficult. For that reason, in the present work, the potential of agar gels as non-invasive samplers of built heritage deterioration products, like crusts and patinas, was evaluated. Different gels of agar and Carbopol® (as control gel) were applied on these built surfaces considering several factors: the treatment time, the effectiveness of the addition of EDTA (ethylenediaminetetraacetic acid, C10H16N2O8) and its concentration and the use of a buffer at pH 7.5. All these factors were evaluated in order to determine the capacity of these gels as sampling systems under non-controlled atmospheric conditions. The results obtained in the assays were evaluated by visual examination, by evolution of pH and by the most important techniques used in the risk assessment analysis of the built heritage (Raman spectroscopy, scanning electron microscope (SEM)/energy dispersive X-ray (EDX) and inductively coupled plasma mass spectrometry (ICP-MS)). In this evaluation, the agar gels showed an intrinsic capacity as sampler with respect to the gel Carbopol® and thus, the best option between the studied gels consisted on agar gels with 2 % of EDTA and the longest application time. On the whole, the agar gels showed an interesting potential as non-invasive samplers of built heritage deterioration materials which should be studied more in depth.

Spectroscopic study of the degradation products in the holy water fonts in Santa Maria della Steccata Church in Parma (Italy).

Two holy water fonts (dated at the beginning of the XVII century) in the Santa Maria della Steccata Church in Parma (Italy) have recently been restored. Before the intervention, a detailed investigation on their degradation products was carried out to understand the mechanisms of alteration of the materials and to suggest appropriate restoration procedures. The analyses were performed by means of powder X-ray diffraction (XRD), micro-Fourier transform infrared (FTIR) and micro-Raman spectroscopies. Calcite, iron oxides, silicates and sodium chloride (from salted holy water) were found in the red coloured calcarenite. On and under the lead coverings, different lead oxides (mainly massicot), other lead salts (lead basic carbonate, cerussite, plumbonacrite Pb10O(OH)6(CO3)6 and lead-chlorine compounds as laurionite PbOHCl and phosgenite Pb2CO3Cl2) were identified by Raman spectroscopy and XRD. Haematite alpha-Fe2O3, goethite alpha-FeO(OH) and lepidocrocite gamma-FeO(OH) were found on and around the iron hinges. Lead compounds and sodium chloride, through crystallization and solubilization cycles, were responsible for the stone's degradation, whereas the iron corrosion materials on the hinges produced mechanical stress and cracks in the stone. Various suggestions have been given on how to restore these fonts and to remove the causes of damage.

Fluorescence correlation spectroscopy as a tool to investigate single molecule probe dynamics in thin polymer films.

Fluorescence correlation experiments were performed on rhodamine 6G in PDMS spin-coated films on glass surfaces. With polarised excitation, ensemble bleaching of the dye and single molecule intensity fluctuations were observed. From the statistics of single molecule intensity data taken at different positions in the film, correlation functions were calculated. Two modes of motion with exponential decay shapes and correlation times of tau(c) = 0.15 s and tau(c) = 0.7 s could be detected. Potential origins of intensity fluctuations are lateral diffusion, rotational diffusion or intramolecular fluctuations of dyes involving spectral diffusion or photoinduced processes. From the experimental results, lateral diffusion can be ruled out as a motional mode. Single molecule fluctuations are assigned to changes of the molecular configuration of the dyes, which are rigidly bound to the glass. To assess the environmental influence on such molecular motions, the bulk viscosity of the PDMS was varied over two orders of magnitude, leading to changes of tau(c) of the slow mode by a factor of four. This result proves the sensitivity of the single molecule fluctuations to the molecular scale dynamics of the surrounding polymer matrix and makes the correlation time a measure of the local environment of dye probes.

Application of gas chromatography-mass spectrometry analysis to the study of works of art: paint media identification in polychrome multi-material sculptures.

A new gas chromatographic-mass spectrometric procedure for characterizing both drying oils and proteinaceous binders in samples of painted artworks has been developed. Furthermore, a new analytical procedure for analysis of polysaccharide materials through identification of the monosaccharide constituents is proposed. The methods have been applied to characterizing binding media of the different layers of the polychrome surface in the multi-material sculptures from the sanctuary of Santa Maria delle Grazie in Mantova, Italy. It was found that animal glue was the main binder in the priming layer of all statues, whereas more complex mixtures were used in the paint layers. Generally, a drying oil was present, most often linseed oil alone or in combination with other organic binders.

The Strength of Long-Range Forces across Thin Liquid Films.

We present experimental results on the instability of thin liquid polydimethylsiloxane films intercalated between a solid substrate and a liquid surrounding medium. The instability is induced by long-range van der Waals forces across the film. From the characteristic wavelength of the instability and from the apparent contact angle of the equilibrium structures, we deduce an effective Hamaker constant (A132) about 2-3 orders of magnitude higher than what is expected from calculations based on the individual Hamaker constants. With air as the surrounding medium, we obtain the expected values. Copyright 1999 Academic Press.