One-step fabrication of robust and durable superamphiphobic, self-cleaning surface for outdoor and in situ application on building substrates.

HYPOTHESIS: Water and oil inhibition treatment is essential for protecting natural and artificial stone surfaces. Bioinspired super-antiwetting surfaces with "lotus effect", together with superoleophobic properties, can be achieved combining very low-surface-energy materials and suitable surface roughness. Exploiting the natural roughness of stone surfaces, the simple and inexpensive fabrication of superamphiphobic surfaces through the coating dispersion deposition is expected. It seems the ideal method for the safeguard of contemporary and historical constructions, since the physical, chemical and aesthetic properties can be maintained. EXPERIMENTS: The new coating agent (3-perfluroether-amidopropylsilane) was synthesized via one-step amidation. Hydrophobicity, robustness and environmental durability were systematically studied on stone surfaces through several tests: contact angle (CA), contact angle hysteresis (CAH), water inhibition efficiency, vapor diffusivity, chemical and mechanical resistance, artificial and field-exposure ageing. FINDINGS: The as-prepared coating demonstrated superamphiphobicity (oil and water CA > 150° with CAH < 10°) on stones with low and high porosity. Moreover, it manifested very high water inhibition efficacy while maintaining high vapor diffusivity and aesthetic properties of substrates. The superhydrophobic coating showed good robustness towards corrosive chemical agents, peeling, mechanical abrasion, water immersion and environmental weathering, thereby permitting various outdoor applications, including stone protection in rainy regions where acid rain is also present.

Identification of complex structures of paintings on canvas by NMR: Correlation between NMR profile and stratigraphy.

Paintings on canvas are complex structures created by superimposing layers of different composition. Investigations on the structure of these artworks can provide essential information on their state of conservation, pictorial technique, possible overpaintings, and in planning a proper conservation plan. Standard methods of investigation consist in sampling a limited number of fragments for stratigraphic analyses. Despite the recognized validity of these methods, they are affected by evident limitations. Nuclear magnetic resonance (NMR) profiling, often named NMR stratigraphy, is an NMR relaxometry technique applied by single-sided portable devices developed to overcome the disadvantages of microinvasive stratigraphic analyses. The potential of this approach on artworks, including wall paintings and a few examples of painted canvas, is described in the literature. In this study, NMR profiles of painting on canvas were examined by analyzing transverse relaxation time data by T2 quasi-continuous distributions and the results compared with standard stratigraphic cross-sections analysis. Combining signal intensity and T2 quasi-continuous distributions, the identification of textile, preparatory, and paint layers was enhanced. The diction "NMR stratigraphy" for these inhomogeneous layered artworks is also discussed. Indeed, unlike the stratigraphic cross-sections, NMR profiles provide information on a volume (flat slice), rather than on a surface, and the collected signal can derive from nonuniform and partially overlapping layers. This study paves the way for extensive investigations on relaxation time quasi-continuous distributions in various binder/pigment mixtures in order to improve the reliability of NMR profile as an innovative, non-invasive, and nondestructive method for analyzing paintings on canvas.

Dual Functionalities of Few-Layered Boron Nitrides in the Design and Implementation of Ca(OH)2 Nanomaterials toward an Efficient Wall Painting Fireproofing and Consolidation.

Preserving ancient wall paintings from damage has become a challenge over the years. Nanosized calcium hydroxide (Ca(OH)2) has been identified as a promising material to preserve wall paintings. However, the synthesis of nanosized Ca(OH)2 is extremely difficult. Here, we demonstrate a breakthrough in wall painting protection enabled by boron nitride nanosheets (BNNSs) through strategic synthesis Ca(OH)2-BNNS nanohybrids using an aqueous method. The BNNS have two significant functionalities in the design and implementation of the Ca(OH)2 nanomaterials. First, the introduction of BNNS results in the successful synthesis of uniform and nanosized Ca(OH)2 (∼80 nm) in the nanohybrids, which can be attributed to the supersaturation-induced "etching-stripping" mechanism. More interestingly and importantly, a unique gradient penetration structure is strategically formed when applying Ca(OH)2-BNNS hybrids on the wall paintings, i.e., the BNNS-rich layer will be at the surface of wall painting, whereas Ca(OH)2 nanomaterials prefer to penetrate deep in to the wall paintings. This gradient structure will allow the BNNS-rich layer to protect the wall paintings from fire, which is the first report to date among the protection materials for wall paintings; at the same time, nanosized Ca(OH)2 shows superior wall painting consolidation strength compared to commercial Ca(OH)2 material. These results endow new applications of the newly emerging two-dimensional nanomaterials for protecting cultural heritage.

An Environmental Friendly Fluorinated Oligoamide for Producing Nonwetting Coatings with High Performance on Porous Surfaces.

The changes in the surface wettability of many materials are receiving increased attention in recent years. It is not too hard to fabricate resistant hydrophobic surfaces through products bearing both hydrophobic and reactive hydrophilic end groups. More challenging is obtaining resistant nonwetting surfaces through noncovalent reversible bonds. In this work, a fluorinated oligo(ethylenesuccinamide), soluble in solvent benign for operators and environment, has been synthesized. It contains two opposite functional groups (perfluoropolyether segments and amidic groups) (SC2-PFPE) that provide water repellency while hydrophilicity is retained. Its performance has been tested on porous calcarenite and investigated by magnetic resonance imaging, water capillary absorption, and vapor diffusivity tests. The results demonstrate that SC2-PFPE modifies the wettability of porous substrates in a drastic and durable way and reduces the vapor condensation inside the pore space due to the perfluoropolyether segments that act at the air/surface interface.

Stone porosity, wettability changes and other features detected by MRI and NMR relaxometry: a more than 15-year study.

Scientists applying magnetic resonance techniques to cultural heritage are now a quite vast and international community, even if these applications are not yet well known outside this community. Not only laboratory experiments but also measurements in the field are now possible, with the use of portable nuclear magnetic resonance (NMR) instruments that enable non-invasive and non-destructive studies on items of any size, of high artistic and historical value as well as diagnosis of their conservation state. The situation was completely different in the second half of the 1990s when our group started working on applications of NMR to cultural heritage, by combining the knowledge of NMR for fluids in porous media at the University of Bologna, with the skilfulness of the chemists for cultural heritage of CNR and University of Florence, and Safeguarding Cultural Heritage Department of Aosta. Since then, our interest has been mainly devoted to develop methods to study the structure of pore space and their changes as a result of the decay, as well as to evaluate performance of the protective and conservative treatments of porous materials like stone, ceramic, cements and wood. In this paper, we will review the pathway that led us from the first tentative experiments, in the second half of the 1990s to the current work on these topics.

Water vapor absorption in porous media polluted by calcium nitrate studied by time domain nuclear magnetic resonance.

Nuclear magnetic resonance relaxation analysis of liquid water (1)H nuclei in real porous media, selected for their similar composition (carbonate rocks) and different pore space architecture, polluted with calcium nitrate, is presented to study the kinetics of water condensation and salt deliquescence inside the pore space. These phenomena are responsible for deterioration of porous materials when exposed to environmental injury by pollution in a humid atmosphere. The theory is well described for simple pore geometries, but it is not yet well understood in real porous media with wide distributions of pore sizes and connections. The experiment is performed by following in time the formation of liquid water inside the pore space by T(1) and T(2) relaxation time distributions. The distributions allow one to see the effects of both the salt concentration and the pore space structure on the amount of water vapor condensed and its kinetics. It is shown that, for a given lithotype, even with different amounts of pollutant, the rate-average relaxation time T(1ra) tends to increase monotonically with NMR signal, proportional to the amount of liquid water. T(1ra) is often inversely associated with surface-to-volume ratio. This suggests a trend toward the filling of larger pores as amounts of liquid water increase, but it does not indicate a strict sequential filling of pores in order of size and starting with the smallest; in fact, relaxation time distributions show clearly that this is not the case. Increased amounts of salt lead to both markedly increased rates and markedly increased amounts of water absorption. NMR measurements of amounts of water, together with relaxation time distributions, give the possibility of information on the effect of pollution in porous materials exposed to humid atmospheres but sheltered from liquid water, even before the absorption of large amounts of moisture and subsequent damage. These phenomena are of importance also in other fields, such as the exploitation of geothermal energy.

Investigating morphological changes in treated vs. untreated stone building materials by x-ray micro-CT.

Calcareous stones have been largely used to build historical buildings. Among these, the calcarenites are usually characterized by a high content of calcite and a high open porosity, which make them very sensitive to the weathering caused by physical and chemical agents. In order to prevent their deterioration and to retard their decay, different protective products-mainly polymers-are applied on the stone artefact surfaces. In this work we apply the methodology tested in a preliminary study to investigate the morphological changes of the internal structure of a biocalcarenite (Lecce stone) by micro x-ray computed tomography (micro-CT). The porosity and other morphological parameters of the rock before and after the conservation treatment were calculated on a significant number of samples. The Student's t test was applied for statistical comparison. The results reveal that the treatment with Paraloid B72 (PB 72) is homogenously distributed and causes small changes to the natural properties of the rock, whereas the application of a fluoroelastomer (NH) causes an appreciable decrease in porosity and variation in terms of wall thickness distribution, probably resulting from its inhomogeneous distribution.

Nuclear magnetic resonance for cultural heritage.

Nuclear magnetic resonance (NMR) portable devices are now being used for nondestructive in situ analysis of water content, pore space structure and protective treatment performance in porous media in the field of cultural heritage. It is a standard procedure to invert T(1) and T(2) relaxation data of fully water-saturated samples to get "pore size" distributions, but the use of T(2) requires great caution. It is well known that dephasing effects due to water molecule diffusion in a magnetic field gradient can affect transverse relaxation data, even if the smallest experimentally available half echo time tau is used in Carr-Purcell-Meiboom-Gill experiments. When a portable single-sided NMR apparatus is used, large field gradients due to the instrument, at the scale of the sample, are thought to be the dominant dephasing cause. In this paper, T(1) and T(2) (at different tau values) distributions were measured in natural (Lecce stone) and artificial (brick samples coming from the Greek-Roman Theatre of Taormina) porous media of interest for cultural heritage by a standard laboratory instrument and a portable device. While T(1) distributions do not show any appreciable effect from inhomogeneous fields, T(2) distributions can show strong effects, and a procedure is presented based on the dependence of 1/T(2) on tau to separate pore-scale gradient effects from sample-scale gradient effects. Unexpectedly, the gradient at the pore scale can be, in some cases, strong enough to make negligible the effects of gradients at the sample scale of the single-sided device.