M. Alvarez de Buergo

Protective patinas applied on stony façades of historical buildings in the past

Abstract The ochre patina that covers the limestone facades of Palacio de Nuevo Baztan is composed of calcite, clay minerals, gypsum, quartz, potassium feldspar, alongside traces of calcium oxalates, calcium phosphates, iron oxides and hydroxides. It is a polistratified film, rich in Ca, Si, Al and P, as well as Mg, K, Fe and Cl. Results obtained indicate that the origin of the patina lies in a treatment applied on the stone in the past, consisting of a mixture of lime, gypsum, milk-derived compounds and inorganic earth pigments. This film has protected the stone on which it was applied, and should be preserved in any further stages of intervention on the stone facades.

Determination of anisotropy to enhance the durability of natural stone

Anisotropy is a petrophysical property of natural stone and other construction materials that determines their quality and resistance to decay due to a variety of agents, such as water. A study was conducted on nine types of stone widely used in Spains built heritage, using six previously defined anisotropy indices. These indices can be used to determine the degree of anisotropy, which helps explain the differential decay observed in stone materials quarried in the same bed and used to build the same structure. The conclusion reached is that anisotropy should be determined in the natural stone used both to restore the architectural heritage and in new construction, since the appropriate choice of material quality ensures greater resistance to decay and, therefore, increased durability. Materials with the lowest possible anisotropy should be selected, as this property governs their hydraulic behaviour: the lower the anisotropy in a material, the better its behaviour in relation to water and the longer its durability.

Overview of recent knowledge of patinas on stone monuments: the Spanish experience

Abstract The historic treatment of stonework has often been linked to the artificial application of patinas, mainly for aesthetic and protective reasons. Increasingly, however, researchers have identified a possible combined origin for patinas that has linked natural, biological processes to those associated with an artificial, man-made origin. This suggests that, although coatings may have been initially applied on purpose, they transform over time with the aid of micro-organisms and other chemical interactions. The original mixture applied to create a patina could include lime and/or gypsum, water, natural pigments and organic additives. However, their present-day mineralogy is varied and includes a wide range of minerals from calcium carbonates to calcium sulphates, calcium oxalates, calcium phosphates, silicates (quartz, feldspar, clay minerals) and iron oxides/hydroxides. Patinas have been studied in detail in Greece and Italy, but rarely in Spain. In this paper, existing knowledge on Spanish patinas is co-ordinated and previous and current research summarized. Emphasis is placed on artificial patinas initially applied to protect stone. These both appear to effectively protect the stone substrates on which they were applied and provide an insight into historical techniques of stone conservation. Because of this their preservation should be a strong consideration in restoration projects. Ongoing research focuses on the challenges of reproducing patinas, based on historical references.

Laser-induced fluorescence and FT-Raman spectroscopy for characterizing patinas on stone substrates.

AbstractThis article reports on a compositional investigation of stone patinas: thin colored layers applied for protective and/or aesthetic purposes on architectural or sculptural substrates of cultural heritage. The analysis and classification of patinas provide important information of historic and artistic interest, as their composition reflects local practices, the availabilities of different materials, and the development of technological knowledge during specific historical periods. Model patinas fabricated according to traditional procedures and applied onto limestone, and a historic patina sample from the main façade of the San Blas Monastery in Lerma (a village in the province of Burgos, Spain), were analyzed by laser-induced fluorescence and Fourier transform Raman spectroscopy. The results obtained demonstrate the ability of these two analytical techniques to identify the key components of each formulation and those of the reaction products which result from the chemical and mineralogical transformations that occur during aging, as well as to provide information that can aid the classification of different types of patinas. FigureCross section of model patina (left) and FT-Raman spectrum of historic patina from the façade of San Blas Monastery, Lerma, Burgos, Spain (right).

Colmenar Limestone, Madrid, Spain: considerations for its nomination as a Global Heritage Stone Resource due to its long term durability

Abstract Colmenar Limestone is one of the traditional materials most commonly used in monuments in Madrid, Spain. The petrophysical properties of this stone determine its high resistance to decay. Its low water absorption and pore size distribution favour good hydraulic behaviour, which is likewise furthered by its high ultrasound velocity and low anisotropy. The durability findings pursuant to the 280 freeze–thaw, 42 thermal shock, 30 salt crystallization and 120 salt mist cycles conducted confirmed the stones resistance to decay in these simulated aggressive environments. The mass loss recorded in the samples and the variation in petrophysical parameters were generally very low after all except the salt crystallization trials, which induced loss of cohesion on the stone surface, increased roughness and the formation of concentric microcracks, sub-parallel to the more exposed surface, that also affected the arris and vertices of the specimens tested.

Limestone on the ‘Don Pedro I’ facade in the Real Alcázar compound, Seville, Spain

Abstract This paper discusses the research conducted prior to restoring the ‘Don Pedro I’ facade on the Real Alcázar or royal palace at Seville, Spain. The different types of stone on the facade were located and characterized, and their state of decay mapped. Although other materials (brick, rendering, ceramics, marble) are present on the facade, its main elements are made from two types of limestone: palomera and tosca, each in a different state of conservation and exhibiting distinct behaviour. Colour parameters, real and bulk densities, compactness, open porosity, water saturation coefficient and total porosity were determined to characterize the two varieties. In addition, ultrasonic techniques were used to map the various levels of decay on the facade, stone by stone, for future interventions. The findings show that owing to its petrographical and petrophysical properties, palomera stone is of a lower quality than tosca stone, and has undergone more intense deterioration.

Laser Removal of Protective Treatments on Limestone

This work presents an investigation of the laser removal of polymeric materials acting as consolidants and water-repellents on limestone used on buildings of architectural and artistic value. The removal of the consolidant Paraloid B-72 and the water-repellent product Tegosivin HL-100, applied on samples of Colmenarand Bateig limestone, was studied as a function of the laser wavelength, by using the four harmonics of a Q-switched Nd:YAG laser (1064, 532, 355 and 266 nm). Elimination of the coatings and subsequent surface modifications were monitored through colorimetry, roughness measurements and scanning electron microscopy (SEM). The fundamental laser radiation was effective in removing the treatments, although thermal alteration processes were induced on the calcite crystals of the limestone. The best results were obtained by irradiation in the near UV at 355 nm.