This study compares the consolidation efficiency and compatibility of three selected alkoxysilanes on two porous carbonate and silicate substrates. Emphasis was given to artificially induced microstructural defects and subsequent restoration of mechanical and physical properties. Two newly engineered formulations (1) a TiO₂ modified tetraethyl-orthosilicate in isopropanol with 70% active content and (2) a TiO₂ modified alkyl-trialkoxysilane in isopropanol with 75% active content were compared to a commercial product (3), a solvent free tetraethyl-orthosilicate with 99% active content. Treatments were evaluated by scanning electron microscopy, mercury intrusion porosimetry, colour impact and their effect on dynamic modulus of elasticity, splitting tensile- and flexural strengths, capillary water absorption and water vapour permeability. A key outcome was that mechanical strength gain induced by treatments is primarily governed by a stone’s texture and microstructure, and secondarily by the gel deposition rate of consolidants. Likewise, the kinetics of the gel-forming reaction during curing is dependent not only on the product but also on the substrate. Therefore, the moisture related properties and the visual impact develop during time. There is no general trend on how it evolves in time, which can lead to incorrect interpretations of treatment compatibility. The results prove that wide-ranging treatment performance is obtained when applying the same products on different substrates.

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.