An Iberian Heritage: Hispano-Moresque architectural tiles in Portuguese and Spanish collections

This is the first archaeometric study comparing Hispano-Moresque tiles from different Portuguese and Spanish collections, no other published one being known at the time of writing. Despite the increasing interest in the Iberian ceramic cultural heritage, a specific study dedicated to architectural tiles was lacking. With this in mind, this thesis offers a first approach on the technological features of these impressive – although somehow undervalued – architectural tiles. With this work, important Portuguese and Spanish Hispano-Moresque tile collections are characterised, compared and studied: National Palace of Sintra (Portugal) (PNS), Monastery of Santa Clara-a-Velha (Coimbra, Portugal) (SCV), archaeological site of Santo António da Charneca (Barreiro, Portugal) (SAC), Instituto Valencia de Don Juan (Madrid, Spain) (IVDJ), Casa de Pilatos (Seville, Spain) (CPS) and Museo de Cerámica y Artes Sumtuarias “González Marti” (Valencia, Spain) (MCV). The aim is to provide a physicochemical characterisation of both the glazes and the ceramic bodies of the tiles to better understand the production technology. The methodology proposed for this study had the main purpose of developing a minimally invasive and essentially non-destructive approach with complementary analytical techniques that will allow for replication in future studies with other Hispano-Moresque tile collections. The techniques chosen were: Micro-Particle Induced X-Ray Emission (μ-PIXE), Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS), Scanning Electron Microscopy with X-ray Microanalysis (SEM-EDS), μ-Raman spectroscopy, Micro-X-ray diffraction (μ-XRD) and Synchrotron Radiation Micro-X-ray diffraction (SR-μ-XRD). The archaeometric study concluded that calcareous clays were the standard material used for the ceramic bodies of the tiles. Lime content is frequently higher than 20 wt.%, which is a high value among the typical calcareous clays analysed in the literature, although within the expected results for tinopacified ceramic bodies. The glaze technology employed in Hispano-Moresque tiles followed the Islamic tradition that was introduced in the Iberian Peninsula from the 8th century onwards. High-lead glazes (ca. 30-50 wt.% PbO) were identified in all analysed samples. Two types of high-lead glazes were identified: “transparent” and tin-opacified. Besides the disparity in tin contents, the two glaze types also evidence differences in sodium and lead values. A sodium compound (most likely NaCl) may have been added to compensate the lower PbO content in tin-opacified glazes. The pictorial layer is composed of five colours: white (SnO2), blue (SnO2 + CoO), green (CuO), amber (Fe2O3) and brown (MnO). These colours exhibit different shades depending on the glaze recipe, its thickness and the influence of the underlying ceramic body. White and blue are consistently tin-opacified, whereas most green, amber and brown glazes are transparent. The results of the archaeometric study identify a widespread ceramic technology. Nevertheless, it is still visible a higher proximity between the CPS, IVDJ-Seville, SCV and PNS collections – although with differences among them – whereas the MCV and IVDJ-Toledo groups display distinct features that attest for their different provenance

Estudo da camada pictórica na azulejaria portuguesa do século XVII

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para a obtenção do grau de Mestre em Conservação e Restauro Área de especialização: Cerâmica e VidroEstudou-se um conjunto de fragmentos de azulejos datados do século XVII, de produção portuguesa,cedido pelo Museu Nacional do Azulejo. O objectivo foi caracterizar morfológica e quimicamente a camada pictórica da azulejaria portuguesa do século XVII. O estudo utilizou uma abordagem multi-analítica, incluindo a espectrometria de fluorescência de raios X dispersiva de energias (μ-EDXRF), espectroscopia de Raman, o microscópio electrónico de varrimento com microanálise de raios X (SEM-EDS), e técnicas de observação incluindo o SEM e microscopia óptica. A azulejaria portuguesa do século XVII caracteriza-se por uma paleta cromática relativamente rica, que engloba o azul, amarelo, laranja, verde, púrpura, um tom púrpura acastanhado e ainda outro castanho muito escuro utilizado em contornos. As cores integram um fundo branco – o vidrado estanífero característico da majólica. Confirmou-se que o azul se deve ao óxido de cobalto, o púrpura ao óxido de manganês e um dos verdes, de aparência transparente, ao óxido de cobre. Os resultados indicam que o amarelo será uma variante do pigmento amarelo de Nápoles (antimoniato de chumbo), constituído por um óxido triplo de Pb-Sb-Zn. As outras cores são obtidas através de misturas: o laranja resulta da adição de hematite ao pigmento amarelo, o verde-seco resulta da adição de óxido de cobalto também ao pigmento amarelo, e os vários tons entre púrpura e castanho resultam da mistura de hematite com óxido de manganês em teores variáveis. Observaram-se morfologias distintas das cores: o amarelo, laranja e castanho-escuro permanecem à superfície do vidrado e conferem-lhe cores opacas. O azul, o verde-cobre e o púrpura difundem no vidrado em profundidade e, por vezes, horizontalmente. Os seus óxidos dissolvem-se na matriz vítrea,obtendo-se uma cor transparente. Com o verde-seco ocorre uma separação dos componentes da cor, na medida em que as partículas de pigmento amarelo permanecem à superfície, enquanto o azul difunde no vidrado

Qualidade do ar interior em habitações: fontes emissoras de poluentes

Nos últimos anos, a qualidade do ar interior tem emergido como uma das principais preocupações para os utilizadores, proprietários e gestores de edifícios. A consciência e procura de ambientes interiores saudáveis têm vindo a aumentar, sendo que é generalizado o reconhecimento da importância de ambientes interiores com concentrações de poluentes aceitáveis, confortáveis e produtivos. As pessoas gastam cerca de 90 por cento do seu tempo em ambientes fechados, sendo que o ar dentro de habitações e noutros edifícios pode ser mais poluído do que no ar exterior. Nas habitações diversas fontes emissoras de poluentes estão presentes e a distância entre estas fontes e os ocupantes é muito reduzida. Isto significa que a exposição a poluentes do ar dentro das habitações pode ser muito elevada. O presente estudo teve como objetivo caraterizar a exposição a fontes interiores em habitações. Foram estudadas as seguintes fontes emissoras: lareiras abertas e lareiras fechadas com recuperador de calor com queima de pinho e briquetes; confeção de alimentos, incluindo preparações de fritos e cozidos, bem como o uso de torradeiras elétricas. A exposição de seres humanos a poluentes durante o sono também foi avaliada. As medições de poluentes, como material particulado (PM1, PM2,5, PM10), ozono (O3), monóxido de carbono (CO), dióxido de carbono (CO2), compostos orgânicos voláteis (COVs) e formaldeído (CH2O), e parâmetros de conforto, como temperatura e humidade relativa, foram realizadas em três casas com caraterísticas diferentes. A análise temporal dos dados e a comparação entre as concentrações de poluentes medidas no interior e exterior foram utilizadas para avaliar o impacte das fontes avaliadas. Os resultados indicaram que os seres humanos estão expostos a concentrações elevadas de poluentes quando estão perto de fontes específicas. As medições efetuadas em espaços com lareiras indicaram que as concentrações foram mais elevadas no caso da lareira aberta aquando da combustão de pinho. As concentrações de partículas, COVs, CO e CH2O ultrapassaram os valores limite definidos pela legislação. Durante as atividades de culinária as concentrações de COVs, CH2O e partículas medidas na cozinha também excederam os valores limite definidos pela legislação nacional. As concentrações foram mais elevadas para a confeção de alimentos de fritos em fogão a gás e quando a torradeira foi utilizada para um pão bastante torrado. Durante a noite foi observado o aumento das concentrações de CO2 e concentrações superiores de poluentes foram registadas para porta e janela fechadas

Prevenção e segurança no trabalho em indústria metalomecânica

Relatório de estágio apresentado para obtenção do grau de Mestre em Segurança e Higiene no TrabalhoAo longo dos tempos a segurança, saúde e higiene no trabalho têm vindo a ganhar enorme importância nas organizações não só por constituir uma obrigação legal, mas também por ser vista como uma vertente essencial para manter a integridade física e psicológica dos trabalhadores, através de melhores condições de trabalho, além da enorme importância na prevenção de lesões e doenças profissionais, promovendo a produtividade laboral e a redução de custos. A segurança, saúde e higiene no trabalho são, pois, fundamentais para o êxito de uma empresa pelos diversos benefícios que promove. Deste modo, o presente relatório insere-se no âmbito do trabalho desenvolvido numa indústria metalomecânica, tendo como principal objetivo a elaboração de uma avaliação de riscos em toda a empresa, com posterior definição do plano de ações corretivas, acompanhamento das ações identificadas, assim como o seguimento da implementação e eficácia dessas ações. Desta forma, assumiu-se a responsabilidade pelo acompanhamento e controlo de ações corretivas e preventivas relacionadas com substâncias químicas, segurança contra incêndios, organização da emergência, máquinas e equipamentos de trabalho, ruído ocupacional, equipamentos de proteção individual e coletiva, realizar ações de sensibilização e formação, como também o acompanhamento e atualização de bases de dados em segurança e saúde no trabalho e apoio no reporte interno de acidentes e quase-acidentes. Em prol da melhoria contínua da gestão do risco foram realizadas semanalmente inspeções de segurança. Para o efeito foram aplicadas diversas metodologias, nomeadamente a análise documental e legislativa, técnicas de observação de atividades e de setores de trabalho, lista de verificação de inspeção de segurança no trabalho (checklist), entrevistas informais aos colaboradores, como também a aplicação do método de avaliação de riscos utilizado na empresa. Como resultado do trabalho desenvolvido foi possível assegurar as condições de segurança e higiene no trabalho na empresa, mas também identificar e implementar medidas de melhoria em diversas áreas da segurança e higiene no trabalho, em prol de uma cultura preventiva de acidentes. Também foi proposta uma adaptação da matriz de avaliação de riscos, por forma a facilitar a melhor identificação de perigo e avaliação do risco de acordo com a tarefa, atividade ou processo realizado em determinado setor de atividade de trabalho.Over the years, safety, health and hygiene at work have gained enormous importance in organizations not only as a legal obligation, but also because it is seen as an essential strand to maintain the physical and psychological integrity of workers through improved conditions of work, in addition to the enormous importance in the prevention of occupational injuries and diseases, promoting labor productivity and cost reduction. Safety, health and hygiene at work are therefore fundamental to the success of a company for the various benefits it promotes. Therefore, this report is part of the work carried out in a metal-mechanic industry, with the main objective being the elaboration of a risk assessment throughout the company, with subsequent definition of the corrective action plan, follow-up of the identified actions, as well as the follow-up of the implementation and effectiveness of these actions. In this way, responsibility for the monitoring and control of corrective and preventive actions related to chemical substances, fire safety, emergency organization, machinery and work equipment, occupational noise, individual and collective protection equipment, and training, as well as the monitoring and updating of databases on occupational safety and health and support in the internal reporting of accidents and near-accidents. In order to continuously improve risk management, weekly safety inspections were carried out. For this purpose, a number of methodologies were applied, namely documentary and legislative analysis, observation and activity observation techniques, checklist, informal interviews with employees, as well as the application of the method of risk assessment used in the company. As a result of the work carried out, it was possible to ensure the safety and hygiene conditions at work in the company, but also to identify and implement improvement measures in several areas of occupational safety and hygiene, in favor of a culture of accident prevention. It was also proposed an adaptation of the risk assessment matrix, in order to facilitate the better identification of risk and risk assessment according to the task, activity or process performed in a given sector of work activity

a review

Este estudo contou com o financiamento da Fundação para a Ciência e Tecnologia: Projecto ChromAz (PTDC/HARHIS/1899/2020), Projecto White Glazes (CEECIND/00882/2017) e Unidade de I&D Vicarte (UIDP/00729/2020 e UIDB/00729/2020). Os autores agradecem também aos revisores, cujas sugestões contribuíram para melhorar este trabalho.This paper summarises the available information to date on the pigments used on Portuguese azulejos between the late 16th century and the beginning of the 19th century. Most references cited focus on 17th-century tiles, followed by the 16th century, whereas there is very little information on the 18th and 19th centuries. Regardless of chronology, the Portuguese azulejo palette uses cobalt, copper, manganese, and iron oxides to obtain blue, green, purple, and dark brown, respectively. Yellow is obtained through the Naples yellow pigment, which could be mixed with cobalt for obtaining green, or with iron oxide for the orange colour. Blue and yellow are the most studied colours and the currently available knowledge allows us to relate changes in their chemical composition to specific time periods.publishersversionpublishe

A multi-analytical non-invasive study

Funding Information: Funding has been provided by the Fundacão para a Ciência e a Tecnologia (FCT). This work is the result of the projects “ChromAz: the Chromatic Journey of the Portuguese Azulejo” ( https://doi.org/10.54499/PTDC/HAR-HIS/1899/2020 ), White Glazes ( https://doi.org/10.54499/CEECIND/00882/2017/CP1462/CT0020 ), and LumiGLAD ( https://doi.org/10.54499/2020.00252.CEECIND/CP1586/CT0002 ). The work was carried out at the VICARTE Research Unit ( https://doi.org/10.54499/UIDB/00729/2020 and https://doi.org/10.54499/UIDP/00729/2020 ), the Associated Laboratory for Green Chemistry – Clean Technologies and Processes (LA/P/0008/2020) and LIBPhys-UNL Research Unit ( https://doi.org/10.54499/UIDB/04559/2020 and https://doi.org/10.54499/UIDP/04559/2020 ). Publisher Copyright: © 2024 The Author(s)This work provides an overview of the pigments used by Portuguese azulejo painters through the study of 34 glazed tiles belonging to the National Azulejo Museum in Lisbon, Portugal. The tiles are dated from the late 16th century to the early 19th century, with most samples attributed to the 17th and 18th centuries. Building on a previous study where the chemical composition of the 17th-century colour palette was characterised [1], we used a non-invasive methodology to further identify compositional differences among groups of colours spanning a wider timeframe. Blue, white, yellow, orange, purple, green and brown decorations were analysed by EDXRF to obtain qualitative and (in some samples) quantitative information on their chemical composition. µ-Raman spectroscopy was used to identify the main colouring agents. Finally, colorimetric measurements of the different hues of each colour were performed to address the relation between colour and chemical composition. Our results show that greens could be obtained through a copper-based pigment or by mixing lead-antimonate with cobalt-blue pigment. Although cobalt is the colouring agent of all blue decorations, compositional differences suggest the use of different types of raw materials or the addition of specific reagents to modify the hue. On the other hand, yellow hues ranging from lemon yellow to orange were manufactured by adding zinc, tin, or iron oxide to a lead antimonate base. Finally, a manganese ore was used to make the purple pigment. Overall, we noted that while the basic pigments remained the same, the colour palette was progressively widened during the 18th century. This was done by using more pure pigments (i.e., with less iron), by changing the ratio in pigment mixtures (i.e., blue and yellow), or by overlapping colour layers for artistic effects. Finally, the results of the chemical and colorimetric analyses are always influenced by the concentration of the pigment in the glaze, its thickness and the overlapping of pigments used by azulejo painters to expand the shades available for the final artistic composition.publishersversionpublishe

reelaboración experimental de recetas históricas e influencia del proceso de vidriado en el análisis in situ de obras de arte históricas

Funding Information: Funding has been provided by the Fundação para a Ciência e a Tecnologia (FCT); The work was carried out at the Associated Laboratory for Green Chemistry – Clean Technologies and Processes (LA/P/0008/2020). Publisher Copyright: © 2023 The AuthorsNaples yellow was widely used across different types of artwork. Technical studies identified a binary Pb–Sb type as well as modified ternary variants with either zinc or tin in the structure. Although these variants were the object of previous experimental studies, a better understanding of the impact of the glazing procedure on the chromatic, chemical and crystallographic characteristics of the pigment is still lacking. In this work, several historical Naples yellow recipes were re-worked and subsequently applied and fired on test tiles, over a white glaze. The results show that the interaction between pigment and glaze produces important modifications to the colour, chemistry and structure of the pigment. Such modifications will strongly impact the reconstruction of historical recipes, with major consequences for identifying Naples yellow variants on artwork and investigating artistic practices.publishersversioninpres

Cistercian Pavements from Santa Maria de Alcobaça Abbey: first examples of tin-glazed tiles in Portugal

The Mosteiro de Alcobaça (Alcobaça Monastery, founded in 1153) was built to the image of Clairvaux Abbey, founded by the Cistercian abbot St. Bernard. In many ways Alcobaça mirrored the original concepts of the Cistercian Order, with an austere architectural style and shedding signs of richness. The glazed tiles found on the pavement of the deambulatory and some adjacent chapels are some of the first examples of lead-tin glazes in Christian Portugal. For the first time, these tiles were analytically characterized, to determine their chemical composition, production technology and decoration technique. The analytical techniques used were μ-PIXE (particle-induced X-ray emission), SEM-EDS (scanning electron microscopy with energy-dispersive X-ray spectrometry), and μ-Raman spectroscopy

Impact of Biomass Home Heating, Cooking Styles, and Bread Toasting on the Indoor Air Quality at Portuguese Dwellings: A Case Study

This study evaluated the emissions of specific indoor sources usually present in Portuguese dwellings in order to understand their impact on the indoor air quality. With this aim, three typical activities were studied including home heating using two types of fireplaces (open and closed) and biofuels (pinewood and briquettes), cooking styles (frying and boiling) in different types of kitchen appliances, and several levels of bread toasting. The levels of specific pollutants were found to be above the established Portuguese limit values including VOCs, formaldehyde, and particulate matter (PM2.5 and PM10). Although these emissions are transient and short in duration, the resulting concentrations are high and can severely impact the occupants’ daily exposure. Besides promoting good ventilation, the choice of residential appliances with low emissions should be taken into account. In addition, it is important that occupants perform specific activities following the best practices so that their exposure to pollutants is minimized

Mineralogical Characterization of Hispano-Moresque Glazes: A μ-Raman and Scanning Electron Microscopy with X-Ray Energy Dispersive Spectrometry (SEM-EDS) Study

This work explores the combination of μ-Raman spectroscopy and scanning electron microscopy with X-ray energy dispersive spectrometry (SEM-EDS) for the study of the glazes in 15th–16th century Hispano-Moresque architectural tiles. These are high lead glazes that can be tin-opacified or transparent, and present five colors: tin-white, cobalt-blue, copper-green, iron-amber, and manganese-brown. They are generally homogenous and mineral inclusions are mostly concentrated in the glaze-ceramic interface. Through SEM-EDS, these inclusions were observed and chemically analyzed, whereas μ-Raman allowed their identification on a molecular level. K-feldspars, wollastonite and diopside were the most common compounds, as well as cassiterite agglomerates that render the glaze opaque. Malayaite was identified in green glazes,and andradite and magnesioferrite in amber glazes. Co–Ni–ferrites were identified in blue glazes, as well as Ni–Fe–olivines. Manganese-brown is the color where most compounds were identified: bustamite, jacobsite, hausmannite, braunite, and kentrolite. Through the μ-Raman analysis of different areas in large inclusions previously observed by SEM, it was possible to identify intermediate phases that illustrate the reaction process that occurs between the color-conferring compounds and the surrounding lead glaze. Furthermore, the obtained results allowed inference of the raw materials and firing temperatures used on the manufacture of these tiles