Search

Although nuclear magnetic resonance (NMR) is recognized as a powerful tool in many areas of research, among the investigative techniques used in the field of cultural heritage its application is still largely unknown. One of the reasons for this is that artifacts are complex heterogeneous systems whose analysis requires a multi-disciplinary approach. In addition, major drawbacks in the analysis of objects belonging to cultural heritage are their limited quantity, number of samples collected from the artifact, and their immovability. Consequently, a methodological approach where non-destructive, and possibly non-invasive techniques are used, is advisable. In recent years, thanks to the development of portable instruments, there has been an increasing use of the NMR methodology in the cultural heritage field. The use of portable NMR has allowed us to study several materials in the cultural heritage, such as frescoes, stones, wood, paper, and paintings, to address the challenges in monitoring dampness in historical masonries, to evaluate the penetration depth of a hydrophobic treatment into a porous material, and to study of the effect of cleaning procedures on artifacts. In this paper, recent studies illustrating the potential of NMR portable methodologies in this field of research are reported.

Water release is a crucial aspect when considering cleaning effects on water-sensitive materials. In conservation practice, a water-based cleaning method which limits water release is very often needed. Unfortunately, this is not accompanied by an appropriate measure of the effectively released water. In this paper, water release has been measured by comparing traditional cleaning formulations, such as paper pulp and sepiolite, with several gar gel formulations, used by both Italian and European conservators. The assessment has been carried out by the gravimetric method, using three different stone material specimens as reference: Noto calcarenite, Manciano sandstone and Black Bergamo limestone, whose porosity values and distributions are known. Moreover, water distribution has been evaluated by portable NMR tests. Different commercial agar gel products (Bresciani, CTS, Sigma), having different concentrations (3, 4, and 5%), application modes (rigid at room T or fluid warm gels, with and without inserting Japanese tissue paper), and geometry (horizontal in gravity force direction or vertical), have been compared to obtain a full scenario among different water release mechanisms present in real conservation works. The paper faces the important issue of preparing reproducible chemical or water pads as well, useful for further research aimed at comparing cleaning effects in heritage conservation. The most interesting quantitative results can be summarized as follows. The water release measured from paper pulp and sepiolite was found to be 2 to 4 times higher than from any tested agar gel. Water release decreases by increasing agar concentration; an increase in the agar concentration by 1% induces a decrease in water release in the range 16.98–66.88 g depending on the stone; the increase from 4% to 5% is more obvious with respect to that from 3% to 4%. It is possible to assess the effect of the presence of Japanese paper, which is able to reduce the water release from 18 to 76%, depending on the stone and on the agar used. The gravimetric results were also used in the preliminary calibration tests of a contact probe named System Unit Salinity Index (SUSI), recently patented and useful in providing humidity and salinity indexes in a given porous material.

Sustainability of leather lies in how the hide, a sustainable, naturally renewable, raw material, is processed. Tanning chemistry has been a limiting factor for leather sustainability. In this study, a host-guest synthesis strategy was selected to modify one of the most widely used tanning polymer, MIDA DD, and obtain a new hybrid tanning system containing β-cyclodextrin, and leather drastically less impactful on the earth and people. Poly[2]pseudorotaxane Side-Chain Complexes (PSCCs) have been obtained by threading β-cyclodextrin units onto the side-chains of the commercial MIDA DD. The formation of PSCCs in aqueous solution was investigated by using 1D NMR, ATR-FTIR and TGA experiments. The ability of PSCCs to stabilize the collagen matrix was tested at laboratory and industrial pilot scale by micro-DSC, ATR-FTIR and solid-state NMR techniques. The physical and mechanical performance of the obtained crust leather was determined by standard tests used in tanning industry. Side-chain poly[2]pseudorotaxanes showed better tanning performances than the fossil-based MIDA DD, the most effective supramolecular tannins being obtained by mixing β-CD and MIDA DD in ratios close to 1/1 (w/w). The new tanning mixtures allow for significantly reducing both the amount of fossil-based MIDA-DD polymer in the current tanning processes (by 45%) and the free bisphenol content in leather crust (by more than 80%) due to the presence of bio-based β-CD in the composition of the new supramolecular tanning agents. The findings disclosed here pave the way for the CDs’ employment in improving the sustainability of tanning processes.