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Grisaille was the first paint applied on stained-glass panels, used in Europe since the twelfth century. Historical written sources described the use of iron and copper together with a high lead-silica base glass in the grisailles production. This project aims to study the evolution of the grisaille paint composition throughout time and the changes in the raw materials used in their production using non-destructive and non-invasive techniques. To achieve this objective, 23 grisaille samples dated from the 13th to the twentieth centuries from nine different countries (Portugal, Poland, United Kingdom, Sweden, Norway, Belgium, Low Countries, Germany, and France) were studied by means of micro particle-induced X-ray emission (μ-PIXE), micro energy dispersive X-ray fluorescence (μ-EDXRF), laser-induced breakdown spectroscopy (LIBS), laser-induced fluorescence (LIF), non-linear optical microscopy (NLOM) in the modality of multiphoton excitation fluorescence (MPEF) and optical microscopy (OM). The results showed that it was possible to identify compositional differences and patterns throughout the samples when compared with literature results. The preference for using copper in central and south-central European countries and the addition of new compounds (CoO, Cr2O3, MnO) as colouring agents since the nineteenth century was verified. The LIBS analyses allow the identification of boron on two samples, confirming the change of base glass components since the seventeenth century. The NLOM-MPEF showed the capability of this technique to measure the grisaille paint layers’ thickness. This non-invasive multi-analytical and complementary approach proves itself efficient in identifying changes in the grisaille’s composition throughout time, which can be interpreted as changes in the raw materials and manufacture used in the production of these paint materials., This research has been funded by the H2020 European project IPERION HS (Integrated Platform for the European Research Infrastructure ON Heritage Science, GA 871034), by the Spanish State Research Agency (AEI) through project PID2019-104124RB-I00/AEI/, by the Fundação de Ciência e Tecnologia de Portugal (project ref. UIDB/EAT/00729/2020, UIDP/00729/2020, LA/P/0008/2020, UIDB/ 04349/2020 and PTDC/ART-PER/1702/2021, researcher grant CEECIND/02249/2021 and doctoral grant ref. PD/BD/136673/2018) and by project TOP Heritage-CM (S2018/NMT-4372) from Community of Madrid.

Additional file 1: Table S1. Composition (wt. %) of the glass support of each sample as obtained by μ-EDXRF.

22 pags., 7 figs., 3 tabs., Historical glass-based objects undergo, since the time of their manufacture, different degradation phenomena that are related to their composition and to the environment to which they were exposed. Three-dimensional (3D) structural and chemical characterization of the degradation layers is important to select the most adequate conservation strategies for glass objects. Optical microscopy (OM) is the most frequently used non-destructive method to examine the surface of historical glasses; however, the 3D structural assessment of alteration layers requires applying the destructive modality of this technique to conduct a cross-sectional study. In this work, a different approach for structural and compositional characterization of alteration layers on model medieval-like glasses is presented, based on the combination of the laser spectroscopies of laser-induced breakdown spectroscopy (LIBS), laser-induced fluorescence (LIF) and FT-Raman, and the emerging, cutting edge technique of nonlinear optical microscopy (NLOM) in the modality of multiphoton excitation fluorescence (MPEF). The results obtained through this multi-analytical photonic approach were compared with those retrieved by examination of the surface and cross sections of the samples by OM and scanning electron microscopy–energy-dispersive X-ray spectroscopy (SEM–EDS). While the combination of LIBS, LIF and FT-Raman served to assess the composition of the various alteration layers, the use of MPEF microscopy allowed the non-destructive determination of the thicknesses of these layers, showing for both thickness and composition a good agreement with the OM and SEM–EDS results. Thus, the proposed approach, which avoids sample preparation, illustrates the capability of non-destructive, or micro-destructive in the case of LIBS, laser spectroscopies and microscopies for the in situ study of glass objects of historic or/and artistic value., This research has been funded by the Spanish State Research Agency (AEI) through projects PID2019-104124RB-I00/AEI/1013039/501100011033, the CSIC General Foundation (ComFuturo Programme), by project TOP Heritage-CM (S2018/NMT-4372) from Community of Madrid, by the H2020 European project IPERION HS (Integrated Platform for the European Research Infrastructure ON Heritage Science, GA 871034). Support by CSIC Interdisciplinary Platform “Open Heritage: Research and Society” (PTI-PAIS) is acknowledged. M.O. thanks CSIC for a contract. Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature

Aquest treball presenta els resultats de l’estudi arqueomètric portat a terme en mostres de mosaics romans procedents d’Itàlica i Carmona (Sevilla). L’objectiu principal de l’estudi va consistir en la caracterització químico-física de tessel. les de vidre i fragments de morter per a determinar la seva composició, avaluar el seu estat de conservació i estudiar la seva tecnologia de fabricació. Les mostres es varen caracteritzar mitjançant lupa binocular, microscòpia electrònica de rastreig i microanàlisi de dispersió d’energia de raigs X, espectrofotometria visible, difracció de raigs X i anàlisi petrogràfic. Els resultats varen indicar que les tessel. les es realitzaren amb vidre de silicat sòdic càlcic, tot i que una d’elles va mostrar elevats continguts d’òxids de plom i coure. Les mostres procedents d’Itàlica presentaren una menor degradació que les de Carmona, com a conseqüència de la humitat retinguda per el mosaic. Així mateix, els resultats varen indicar que en les tessel. les es va fer servir un vidre d’inferior qualitat tècnica que l’emprat en peces de vaixella., Este trabajo presenta los resultados del estudio arqueométrico realizado en muestras de mosaicos romanos procedentes de Itálica y Carmona (Sevilla). El objetivo principal del estudio consistió en la caracterización químico-física de teselas de vidrio y fragmentos de mortero para determinar su composición, evaluar su estado de conservación y estudiar su tecnología de fabricación. Las muestras se caracterizaron mediante lupa binocular, microscopía electrónica de barrido y microanálisis de dispersión de energía de rayos X, espectrofotometría visible, difracción de rayos X y análisis petrográfico. Los resultados indicaron que las teselas se realizaron con vidrio de silicato sódico cálcico, aunque una de ellas mostró elevados contenidos de óxidos de plomo y cobre. Las muestras procedentes de Itálica presentaron una menor degradación que las de Carmona, como consecuencia de la humedad retenida por el mosaico. Asimismo, los resultados indicaron que en las teselas se utilizó un vidrio de inferior calidad técnica que el empleado en piezas de vajilla. Resum: This work reports results of the archaeometric study carried out on Roman mosaic samples from Italica and Carmona (Spain). The main objective of the research was the chemical-physical characterization of both glass tesserae and mortar fragments to determine their composition, to evaluate their state of conservation and to study their production technology. Samples were characterized by binoculare glass, scanning electron microscopy and energy dispersive X-ray spectrometry, visible spectrophotometry, X-ray diffraction and petrographic analysis. Results indicated that tesserae were made with soda-lime silicate glass, even though one of them showed high contents of lead and copper oxides. Italica samples showed a lower degradation than those from Carmona, as a consequence of humidity retained by the mosaic. Results also indicated that glass used in tesserae had a lower technical quality than that used in tableware pieces.

Additional file 1: Fig. S1. Distribution inside each desiccator during the (a) First test: selection of the best formic sink, (b) Second test: Optimization of silica gel. Fig. 2. SEM image of (a) the silica gel surface and (b) the deposits formed. Fig. 3. SEM image of the steel (a) before the test and (b) after the test. Table 1. Assignment of FTIR-ATR bands for silica gel.

UID/EAT/00729/2019 PD/BD/136673/2018 Grisaille is one of the oldest and most widely used vitreous paint applied for the production of stained-glass panels and Debitus is one of the most renowned commercial brands whose grisailles are frequently used for the chromatic reintegration in stained-glass window restoration. This article presents the morphological, chemical and thermal analyses of five grisailles from Debitus, to evaluate their properties before and after firing with the objective of knowing their future stability. The characterisation was carried out by optical microscopy, scanning electron microscopy, particle induced X-ray emission, X-ray diffraction, and infrared thermography. This study showed a well-balanced ratio between the different components and a good interdiffusion into the glass, as well as a consistent thermal behaviour between them and with the glass, which indicates the good stability and durability of these materials. publishersversion published

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UID/EAT/00729/2019 SFRH/BPD/108403/2015 publishersversion published

The main purpose of this research is to understand the production of glass in Portugal during the 18th and the 20th centuries with the aim of assessing the best procedures to be adopted in the conservation of this important legacy. This study starts with the reproduction of glass recipes existing in the Portuguese arcana, a kind of a secret notebook about glass production. With the reproduction of these recipes, it will be possible to initiate a systematic study of the glass production in Portugal, during the mentioned chronological period. This research is important not only for the history of glass in Portugal but also for the production of glass in Europe during the 18th to the 20th centuries. Through the studies already carried out about the arcana, it was possible to observe a great richness and complexity in these documents, with much information yet to be revealed about the industrial production of glass in Portugal. The ultimate goal is to establish hypotheses for the provenance of some glass objects present in Portuguese museums using an archaeometric approach to compare the reproduced glasses with the historical ones. publishersversion published

The most innovative procedure for preventive conservation of library holdings, especially those of historical interest, lies in the evaluation of environmental parameters witch have a negative effect on the conservation of such materials. The application of sensors permits for full, accurate and secure monitoring of environmental conditions and allows for the prediction of chemical-physical mechanisms of degradation, as well as of the most suitable procedures for controlling them. The sensors used in the present study were prepared by the sol-gel method and change colour when variations in the evaluated parameters occur. All of the sensors are reversible, reusable and can be regenerated. Temperature, relative humidity, illumination and acidity were the parameters evaluated. In the first stage, conventional apparatus were used to determine the critical ranges of variation for such parameters. Subsequently optical sensors sensitive in such ranges were designed and prepared. These sensors were calibrated and distributed throughout the rooms containing the holdings (approximately 3.200 square meters). The optical response of the sensors (change of colour) was recorded by visible spectrophotometry during the spring and summer of 2009. The use of sensors has the following advantages: low cost, no need for wires or apparatus during exposure, small size, reversibility, and short response time. The resulting data have revealed the environmental conditions of the conservation of the holdings, including environmental acidity, a parameter that could not be evaluated previously through conventional procedures. El procedimiento más innovador de conservación preventiva de los fondos documentales de bibliotecas, especialmente los de carácter histórico, consiste en la evaluación de los parámetros ambientales que afectan negativamente a la conservación de los materiales implicados. La aplicación de sensores permite la monitorización completa, precisa y segura de las condiciones ambientales, predecir los mecanismos quimicofísicos de degradación y los procedimientos más adecuados para controlarlos. Los sensores de este estudio se prepararon por el procedimiento sol-gel y experimentan un cambio de color cuando varían los parámetros a evaluar. Todos los sensores son reversibles, regenerables y reutilizables. Los parámetros evaluados han sido temperatura, humedad relativa, iluminación y acidez. En la primera etapa se utilizaron aparatos convencionales para determinar los intervalos críticos de variación de dichos parámetros. Posteriormente se diseñaron y prepararon sensores ópticos con sensibilidad en esos intervalos, se calibraron y se distribuyeron en las salas de los fondos documentales (aproximadamente 3.200 m2). La respuesta óptica de los sensores (cambio de color) se registró mediante espectrofotometría visible durante la primavera-verano de 2009. El uso de estos sensores presenta las siguientes ventajas: bajo coste, ausencia de cables y aparatos durante la exposición, pequeño tamaño, reversibilidad y tiempos cortos de respuesta. Los resultados han permitido conocer las condiciones ambientales de conservación de los fondos documentales, incluyendo la acidez ambiental que hasta ahora no es posible evaluar con los procedimientos convencionales disponibles.

Deixant a part prejudicis miops, hem pres com a punt de partida del present estudi un nou enfoc que ens permetera confirmar que, sota l'escorça del llarg poema de tall èpic Seidia hi havia un alé esperonador;un missatge que ultrapassava el llindar de l'enyor historicista, satisfet i anacrònic. Mossén Joaquim Garcia Girona no és pas un poeta més ,desintonitzat i estantís; un cantor d'enyorances vàcues encabides en versos innocus, perpetuadors d'una imatge desfigurada -un miratge al·lucinat- del que una Renaixença autèntica hagués fet esperable. L'autor és un sacerdot renaixentista i la seua obra, Seidia, és el reflex que així ho evidencia., Ignoring short-sighted pre-conceived views, we have adopted, as a starting point of the present study , a new approach that will enable us to state that under the surface of the epic poem Seidia there was a stimulating breath, a message that surpassed the threshold of anachronistic and self-satisfied historicist nostalgia. Rev. Joaquim Garcia Girona is not just another untuned and stagnant poet, he is not a singer of empty nostalgia wrapped in harmless verse which perpetuates a distorted image -a hallucinated image- which could be expected in an authentic Renaissance. The author is a Renaissance priest and his poem Seidia is the evident reflection of this fact.

Inside the almost monocolor panorama that literature in Castelló de la Plana presents along the first third of the XX century -dominated by a «Iandscape painten» aesthetics-, it shines for its own values «Ioesa»by Maximià Alloza. This is the unique work that shares the purposes of renewing of the Valencian authors in modernistic times. Published in 1914, «Ioesa» was a bomb: his author was accused of having done a foreign piece of work, alien to the usual poetry of that time. As a result of these attacks (certainly, not justified), Maximià Alloza left writing and found shelter in the world of painting.

Several treatments appear in the bibliography to clean the tarnished silver. However, the information about the aspect and efficiency of the cleanings is spread or not completely detailed in these works. With this purpose, a worldwide survey has been carried out to identify of the most common treatments for cleaning tarnished silver and the personal experience of professionals about the frequency of use, the cleaning efficiency, the surface appearance, the application speed, the difficulty and the applicability. This paper contains the results of this survey., The authors kindly acknowledge the help to all professionals who answered the survey. This work has been partially funded by the project CREMEL II Ref. HAR2011-22402, the pre- doctoral FPI grant BES-2012-052716 from the Spanish Ministry of Economy and Competitiveness (MINECO), the FCT post-doctoral fellowship (ref. SFRH/BPD/108403/2015) from the Portuguese Ministry of Science and Technology, and GEOMATERIALES 2-CM Program Ref. S2013/MIT-2914. Finally, the authors want to mention the professional support of the Spanish Network on Science and Technology for the Conservation of Cultural Heritage (TechnoHeritage).

Esta investigação teve como objetivo iniciar um estudo sistemático de quais seriam as composições de vidro utilizadas nas fábricas portuguesas entre os séculos XVIII e XX. Para tal, foram estudados os três arcanos conhecidos de fábricas de vidro portuguesas. Os arcanos – cadernos de apontamentos secretos – são atribuídos a fábricas e/ou vidreiros portugueses e contêm informação valiosa sobre a produção de vidro em Portugal desde o seu apogeu, século XVIII, até o seu declínio aproximado no século XX. Deste arcano foram selecionadas receitas de vidro de cristal incolor, uma das composições mais típicas neste período, pertencentes aos três arcanos de vidro portugueses conhecidos até à data – cinco receitas do arcano da Marinha Grande, cinco receitas do arcano da Fábrica das Gaivotas e três receitas do arcano de Castro e Oliveira Guerra. De modo a caracterizar os vidros reproduzidos recorreu-se a um conjunto de análises complementares como a micro fluorescência de raios-X dispersiva de energias, espetroscopia de absorvância de UV-Vis, calorimetria diferencial de varrimento, dilatometria, dureza Vickers, microscopia ótica e micro espetroscopia de Raman. As receitas selecionadas comprovaram-se viáveis de reproduzir e com boas propriedades térmicas para permitir a trabalhabilidade e criação de peças. Através dos testes de dureza concluiu-se que o vidro resultante permite a aplicação de técnicas de decoração como a gravação e lapidação, muito utilizadas pela Europa no período em questão. Foi comprovada também a semelhança em termos de composição com alguns dos vidros históricos expostos em museus portugueses e atribuídos a produção nacional. Foi ainda discutido o valor de cada arcano enquanto objeto histórico. A reprodução destas amostras irá permitir efetuar testes de envelhecimento e criação de propostas de conservação, bem como a construção de uma base de dados de composições da época, de modo a ser possível fazer atribuições dos vidros históricos, até à data de proveniência desconhecida, a indústrias portuguesas.