Carreaux de pavement is a type of mediaeval tile common in northwestern Europe, whose method of producing has been unknown until now. In this article, the kiln firing conditions of the unique carreaux de pavement found in the Iberian Peninsula were determined by comparing the physicochemical and mineralogical properties of the archaeological tiles with those of some reproductions of the tile's body manufactured in the laboratory (replica) made by varying the firing temperature and time, as well as the sample size and thickness. The resistance to acid digestion exhibited by the fired samples was especially revealed. According to the results and the modelling performance with the collected data, it was established that the maximum firing temperature was between 900 and 975 °C, and the time was longer than 24 h. These results show the technology used by mediaeval French potters and are a basis for future studies.

This manuscript provided one of the first scientific studies performed on ancient Spanish liturgical vestments by using a multitechnical physicochemical approach. The interlining and lining fabrics were done by cotton and the core of threads by silk. Silver, gold and little amounts of copper were detected. The highest values of gold were found in the metal threads of the cope and the gallon of the chasuble. Two layers were identified: the internal composed by silver and the external by silver and gold. The fibers were proved to be degraded and also the surface of the metal, where scratches and silver-based compounds were detected due to environmental and anthropogenic actions. Indigo was employed as dye in the blue and green fabrics. Wax was detected in the yellow fibers, although other dyes could not be discarded. The materials used in the restoration processes were of minor quality.

The walls of the Alcazar Palace in Seville have been covered with ceramic tiles of different styles that were manufactured with different techniques. Several studies have been carried out on these ceramics, but no interest has been paid to the tiles manufactured by the workshop of the Valladares family, one of the most productive ceramic workshops in Triana (Seville). In this work, tiles that were made in the Valladares workshop are studied for the first time. The tiles from the Cenador del Leon built in 1645-1646 were chosen. The experimental studies suggest that the ceramic body was manufactured with silico-calcareous clay. This raw material was heated to a temperature of ca. 900 degrees C. A nondestructive and on-site analytical procedure was applied first. Microsamples were also taken and studied through microanalytical techniques. The maiolica style was used by Benito de Valladares for tile manufacture. The glaze phases were constituted by two layers. The pigments and doping elements used to obtain different colors were characterized. Valladares' work is considered as a continuation of Augusta's work; therefore, a comparison between both ceramists has been realized to better understand the ceramics production in southern Spain during the sixteenth to seventeenth centuries.

Pseudopolyrotaxanes (PPRs) are supramolecular structures consisting of macrocycles able to thread on a linear polymer chain in a reversible, non-covalent way, often referred to in the literature as "molecular necklaces". While the synthesis and reaction mechanisms of these structures in solution have been widely described, their solvent-free production has received little attention, despite the advantages that this route may offer. We propose in this work a kinetic mechanism that describes the PPR formation in the solid phase as a process occurring in two consecutive stages. This mechanism has been used to investigate the spontaneous formation of a PPR that occurs when grinding alpha-Cyclodextrin (alpha-CD) with polyethylene glycol (PEG). In the threading stage, the inclusion of the polymer and subsequent release of the water molecules lodged in the cavity of the macrocycle cause vibrational changes that are reflected in the time-dependence of the FTIR-ATR spectra, while the further assembly of PPRs to form crystals produces characteristic reflections in the XRD patterns, due to the channel-like arrangement of CDs, that can be used to track the formation of the adduct in crystalline form. The effects that working variables have on the kinetics of the reaction, such as temperature, feed ratio, molar mass of the polymer and the introduction of an amorphous block in the polymer structure, have been investigated. The rate constants of the threading step increase with the temperature and the activation energy of the process increases at lower proportions of CD to PEG. This is attributed to the lower degree of covering of the polymer chain with CDs that reduces the hydrogen-bonding driven stabilization between adjacent macrocycles. The formation of crystalline PPR, which takes place slowly at room temperature, is markedly promoted at higher temperatures, with lower proportions of CD favoring both the formation and the growth of the crystals. The molar mass of the polymer does not modify the typical channel-like arrangement of packed PPRs but the conversion into crystalline PPR diminishes when using PEG1000 instead of PEG400. At a microscopic level, the crystals arrange into lamellar structures, in the order of hundreds of nm, embedded in an amorphous-like matrix. The introduction of a polypropylene oxide block in the structure of the polymer (Pluronic L62) renders poorer yields and a considerable loss of crystallinity of the product of the reaction. The methodology here proposed can be applied to the general case of inclusion complexes of CDs with drugs in the solid phase, or to multicomponent systems that contain polymers as excipients in pharmaceutical formulations along with CDs.

In this study, the thermal behavior of a series of leishmanicidal selenocyanate and diselenide biological active compounds has been studied by means of differential scanning calorimetry, X-ray diffraction and thermogravimetry in order to establish thermal stability criteria and investigate their polymorphism. Moreover, stability under acid, alkaline and oxidative media was tested using high-performance liquid chromatography with fluorescence detection. The results of the experiments show that there are five types of polymorphic behaviors for the studied compounds. In addition, relationship is found among stability and a series of structural effects and stress conditions of compounds.

Several medieval tiles from Tiebas Castle in Navarre, classified as carreaux de pavement, were mineralogically analyzed. The aim was to add information to the very scarce analytical data available for carreaux de pavement in order to provide a quality primary work, mainly descriptive, in this topic. The characterization techniques applied were: optical microscopy (OM), colorimetry, Fourier transform infrared (FT-IR) spectroscopy, differential thermal analysis and thermogravimetry (DTA-TG), X-ray fluorescence (XRF) spectroscopy, petrographic microscopy (PM), X-ray diffraction (XRD), scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDS). The tiles comprised three layers: a top glaze with mainly silicon and lead-based compounds; a thin layer of silicoaluminate (very possibly kaolinite) called engobe under it; and the pastes, composed of quartz, hematite, potassium feldspars and calcite. Honey glazes were richer in iron, being copper-based compounds responsible for dark green glazes. The orangish-reddish color of the pastes was provided by hematite. Although the tiles were found in three different locations within the castle, no significant differences were detected among them. The carreaux de pavement from Tiebas had similarities with that from the Bordeaux region. According to the composition data and thickness of tiles from other French carreaux de pavement, the Tiebas artifacts were dated to the 13th century.

In this work, it is reported that thermal analysis techniques such as TG, DTA and X-ray thermodiffraction, performed in air or nitrogen atmosphere, are very useful for evaluating and characterizing the pigments and the supports used for the manufacture of wall paintings from the San Isidoro del Campo Monastery (fifteenth century) in which different scenes from the life of San Jeronimo are represented. The use of thermal techniques has allowed for collecting information on the technology and raw materials used in the manufacture of these wall paintings. The composition of the different colours forming the wall paintings is the following: blue by azurite, green by atacamite, red by iron oxide (hematite), cinnabar and ochre by iron oxyhydroxides (goethite), black by carbon and white by calcite. In all the colours, calcite and quartz were also identified. The paintings were performed by using the fresco technique. The support mortars are constituted of calcite, quartz and straw.

The mainly use of infrared spectroscopy and colorimetry allowed the characterization of the pigments and compounds of the wall paintings from the Monastery of San Isidoro del Campo in Seville, dated on the 15th century. Calcite, quartz and albite were detected in the ground mortar layers. As pigments, red ochre, yellow ochre, paratacamite, atacamite, azurite and carbon black were used, and also lime as the binder, therefore the fresco technique was employed. Both FTIR-ATR and FTIR (in transmission) experiments were performed. Comparison between materials used in some of the wall paintings from Seville in this period was performed. The article revealed important information about wall paintings within a historical context related to the 15th century Catholic Reformation.

The degradation processes that occurred on metal threads applied in the embroidery used for clothing and in the ornamentation of sculptures, the Sevillian Holy Week processions, and Portuguese and Spanish palace and museum are thoroughly analyzed. Some threads from the 14th and 18-19th centuries were considered. In the metal threads, sulphur- and chlorine-based compounds were detected either individually or together, depending on the degradation process. Basic silver carbonate, sodium bicarbonate and copper-based compounds were also observed. The different degradation processes were attributed to different factors, such as environmental contamination, degradation of the fibrous cores, and inadequate cleaning and/or mechanical treatments. (C) 2018 Elsevier Masson SAS. All rights reserved.

This work comprises an exhaustive study of Spanish decorative leathers dating from the 12th to 14th centuries. These paintings are considered a key example of a crucible of artistic styles: Gothic, Islamic and Florentine Trecento. The goal of this work was to use the scientific information provided by a number of experimental techniques - namely EDX, micro-FTIR, micro-Raman and micro-XRD - to assess the dating of the wooden vault, leather preparation and filling fibres. Another goal was to assess the artistic technique based on the characterization of pigments and the differentiation between original materials and those added throughout its history. Gypsum was the original preparation layer extended over the leather. A new preparation stratum was added in further interventions with the artwork. The original pictorial materials and those used during refurbishments have been identified. Original pigments were: red lead, Mars red, red lake, cinnabar, lapis lazuli, red ochres, raw sienna, white lead and charcoal black. Gilding was also found. Pigments added during restoration were: barite, emerald green, rutile, anatase, Mars red, cadmium red, lithopone, cadmium yellow, charcoal black and orpiment.

This book collects the abstracts of the communications presented in the 5th Historic Mortars Conference (HMC 2019) organized by the Heritage, Materials & Environment (MIMED) Research Group of the Chemistry Department of the University of Navarra at the School of Sciences in Pamplona from 19 to 21 June 2019.

Proceedings of the 5th Historic Mortars Conference (HMC 2019) held at the University of Navarra in Pamplona from the 19th to the 21st June 2019.

El Fórum Ibérico de la Cal, FICAL, es una asociación sin ánimo de lucro cuyo objetivo es el desarrollo de la investigación, la formación y la difusión de la producción y el uso de la cal. Después de las exitosas V Jornadas celebradas en el LNEC de Lisboa, la Universidad de Navarra toma el relevo y organizará en Pamplona, en la Facultad de Ciencias, las VI Jornadas FICAL, del 28 al 30 de mayo de 2018. Estas Jornadas están abiertas a participantes de distintas procedencias e intereses: restauradores, arquitectos y arquitectos técnicos, químicos, geólogos, ingenieros civiles y de materiales, historiadores, científicos, profesionales del sector industrial, estudiantes, empresas productoras¿ con el común denominador de conocer más posibilidades de aplicación, características, comportamiento y aspectos innovadores y tecnológicos en relación con la cal. Se conocen aplicaciones de la cal desde tiempos inmemoriales, particularmente en construcción: morteros, soportes decorativos y pictóricos. La cal es un material íntimamente ligado al Patrimonio Histórico-Artístico y se sigue produciendo a partir de las mismas materias primas. Destacan, entre sus características, la plasticidad de las argamasas que utilizan cal, su capacidad higroscópica y desinfectante, sus propiedades aislantes y su durabilidad. La cal es perfectamente compatible con estructuras antiguas, es idónea para procesos de restauración y rehabilitación, pero también tiene interés en obra nueva porque aporta estabilidad,

This work reports the obtaining of lime-based grouts as repairing materials. Microsilica was added as pozzolanic additive to enhance the compressive strength of the hardened grouts. Sodium oleate, as water repellent admixture, and different superplasticizers (SPs) were also incorporated to reduce the water absorption and to enhance the injectability of the grouts. Polycarboxylate ether (PCE), polynaphthalene sulfonate (PNS), melamine sulfonate (MMS) and polyacrylic acid (PA) were tested as SPs. Regarding the fluidity of the grouts, PCE was seen to improve the injectability, followed by PNS, MMS and PA. However, PCE addition was also accompanied by a severe delay in the setting time. The other three superplasticizers did not provoke significant delays in the hardening of the samples. The water contact angle underwent an increase pointing to an effective hydrophobization of the surface as a consequence of the water repellent admixture. The combination with PCE was the most effective in keeping the water repellency in comparison with the control sample (lime grout + oleate). MMS yielded high compressive strengths and durability of the mortars, in the face of freezing-thawing cycles, was enhanced.

El presente trabajo tiene como principal objetivo estudiar las interacciones que se producen cuando se adicionan separadamente dos superplastificantes (PNS ¿sulfonato de polinaftaleno- y LS ¿lignosulfonato-) a un conglomerante aéreo (cal aérea Cl 90-S) y a uno hidráulico formado por cal aérea a la que se le ha añadido metacaolín como material puzolánico, y los efectos que dichas adiciones tienen en las propiedades de los sistemas. Para la fabricación de los morteros, se empleó árido calcáreo. Adicionalmente, se efectuaron ensayos de durabilidad en morteros con la composición citada, sometiéndolos a ciclos de hielo-deshielo y a ataque con sulfatos. Aunque se realizaron algunas medidas con las pastas en estado fresco, la mayoría de los experimentos (resistencia a compresión y a flexión, TG-ATD, DRX, FTIR-ATR, porosimetría de intrusión de mercurio) se realizaron tras períodos de fraguado del mortero de 7, 28, 91, 182 y 365 días. Se detectaron fases silicatadas y silicoaluminatadas en los morteros estudiados, a pesar de que las experiencias se realizaron a temperatura ambiente y con un bajo porcentaje de material puzolánico (¿20 %). La presencia de LS impidió el proceso de carbonatación, lo que a su vez provocó un decrecimiento en los valores de resistencia mecánica cuando se trataba de morteros hidráulicos. Se observó asimismo una mayor porosidad y un mayor tamaño medio de poro en el caso de sistemas con LS. La durabilidad (ciclos hielo-deshielo) de los morteros mejoró notable

Los morteros de relleno o inyección, especialmente destinados a reparación de cavidades y defectos de albañilería, deben fluir adecuadamente en estado fresco y combinar resistencia y durabilidad. Para conseguir algunas de estas características pueden utilizarse aditivos químicos: superplastificantes, para mejorar la fluidez; adiciones puzolánicas, para conseguir resistencias adecuadas en ambientes con limitado acceso de CO2 y una mejora de la durabilidad; e hidrofugantes, de manera que, sin perjudicar la permeabilidad de estos materiales al vapor de agua, se evite la penetración de agua por capilaridad mejorando la durabilidad. Sin embargo, en la mayor parte de los casos, toda la información disponible se circunscribe al efecto de un único aditivo, sin contemplar el posible efecto conjunto o incluso sinérgico de las combinaciones más interesantes de dos o más aditivos y/o adiciones puzolánicas. El estudio de las sinergias entre estos componentes ofrece posibilidades muy interesantes de avance científico-técnico. Precisamente este es el objetivo del trabajo: diseño de nuevos morteros de inyección de cal que puedan ser utilizados para la restauración del Patrimonio Edificado mediante combinación adecuada de aditivos superplastificantes (éteres de policarboxilato, condensados de naftaleno-formaldehído, sulfonato de melamina y ácido poliacrílico), hidrofugante (oleato sódico) y adiciones minerales puzolánicas (microsílice y metacaolín).

A new range of repair lime mortars were obtained by using as superplasticizer a polynaphthalene sulfonate-based polymer (PNS) and metakaolin as pozzolanic addition. Adsorption isotherms showed that PNS exhibited a high affinity for air lime particles with 52.08 mg¿g-1 as maximum sorption capacity in pure air lime media. Mathematical treatment of experimental data showed an optimal adjustment to a Freundlich model, in which interactions arising from multilayer adsorption are taken into account. The experimental results suggested a great interaction of PNS with air lime media (pure air lime or air lime with MK). Zeta potential curves of air lime systems titrated with PNS showed a larger zeta potential reduction, giving rise to a charge reversal, as a consequence of the high anionic charge density of this polymer (2.44 meq of anionic charge¿g-1). A flat adsorption was proposed as the attachment model of this admixture, owing to its higher anionic charge density and to its linear shape. The electrostatic repulsion was then the main action mechanism to explain the PNS function. In the hardened state, the combination of PNS and MK resulted sometimes in moderate mechanical strength increases and in a clear enhancement of the durability in the face of freezing-thawing cycles.

This contribution dealt with the design of different air lime mortars and pastes by combining a nanostructured pozzolanic additive, nanosilica, and different dispersing agents, superplasticizers (two different polycarboxylate ethers (PCE), a polynaphthalene sulfonate-based polymer (PNS) and a lignosulfonate (LS)). In pure air lime systems, the highest effectiveness was shown by the PCE1, whereas the PNS was the less effective superplasticizer. In samples with nanosilica, the PCE1 was also the most effective superplasticizer. LS was seen to be effective at low dosages. In the presence of the pozzolanic additive, there was a high consumption of polycarboxylates. Nanosilica provided no ¿active¿ adsorption sites, resulting in a slight decrease of the zeta potential values. PCE1 showed low adsorbed amounts, better dispersing action and required lower dosage of plasticizing agent. There was a positive combination between lime mortars with nanosilica and polycarboxylates, which resulted in a mechanical strength improvement. Also the combined presence of nanosilica, for example, with PNS or with LS yielded better compressive strengths, being LS more effective than PNS: SEM images showed the better formation of C-S-H phases in LS-mortars.

The obtaining of self-cleaning mortars is very interesting to apply them in Built Heritage. Atmospheric pollutants, mainly carbonaceous particles and gases like NOx and SO2 can lead to severe aesthetic and functional damages in artworks. In the case of mortars and renders, the use of photocatalysts -usually based on TiO2- can be worthy of consideration. Photocatalysts, after being activated by light, are able to oxidize pollutants avoiding their deposition onto building materials. In this work, different air lime mortars modified upon the addition of TiO2-based photocatalysts were obtained and studied. Photocatalysts can be incorporated in bulk and the changes in fresh state properties were studied as well as the effect of the presence of the photocatalysts on the pore structure and mechanical resistance. Finally, the photocatalytic efficiency of these materials was carried out by means of a NOx abatement test. Results showed that the presence of the photocatalysts had a positive impact on the preservation of the lime mortars characteristics.

A superplasticizing admixture of natural origin, lignosulfonate (LS), was incorporated to air lime mortars sometimes modified with a pozzolanic additive, metakaolin, to obtain a new range of repair mortars to be applied in Built Heritage. LS improved the flowability of the air lime samples and showed good slump retention over time: for example, after 150 minutes of the air lime pastes preparation, blends with LS lost only ca. 13% of the slump value. Experimental results showed that LS interfered with the carbonation due to its ability to form Ca2+ complexes. Adsorption isotherms and zeta potential measurements showed that LS was scarcely adsorbed onto lime and C-S-H particles. Due to its branchy structure, LS exhibited an adsorption mechanism leading to steric hindrance as the main responsible mechanism for avoiding flocculation. The presence of free LS molecules in the dispersion was seen to improve the plasticizing effect of this polymer. Flexural and compressive strengths as well as the durability in the face of freezing-thawing cycles of these mortars were also determined to assess the applicability of these repair mortars.

The rationale is that polyphosphate-CAC matrices have shown interesting potential to solidify/stabilize heavy metals, owing to the aforementioned acid-base reaction that yields a compact and low porous matrix mainly composed of ACP - amorphous calcium phosphate -, which can be able to retain hazardous compounds. We aimed to take advantage of the reactivity of one of the sludge components: the sludges with relatively large concentrations of phosphate are expected to act themselves as reactants that, interacting with the CAC, could result in a very effective retaining system of the sludge constituents. Sludge samples from two locations have been incorporated in high proportion within the mix. We discussed the effects of the sludge on the CAC mortar and a possible interaction mechanism is provided.

Although CAC is used in many building as well as industrial structures, its modification upon addition of photocatalytic additives has not yet been addressed and that is precisely the purpose of the present work. We intend to obtain for the first time depolluting CAC mortars modified with different amounts of TiO2. The effect of the TiO2 incorporation on setting time, compressive strength and mineralogical composition of the CAC mortars will be assessed. PCO efficiency of these TiO2-bearing CAC mortars will be also measured by means of the NOx abatement. The modified depolluting mortars could be then applied in different tunnels, industrial floors and urban areas in which CACs are usually applied.