RESUMEN
Mineral nanoparticle suspensions with consolidating properties have been successfully applied in the restoration of weathered architectural surfaces. However, the design of these consolidants is usually stone-specific and based on trial and error, which prevents their robust operation for a wide range of highly heterogeneous monumental stone materials. In this work, we develop a facile and versatile method to systematically study the consolidating mechanisms in action using a surface forces apparatus (SFA) with real-time force sensing and an X-ray surface forces apparatus (X-SFA). We directly assess the mechanical tensile strength of nanosilica-treated single mineral contacts and show a sharp increase in their cohesion. The smallest used nanoparticles provide an order of magnitude stronger contacts. We further resolve the microstructures and forces acting during evaporation-driven, capillary-force-induced nanoparticle aggregation processes, highlighting the importance of the interactions between the nanoparticles and the confining mineral walls. Our novel SFA-based approach offers insight into nano- and microscale mechanisms of consolidating silica treatments, and it can aid the design of nanomaterials used in stone consolidation.
RESUMEN
Solution composition-sensitive disjoining pressure acting between the mineral surfaces in fluid-filled granular rocks and materials controls their cohesion, facilitates the transport of dissolved species, and may sustain volume-expanding reactions leading to fracturing or pore sealing. Although calcite is one of the most abundant minerals in the Earth's crust, there is still no complete understanding of how the most common inorganic ions affect the disjoining pressure (and thus the attractive or repulsive forces) operating between calcite surfaces. In this atomic force microscopy study, we measured adhesion acting between two cleaved (104) calcite surfaces in solutions containing low and high concentrations of Ca2+ ions. We detected only low adhesion between calcite surfaces, which was weakly modulated by the varying Ca2+ concentration. Our results show that the more hydrated calcium ions decrease the adhesion between calcite surfaces with respect to monovalent Na+ at a given ionic strength, and thus Ca2+ can sustain relatively thick water films between contacting calcite grains even at high overburden pressures. These findings suggest a possible loss of cohesion and continued progress of reaction-induced fracturing for weakly charged minerals in the presence of strongly hydrated ionic species.
RESUMEN
A nano-silica consolidant and nano-titania modified tetraethyl-orthosilicate were applied on two building stones, a carbonate and a silicate, by brush, poultice or capillary absorption. Neutron radiography was used to monitor capillary water absorption, and to analyse changes in physical properties caused by heat treatment of specimens for the purposes of artificially ageing and different treatment applications with stone consolidants. Moreover, ultrasonic pulse velocity and gravimetrically determined water absorption were analysed to cross-validate neutron radiography. The results reveal that reactive systems like tetraethyl-orthosilicates need an unknown period for polymerisation, which makes nano-silica consolidants more favourable for construction follow-up work. While polymerisation is incomplete, hydrophobic behaviour, water trapping and pore clogging are evident. Within the tetraethyl-orthosilicate treatment, poultice and brushing are strongly influenced by the applicant, which results in wide ranging amounts of water absorbed and anomalous water distributions and kinetics. The carbonate lithotype displays polymerisation initiated in the core of the specimen, while the lateral surfaces are still mostly hydrophobic. Reaction time differences can be attributed to the different amounts of consolidants applied, which is a result of the chosen application settings. Artificial ageing of stone specimens is a prerequisite when mechanical strength gain is studied, as demonstrated by sound speed propagation.
RESUMEN
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.