New ambient temperature liquid calcium alkoxides, [Ca(O(CH2CH2O)3CH3)2] (1) and [Ca(O(CH2CH2O)3CH2CH3)2] (2), together with [Ca(OCH2C(CH3)3)2] (3), were synthesised by reaction of ammonia-activated calcium with the appropriate alcohol. Their potentiality as stone consolidant products was investigated and compared with those of other alkoxides: [Ca(OCH2CH3)2(CH3CH2OH)4] (4), [Ca(OCH3)2] (5), [{Ca(OCH2CH2OCH3)2}9] (6), already described in the literature. Reaction of 1–3 with the atmosphere was studied, final products analysed and kinetic pathways investigated. The reaction produces CaCO3 and the vaterite/calcite ratios observed in the coatings generated from isopropyl alcohol solutions of 1–6 were found to considerably vary with the alkoxide precursor, which has a strong influence also on the morphology of the produced films. Furthermore, their efficiency as stone consolidants was tested by ultrasound measurements.
Wall paintings and architectural surfaces in outdoor environments are exposed to several physical, chemical and biological agents, hence they are often treated with different products to prevent or slow down their deterioration. Among the factors that have to be taken into account in the selection of the most suitable treatment for decorated surfaces, the aesthetic compatibility with the substrate is of great importance in the cultural heritage field; minimizing colour variation after treatment application is a crucial issue in particular for painted surfaces. In the framework of the European Project Nanomatch the color variation induced on wall painting mock-ups by the two innovative consolidants (calcium alkoxides) developed was evaluated using colorimetry in comparison with two traditional products. In this work these innovative consolidants have been also tested in combination with two commercial biocides and the results of colorimetric measurements discussed. Moreover, as the univariate approach didn’t allow to draw clear conclusions on the relation between the different sources of data variability, multivariate analysis was performed on colorimetric data. Principal Component Analysis and multi-way Parallel Factor Analysis (PARAFAC) were successfully applied to colorimetric data to investigate the short-term effects of the application of different consolidants on wall painting surfaces, making it possible to study at the same time the different sources of data variability, i.e. treatments, painting techniques, pigments. Finally, a ranking list of the treatments under study in terms of colour variation induced on the surface was established, in function of the painting technique and pigment, taking also in consideration the combination consolidant/biocide. In particular, given the true multi-way nature of the data, PARAFAC model turned out to be extremely useful in the study of the dependence of colour variation on pigments, a critical issue for painted surfaces, that was not clear using univariate approach. Multivariate approach to colorimetric data and especially 3-way PARAFAC method resulted a powerful technique to evaluate in short-term the color compatibility of consolidants for wall paintings, improving data interpretation and visualization, and thus outperforming the univariate statistical analysis.
The combination of multiple physical, chemical and biological factors causes the weathering of limestone used in the field of cultural heritage. To overcome the limitations of traditional consolidating products and to meet the requirements of the historical building substrates, during the European collaborative project NANOMATCH, alkaline earth alkoxides were developed and studied as consolidating agents for limestone. Among these new products, calcium ethoxide, with the formula Ca(OEt)2, was chosen for this study and investigated in depth as an alternative consolidating treatment. It was first characterized through a study of the carbonation process: its kinetics, reaction pathway and the evaluation of formed mineralogical phases. Subsequently, it was applied on limestones with different total open porosity to test its performance as a consolidating agent. The compatibility and the efficiency of the treatment were investigated with a multi-technique approach and compared with results obtained with a reference product, based on nanolime. This study indicates that calcium ethoxide shows better results with respect to the reference product, both in terms of compatibility and consolidation effect.
Calcium ethoxide nanosuspension, a consolidating product developed during the European Nanomatch project, is here modified by adding two different solvents, 2-butanol and n-butylacetate, chosen for their different boiling points with respect to ethanol, the solvent employed in a previous work to dilute the original product. Fourier transform infrared spectroscopy (µFT-IR) was used to understand how the presence of these new solvents can influence the kinetics of the carbonation process and the pathway reaction. Furthermore, coatings derived from nanosuspensions were maintained for specific time intervals at controlled relative humidity conditions (RH = 50% and RH = 90%); the formed mineralogical phases were characterized by µFT-IR and X-ray diffraction (XRD). Results indicate that the used solvents can influence the kinetic and reaction pathways, while the phases formed at the end of the carbonation process are influenced by both solvents and RH conditions. The effectiveness of calcium ethoxide based product diluted in 2-butanol and n-butylacetate as limestone consolidants was evaluated with drilling resistance measurement system (DRMS) and ultrasound pulse velocity (UPV). The impact on color coordinates was also assessed. The results were compared with those obtained with the same product diluted in ethanol and a commercial nanolime. The use of these solvents gave different and better results in terms of efficacy.