External surfaces of stones used in historic buildings often carry high artistic value and need to be preserved from the damages of time, especially from the detrimental effects of the weathering. This study aimed to test the effectiveness and compatibility of some new environmentally-friendly materials for stone consolidation, as the use thereof has been so far poorly investigated. The treatments were based on combinations of an aqueous solution of di-ammonium phosphate (DAP) and two calcium-based nanomaterials, namely a commercial nanosuspension of Ca(OH)₂ and a novel nanosuspension of calcite. The treatments were applied to samples of two porous stones: a limestone and a sandstone. The effectiveness of the treatments was assessed using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy, ultrasound pulse velocity test, colour measurements, and capillary water absorption test. The results suggest that the combined use of DAP and Ca-based nanosuspensions can be advantageous over other commonly used consolidants in terms of retreatability and physical-chemical compatibility with the stone. Some limitations are also highlighted, such as the uneven distribution and low penetration of the consolidants.

The consolidation of degraded carbonate stone used in ancient monuments is an important topic for European cultural heritage conservation. The products most frequently used as consolidants are based on tetraalkoxy- or alkylalkoxy-silanes (in particular tetraethyl-orthosilicate, TEOS), resulting in the formation of relatively stable amorphous silica or alkylated (hydrophobic) silica inside the stone pores. However, silica is not chemically compatible with carbonate stones; in this respect, nanocalcite may be a suitable alternative. The present work concerns the preparation of water suspensions of calcite nanoparticles (CCNPs) by controlled carbonation of slaked lime using a pilot-scale reactor. A simplified design of experiment was adopted for product optimization. Calcite nanoparticles of narrow size distribution averaging about 30 nm were successfully obtained, the concentration of the interfacial agent and the size of CaO being the most critical parameters. Primary nanoparticle aggregation causing flocculation could be substantially prevented by the addition of polymeric dispersants. Copolymer-based dispersants were produced in situ by controlled heterophase polymerisation mediated by an amphiphilic macro-RAFT (reversible addition-fragmentation transfer) agent. The stabilized CCNP aqueous dispersions were then applied on carbonate and silicate substrates; Scanning Electron Microscopy (SEM)analysis of cross-sections allowed the evaluation of pore penetration, interfacial binding, and bridging (gap-filling) properties of these novel consolidants.

The use of sustainable additives such as sucrose for improving the properties of lime-based materials can contribute to a wider use of such low-carbon binders with applications in both civil engineering and conservation of the built heritage. Various sucrose-modified lime pastes were prepared, and their microstructure, fresh and hardened properties, and carbonation rate were assessed with an array of analytical techniques. It was found that sucrose acts as a water-reducing agent with relevant effects on both, fresh and hardened properties of pastes while allowing carbonation to occur homogeneously across the whole sample without the formation of carbonation rims. Such effects were enhanced when sucrose was added to the mixture after the slaking as pastes show higher mechanical strength and carbonate at a slower rate. When sucrose was added before the slaking, pastes show high elasticity, low mechanical strength, and carbonate faster due to their fine microstructure.