Durability assessment to environmental impact of nano-structured consolidants on Carrara marble by field exposure tests.

The EU policy of reducing the emissions of combustion generated pollutants entails climate induced deterioration to become more important. Moreover, products applied to preserve outdoor built heritage and their preliminary performance tests often turn out to be improper. In such context, the paper reports the outcomes of the methodology adopted to assess the durability and efficiency of nano-based consolidating products utilized for the conservation of carbonate artworks, performing field exposure tests on Carrara marble model samples in different sites in the framework of the EC Project NANOMATCH. Surface properties and cohesion, extent and penetration of the conservative products and their interactions with marble substrates and environmental conditions are here examined after outdoor exposure for eleven months in four different European cities and compared with the features of undamaged and of untreated damaged specimens undergoing the same exposure settings.

Aragonite crystals grown on bones by reaction of CO2 with nanostructured Ca(OH)2 in the presence of collagen. Implications in archaeology and paleontology.

The loss of mechanical properties affecting archeological or paleontological bones is often caused by demineralization processes that are similar to those driving the mechanisms leading to osteoporosis. One simple way to harden and to strengthen demineralized bone remains could be the in situ growth of CaCO3 crystals in the aragonite polymorph - metastable at atmospheric pressure -which is known to have very strong mechanical strength in comparison with the stable calcite. In the present study the controlled growth of aragonite crystals was achieved by reaction between atmospheric CO2 and calcium hydroxide nanoparticles in the presence of collagen within the deteriorated bones. In a few days the carbonation of Ca(OH)2 particles led to a mixture of calcite and aragonite, increasing the strength of the mineral network of the bone. Scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDS) and Fourier transform infrared (FT-IR) spectrometry showed that aragonite crystallization was achieved. The effect of the aragonite crystal formation on the mechanical properties of the deteriorated bones was investigated by means of X-rays microtomography, helium porosimetry, atomic force microscopy (AFM), and Vickers microhardness techniques. All these data enabled to conclude that the strength of the bones increased of a factor of 50-70% with respect to the untreated bone. These results could have immediate impact for preserving archeological and paleontological bone remains.

Cosolvent gel-like materials from partially hydrolyzed poly(vinyl acetate)s and borax.

A gel-like, high-viscosity polymeric dispersion (HVPD) based on cross-linked borate, partially hydrolyzed poly(vinyl acetate) (xPVAc, where x is the percent hydrolysis) is described. Unlike hydro-HVPDs prepared from poly(vinyl alcohol) (PVA) and borate, the liquid portion of these materials can be composed of up to 75% of an organic cosolvent because of the influence of residual acetate groups on the polymer backbone. The effects of the degree of hydrolysis, molecular weight, polymer and cross-linker concentrations, and type and amount of organic cosolvent on the rheological and structural properties of the materials are investigated. The stability of the systems is explored through rheological and melting-range studies. (11)B NMR and small-angle neutron scattering (SANS) are used to probe the structure of the dispersions. The addition of an organic liquid to the xPVAc-borate HVPDs results in a drastic increase in the number of cross-linked borate species as well as the agglomeration of the polymer into bundles. These effects result in an increase in the relaxation time and thermal stability of the networks. The ability to make xPVAc-borate HVPDs with very large amounts of and rather different organic liquids, with very different rheological properties that can be controlled easily, opens new possibilities for applications of PVAc-based dispersions.

Structural and mechanical properties of "peelable" organoaqueous dispersions with partially hydrolyzed poly(vinyl acetate)-borate networks: applications to cleaning painted surfaces.

The preparation and structural characterization of a family of viscoelastic dispersions of borate cross-linked, 80% hydrolyzed poly(vinyl acetate) (80PVAc) in aqueous-organic liquids are presented. Correlations between mechanical properties (from rheological measurements) and the degree and nature of cross-linking (from (11)B NMR spectroscopy) are reported, and the results are used to assess their potential as low-impact cleaning agents for the surfaces of paintings. Because the dispersions can be prepared at room temperature by simple procedures from readily available materials and can contain up to 50% (w/w) of an organic liquid, they offer important advantages over previously described cleaning agents that are based on fully hydrolyzed PVAc (i.e., poly(vinyl alcohol). The mechanical properties of the various aqueous-organic dispersions, as determined quantitatively by rheological investigations and qualitatively by their ease of removal from a solid surface (i.e., the so-called "peel-off" ability) have been tuned systematically by varying the amount of organic liquid, its structure, and the concentrations of borax and 80PVAc. The (11)B NMR studies demonstrate that the concentration of borate ions actively participating in cross-linking increases significantly with the amount of organic liquid in the mixture. The degree of cross-linking remains constant when the 80PVAc and borax concentrations are varied, as long as their ratios are kept constant. Some of the 80PVAc-borax dispersions have been tested successfully as cleaning agents on the surface of a 16th-17th century oil-on-wood painting by Lodovico Cardi, "Il Cigoli", that was covered by a brown patina and on the surface of a Renaissance wall painting by Vecchietta in Santa Maria della Scala, Siena, Italy, that had a degraded polyacrylate coating from a previous conservation treatment.

Poly(vinyl alcohol)-borate hydro/cosolvent gels: viscoelastic properties, solubilizing power, and application to art conservation.

We report the development of a new type of hydrogel in which a cosolvent has been added to the water component. The gel networks are based on the well-known poly(vinyl alcohol)-borate systems (PVA-borate). However, it is shown that the rheological and solubilizing properties of the hydrogels can be modified drastically by the addition of a cosolvent. The studies have focused on 1-propanol as the added liquid, although it is shown that others (propylene carbonate, 1-pentanol, cyclohexanone, and 2-butanol) are amenable to making modified hydrogels as well. In addition to the rheological measurements, the gels have been investigated by differential scanning calorimetry (free water index) and determination of their solubilizing power. Finally, the gels have been applied to clean and oxidized varnish (patina) from the surface of a XVI-XVII century oil-on-wood painting by Ludovico Cardi detto il Cigoli. The mode of cleaning by and removal of the PVA-borate water/1-propanol gel from the painted surface demonstrate several advantages over other gels used in art conservation.