Nuestros investigadores

Adrián Durán Benito

Facultad de Ciencias. Universidad de Navarra
Líneas de investigación
Archaeology, Architecture, Art, Chemistry, Construction and Building Technology, Instruments and Instrumentation, Materials Science, Metallurgical and Metallurgical Engineering, Microscopy, Mineralogy, Spectroscopy

Publicaciones científicas más recientes (desde 2010)

Autores: Ruiz Ardanaz, I.; Lasheras Adot, María Esther; Durán Benito, Adrián (Autor de correspondencia)
ISSN 2075-163X  Vol. 11  Nº 2  2021  págs. 153
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.
Autores: Pérez-Rodríguez, J. L., (Autor de correspondencia); Franquelo, M. L. ; Durán Benito, Adrián
ISSN 1388-6150  Vol. 143  Nº 4  2021  págs. 3257 - 3265
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.
Autores: Durán Benito, Adrián (Autor de correspondencia); Perez-Rodriguez, J. L.;
ISSN 0924-2031  Vol. 111  2020  págs. 103153
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.
Autores: Durán Benito, Adrián (Autor de correspondencia); Perez-Maqueda, R. ; Perez-Rodriguez, J. L.;
ISSN 1296-2074  Vol. 36  2019  págs. 135 - 142
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.
Autores: Franquelo, M.L., (Autor de correspondencia); Durán Benito, Adrián; Perez-Rodriguez, J.L.;
ISSN 1386-1425  Vol. 218  2019  págs. 331 - 341
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.
Autores: De Diego Díaz, Beatriz; Durán Benito, Adrián; Alvarez-Garcia, M. R.; et al.
Revista: FUEL
ISSN 0016-2361  Vol. 245  2019  págs. 240 - 246
In this paper, the use of techniques such as TGA, FTIR-ATR and XRD has provided valuable information about the lignocellulosic wastes in anaerobic digestion (AD) processes. A deep study of their break-down in solid state could improve the management of these recalcitrant substrates. Representative wastes (artichoke -ART-, asparagus -ASP-, the co-digestion of both -AcoD-and pure cellulose -CELL-) were assessed in batch. The main obtained results were related to biochemical parameters. As the biomethanization progressed, hemicellulose, cellulose and lignin were weakened as shown by TGA, and cellulose crystallinity decreased as demonstrated by XRD. Additionally, results from FTIR-ATR allowed hypothesizing that the formation of acetate in solid state did not always lead to its solubilisation, thus hindering biogas formation. AcoD and CELL were the most successful in releasing the newly formed acetate from the solid fraction to the aqueous medium, increasing its bioavailability, which was supported by the higher biogas production.
Autores: Durán Benito, Adrián; González Sánchez, Jesús Fidel; Fernández Álvarez, José María; et al.
ISSN 2073-4360  Vol. 10  Nº 8  2018  págs. 824
A new range of grouts prepared by air lime and metakaolin (MK) as a pozzolanic admixture has been obtained by using as dispersing agents two polymers, namely poly-naphthalene sulfonate (PNS) and lignosulfonate (LS), with the aim of improving the fluidity of the fresh grouts. Fluidity and setting times of the grouts were assessed. Differences in the molecular architecture and in the anionic charge density explained the different adsorption of the polymers and the different performance. The higher anionic charge of PNS and its linear shape explained its better adsorption and effectiveness. The pozzolanic reaction was favoured in grouts with PNS, achieving the highest values of compressive strength (4.8 MPa after 182 curing days). The addition of PNS on lime grouts slightly decreased the frost resistance of the grouts (from 24 freeze-thaw cycles for the polymer-free samples to 19 or 20 cycles with 0.5 or 1 wt % of PNS). After the magnesium sulphate attack, grouts were altered by decalcification of hydrated phases and by formation of hexahydrite and gypsum. A protective role of portlandite against magnesium sulphate attack was clearly identified. Accordingly, the polymer LS, which preserves a significant amount of Ca(OH)2, could be an alternative for the obtaining of grouts requiring high sulphate attack resistance.
Autores: Perez-Rodriguez, J. L., (Autor de correspondencia); Perez-Maqueda, R.; Franquelo, M. L.; et al.
ISSN 1388-6150  Vol. 134  Nº 1  2018  págs. 15 - 22
In this work, it is reported that thermal analysis techniques such as differential thermal analysis and thermogravimetric analysis are very useful for evaluating metals threads and fibres used in the manufacture of historical artifacts. Thermal analysis has been used to characterize the silk, cotton and linen employed as supports and the copper, silver and aluminium as the metallic components in the studied threads. Other organic compounds, mainly added for the conservation of the threads, have also been characterized.
Autores: Perez-Rodriguez, J. L.; Robador, M. D.; Albardonedo, A. ; et al.
ISSN 1296-2074  Vol. 31  2018  págs. 112 - 121
The majority of the studied artworks were altarpieces, sculptures and/or wood-based works from different periods. Non-traditional gilding techniques have been first described in this paper, such as those that employ materials as oil in the gilding on bole, glue and bole with lead white in mordant gilding, vermilion in the preparation layers; and brass gilding or those with aluminium, lead chromate, mica or corla trying to imitate the golden hue in restoration or repaint processes. For the determination of the composition of the different gilded layers, spectroscopic techniques, such as FTIR and micro-Raman, and SEM-EDX elemental chemical analyses were successfully used. (C) 2017 Elsevier Masson SAS. All rights reserved.
Autores: Perez-Rodriguez, J. L.; Albardonedo, A. ; Robador, M. D.; et al.
ISSN 1431-9276  Vol. 24  Nº 5  2018  págs. 574 - 590
Gilding threads collected from Spanish and Portuguese palaces and from the embroideries and adornments of sculptures of the Virgin and Christ that form part of Sevillian Holy Week were analyzed and compared (20 artifacts were evaluated). The study covered a broad time period with examples from the 13th to 14th centuries, 18th to 20th centuries, and also including modern embroideries. A combination of scanning electron microscopy and energy-dispersive X-ray spectroscopy was used. The knowledge of the layered structures of the threads has provided very valuable information regarding the manufacturing techniques. The different metal threads found in the embroidery studied consisted of gold, silver, copper, and alloys of these metals and aluminium. The fabrication procedures often differed in the different workshops and changed with time. In the modern embroideries, a decrease of precious metal concentration was detected. The threads were wound around a core of silk threads.
Autores: Alcolea Devesa, Verónica; Garnica Calvo, Pablo; Palop Cubillo, Juan Antonio; et al.
ISSN 1420-3049  Vol. 22  Nº 8  2017  págs. 1314
The physicochemical properties of a compound play a crucial role in the cancer development process. In this context, polymorphism can become an important obstacle for the pharmaceutical industry because it frequently leads to the loss of therapeutic effectiveness of some drugs. Stability under manufacturing conditions is also critical to ensure no undesired degradations or transformations occur. In this study, the thermal behaviour of 40 derivatives of a series of sulphur and selenium heteroaryl compounds with potential antitumoural activity were studied. In addition, the most promising cytotoxic derivatives were analysed by a combination of differential scanning calorimetry, X-ray diffraction and thermogravimetric techniques in order to investigate their polymorphism and thermal stability. Moreover, stability under acid, alkaline and oxidative media was tested. Degradation under stress conditions as well as the presence of polymorphism was found for the compounds VA6E and VA7J, which might present a hurdle to carrying on with formulation. On the contrary, these obstacles were not found for derivative VA4J.
Autores: Garofano, I. ; Perez-Rodriguez, J. L.; Robador, M. D.; et al.
ISSN 1296-2074  Vol. 22  2016  págs. 1028 - 1039
This study attempts to establish the advantages and limitations of the combined use of portable UV¿Vis-FORS and XRF-XRD portable equipment for the non-invasive characterisation of pigments from Roman wall paintings from Seville, Spain, dated to the first and second century AD. XRD revealed the presence of calcite, dolomite and aragonite, indicating the colour white. Egyptian blue was identified using FORS and XRF, and additional information was obtained with XRD. For the colour green, FORS and mainly FTIR and colorimetry enabled the distinction between glauconite and celadonite, although other techniques were necessary to classify all components of the green areas by determining the presence of cuprorivaite, chlorite and chromium. For the colours yellow and red, the presence of goethite, yellow ochre, cinnabar and haematite was confirmed using FORS and XRF in some cases; the results were corroborated by XRD. Chromatic characterisation and the values of inflection points of FORS spectra enabled a better differentiation between reddish colours (orange, brown, purple and pink). The XRD and XRF techniques revealed that violet was created by mixing red haematite and Egyptian blue and slight variations in FORS spectra confirmed this.
Autores: Durán Benito, Adrián; Sirera Bejarano, Rafael; Pérez Nicolás, María; et al.
ISSN 0008-8846  Vol. 81  2016  págs. 1 - 15
The effect of chlorides and nitrates of Li(I), Cr(III), Zn(II), Cu(II), Pb(II) nitrate and Cr(VI) (chromate) on the early hydration of ternary cement system of calcium aluminates (CA, CA2, C12A7) was reported. Li(I) and Cr(III) caused a strong acceleration of the hydration, while Zn(II) as well as chromate gave rise to a slight acceleration. On the contrary, Pb(II) and Cu(II) retarded the hydration. A clear formation of AFm phases during the first hydration stages was found and related to the acceleration ability. Anions (nitrate or chloride as counterions or even chromate) were able to be incorporated into the interlayer space of AFm, yielding insoluble and stable compounds. A balance between the insolubility of the metal hydroxides (dependant on the low amphoteric character of the compound) and the ability of the formation of AFm hydrates seems to be very important to lean the equilibrium towards the retarding of the hydration or towards the acceleration, respectively.
Autores: Pérez Nicolás, María; Durán Benito, Adrián; Navarro Blasco, Íñigo; et al.
ISSN 0008-8846  Vol. 82  2016  págs. 11 - 22
Polynaphtalenesulfonate (PNS) and lignosulfonate (LS) were tested as superplasticizers in pastes and mortars of pure air lime and air lime with a pozzolanic additive, nanosilica (NS). LS showed a better plasticizing effect than PNS: the flowability of the samples with LS as well as the slump retention over time was larger. LS strongly hindered carbonation due to its ability to form Ca2+ complexes. In mortars with NS, PNS was seen to interfere with the C-S-H formation, resulting in lower mechanical strengths. Adsorption isotherms and zeta potential showed that PNS was more adsorbed than LS onto lime and C-S-H particles. PNS acted mainly through electrostatic repulsion owing to its high anionic charge density and flat adsorption. However, LS was more efficient as superplasticizer in air lime media, steric hindrance being the main mechanism responsible for avoiding flocculation. Furthermore, LS yielded high compressive strengths in mortars with NS.
Autores: Garofano, I. ; Robador, M. D. ; Perez-Rodriguez, J. L. ; et al.
ISSN 0955-2219  Vol. 35  Nº 15  2015  págs. 4307 - 4319
For the purpose of chemical characterization, a selection of 29 ceramic fragments from the 11th to 15th century has been made from materials excavated in the Seville Alcazar Palace. The PIXE elemental analysis results indicated that the ceramic bodies can be divided into four groups. The XRD identification of the phases present in the bodies revealed differences in the firing temperatures. The PIXE analysis of the glazes revealed variable PbO and SnO2 contents. The latter component was not detected in all the glazes. Cu, Co, Mn, Fe and Sb elements were associated with green, blue, black and yellow colours, respectively. Some glazes were covered by iridescent layers constituted by lead carbonate and phosphates due to alteration of the glazes. It was also possible to detail the microstructure and composition of the ultimate surface layers responsible for the lustre effect observed in two of the ceramic samples using PIXE and Rutherford backscattering spectrometry (RBS).
Autores: Navarro Blasco, Íñigo; Durán Benito, Adrián; Pérez-Nicolás, M.; et al.
ISSN 0301-4797  Vol. 159  2015  págs. 288 - 300
Phosphate coating hazardous wastes originated from the automotive industry were efficiently encapsulated by an acid¿base reaction between phosphates present in the sludge and calcium aluminate cement, yielding very inert and stable monolithic blocks of amorphous calcium phosphate (ACP). Two different compositions of industrial sludge were characterized and loaded in ratios ranging from 10 to 50 wt.%. Setting times and compressive strengths were recorded to establish the feasibility of this method to achieve a good handling and a safe landfilling of these samples. Short solidification periods were found and leaching tests showed an excellent retention for toxic metals (Zn, Ni, Cu, Cr and Mn) and for organic matter. Retentions over 99.9% for Zn and Mn were observed even for loadings as high as 50 wt.% of the wastes. The formation of ACP phase of low porosity and high stability accounted for the effective immobilization of the hazardous components of the wastes.
Autores: Perez-Rodriguez, J.L.; Durán Benito, Adrián
ISSN 0038-7010  Vol. 47  Nº 3  2014  págs. 223 - 237
Autores: Beck, L.; Rousseliere, H.; Castaing, J.; et al.
Revista: TALANTA
ISSN 0039-9140  Vol. 129  2014  págs. 459 - 464
Study of prehistoric art is playing a major role in the knowledge of human evolution. Many scientific methods are involved in this investigation including chemical analysis of pigments present on artefacts or applied to cave walls. In the past decades, the characterization of coloured materials was carried on by taking small samples. This procedure had two main disadvantages: slight but existing damage of the paintings and limitation of the number of samples. Thanks to the advanced development of portable systems, in-situ analysis of pigment in cave can be now undertaken without fear for this fragile Cultural Heritage. For the first time, a portable system combining XRD and XRF was used in an underground and archaeological environment for prehistoric rock art studies. In-situ non-destructive analysis of black prehistoric drawings and determination of their composition and crystalline structure were successfully carried out. Original results on pigments used 13,000 years ago in the cave of Rouffignac (France) were obtained showing the use of two main manganese oxides: pyrolusite and romanechite. The capabilities of the portable XRD-XRF system have been demonstrated for the characterization of pigments as well as for the analysis of rock in a cave environment. This first in-situ experiment combining X-ray diffraction and X-ray fluorescence open up new horizons and can fundamentally change our approach of rock art studies.
Autores: Garofano, I.; Robador, M.D.; Durán Benito, Adrián
ISSN 0003-813X  Vol. 56  Nº 4  2014  págs. 541 - 561
This study discusses the materials and traditional knowledge used in the manufacture and application of lime mortars and stuccoes by Romans and Arabs in Seville (southern Iberian Peninsula). All of the samples studied contain calcite as a binder, combined with aggregates based on river sand from the filling materials of the Guadalquivir River's depression, located in the vicinity of the Real Alcazar Palace in Seville, Spain, where the artefacts were discovered. The Romans used high-quality production technology, as evidenced by the careful selection of raw materials as well as by the adequate binder-to-aggregate ratio and the elevated homogeneity of the mortars and stuccoes. The suitable distribution of aggregates resulted in higher density values for Roman fragments than for Arabic ones. Results derived from Arabic samples suggest a decline in technology manufacture over time. This work provides useful information, particularly regarding the Roman and Arabic periods in the Iberian Peninsula. The analytical techniques employed in this study were X-ray diffraction ( XRD), X-ray fluorescence ( XRF)-using conventional and portable systems, scanning electron microscopy ( SEM), petrographic microscopy, differential thermal analysis/thermogravimetry ( DTA/ TG), particle-size analysis and mercury intrusion porosimetry.
Autores: Durán Benito, Adrián; Navarro Blasco, Íñigo; Fernández Álvarez, José María; et al.
ISSN 0950-0618  Vol. 58  2014  págs. 147 - 158
The performance of air lime mortars modified by the incorporation of large amounts of nanostructured colloidal silica ¿ nanosilica, NS - (6, 10 and 20 wt.% with respect to lime) was the main objective of this work. Fresh mixture properties (water demand, setting time and plastic shrinkage), mechanical strengths up to one year and specimens¿ durability after accelerated ageing conditions (climatic chamber, freeze-thaw cycles and sulfate attack by MgSO4 corrosion test) were evaluated. NS was seen to have a strong pozzolanic activity in air lime media. Although the addition of NS gave rise to an increase in volume contraction, the superficial cracking caused by the drying shrinkage was reduced. A noticeable increase in the compressive strength values was observed in the NS-bearing mortars owing to the NS filler effect and the C-S-H formation, as proved by SEM examination and MIP analysis. A honeycomb-shaped network of C-S-H phases appeared as the prevailing microstructure in mortars with large NS additions. In the face of accelerated ageing processes, the presence of NS made the mortars more durable, delaying the progress of decay.
Autores: Sirera Bejarano, Rafael; Álvarez Galindo, José Ignacio; Durán Benito, Adrián; et al.
ISSN 2255-453X  Vol. 2  Nº 1  2014  págs. 83 - 92
Los medios audiovisuales son herramientas adecuadas hoy en día para ilustrar el desarrollo de las clases magistrales impartidas por el profesor universitario. El alumno se desenvuelve con soltura en estos soportes, y la utilización de estos medios es un óptimo complemento para una buena comprensión del tema. Particularizando esta acción en estudios experimentales, como la Química, las ventajas que aporta el empleo de estos materiales son claras, tanto en el entendimiento de los temas como en el propio acercamiento del alumno a aspectos más prácticos y relacionados con el ejercicio profesional al que se dedicarán cuando finalicen los estudios. El presente trabajo evalúa los resultados de aplicar las nuevas tecnologías en la enseñanza de la Química a estudiantes de la Universidad de Navarra. Se pretende identificar elementos propios del ejercicio profesional del químico y relacionar los contenidos teórico-prácticos de las asignaturas con el mismo, consiguiendo además con ello un mejor conocimiento de la materia objeto de estudio. La percepción de los alumnos ha sido ciertamente positiva en términos de un incremento de interés por las materias implicadas y de una mejora en la comprensión de las mismas.
Autores: Fernández Álvarez, José María; Navarro Blasco, Íñigo; Durán Benito, Adrián; et al.
ISSN 0301-4797  Vol. 140  2014  págs. 1 - 13
Polyphosphate-modified calcium aluminate cement matrices were prepared by using aqueous solutions polluted with toxic metals as mixing water to obtain waste-containing solid blocks with improved management and disposal. Synthetically contaminated waters containing either Pb or Cu or Zn were incorporated into phosphoaluminate cement mortars and the effects of the metal¿s presence on setting time and mechanical performance were assessed. Sorption and leaching tests were also executed and both retention and release patterns were investigated. For all three metals, high uptake capacities as well as percentages of retention larger than 99.9% were measured. Both Pb and Cu were seen to be largely compatible with this cementitious matrix, rendering the obtained blocks suitable for landfilling or for building purposes. However, Zn spoilt the compressive strength values because of its reaction with hydrogen phosphate anions, hindering the development of the binding matrix.
Autores: Durán Benito, Adrián; López-Montes, A.; Castaing, J.; et al.
ISSN 0305-4403  Vol. 45  2014  págs. 52 - 58
A system of complementary X-ray diffraction (XRD) and fluorescence (XRF) was used for non-invasive in situ identification of inorganic materials in a highly valuable illuminated parchment, now preserved at the Archive of the Royal Chancellery in Granada (Spain), via which King Enrique IV (1425¿1474) conferred nobility on Gil Fernandez and Alonso Covo. The study of organic matter, by capillary electrophoresis (CE), could not be performed without taking microsamples that had also been used to confirm ¿ by micro-Raman spectroscopy and scanning electron microscopy (SEM¿EDX) ¿ the nature of inorganic materials that had been identified by XRD¿XRF. Gold and silver were detected as well as lead tin oxide in yellow, azurite in blue, vermilion and minium in reddish colours and malachite in green. Calcite was applied to the entire sheets and gypsum to the text area. Iron-based ink was used for the parchment text. These analyses enable the document to be put into its historical context; they serve as a starting point in a comparative study with other similar documents, for the reconstruction of its documentary archaeology.
Autores: Navarro Blasco, Íñigo; Pérez-Nicolás, M.; Fernández Álvarez, José María; et al.
ISSN 0950-0618  Vol. 73  2014  págs. 1 - 12
Two polycarboxylate ether copolymers were assessed as superplasticizers (SPs) for hydrated lime pastes modified with two reactive compounds, nanosilica (NS) and ceramic metakaolin (MK). Characterization of the molecular structure of the SPs by Size Exclusion Chromatography, XRD, FTIR and MALDI-TOF (Matrix Assisted Laser Desorption Ionization Time-of-Flight) mass spectrometry was performed. The structures of the polymers were seen to be star- and worm-like shapes. A close relationship was found between the molecular architecture and the flowability of the pastes, being the star-shaped plasticizer the most efficient. Zeta potential assessment allowed us to elucidate a steric hindrance as the main action mechanism for these polymers. The large specific surface area of nanosilica led to a large SPs consumption as compared with metakaolin with lower surface area. However, SPs in MK¿lime samples were attached favourably on the C¿S¿H and aluminate hydrates, so that the dispersing action was greater with respect to NS¿lime suspensions.
Autores: Perez-Rodriguez, J. L.; Robador, M. D.; Centeno, M. A.; et al.
ISSN 1386-1425  Vol. 120  2014  págs. 602 - 609
This work describes a comparative study between in situ applications of portable Raman spectroscopy and direct laboratory measurements using micro-Raman spectroscopy on the surface of small samples and of cross sections. The study was performed using wall paintings from different sites of the Alcazar of Seville. Little information was obtained using a portable Raman spectrometer due to the presence of an acrylic polymer, calcium oxalate, calcite and gypsum that was formed or deposited on the surface. The pigments responsible for different colours, except cinnabar, were not detected by the micro-Raman spectroscopy study of the surface of small samples taken from the wall paintings due to the presence of surface contaminants. The pigments and plaster were characterised using cross sections. The black colour consisted of carbon black. The red layers were formed by cinnabar and white lead or by iron oxides. The green and white colours were composed of green emerald or atacamite and calcite, respectively. Pb3O4 has also been characterised. The white layers (plaster) located under the colour layers consisted of calcite, quartz and feldspars. The fresco technique was used to create the wall paintings. A wall painting located on a gypsum layer was also studied. The Naples yellow in this wall painting was not characterised due to the presence of glue and oils. This study showed the advantage of studying cross sections to completely characterise the pigments and plaster in the studied wall paintings.
Autores: Álvarez Galindo, José Ignacio; Fernández Álvarez, José María; Navarro Blasco, Íñigo; et al.
ISSN 1044-5803  Vol. 80  2013  págs. 36-49
The addition of a pozzolanic nanosized material, nanosilica (NS), onto lime binding materials was carried out with the aim of assessing the microstructural modifications attained by its presence that were related to the mechanical behavior. Simultaneously, a comparative study between five different drying methods for water removal was reported, and their influence on the pore structure evaluation is discussed. Solvent-exchange with isopropanol and freeze-drying methods were shown to remove the excess of free water efficiently, allowing us to measure the gel pores (< 10 nm) of the calcium silicate hydrated (C-S-H) phases and yielding the largest surface area values. By using vacuum drying, oven drying at 60ºC or oven drying at 105ºC macro-, meso- and micropores could not be properly measured. On the other hand, the addition of NS dramatically altered the mesopore range. As a result of the intercalation of NS particles between lime particles, a drop in the population of large and medium capillary pores (in the range of 20-100 nm) was observed, leading to reduced overall porosity. The NS was clearly proven to act as nanofiller. Finally, this filling effect of NS together with the development of C-S-H gel, as a consequence of the pozzolanictype reaction proved by the increase of population in the micropore range, notably enhanced the compressive strength of the lime binding materials, yielding values more than twice those of the NS-free materials.
Autores: Navarro Blasco, Íñigo; Fernández Álvarez, José María; Durán Benito, Adrián; et al.
ISSN 0950-0618  Vol. 48  2013  págs. 218 - 228
The recycling of WFS in calcium aluminate cement mortars at high level of replacement (50%) was studied. Consistency and setting time were measured in fresh mortars. Two different curing conditions were used, the second one with the aim of enhancing the formation of stable cubic calcium aluminate hydrates. Compressive strength, pore size distribution and SEM examination were carried out to assess the effectiveness of CAC matrix in the recycling of WFS. The effect of the incorporation of a polymeric admixture - a chitosan derivative - was also explored. Leaching studies on hardened mortars of three target pollutants of the WFS (toxic metals Pb, Cr and Zn) were also done to evaluate their immobilization. By comparison with OPC mortars, the use of CAC showed several advantages, improving the compressive strength and the toxic metal retention.
Autores: Navarro Blasco, Íñigo; Durán Benito, Adrián; Sirera Bejarano, Rafael; et al.
ISSN 0304-3894  Vol. 260  2013  págs. 89-103
The ability of calcium aluminate cement (CAC) to encapsulate toxic metals (Pb, Zn and Cu) was assessed under two curing conditions. Changes in the consistency and in the setting time were found upon the addition of the nitrates of the target metals. Both Pb and Cu caused a delay in CAC hydration, while Zn accelerated the stiffening of the mortar. Compressive strengths of the metal-doped mortars, when initially cured at 60ºC / 100%RH, were comparable with that of the free-metal mortar. Three different pore size distribution patterns were identified and related to the compounds identified by XRD and SEM. Sorbent capacities of CAC for the toxic metals were excellent: a total uptake was achieved for up to 3 wt.% loading of the three metals. In this way, CAC mortars were perfectly able to encapsulate the toxic metals, allowing the use of CAC for waste management as proved by the leaching tests.
Autores: Fernández Álvarez, José María; Durán Benito, Adrián; Navarro Blasco, Íñigo; et al.
ISSN 0008-8846  Vol. 43  Nº 1  2013  págs. 12 - 24
The effect of individual and combined addition of both nanosilica (NS) and polycarboxylate-ether plasticizer (PCE) admixtures on aerial lime mortars was studied. The sole incorporation of NS increased the water demand, as proved by the mini-spread flow test. An interaction between NS and hydrated lime particles was observed in fresh mixtures by means of particle size distribution studies, zeta potential measurements and optical microscopy, giving rise to agglomerates. On the other hand, the addition of PCE to a lime mortar increased the flowability and accelerated the setting process. PCE was shown to act in lime media as a deflocculating agent, reducing the particle size of the agglomerates through a steric hindrance mechanism. Mechanical strengths were improved in the presence of either NS or PCE, the optimum being attained in the combined presence of both admixtures that involved relevant microstructural modifications, as proved by pore size distributions and SEM observations.
Autores: Perez-Rodriguez, J. L.; Robador, M. D.; Jimenez de Haro, M. C.; et al.
ISSN 2050-7445  Vol. 1  Nº 4  2013  págs. 1 - 11
Background The first stable material used to create a gilded surface was gold. False gold was also found in the form of copper-zinc powders or silver covered with resin. There are various ways to make gold leaf adhere to a large surface area. The identification of the materials and processes to make the gilding and the use of non- invasive techniques for gilding study is still an open problem. The gilding of the medallions from the Mudejar palace of Sevilla Alcazar was investigated, and their components were characterised using non-invasive (in situ and laboratory) techniques such as X-ray fluorescence, ¿-Raman, infrared spectroscopy, X-ray diffraction and scanning electron microscopy coupled with energy dispersive X-rays. Cross-sections of golden support were also performed and studied by SEM-EDX. Results The leaf adhered to the surface was primarily a gold alloy. However, copper, silver and zinc were also found. A layer of lead chromate with some lead sulphate was between the alloy and the support. This yellow pigment (lead chromate) and the layers of bole and white lead were characterised in cross-sections prepared from samples taken from the medallions in which the golden layer was missing. The support was composed of gypsum. Another golden layer applied in oldest time period was also found. Conclusion The non-invasive techniques provided useful information about the characterisation of the components of the golden medallions. However, complete characterisation of the medallions required the use of other techniques such as mass spectrometry and scanning electron microscopy- energy dispersive X-ray. This is the first time that lead chromate has been detected in gildings. The external gilding was applied at the beginning of the 19th century using mordant oil (linseed oil).
Autores: Justo-Estebaranz, A.; Herrera, L. K.; Durán Benito, Adrián; et al.
ISSN 0039-3630  Vol. 57  Nº 1  2012  págs. 21-28
The restoration of the Cavaille-Coll Romantic organ housed in La Merced Church of Burgos, Spain is described in this paper. The organ was affected by a fire that took place in the church. The effect of the fire on the pipes differed depending on their location within the instrument. A combination of analytical techniques (X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray analysis, particle-induced X-ray emission, metallography, and specific density) allowed the accurate determination of the microstructures and compositions of the alloys used to make the different pipes of the organ, some of which had a high tin content and others which had a high lead content. The most damaged pipes were replaced by reconstructed pipes made out of metallic sheets of the same composition as the originals, to ensure a historically accurate sound.
Autores: Perez-Rodriguez, J. L.; Durán Benito, Adrián; Arquillo, D.; et al.
Revista: MACLA
ISSN 1885-7264  Vol. 16  2012  págs. 48 - 49
Autores: Franquelo, M. L. ; Durán Benito, Adrián; Castaing, J. ; et al.
Revista: TALANTA
ISSN 0039-9140  Vol. 89  2012  págs. 462 - 469
This paper presents the novel application of recently developed analytical techniques to the study of paint layers on sculptures that have been restored/repainted several times across centuries. Analyses were performed using portable XRF, mu-XRD and mu-Raman instruments. Other techniques, such as optical microscopy, SEM-EDX and mu-FTIR, were also used. Pigments and other materials including vermilion, minium, red lac, ivory black, lead white, barium white, zinc white (zincite). titanium white (rutile and anatase), lithopone, gold and brass were detected. Pigments from both ancient and modern times were found due to the different restorations/repaintings carried out. mu-Raman was very useful to characterise some pigments that were difficult to determine by mu-XRD. In some cases, pigments identification was only possible by combining results from the different analytical techniques used in this work. This work is the first article devoted to the study of sculpture cross-section samples using laboratory-made mu-XRD systems.
Autores: Beck, L.; Rousseliere, H.; Castaing, J.; et al.
ISSN 1960-1360  Vol. 36  2012  págs. 139 - 152
La Grotte de Rouffignac (Dordogne, France) est un site d'art paléolithique qui renferme de nombreux dessins réalisés au trait noir (mammouths, bisons, rhinocéros laineux, chevaux, bouquetins...). Bien qu'aucune datation directe n'ait été réalisée à ce jour, les œuvres graphiques de cette caverne sont en général rattachées au Magdalénien.
Autores: Durán Benito, Adrián; Robador, M. D.; Perez-Rodriguez, J. L.;
ISSN 1558-3058  Vol. 6  Nº 3  2012  págs. 342-358
This study focused on the degradation processes for two historic buildings, one in a rural and one in an urban environment. Samples collected from the Romanesque Church of Torme and from two areas of the Cathedral of Burgos were studied by using optical and electron microscopy, x-ray spectrometry, x-ray diffraction, Fourier transform infrared spectroscopy and thermal analysis (TG/DTA/DTG). As result of the action of microorganisms, weddellite and whewellite were found to have formed over the entire external walls of the Church of Torme, built with dolomitic rock. Gypsum, formed by the effects of atmospheric pollution, appeared on lime plasters applied as protective coatings on the external stones of Burgos' Cathedral. Also discussed in this study is the different composition of these plasters, based on the use of calcareous and siliceous aggregates.
Autores: Durán Benito, Adrián; Franquelo, M. L.; Centeno, M. A.; et al.
ISSN 0377-0486  Vol. 42  Nº 1  2011  págs. 48 - 55
An Arabic manuscript, supposed to be from the 14th century, was investigated and its components (pigments and dyestuffs) characterised using micro-Raman and X-ray fluorescence (XRF) spectroscopy, the latter employing a portable XRF/X-ray diffraction (XRD) system. The presence of anatase, rutile, calcite, barite, zinc oxide, carbon black, vermilion, hematite, goethite, beta-naphthol, copper phthalocyanine, pigmosol green and a brass-based pigment was detected in the different zones of the illuminated manuscript. The detection of titanium oxides, barite and organic synthetic colourants such as beta-naphthol and copper phthalocyanine and derived compounds provides indisputable indication of forging, repainting or retouching after the 19th century in the image of the manuscript.
Autores: Romero-Pastor, J.; Durán Benito, Adrián; Rodriguez-Navarro, A. B.; et al.
ISSN 0003-2700  Vol. 83  Nº 22  2011  págs. 8420 - 8428
This work shows the benefits of characterizing historic paintings via compositional and microtextural data from micro-X-ray diffraction (¿-XRD) combined with molecular information acquired with Raman microscopy (RM) along depth profiles in paint stratigraphies. The novel approach was applied to identify inorganic and organic components from paintings placed at the 14th century Islamic University¿Madrasah Yusufiyya¿in Granada (Spain), the only Islamic University still standing from the time of Al-Andalus (Islamic Spain). The use of ¿-XRD to obtain quantitative microtextural information of crystalline phases provided by two-dimensional diffraction patterns to recognize pigments nature and manufacture, and decay processes in complex paint cross sections, has not been reported yet. A simple Nasrid (14th century) palette made of gypsum, vermilion, and azurite mixed with glue was identified in polychromed stuccos. Here also a Christian intervention was found via the use of smalt, barite, hematite, Brunswick green and gold; oil was the binding media employed. On mural paintings and wood ceilings, more complex palettes dated to the 19th century were found, made of gypsum, anhydrite, barite, dolomite, calcite, lead white, hematite, minium, synthetic ultramarine blue, and black carbon. The identified binders were glue, egg yolk, and oil.
Autores: Perez-Rodriguez, J. L.; Durán Benito, Adrián; Perez-Maqueda, L. A.;
ISSN 1388-6150  Vol. 104  Nº 2  2011  págs. 467 - 474
In this study, the decomposition behaviour of unaltered and altered dolomitic rock samples used in Cultural Heritage buildings was studied by simultaneous TG-DTA experiments at different atmospheres, X-ray diffraction in a high-temperature chamber, and evolved gas analysis. The components of dolomite rock samples and hydrated calcium oxalate formed during the alteration processes of the rocks were characterized, and the decomposition mechanisms of these components were determined. The TG-DTA experiments carried out at CO(2) atmosphere were used to determine the carbonate compounds in the rock samples. The TG-DTA study characterized the presence of organic compounds formed during the biological degradation of the rock samples, possibly responsible of the hydrated calcium oxalate formation.
Autores: Perez-Rodriguez, J. L.; Durán Benito, Adrián; Centeno, M. A.; et al.
ISSN 0040-6031  Vol. 512  Nº 1-2  2011  págs. 5 - 12
This work describes the thermal transformation of patina samples formed on the surface of dolomitic rocks used to build the Romanesque Torme's Church (Burgos, Spain). Analyses were performed using a combination of high-temperature XRD, simultaneous TG/DTA and gas mass spectrometry. The XRD analysis revealed the presence of hydrated calcium oxalates. The following three steps were proposed for the thermal transformation of the raw material: dehydration of weddellite/whewellite to form calcium oxalate, transformation of calcium oxalate to calcium carbonate, and formation of calcium oxide produced via decomposition of the calcite. DTA/TG and mass spectrometry analyses confirmed this mechanism. In addition, a high proportion of organic compounds was detected and was possibly formed via degradation of products applied for the building's conservation by the action of microorganisms attack. Mass spectrometry analysis revealed CO (and CO2) gas evolved during the transformation of CaC2O4 to CaCO3. The CO2 gas also appears at 765 °C due to the decomposition of calcium carbonate, and it appears over a large range of temperatures due to the decomposition of organic compounds. The TG analyses performed in a CO2 atmosphere were used to determine the percentages of Ca and Mg contained in dolomite, and the calcium carbonate formed by oxalate decomposition. DRIFTS and mass spectrometry results revealed the presence of several aliphatic and/or aromatic compounds containing Cdouble bond; length as m-dashO groups.
Autores: Espejo Arias, T.; Lazarova Stoytcheva, I.; Campillo Garcia, D.; et al.
ISSN 0211-3589  Vol. 32  Nº 2  2011  págs. 519 - 532
El texto que presentamos recoge las principales conclusiones que han derivado de los estudios sobre la Colección de documentos árabes del Archivo Histórico Provincial de Granada. Compuesta principalmente por documentos de carácter jurídico, el análisis del contenido de cada uno de ellos en relación con la materialidad del soporte y las tintas así como la coincidencia en el diseño y planificación de la página revelan el uso de idénticos protocolos de ejecución. Esta investigación nos está permitiendo, además, establecer coincidencias relevantes relacionadas con los procesos de elaboración del papel entre los últimos años de permanencia de los árabes en la Península Ibérica y los primeros tras la incorporación del territorio a la Corona de Castilla y, sobre todo, con el modo de ejecutar el documento de archivo en sus formas externa e interna. This paper presents the main conclusions of our study of the Arabic documents preserved in the Archivo Histórico Provincial of Granada. The analysis of the contents of each document, the materials and inks used in their support, and also the similarities of the page layout reveals the use of identical production protocols. Furthermore, this research also enables us to establish important similarities between the paper production processes in the latter stages of the Islamic rule in the Iberian Peninsula and the earlier stages of its incorporation in the Crown of Castilla in particular in relation to how the archival documents were issu
Autores: Herrera, L. K.; Durán Benito, Adrián; Justo, A.;
ISSN 1579-8410  Vol. 21  2011  págs. 13-18
Autores: Franquelo, M. L.; Durán Benito, Adrián; Arquillo, D.; et al.
ISSN 0038-7010  Vol. 44  Nº 7-8 ; S1  2011  págs. 464 - 468
The chromatic characterization of the external part of the sculpture showed homogeneity values in the majority of the colored zones. The optical microscopy study showed different layers in the painting cross-sections. The complex polychromy was attributed to several restoration processes carried out along the time. The composition of the different layers of painting cross-sections was studied using the micro-Raman technique. The micro-Raman technique was very useful in characterizing some pigments that are difficult to determine by other experimental techniques. The study showed the presence of several pigments that had been applied in ancient and recent times.
Autores: Garofano, I.; Durán Benito, Adrián; Perez-Rodriguez, J. L.; et al.
ISSN 0038-7010  Vol. 44  Nº 7-8 ; S1  2011  págs. 560 - 565
Full identification of pigments used in wall paintings by Romans and Arabs that were recently discovered was achieved by the combined application of several spectroscopy methods. Identification of pigments was provided by the use of micro-Raman and FT-IR spectroscopy, while UV-Visible spectroscopy and chromatic studies permitted the authors to identify slight variations of hue attributed to mixtures of pigments. Natural earths and minerals were detected as the main pigments employed by both civilizations, although some differences were found between them. Red ochre, vermilion, yellow ochre, Egyptian blue, green earth, calcite, carbon, and possibly ivory blacks were identified in the Roman paintings. Only hematite and calcite were observed in the Arabic fragments.
Autores: Durán Benito, Adrián; Perez-Rodriguez, J. L.; Jimenez de Haro, M. C.; et al.
ISSN 0305-4403  Vol. 38  Nº 9  2011  págs. 2366 - 2377
A portable XRD/XRF system and complementary laboratory techniques were employed to improve the knowledge of the procedures used to create Roman and Arabic wall paintings. Integrated physico-chemical investigations were conducted on fragments of artworks collected from the archaeological excavation of the Patio de Banderas in the Reales Alcazares¿ Palace of Seville (Spain), and a comparative study on the pigments from both historical periods was performed. As a result, pigments such as vermilion, red ochre, yellow ochre, green earth, Egyptian blue, carbon and phosphor-based black pigments were detected in Roman samples; however, in the Arabic fragments, only haematite was observed. In addition, the size and shape of the particles of the wall paintings were studied with an XRD 2-dimensional detector and SEM-EDX.
Autores: Durán Benito, Adrián; Castaing, J.; Walter, P.;
ISSN 0947-8396  Vol. 99  Nº 2  2010  págs. 333 - 340
The full identification of artwork materials requires not only elemental analysis but also structural information of the compounds as provided by X-ray diffraction (XRD). This is easily done when taking samples (or micro-samples) from artworks. However, there is an increasing interest in performing non-destructive studies that require adapted XRD systems. Comparative study of synchrotron high-resolution X-ray powder diffraction (SR-HRPD) and laboratory non-destructive systems (portable XRD and micro-XRD) is the main objective of this work. There are no qualitative differences among the three systems as for detected phases in the Pompeian wall paintings that were studied, except in the case of minority phases which only were detected by SR-HRPD. The identified pigments were goethite, hematite, cinnabar, glauconite, Pompeian blue, together with calcite, dolomite and aragonite. Synchrotron XRD diagrams show better resolution than the others. In general, the peak widths in the diagrams obtained with the portable XRD system are similar to those obtained by micro-diffraction equipment. Factors such as residual divergence of X-ray sources, incidence angle and slit or collimator size are discussed in relation with the quality of XRD diagrams.
Autores: Durán Benito, Adrián; Robador, M. D.; Jimenez de Haro, M. C.; et al.
ISSN 0465-2746  Vol. 60  Nº 297  2010  págs. 83 - 95
The present article describes a chemical and physical study of the colour, chemical composition and mineral phases of the decorative materials in the Seville City Hall Chapter House ceiling. The findings showed that the inner most layer of material, calcite, was covered with white lead, in turn concealed under a layer of gilded bole. The ceiling underwent re-gilding, also over bole, due in all likelihood to wear on the original gold leaf. In the nineteenth century, the entire ceiling with the exception of the inscriptions was whitewashed with calcite and white lead. Silver was employed on King John I's sword (coffer 27). Gold leaf was used to adorn the royal attributes: crowns, belts, sceptres, swords and rosary beads. The high reliefs were likewise gilded. The pigments identified on the ceiling adornments included azurite, malachite, vermilion and gas black. A lime and ground dolomite mortar was used throughout.
Autores: Pages-Camagna, S.; Laval, E.; Vigears, D.; et al.
ISSN 0947-8396  Vol. 100  Nº 3  2010  págs. 671 - 681
The concurrence and complementarities of obtained images under various wavelengths and the elemental and structural analyses provided by XRF and XRD, using portable non-invasive systems, have allowed for obtaining accurate data about the employed pictorial technique in two Egyptian wall paintings dating from the New Kingdom. Thus, compounds such as Egyptian blue, Egyptian green, goethite, jarosite, hematite, calcite, anhydrite or huntite have been detected in the paintings. The performance of the measurements by the different techniques and its contribution to the knowledge of the materials are discussed. They notably give a clue on the origin of arsenic compounds, unexpectedly detected in some decors.
Autores: Durán Benito, Adrián; Siguenza, M. B.; Franquelo, M. L.; et al.
ISSN 0003-2670  Vol. 671  Nº 1-2  2010  págs. 1 - 8
This paper describes one of the first case studies using micro-diffraction laboratory-made systems to analyse painting cross-sections. Pigments, such as lead white, vermilion, red ochre, red lac, lapis lazuli, smalt, lead tin yellow type I, massicot, ivory black, lamp black and malachite, were detected in cross-sections prepared from six Bartolome Esteban Murillo paintings by micro-Raman and micro-XRD combined with complementary techniques (optical microscopy, SEM-EDS, and FT-IR). The use of micro-XRD was necessary due to the poor results obtained with conventional XRD. In some cases, pigment identification was only possible by combining results from the different analytical techniques utilised in this study.
Autores: Espejo, T.; Durán Benito, Adrián; Lopez-Montes, A.; et al.
ISSN 1296-2074  Vol. 11  Nº 1  2010  págs. 50 - 58
This work focuses on the study of paper and textiles used in the binding of a series of manuscripts that share some specific characteristics that lead us to speculate on the possibility of a transitional codicological typology from the Arabic to the Christian book in Al-Andalus during the 15th century. The books we analyzed belong to the collection of the Historical Archive of Malaga, the Archive of Sacromonte Abbey, in Granada, the School of Arabic Studies and the Library of RP. Escolapios, also in Granada. Paper physical study was performed by microscopic and spectroscopic techniques. A routine and objective method, Fourier Transform Infrared (FIR) spectroscopy, was employed and proved to be a useful technique for the characterization of cellulosic fibres, main component of paper from the boards and the envelope flap pasteboards, and the fabric lining from the cover. The results of our research will help us to date, identify and study the evolution of the techniques, proving that the materials and innovations of the Italian paper manufacturing processes were perfectly known in the south of modern day Spain, before the Christian Reconquest.
Autores: Durán Benito, Adrián; Perez-Maqueda, L. A.; Poyato, J.; et al.
ISSN 1388-6150  Vol. 99  Nº 3  2010  págs. 803 - 809
Roman ancient mortars have been widely studied, in connection with both diagnosis and application required for restoring. Thermoanalytical experiments performed on mortars from Pompeii and Herculaneum provided a very good understanding of the technology employed. The mortars from Pompeii were obtained by the proper mixing of lime and marble grains while mortars of Herculaneum by lime and silicates compounds. The position of the endothermic peak of calcite decomposition showed important variations in the different samples studied, which was assigned to the different crystallinity and particle sizes. Experiments under CO(2) flow confirmed the presence of magnesium calcium carbonates.
Autores: Perez-Rodriguez, J. L.; Durán Benito, Adrián; Sanchez-Jimenez, P. E.; et al.
ISSN 0002-7820  Vol. 93  Nº 8  2010  págs. 2392 - 2398
Pyrophyllite is a raw material of significant interest due to its large number of applications. Most of these applications require a thermal transformation of pyrophyllite; this thermal transformation implies the release of structural OH groups and the formation of new phases. In this paper, we report on the dehydroxylation of pyrophyllite and the reversibility of the process. A value of 224 +/- 16 kJ/mol for the dehydroxylation of pyrophyllite was obtained. In addition, it was observed that the partially or totally dehydroxylated pyrophyllite suffered a partial reversible rehydroxylation when cooled to room temperature. This rehydroxylation was substantiated by thermogravimetric measurements, while infrared spectroscopic studies showed that, during the rehydroxylation, the intensity of the OH band at 3675 cm-1 increased as two new bands at 3690 and 3702 cm-1 appeared. This rehydroxylation process was heavily influenced by the particle size of the pyrophyllite. Thus, smaller particles (< 1 mu m) showed a larger rehydroxylation percentage (about 12%), while the larger ones (20-40 mu m) showed a smaller percentage (about 1.6%). The extent of rehydroxylation also depended on the dehydroxylation temperature and reached a maximum value at 750 degrees C.
Autores: Robador, M. D.; Perez-Rodriguez, J. L.; Durán Benito, Adrián
ISSN 0305-4403  Vol. 37  Nº 10  2010  págs. 2426 - 2432
This paper deals with some of the hydraulic structures of Augusta Emerita (Merida, Spain), specifically those found in the Mithraeum House. In particular, we describe and characterise the hydraulic mortars and coatings of the viridarium water channel. The recipient of the channel was covered with two hydraulic mortars and a finishing coating. Hydrated lime was used as binder. Calcite grains with different morphology have been observed in the mortars studied. The siliceous aggregate was composed of quartz, mica and feldspars. Ceramic fragments, which were added to the mortar to improve its hydraulic properties, were composed of quartz, mica, iron oxides, anorthite and an amorphous phase; aluminium-iron silicates were used as raw materials for their manufacture. We discuss the interactions between the hydrated lime and the surface of the ceramics in the mortars.
Autores: Durán Benito, Adrián; Jimenez de Haro, M. C.; Perez-Rodriguez, J. L.; et al.
ISSN 0003-813X  Vol. 52  2010  págs. 286 - 307
The employment of synchrotron techniques complemented by conventional laboratory systems has allowed us to deepen and improve our knowledge of Roman wall painting procedures. The palette identified in wall paintings from Pompeii and Herculaneum from the second century bc includes goethite, hematite, cinnabar, glauconite, Egyptian blue, and other components such as calcite and aragonite. Proof of the use of organic binders is provided by FTIR and PY-GC/MS. Therefore, the possibility of the use of 'a secco' techniques cannot be ruled out. Pigments in wall paintings are usually found in small percentages and conventional X-ray diffractometers do not detect them. Synchrotron radiation - high-resolution X-ray powder diffraction has allowed identification with only a few micrograms of sample.
Autores: Romero-Pastor, J.; Durán Benito, Adrián; Rodriguez-Navarro, A.; et al.
Revista: MACLA
ISSN 1885-7264  Vol. 13  2010  págs. 185 - 186
Autores: Herrera, L. K.; Justo, A.; Durán Benito, Adrián; et al.
ISSN 0947-8396  Vol. 99  Nº 2   2010  págs. 391 - 398
A complete characterisation of fibres used in Spanish artwork is necessary to provide a complete knowledge of these natural fibres and their stage of degradation. Textile samples employed as painting supports on canvas and one sample of unprocessed plant material were chosen for this study. All the samples were investigated by synchrotron radiation X-ray diffraction (SR-XRD). Flax and cotton have the Cellulose I structure. The values of the crystalline index (CI) were calculated for both types of fibres. The structure of Cellulose IV was associated with the unprocessed plant material. The information obtained by SR-XRD was confirmed by laboratory techniques including scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR).
Autores: Eveno, M.; Durán Benito, Adrián; Castaing, J.;
ISSN 0947-8396  Vol. 100  Nº 3  2010  págs. 577 - 584
It is rare that the analyses of materials in paintings can be carried out by taking micro-samples. Valuable works of art are best studied in situ by non-invasive techniques. For that purpose, a portable X-ray diffraction and fluorescence apparatus has been designed and constructed at the C2RMF. This apparatus has been used for paintings of Rembrandt, Leonardo da Vinci, Van Gogh, Mantegna, etc. Results are given to illustrate the performance of X-ray diffraction, especially when X-ray fluorescence does not bring sufficient information to conclude.
Autores: Durán Benito, Adrián; Jimenez de Haro, M.C;
Libro:  La colección de documentos árabes del Archivo Histórico Provincial de Granada. Estudio, edición y facsímil digital
2020  págs. 14-31
Autores: González Sánchez, Jesús Fidel; Navarro Blasco, Íñigo; Durán Benito, Adrián; et al.
Libro:  Proceedings PRO 130 : 5th Historic Mortars Conference
2019  págs. 330 - 345
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.
Autores: González Sánchez, Jesús Fidel; Navarro Blasco, Íñigo; Durán Benito, Adrián; et al.
Libro:  Tradición, versatilidad e innovación en la cal: un material de excelencia
2018  págs. 251 - 262
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).
Autores: Durán Benito, Adrián; González Sánchez, Jesús Fidel; Navarro Blasco, Íñigo; et al.
Libro:  Tradición, versatilidad e innovación en la cal: un material de excelencia
2018  págs. 228 - 240
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
Autores: Pérez Nicolás, María; Durán Benito, Adrián; Sirera Bejarano, Rafael; et al.
Libro:  Proceedings of the 4th Historic Mortars Conference HMC 2016
2016  págs. 375 - 382
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.
Autores: Fernández Álvarez, José María; Pérez Nicolás, María; Durán Benito, Adrián; et al.
Libro:  Proceedings of the 4th Historic Mortars Conference HMC 2016
2016  págs. 721 - 728
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.
Autores: Durán Benito, Adrián; Sirera Bejarano, Rafael; Pérez Nicolás, María; et al.
Libro:  Proceedings of the 4th Historic Mortars Conference HMC 2016
2016  págs. 383 - 390
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.
Autores: Pérez Nicolás, María; Navarro Blasco, Íñigo; Durán Benito, Adrián; et al.
Libro:  Proceedings of the 4th Historic Mortars Conference HMC2016
2016  págs. 688 - 695
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.
Autores: Navarro Blasco, Íñigo; Sirera Bejarano, Rafael; Pérez Nicolás, María; et al.
Libro:  Proceedings of the 14th International Congress on the Chemistry of Cement (CD): Section 6, Alternative binders
2015  págs. 1 - 11
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.
Autores: Durán Benito, Adrián; Navarro Blasco, Íñigo; Pérez Nicolás, María; et al.
Libro:  Proceedings of the 14th International Congress on the Chemistry of Cement (CD): Section 4, Admixtures
2015  págs. 1 - 8
The behaviour of different superplasticizers admixtures was assessed for hydrated lime pastes and mortars. Sometimes, air lime pastes and mortars were modified with two supplementary cementing materials (SCMs), namely nanosilica (NS) and metakaolin (MK). Two different polycarboxylate ethers, a lignosulfonate and a naphthalene condensed sulfonate superplasticizer were added to lime pastes and mortars and their effects on fresh-state properties as well as on the mechanical strengths were evaluated. A close relationship was found between the molecular architecture of the plasticizers and the flowability of the pastes. Zeta potential assessment allowed us to elucidate the main action mechanisms for these admixtures. In the case of polycarboxylate ethers, the large specific surface area of nanosilica led to a large SPs consumption as compared with metakaolin with lower surface area. However, polycarboxylate ethers in MK-lime samples were attached favourably to the C-S-H and aluminate hydrates, so that the dispersing action was greater with respect to NS-lime suspensions.
Autores: Pérez Nicolás, María; Navarro Blasco, Íñigo; Durán Benito, Adrián; et al.
Libro:  Proceedings of the 14th International Congress on the Chemistry of Cement (CD): Section 4: Admixtures
2015  págs. 1 - 14
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.
Autores: Garófano, I.; Robador, M. D.; Durán Benito, Adrián
Libro:  Actas X Congreso Ibérico de Arqueometría
2014  págs. 211 - 223
Autores: Navarro Blasco, Íñigo; Durán Benito, Adrián; Fernández Álvarez, José María; et al.
Libro:  Proceedings of the 3rd Historic Mortars Conference HMC 13
2013  págs. 1 - 8
This work deals with the effect of the nanosilica addition on the performance of aerial lime mortars. Several lime mortars were prepared and modified upon the addition of 3, 6, 10 and 20 wt.% of nanosilica. The presence of nanosilica increased the water demand of the fresh mixtures and reduced the appearance of superficial cracks after the spreading of the mortars onto a porous stone. Setting time underwent a delay when the amount of nanosilica ranged from 3 to 10 wt.%. However, samples with 20 wt.% of nanosilica showed a shortened setting time compared to plain lime mortars. Nanosilica reacted with Ca(OH)2 particles, yielding C-S-H compounds and, acting as a nanofiller, nanosilica also caused a pore blockage in the mesoporous range. These facts resulted in an increase in both compressive strength and durability after undergoing freezing-thawing processes. Overall, the addition of nanosilica clearly improves several characteristics of the aerial lime mortars in order to prepare enhanced mixtures to be used for restoration works.
Autores: Durán Benito, Adrián; López Montes, A. M.; Tello Burgos, N.; et al.
Libro:  El Registro Notarial de Torres (1382-1400): edición y estudios
2012  págs. 71 - 104
Autores: Durán Benito, Adrián; Castaing, J.; Lehuede, P.; et al.
Libro:  Della Robbia : dieci anni di studi : dix ans d'etudes
2011  págs. 44 - 49
Autores: Justo, A.; Durán Benito, Adrián; Jiménez de Haro, M. C.; et al.
Libro:  Ciencia y tecnología para la conservación del Patrimonio Cultural
2011  págs. 9 - 12
Autores: Justo-Estebaranz, A. ; Herrera, L. K.; Sigüenza, B. ; et al.
Libro:  La gestión del patrimonio hacia un planteamiento sostenible : actas / VI Congreso Internacional "Restaurar la Memoria" Arpa 2008 La gestión del patrimonio hacia un planteamiento sostenible
2010  págs. 471 - 476
Autores: Durán Benito, Adrián
Libro:  Cuadernos de divulgación científica - Encuentros con la Ciencia
Nº 2  2010  págs. 29 - 33
El estudio cientíco del patrimonio histórico y cultural para un mejor conocimiento de la composición de todo tipo de obras de arte y para la posterior implementación de medidas que ayuden a su restauración y conservación, es una de las aplicaciones más directas que la investigación cientí ca tiene en la sociedad actual. Gracias al desarrollo tecnológico logrado en los ltimos años, se han puesto a punto nuevos equipos de análisis que permiten el estudio no destructivo de las obras
Autores: Lopez Montes, A. M.; Blanc Garcia, M. R.; Durán Benito, Adrián
Libro:  El comentario al libro de las frases (Sharh Al-Yumal) de Ibn Al-Fajjar Al Bayri
2010  págs. 343 - 358
Autores: Álvarez Galindo, José Ignacio (Editor); Fernández Álvarez, José María (Editor); Navarro Blasco, Íñigo (Editor); et al.
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.
Autores: Álvarez Galindo, José Ignacio (Editor); Fernández Álvarez, José María (Editor); Navarro Blasco, Íñigo (Editor); et al.
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.
Autores: Álvarez Galindo, José Ignacio (Editor); Fernández Álvarez, José María (Editor); Navarro Blasco, Íñigo (Editor); et al.
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,