THE ROLE OF TECHNICAL AND NATURAL SCIENCES IN STONE MONUMENTS CARE

Stone monuments maintenance requires the systematic approach which should be based on the cooperation among specialist through more branches, especially from humanities, natural and technical sciences. The main aim of this article is to present the benefit of the cooperation among geologists and civil engineers and share preliminary results of the Czech Ministry of Culture project DG20P02OVV021 “Stone surface topography and its application in stone element restoration field”. Historic stone surfaces often contain stonemasons tool traces as an undoubtable part of historical monument value. The study and protection of the testimony of past is therefore very important. As a part of our project, we are conducting field and laboratory research of historic stone surfaces bearing the original tool traces. The studied area is the Prague urban conservation zone for its stone monuments richness from Romanesque to present days. First, the geological research of the stone masonry surface is conducted in the cooperation with archaeologists. The tool traces are documented, and the state of stone is described. Because of the negative influence of weathering processes on the stone durability, respectively tool traces, we decided to monitor the chosen historical stone surface using the hyperspectral analysis. Based on the analysis results we will be able to better understand the behaviour of stone surface and traces on it during the time.

Non-Invasive Assessment of PVA-Borax Hydrogel Effectiveness in Removing Metal Corrosion Products on Stones by Portable NMR

The cleaning of buildings, statues, and artworks composed of stone materials from metal corrosion is an important topic in the cultural heritage field. In this work the cleaning effectiveness of a PVA-PEO-borax hydrogel in removing metal corrosion products from different porosity stones has been assessed by using a multidisciplinary and non-destructive approach based on relaxation times measurement by single-sided portable Nuclear Magnetic Resonance (NMR), Scanning Electron Microscopy—Energy Dispersive Spectroscopy (SEM-EDS), and Raman Spectroscopy. To this end, samples of two lithotypes, Travertine and Carrara marble, have been soiled by triggering acidic corrosion of some copper coins in contact with the stone surface. Then, a PVA-PEO-borax hydrogel was used to clean the stone surface. NMR data were collected in untreated, soiled with corrosion products, and hydrogel-cleaned samples. Raman spectroscopy was performed on PVA-PEO-borax hydrogel before and after cleaning of metal corrosion. Furthermore, the characterization of the dirty gel was obtained by SEM-EDS. The combination of NMR, SEM-EDS and Raman results suggests that the mechanism behind the hydrogel cleaning action is to trap heavy metal corrosion products, such as Cu2+ between adjacent boron ions cross-linked with PVA. Moreover, the PVA-PEO-borax hydrogel cleaning effectiveness depends on the stone porosity, being better in Carrara marble compared to Travertine.

Research on the Mechanism of Surfactant Warm Mix Asphalt Additive-Based on Molecular Dynamics Simulation

Warm mix asphalt (WMA) technology can bring certain environmental and technical benefits through reducing the temperature of production, paving, and compaction of mixture asphalt. Recent studies have shown that some WMA additives are able to reduce the temperature by increasing the lubricating properties of asphalt binder.-based on the tribological theory, this paper studied the mechanism of adsorbing and lubricating film of base asphalt and WMA on the surface of stone by molecular dynamics (MD) simulation method, and the effect of surfactant WMA additive on the lubrication performance of the shear friction system of “stone–asphalt–stone”. The model of base asphalt lubricating film, including saturates, aromatics, resin and asphaltene, as well as the model of warm mix asphalt lubricating film containing imidazoline-type surfactant WMA (IMDL WMA) additive molecule, were established. The shear friction system of “stone–asphalt–stone” of base asphalt and warm mix asphalt was built on the basis of an asphalt lubrication film model and representative calcite model. The results show that the addition of IMDL WMA additive can effectively improve the lubricity of asphalt, reduce the shear stress of asphalt lubricating film, and increase the stability of asphalt film. The temperature in the WMA lubricating film rises, while the adsorption energy on the stone surface decreases with the increase of shear rate, indicating that the higher the shear rate is, the more unfavorable it is for the WMA lubricating film to wrap on the stone surface. In addition, the shear stress of the WMA lubricating film decreased with increasing temperature, while the shear stress of the base asphalt lubricating film increased first and then decreased, demonstrating that the compactability of the asphalt mixture did not improve linearly with the increase of temperature.

DEVELOPMENT OF WOOD GRINDING. 3. FURTHER TESTING OF GRINDING MODELS

"The study is the continuation of a sequence of works devoted to describing the mechanisms occurring during stone grinding of wood. This part was aimed at further testing of pressurised grinding of spruce wood, which was conducted under controlled laboratory conditions. Testing of the developed theoretical model for power ratio (Pc/Pt) versus energy specific production (Ġw/Pt) produced linears for data representing constant wood moisture content. However, the linears showed almost identical results for fresh woods, and also for drier wood, e.g. wood containing saturated fibres and air-dried wood, although one would expect some differences due to the widely varying constant moisture, from 65% to 15% moisture content. Simplification of the model resulted in (cw + X cm) ΔTp-w ≈ Pt / Ġw, and it led to specific linears, when the members as such were correlated between themselves at several constant wood moisture contents. The results were briefly as follows. Increasing wood feed rate – 0.7, 1.0 and 1.3 mm/s – decreased the specific energy requirement, while increased stone surface speed – 20 and 30 m/s – increased it. The left-hand member or the “X-factor” as named in this context, correlated with the right-hand member or the specific energy requirement and resulted in declining linears. The lower the wood moisture content – 65, 58, 44, 28 and 15% – the smaller was the linear declination, and also the difference due to stone surface speed. The application of an energy balance could be useful in searching for a working wood grinding model. Such a model would enable critical examination of wood grinding conditions. Also, it would help understanding the mechanism of various factors, such as grinding parameters, wood properties and stone burr and sharpness. It seems that there are factors that are not known well enough for further development of grinding. Shower water flow and temperature affect the stone surface temperature as known, but their significance for the energy balance or grinding mechanism are not known. Also, the thin film of pulp slurry between the stone surface and the heat activated wood layer is evidently a significant factor that is connected to the local energy transfer. "

Properties of Cement with Photocatalytic Composite Material

The paper presents the results of the determination of the effect of a photocatalytic composite material (PCM) with the composition SiO2‒TiO2 on the main properties of white Portland cement: heat release during hydration, phase composition and microstructural features of cement stone, pressure strength and self-cleaning ability. PCM was synthesized by a sol-gel method based on tetrabutoxytitanium and finely dispersed diatomite powder and 15% cement was added instead. The presence of PCM in the cement system provided the reduction of the induction period of cement hydration, consolidation of the microstructure of the cement stone with the products of the pozzolanic reaction, the ability to photocatalytic self-cleaning of the cement stone surface.

A Novel Polishing Paste (Mollusk Shells) for Poly (Methylmethacrylate)

Objective. The aim of this study was to evaluate the effectiveness of a mollusk shells polishing paste (Donax obesulus) on the surface roughness of acrylic resin poly (methylmethacrylate) (PMMA). Methods. This study was an in vitro experimental design. A sample size of 72 was divided into 4 groups of n = 18 each. PMMA specimens were prepared and polished with the evaluated pastes using mollusk shells (experimental paste) and pumice stone. Surface roughness (μm) was measured using a profilometer after polishing the PMMA samples. The paired Wilcoxon test was used to evaluate the roughness values at 24 and 48 hours. Then, the Mann–Whitney U test was used to identify the differences between the effects of the two groups evaluated with a significance level of α = 0.05. Results. The roughness difference between the pastes under study was compared, and mean values of 0.50 ± 0.07 μm (mollusk shell paste group) and 0.45 ± 0.12 μm (pumice group) were obtained. No statistically significant differences were found between the experimental paste and pumice stone paste p = 0.309 . The specimens polished with pumice stone paste showed higher roughness values, while those polished with the experimental paste exhibited the lowest values. Conclusion. In summary, mollusk shells polishing paste had a decrease in roughness values compared to pumice, although these differences were not statistically significant.

Consolidation and Adhesion of Pictorial Layers on a Stone Substrate. The Study Case of the Virgin with the Child from Palazzo Madama, in Turin

The study and the restoration of a polychrome limestone statue representing the Virgin with the Child, from Palazzo Madama in Turin (NW Italy) offered interesting conservation issue related to the polychromy on stone. To preserve the pictorial layers, it was necessary to re-establish the cohesion among the different polychrome layers (original and repainted) and the adhesion between polychrome film and the stone substrate. Particular attention was paid to the choice of intervention materials, selected through a preliminary survey of the scientific literature, and then verified by laboratory tests (tape test, colorimetric test, and permeability test). The most suitable product should to be able to penetrate porosity, to consolidate the layers, to make the pictorial film adhere with the stone surface, and to avoid changes in the colour and in the permeability. The material chosen also had to ensure compatibility with the cleaning method that could only take place after the consolidation of the pictorial layers due to the problematic state of preservation. A range of products, characterised by their small particle size and low viscosity, was tested, and a micro-acrylic resin was selected and successfully applied on the polychromy of the sculpture.

A multi-analytical diagnostic approach to study patinas, trace of colours and degradation process on the stone surface of a Renaissance Piety from the Museum of Ancient Art (Castello Sforzesco, Milan)

Alteration dark patinas and traces of colours present on the surface of a marble Piety dating to the Renaissance period and stored at the Castello Sforzesco-Museum of Ancient Art (Milan, Italy) were studied and chemically characterized. For this purpose, a multi-analytical approach based on both portable non-invasive (XRF and colorimetric measurements) and micro-invasive techniques (FTIR/ATR and SEM-EDS), has been applied. The statue has been recently submitted to a restoration before an exhibition at the Louvre Museum and the original appearance of the marble surface recovered thanks to the patina removal. Through the analytical characterization carried out before and after the marble cleaning, the presence of a degradation layer composed by gypsum was evidenced on the stone surface. The origin of this layer is probably ascribable to the exposure of the statue to outdoor environment and interaction with atmospheric pollution. The chemical nature of the coating applied at the end of 19th century and responsible for the patina formation was hypothesized. Finally, the use of pigments originally applied by means of an organic binder was also highlighted.

Synthesis, characteristics, and photocatalytic activity of zinc oxide nanoparticles stabilized on the stone surface for degradation of metronidazole from aqueous solution

Background: The presence of antibiotics such as metronidazole in wastewater even at low concentrations requires searching for a suitable process such as advanced oxidation process (AOP) to reduce the level of pollutants to a standard level in water. Methods: In this study, zinc oxide (ZnO) nanoparticles were synthesized by thermal method using zinc sulfate (ZnSO4 ) as a precursor, then, stabilized on stone and was used as a catalyst, in order to degrade metronidazole by photocalytic process. Effective factors on the removal efficiency of metronidazole including the initial metronidazole concentration, contact time, pH, and 0.9 gL-1 ZnO stabilized on the stone surface were investigated. Results: The X-ray diffraction (XRD) studies showed that the synthesized nanomaterials have hexagonal Wurtzite structure. Also, scanning electron microscopy (SEM) analysis revealed that the average crystalline size of the synthesized ZnO particles was in the range of 1.9-3.2 nm. The spectra represented a sharp absorption edge at 390 nm for ZnO nanoparticles corresponding to band gap of 3.168 eV. The BET-BJH specific surface area of the synthesized ZnO nanoparticles was 25.504 m2 /g. The EDS spectrum of ZnO nanoparticles showed four peaks, which were identified as Zn and O. The maximum removal efficiency was 98.36% for the synthetic solution under a specific condition (pH = 11, reaction time = 90 minutes, ZnO concentration = 0.9 gL-1, and the initial concentration of metronidazole = 10 mgL-1). The photocatalytic degradation was found to follow pseudo-first-order degradation kinetics. Conclusion: Therefore, the ZnO nanoparticles synthesized by thermal decomposition are suitable and effective photocatalytic materials for degradation of pharmaceutical contaminants.