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Techniques of thermal analysis applied to the study of cultural heritage
Abstract
It is increasingly important that chemistry reaches people who have not studied directly this field of science but that, daily, have practices where chemistry is involved in various extents. This is what happens, for instance, in the activities related with the study and the preservation of cultural heritage. In this sense, the present work is a short review of the particular case of techniques based on the thermal analysis and calorimetry applied within the context of the characterization of art and archeological objects, exemplified by various case studies, as the characterization of mortars, preparatory grounds, ancient painting materials and drying oils.
... chemically bonded water and 200-650 C-an exothermic peak from decomposed organic matters (Pires and Cruz, 2007;Krapukaityte et al., 2008;Drebushchak et al., 2011;Bayazit et al., 2014;Fındık et al., 2014;Raja Annamalai et al., 2014). The endothermic peak from the dehydroxylation of kaolinite at 500-650 C can also be observed in some archaeological samples (Raja Annamalai et al., 2014). ...
... Moreover, in the temperature range 450-520 C, the decomposition of magnesium carbonate can occur (Paama et al., 2000). According to Pires and Cruz (2007), the decomposition of calcium carbonate can take place above 600 C. The presence of CO 2 (m/z D 44) on the MS spectra can result from the decomposition of carbonates. It suggests that this step is probably related to the decomposition of carbonates and organic compounds and the elimination of CO 2 (Paama et al., 2000;Pires and Cruz, 2007;Ravisankar et al., 2014;Raja Annamalai et al., 2014). ...
... According to Pires and Cruz (2007), the decomposition of calcium carbonate can take place above 600 C. The presence of CO 2 (m/z D 44) on the MS spectra can result from the decomposition of carbonates. It suggests that this step is probably related to the decomposition of carbonates and organic compounds and the elimination of CO 2 (Paama et al., 2000;Pires and Cruz, 2007;Ravisankar et al., 2014;Raja Annamalai et al., 2014). ...
Modern analytical methods play an important role in archaeological objects, including ceramics. This review focuses on the use of analytical methods such as: gas chromatography coupled mass spectrometry (GC/MS), Fourier transform infrared spectroscopy (FTIR), Time-of-flight secondary ion mass spectrometry (ToF-SIMS), Powder X-ray diffraction (XRD) with thermal analysis (TGA-MS) to study the chemical and mineralogical composition of archaeological samples and organic residues preserved inside. In this paper, special attention was paid to the ToF-SIMS method, which allows the determination of characteristic ions on the surface of ceramic samples.
... Mortar is a composite material employed to assemble bricks or stone or as a finishing layer. The characterisation of ancient mortars provides useful information about how the complex architecture structures were built [1][2][3][4][5]. Lime was used in the antiquity as non-hydraulic cement mixed with pozzolane, specially to build duct drains, cistern and swimming pools [6,7]. ...
... Recently, raw material compositions, as well as the physical, mineralogical and microstructural characteristics of mortar samples from some historic buildings were determined to understand their technology and to produce compatible repair mortars with the existing ones in masonry structures [8,[13][14][15]. Literature reports [1,4,5,8,12] allow to group ancient mortars in two main categories: lime and hydraulic ones. In the first case, the hardening process arises from carbonation of dry or wet lime [16]. ...
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
CO2 flow confirmed the presence of magnesium calcium carbonates.
KeywordsHistoric mortars-Lime-Marble-TG–DTG–DTA-Carbonates decomposition-CO2 flow
... Several techniques are used to characterize mortars: wet chemical analysis, instrumental methods for characterization of organic and inorganic materials as thermal analysis (DTA, TGA, DSC) (Pires and Cruz 2007;Moropoulou et al. 1995) and infra-red spectroscopy (FTIR) (Derrik et al. 1999), physical and mechanical testing for durability and performance assessment, respectively, radiocarbon dating (this technique has recently allowed to date mortars to an accuracy of about 30 years) and X-ray diffraction (XRD) (NORMA UNI EN 13925-1 2006a, b, c). ...
The archaeometric study of ancient mortars can provide important information relating to the raw materials used and their provenance. A mineralogical and petrographic study based on optical and electron microscopy on mortars from the Roman Theatre of Aosta (NW Italy) was carried out. The construction of the theatre is believed to have taken place a few decades after the foundation of Augusta Praetoria, the ancient city of Aosta, in 25 BC. Both original and mortars belonging to four different subsequent restoration interventions were studied. It was possible to detect the areas of origin of the materials used for the historical mortars, which were of local provenance, being characterized by abundant metamorphic minerals, typical of Alpine orogeny. X-ray element maps were also created to better define the distribution of aggregate, binder and porosity. The characterization of the binder was obtained by creating two-dimensional maps of the hydraulic index. These made it possible to distinguish aerial mortar from the Roman age samples and hydraulic mortars for subsequent restorations.
... The thermogravimetric profiles of linseed oil and lead white paint with linseed oil have already been studied by several authors [12,13,14] to characterize binding media in old paintings, to understand the oil hardening process and the effect of lead white on the ageing of the oil binder. Some studies have also been carried out on mortar and calcite structures [15,16]. Thus, although thermogravimetry is used for cultural heritage applications, to our knowledge, more complex paints composed of mixtures of lead white, calcium carbonate and linseed oil have not as yet been investigated. ...
Lead white was a white pigment extensively used in paintings from Antiquity until the beginning of the 20th century. It is composed of hydrocerussite (Pb 3 (CO 3) 2 (OH) 2) and cerussite (PbCO 3). Historical recipes report metallic lead, vinegar and horse manure as ingredients to produce the two lead carbonates. The incorporation of organic CO 2 carrying 14 C representative of the time of manufacture of lead white allows radiocarbon dating of this pigment. One possible protocol for lead white paint preparation for dating is based on the extraction of carbon from lead carbonates by thermal decomposition. Since lead white paints are mixed with a binder and other pigments, a thermogravimetric study was implemented to study CO 2 extraction from each component. The measurements were carried out on samples of modern paints prepared with lead white (lead carbonate), Meudon white (calcium carbonate) and linseed oil. The results show that it is possible to separate the carbon of interest (carrying the 14 C signature: lead white and linseed oil) from the dead carbon coming from geological carbonates (containing no radiocarbon: Meudon white) by heating the paint sample at 400°C. This study provides a better understanding of the thermal behavior of these three paint constituents and confirms the validity of the thermal protocol for the preparation of lead white paints for radiocarbon dating.
... From the multitude of available techniques frequently used in analyzing archaeological artifacts [10,11], the most easily available is FTIR spectroscopy, used as an initial a method of determining composition, most helpful in identifying the organic components within analyzed samples [12][13][14][15]. ...
The samples originate from the funerary cache of a cremation burial mound dating from the Late Bronze Age (according to the Reinecke chronological system, Bronze D—Hallstatt A, according to absolute chronology ca. 1200 cal BC), discovered within the Susani-Grămurada de la Jupani mound (Timiș County, Romania). The pieces are sphere-shaped; however, many show signs of fire from the cremation of the buried person/persons. Together with bronze and gold pieces, they were part of composite necklaces and/or bracelets. Complementary techniques were used in the analysis: TG/DTA, FTIR, XRD, SEM and EDX to determine composition. All the techniques used in the present paper argued that the jewelry analyzed underwent a second burn at temperatures between 500 and 800 °C.
... The thermogravimetric profiles of linseed oil and lead white paint with linseed oil have already been studied by several authors [12,13,14] to characterize binding media in old paintings, to understand the oil hardening process and the effect of lead white on the ageing of the oil binder. Some studies have also been carried out on mortar and calcite structures [15,16]. Thus, although thermogravimetry is used for cultural heritage applications, to our knowledge, more complex paints composed of mixtures of lead white, calcium carbonate and linseed oil have not as yet been investigated. ...
Lead white was a white pigment extensively used in paintings from Antiquity until the beginning of the 20th century. It is composed of hydrocerussite (Pb3(CO3)2(OH)2) and cerussite (PbCO3). Historical recipes report metallic lead, vinegar and horse manure as ingredients to produce the two lead carbonates. The incorporation of organic CO2 carrying ¹⁴C representative of the time of manufacture of lead white allows radiocarbon dating of this pigment. One possible protocol for lead white paint preparation for dating is based on the extraction of carbon from lead carbonates by thermal decomposition. Since lead white paints are mixed with a binder and other pigments, a thermogravimetric study was implemented to study CO2 extraction from each component. The measurements were carried out on samples of modern paints prepared with lead white (lead carbonate), Meudon white (calcium carbonate) and linseed oil. The results show that it is possible to separate the carbon of interest (carrying the ¹⁴C signature: lead white and linseed oil) from the dead carbon coming from geological carbonates (containing no radiocarbon: Meudon white) by heating the paint sample at 400 °C. This study provides a better understanding of the thermal behavior of these three paint constituents and confirms the validity of the thermal protocol for the preparation of lead white paints for radiocarbon dating.
... From the plethora of relevant techniques, IR spectroscopy in its FTIR variant is the most readily available and provides adequate results. In analyzing pottery, FTIR is used to determine composition, with the help of statistical analysis and principal component analysis, being especially helpful in identifying organic components [4][5][6][7]. After establishing composition, thermal analysis, in this case thermogravimetric and differential thermal analysis, is used to estimate the original firing temperature of pottery. ...
A series of 18 ceramic samples consisting of pottery shards from ancient vessels dated to the Neolithic period discovered at Oxenbrickel, Sânandrei, Timiş County, Romania (GPS coordinates: 45°51′3.11″N, 21°10′49.32″), have been analyzed by using thermogravimetric, differential thermal analysis (TG/DTA/HF), XRD analysis and Fourier transform infrared spectroscopy. Vessels such as the ones from Oxenbrickel, carrying marks on their bottoms, are to be found among the discoveries of Vinca, Turdaş, Banat, Boian-Giuleşti, Gradešnica, Karanovo IV Kalojanovec, Precucuteni, Hamangia and the Linear Pottery cultures. The results within the present study indicate the technological level observable at Sânandrei falls within the lower range of known firing temperatures, suggesting a different technological approach specific to the Banat Culture or, more likely, an adaptation to local conditions (i.e., available raw materials and fuel sources).
... Nowadays, a broad range of analytical techniques is available and applied in the preservation of Cultural Heritage [1][2][3]. In this context, destructive and/or invasive techniques should be avoided, whenever possible, to preserve the integrity of the studied artefacts [4,5]. ...
The study of both original and decaying compounds is relevant in understanding the chemistry behind the deterioration processes, above all in open museum contexts where environmental stressors affect the artefacts. In this sense, a combination of non-invasive spectroscopy techniques (Raman spectroscopy, μ-X-ray fluorescence and X-ray diffraction) was applied on an ancient Roman building (130 CE), the "Casa di Diana" Mithraeum at Ostia Antica archaeological site. The aim is to study the raw materials, manufacturing and decaying products of the two observed types of Roman fired bricks (red and yellow) that compose the building. The present study estimates an illite raw material of carbonate-bearing marine clay likely referring to the common deposits of central/southern Italy, which contain calcite as accessory phase and a-plastic fraction constituted by quartz, feldspar and opaques. This clay material was added with volcanic temper characterised by abundant clinopyroxene and analcime (from analcimization of leucite) that are typical of the Roman Province volcanism. The firing would be probably the result of oxidizing conditions, as proved by the hematite presence. Thanks to the existence of specific neoformed mineral phases during firing it was possible to assess different temperatures ranges. In detail, the red/orange bricks, for the existence of gehlenite (formed from calcite and its reaction with silicates), were fired at 800-900 °C range; whereas, the yellow ones are characterised by the lack of gehlenite and the disappearance of illite/muscovite, which indicates firing temperature at over 900 °C. Regarding the decaying products, the gypsum covers most of the surface of most bricks, both red and the yellow ones, but these latter are more susceptible to environmental stressors (sulphates and carbonates). Therefore, this work points out how by integrated non-invasive approaches it is possible trace back to original firing temperature, technology of manufacture, interpreting ceramic data.
... The visual appearance or photometric properties is also of utmost importance. These aspects can be acquired from the use of conventional cameras, mobile phones, or cameras (Pires and Cruz 2007;Navarro et al. 2009;Lerma et al. 2011;Remondino et al. 2011). However, when dealing with archaeological sites, the 3D reconstruction and visualization is usually not fully possible with the use of acquisition devices, because most or part of the assets do not exist nowadays. ...
... The visual appearance or photometric properties is also of utmost importance. These aspects can be acquired from the use of conventional cameras, mobile phones, or cameras (Pires and Cruz 2007;Navarro et al. 2009;Lerma et al. 2011;Remondino et al. 2011). However, when dealing with archaeological sites, the 3D reconstruction and visualization is usually not fully possible with the use of acquisition devices, because most or part of the assets do not exist nowadays. ...
... These aspects can be acquired from the use of conventional cameras, mobile phones, or cameras working in other spectral ranges, such as thermal or infrared cameras. Many works can be found in this regards, such as Dei, Mauro, & Bitossi (1998) ;Guarnieri, Remondino, & Vettore (2006); Pires & Cruz (2007); Navarro et al. (2009) ;Lerma, Cabrelles, & Portalés (2011) and Remondino (2011). ...
3D virtual reconstruction of cultural heritage is a useful tool to reach many goals: the accurate documentation of our tangible cultural legacy, the determination of mechanical alteration on the assets, or the mere shape acquisition prior to restoration and/or reconstruction works, etc. Among these goals, when planning and managing tourism enhancement of heritage sites, it demands setting up specific instruments and tools to guarantee both, the site conservation and the visitors’ satisfaction. Archaeological sites are physical witnesses of the past and an open window to research works and scientific discoveries, but usually, the major structures do no exist nowadays, and the general public takes long time and many efforts to elaborate a mental reconstruction of the volumetry and appearance from these remains. This mental reconstruction is essential to build up a storyline that communicates efficiently the archaeological and historic knowledge and awares the public about its conservation. To develop this process of awareness about conservation, heritage interpretation starts with the mental inmersion of the visitors in the archaeological site, what 3D reconstruction definitely helps to achieve. Different technologies exist nowadays for the3D reconstruction of assets, but when dealing with archaeological sites, the data acquisition requires alternative approaches to be used, as most part of the assets do not exist nowadays. In this work, we will deal with the virtual reconstruction and visualisation of the archaeological site Castellet de Bernabé by following a mixed approach (surveying techniques and archaeological research). We further give a methodology to process and merge the real and virtual data in order to create augmented views of the site.
... TG and DSC were performed on solid-state samples before and after artificial ageing in a Solarbox (indoor light ageing). These techniques have been successfully used in the field of cultural heritage for a wide range of different materials [24,25,[28][29][30][31][32][33], in particular to characterize egg tempera pigmented and unpigmented samples [34], and were thus chosen to investigate the modifications undergone by rabbit skin glue due to the effects of the pigments and artificial ageing. ...
We studied the interactions of rabbit glue, a collagen-based proteinaceous binder, with azurite (Cu3(CO3)2(OH)2), calcium carbonate (CaCO3), hematite (Fe2O3·nH2O), red lead (Pb3O4) and cinnabar (HgS) by Fourier transform infrared spectroscopy (FT-IR). The research was carried out on a set of paint reconstructions, which were analysed before and after artificial light ageing. A deconvolution of the amide I FT-IR absorption peak was performed with a written-in-house LabVIEW program to study the secondary structure of the glue.The changes in the glue conformation highlighted that all the inorganic pigments interact with the proteinaceous binder. The conformational changes were correlated with a loss of stability of the collagen structure, especially after ageing, likely due to the interlayer coordination of metals salts and oxide with protein functional groups. These results were correlated with the lower thermal stability of the glue/pigment mixtures with respect to the pure glue, evidenced by thermogravimetry (TG) and differential scanning calorimetry (DSC) analyses performed in a previous step of this work.
... TG and DSC were performed on solid-state samples before and after artificial ageing in a Solarbox (indoor light ageing). These techniques have been successfully used in the field of cultural heritage for a wide range of different materials [24,25,[28][29][30][31][32][33], in particular to characterize egg tempera pigmented and unpigmented samples [34], and were thus chosen to investigate the modifications undergone by rabbit skin glue due to the effects of the pigments and artificial ageing. ...
The thermal degradation of rabbit skin glue, a collagen-based proteinaceous material used as a paint binder in paintings, was investigated in this paper. Paint reconstructions of the glue on its own or mixed with azurite (Cu3(CO3)2(OH)2), calcium carbonate (CaCO3), hematite (Fe2O3·nH2O) and red lead (Pb3O4) were analysed using a thermoanalytical approach. This method enabled us to investigate the interactions between the glue and pigments before and after artificial indoor light ageing. The study was carried out using differential scanning calorimetry, thermogravimetry and thermogravimetry/FTIR analysis already successfully employed to characterize the paint binders. The results highlighted that all the inorganic pigments interact with rabbit skin glue, thus decreasing the thermal stability of the binder. Light ageing further decreased the thermal stability of pigmented paint replicas, suggesting a moderate increase in the rate of the degradation.
... Infrared thermography (IRT) is a non-destructive technique used for the structural characterization of a large variety of artefacts and widely applied in recent years for the study of Cultural Heritage , Blessey et al. 2010, Pires et al. 2007. Such a technique provides information on defects, inhomogeneities and subsurface features in the investigated sample by monitoring the temperature distribution at its surface. ...
... In the DTA curve, an endothermic peak at 573°C was detected, without weight loss associated with TGA, which corresponds to the quartz transition phase a → b (Newton and Sharp 1987;Moropoulou et al. 1995a;Montoya et al. 2003;Pires and Cruz 2007). ...
De acordo com as evidências históricas e arqueológicas, a Cidade Romana de Ammaia (Marvão, Portugal) terá sido fundada no século I d.C., atingindo o seu auge nos séculos I-II d.C., como importante centro urbano da Lusitânia [1]. Progressivamente, terá sido abandonada até ao século IX, não sendo conhecida até ao momento ocupação posterior. Nos 15 anos de escavações, foram postas a descoberto diversas estruturas arqueológicas da Porta Sul, a praça de entrada na cidade, a área do Forum, as termas, e sob o actual Museu, uma zona habitacional. A área das ruínas encontra-se actualmente sob protecção da Fundação Cidade de Ammaia e a orientação científica da Universidade de Évora.
Para a presente investigação salientam-se as argamassas, materiais de construção cuja preparação depende directamente da quantidade e qualidade da matéria-prima disponível. As argamassas são potencialmente reveladoras do conhecimento das tecnologias de construção/produção artística de uma sociedade, da sua relação com a envolvente e da compreensão da sua evolução (incluindo posteriores intervenções de reconstrução). A metodologia de estudo aplicada às argamassas da Ammaia tem vindo a ser desenvolvida nos últimos 8 anos, em diversos casos de estudo [2]. Métodos como a microscopia óptica, a DRX, a ATG, o SEM-EDS e análise química foram algumas das técnicas utilizadas, que permitiram a identificação da composição mineralógica dos ligantes, dos agregados, das propriedades hidráulicas conferidas por aditivos (ex: pozolanas, fragmentos de tijolo, etc.), da relação ligante/agregado e a análise do seu estado de conservação. As informações obtidas são ainda essenciais para o desenvolvimento de argamassas compatíveis, que poderão ser utilizadas em futuras acções de conservação/restauro.
... Thermal parameters like, for instance, the specific heat and the thermal diffusivity have, in fact, been shown to be affected by the deterioration processes, and their measurement thus provides a tool for monitoring the degradation dynamics in the investigated material [1]. In that respect, a number of different thermal method have been applied to the characterization of cultural heritage material [2][3][4][5][6][7]. Beside the material characterization, the analysis of the structure of an artefact is also often fundamental in order to assess its preservation state. ...
Active infrared thermography is an important non-destructive technique frequently employed in the analysis of cultural heritage. For its capability to show subsurface features in the artifacts, this technique has been used to investigate various kinds of artifacts, composed of different structures and materials. In this work, an overview of its recent applications is presented. In particular, the detection of cold working features in bronze sculpture investigations, of buried features in ancient book bindings, such as their structural characteristics and written scraps re-used in their manufacturing process, and on the investigation of defects and inhomogeneities in illuminations, is reported.
... DSC and TG have successfully been used in the field of cultural heritage [19,20]. There are studies based on DSC analysis that investigate the role of the pigments and driers on the oxidative reactions taking place in the polymerisation of linseed oil. ...
This article presents a multi-analytical approach to investigating the drying, polymerisation and oxidative degradation of linseed oil, which had undergone various treatments known to be undertaken during the nineteenth century in preparation for painting. The oil was mechanically extracted from the same seed lot then processed by different methods: water washing, heat treatments, and the addition of driers, with and without heat. The oil was prepared in 1999 within the framework of the MOLART project. We compared thermogravimetric analysis (TG), which yields macromolecular information, with gas-chromatography mass-spectrometry (GC/MS) and direct exposure mass spectrometry (DE-MS), which provide molecular information. This comparison enabled us to elucidate the role of pre-treatment on the composition of the oil. TG and oxygen uptake curves registered at a constant temperature helped us to identify the different physical behaviour of the oil samples, thus highlighting the presence of hydrolysed, oxidised and crosslinked fractions, as a consequence of the different pre-treatments. GC/MS was used to characterise the soluble and non-polymeric fraction of the oil, to calculate the ratios of palmitic to stearic acid (P/S), and azelaic to palmitic acid (A/P), and to further evaluate the effects of oil pre-treatments. DE-MS using chemical ionisation with CH4, enabled us to establish the chemical composition of the oil in different stages of ageing. DE-MS proved to be a useful tool for a simultaneous semi-quantitative characterisation of the free fatty acids, monoglycerids, diglycerides and triglycerides present in each sample. The combination of thermal analysis with GC/MS and DE-MS enabled a model to be developed, which unravelled how oil pre-treatments produce binders with different physical–chemical qualities.
... In the DTA curve, an endothermic peak at 573°C was detected, without weight loss associated with TGA, which corresponds to the quartz transition phase a → b (Newton and Sharp 1987;Moropoulou et al. 1995a;Montoya et al. 2003;Pires and Cruz 2007). ...
The Roman town of Ammaia (in Marvão Region) is considered one of the most important recent findings of the Roman presence in Portuguese territory. It was settled in Republican times and abandoned in the seventh century. In this research, 17 masonry mortars and renders from the West Tower (South Gate), the residential area near the West Tower, the macellum, the peristylium, the public bath building, the podium of the temple and the portico of the forum were analysed. The methodology of chemical, mineralogical and microstructural characterization has involved several complementary techniques, including stereomicroscopy, X-ray diffraction, thermal analysis and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. The results indicate that the mortars from the beginning of the town's edification were mainly composed of soil (clays). Later, during the main Roman building period, mortars were composed using a calcitic binder and the mortar composition varied according to their use and function. The samples from a period subsequent to the Roman occupation are based on a dolomitic binder. From the present study, relevant information has been acquired about the technological evolution of Roman construction in Ammaia, the historical context of the archaeological structures and guidelines for the conservation and restoration of mortars.
... Infrared thermography (IRT) is a non-destructive technique used for the structural characterization of a large variety of artefacts and widely applied in recent years for the study of Cultural Heritage , Blessey et al. 2010, Pires et al. 2007. Such a technique provides information on defects, inhomogeneities and subsurface features in the investigated sample by monitoring the temperature distribution at its surface. ...
We present an opto-thermal approach based on the use of active infrared thermography (IRT) for the study of texts hidden inside the bookbinding structure of ancient books. In particular we focus our investigation on the detection and characterization of texts on paper scraps, belonging to earlier handwritten or printed leaves, used for the making of bookbindings and lying between the end papers and the cover. A qualitative description of the physical mechanisms allowing the identification of texts is proposed and a comparative analysis of the results obtained by means of different IRT experimental configurations is presented. The results show that active IRT can be a very useful tool for the detection and the identification of underlying texts whose reading can provide useful information on the specific history of ancient books.
... The study was performed on the paint replicas, before and after artificial ageing, using thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR) and size-exclusion chromatography coupled to UVand cold vapour generation atomic fluorescence spectrometry (SEC-UV-CVGAFS). Thermogravimetry has been successfully used in the field of the cultural heritage to study a wide range of different materials1314151617181920 . In paint reconstructions, thermogravimetry is used for characterising the thermal stability of binders and pigments, their interactions and their modifications due to ageing1415161718. ...
... Since thermogravimetric and differential scanning calorimetric analyses are valid tools in the study of the thermal and oxidative stability of drying oils [5][6][7][8][9][10][11], a TG-DSC method was performed on the reconstructed films to understand the changes occurring in the oil films during the very first period after the film laying. The advantage in performing the two analyses simultaneously is associated with the possibility of studying oxidative behaviour and thermal stability both in terms of mass changes and thermal capacity [12]. ...
Thermogravimetry coupled with differential scanning calorimetry (TG–DSC) has been commonly used in the field of conservation
of Cultural Heritage for the study of art objects, especially for the characterisation of inorganic matrixes. In recent years,
thermal analyses have been applied to the study of organic painting materials. The advantages of performing TG–DSC are linked
to the fact that it is micro-destructive technique which does not require any treatment prior the analysis and provide useful
information in relatively short time. The aim of this study is to describe the application of TG–DSC on the study of oil binders
used in contemporary paints. Even if synthetic binders have become increasingly popular in the 20th century, many contemporary
artists still prefer the more traditional media: drying oils. Although the wish of recalling traditional methods, much practical
knowledge in paint preparation by mixing drying oil and pigments and in the behaviour of the mixture has been lost. This is
mainly due to the different composition of contemporary materials in comparison with the traditional ones and may sometimes
lead to different drying properties of the oil paint formulations and consequent problems in the art creation and conservation.
For answer to this artistic need and in particular to the difficulties outlined by artists themselves in producing and employing
oil paints, unpigmented and pigmented oil films were studied after a week, 1 and 2 years of natural drying under laboratory
conditions. Thermal analyses were performed in air flow: the focus of this research was, in fact, to study the thermal and
oxidative behaviours of young films for better understanding the very first processes leading to the formation of the film.
... Differential scanning calorimetry (DSC) and thermogravimetry (TG) analyses have been widely used in the field of art [21][22][23][24] and represent two valuable techniques for the study of the thermal properties of acrylic emulsion materials. The determination of the glass transition temperature (T g ) by DSC is a useful method to define the state of an acrylic material at room temperature. ...
Differential scanning calorimetry (DSC) and thermogravimetry (TG) analyses were used to investigate the influence of inorganic pigments on the photo-oxidative stability of an acrylic emulsion binding medium. For this purpose, three different types of inorganic pigments such as ultramarine blue, cadmium red and hydrated chromium oxide green were selected and mixed with an acrylic emulsion binding medium of poly(n-butyl acrylate/methyl methacrylate). These laboratory mixed paints were analysed before and after UV exposure for different periods of time. In addition, three acrylic commercial paints such as ultramarine blue, cadmium red and chromium oxide green from Liquitex� and Rembrandt� companies were also analysed. The results obtained with both thermal techniques suggested that ultramarine blue has the strongest influence on the photo-oxidative stability of the binding medium. A higher increase of the glass transition temperature Tg was observed by DSC analysis on the UV aged binder mixed with ultramarine blue. This result was confirmed by the TG investigations that showed a gradual decrease of the initial temperature of degradation as well as the strongest decrease of the final mass% of the organic compounds. Similar results were measured from the Liquitex� and Rembrandt� blue paints.
... This work is the follow-up to a previous study characterizing the oil alone which revealed how pre-treatments produce binders with different physical-chemical qualities [28]. TG has been successfully applied in the field of cultural heritage to study a wide range of different materials [28,29,30,31,32,33,34], and, in this paper, we use it to systematically investigate and compare the thermal behaviour of oil paints made with a single source of oil pre-treated in different ways. TG enabled us to assess the effects of the two pigments on the ageing of the oil binder. ...
This paper presents an analytical investigation of paint reconstructions prepared with linseed oil that have undergone typical 19th century treatments in preparation for painting. The oil was mechanically extracted from the same seed lot, which was then processed by various methods: water washing, heat treatments, and the addition of driers, with and without heat. A modern process lead white (Dutch source, Schoonhoven) and a commercially available vine black were used as pigments. The reconstructions were prepared in 1999, and naturally aged from then onwards. We compared thermogravimetric analysis (TG), which yields macromolecular information, with gas chromatography-mass spectrometry (GC-MS) and direct exposure mass spectrometry (DEMS), which both provide molecular information. The study enabled us to quantitatively demonstrate, for the first time, that the parameters used to identify drying oils are deeply influenced by the history of the paint. In particular, here we show that the ratio between the relative amounts of palmitic and stearic acid (P/S), which is used as an index for differentiating between drying oils, is extremely dependent on the pigments present and the age of the paint. Moreover the study revealed that neither the P/S parameter nor the ratios between the relative amounts of the various dicarboxylic acids (azelaic over suberic and azelaic over sebacic) can be used to trace the sorts of pre-treatment undergone by the oil investigated in this study. The final results represent an important milestone for the scientific community working in the field, highlighting that further research is still necessary to solve the identification of drying oils in works of art.
... Thermal parameters like, for instance, the specific heat and the thermal diffusivity have, in fact, been shown to be affected by the deterioration processes, and their measurement thus provides a tool for monitoring the degradation dynamics in the investigated material [1]. In that respect, a number of different thermal method have been applied to the characterization of cultural heritage material [2][3][4][5][6][7]. Beside the material characterization, the analysis of the structure of an artefact is also often fundamental in order to assess its preservation state. ...
Infrared thermography (IRT) is a non-destructive technique that has recently been extensively applied to the investigation
of cultural heritage. It provides information on the surface and subsurface structure of the artefacts by the analysis of
the heat diffusion process within the sample. IRT has been successfully applied to the study of historic large structures
and buildings most of the time by means of the so-called passive approach, where only the naturally occurring temperature changes in the sample are analysed. On the other hand, IRT has also
been applied to the study of other art and historic artefact by applying the so-called active method where the thermal stimulation of the sample is required. In this article, an overview of the applications of active
thermography to the investigation of art and historic artefacts will be presented and discussed.
KeywordsActive infrared thermography–NDT–Cultural heritage
... The study was performed on the paint replicas, before and after artificial ageing, using thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR) and size-exclusion chromatography coupled to UVand cold vapour generation atomic fluorescence spectrometry (SEC-UV-CVGAFS). Thermogravimetry has been successfully used in the field of the cultural heritage to study a wide range of different materials1314151617181920 . In paint reconstructions, thermogravimetry is used for characterising the thermal stability of binders and pigments, their interactions and their modifications due to ageing1415161718. ...
In this work, we characterized paint reconstructions using ovalbumin and casein as binders, and cinnabar (HgS) as a pigment, before and after artificial ageing. Egg and casein are common paint binders that were used historically in the technique of tempera painting. Despite extensive research on the identification of proteinaceous binders in paintings, there is a substantial lack of knowledge regarding the ageing pathway of their protein content, and their chemical interaction with inorganic pigments. Thermogravimetric analysis, infrared spectroscopy and size-exclusion chromatography (SEC) were used to reveal the physico-chemical processes involved in the ageing of proteins in paintings. Taken together, the three techniques highlighted that proteins are subject to both cross-linking and hydrolysis upon ageing, and to a lesser extent, to oxidation of the side chains. Mercury-protein interactions were also revealed using a cold vapour generation atomic fluorescence spectrometer mercury-specific detector coupled to SEC. The study clearly showed that HgS forms stable complexes with proteins and acts as a sensitizer in cross-linking, hydrolysis and oxidation.
During conservation studies different materials are analysed and tested for their solidity in order to be able to carry out precise conservation and restoration measures and to be able to assess their sustainability.
Chemiluminescence is a phenomenon in which an electron is relaxed from an energetical- ly higher orbital into a lower situated condition while simultaneously releasing energy in the shape of photons. As a consequence the stimulated state is caused by a chemical reaction. This process is very specific and occurs during an oxidation reaction among oth- er things. Through the recombination of two peroxides for example a stimulated carbonyl compound is generated which emits its energy as light.
This connection between the oxidation of organic substances and the emission of photons determines the main question, whether chemiluminescence can be used as a method for characterisation of materials which are relevant to the research of conservation.
As a result of a research project between departments of the Bern University of Applied Sciences BFH it was possible to construct a chemiluminescence measuring device and modify it in a way that it could be used for this work.
Within this experiment a standardised method of measurement was tested on different substances, for example adamantylidenadamantan-1.2-dioxetan, and the different im- pacts on the chemiluminescence-signal investigated. Through this process important facts were determined for the concept of measurement, for example precision, proof- and defi- nition perimeters.
Based on the solidity of dammar, a triterpene resin, the method could be experimentally verified within the test using a complex example from conservation research. Within that process published results about the oxidation properties of dammar resin were verified. Due to the specific signal, the thermally initiated responses in inert as well as oxidative gas atmospheres could be documented. The results were compared with established methods like DSC, TGA and ESR spectroscopy and the consistencies to the signals logged.
The already much discussed influence of stabilisers on dammar resin was tested on non- aged and artificially aged specimens using chemiluminescence. Through these previously suggested formulations, effects of certain synergistic composites were detected and con- firmed.
Using the data from the chemiluminescence measurements kinetic calculations about activation parameters were compiled. The identified parameters were used for the prog- nosis of the course of reactions during differently simulated temperature profiles, making a prediction of the materials’ life span possible.
Through these results not only the high performance ability of the method became appar- ent but also the potential of the determined measurement data, mainly in connection with the application within the model-free kinetic.
However, alongside these possibilities limitations of the method were revealed. These are partly caused by the characteristics of the signal which has yet to be mechanistically fully clarified. Simultaneously, further processing of the measurement data via thermokinetic software makes clear that the quality of the calculations of the reaction process is only as good as the quality of the initial data. This suggests the prognoses about the stability of the material only conveys a concept of their qualities.
Historic papers contain valuable information about national, cultural, artistic and historical identity and values of every civilization. Identification of paper materials such as fiber type, sizing, and other materials can significantly help to obtain valuable information concerning old civilizations, their attitude, culture, geographical origin, and etc. However, there are some manuscripts that their writing date remains still unknown. Qualitative and quantitative analytical methods can be used as a tool to identify paper materials and therefore dating of historic papers as a cultural piece. In this research work, the dating feasibility of four unknown historic paper scripts was investigated through analysis and comparison of their materials like characteristic and type of fiber and sizing material with four known samples belonging to Safavid period. For this purpose, different techniques such as optical microscopy, color indictor assay, Fourier Transform Infrared spectroscopy (FTIR), Thermal Gravimetric Analysis (TGA), and Differential Scanning Calorimetry (DSC) were used to characterize paper materials. Using each characterization method, some information about physical, chemical, apparent form, and genus of paper materials were obtained. The results of fiber identification tests including optical microscopy and color indicators assay revealed that, except one sample made of kenaf fiber, all samples were made of flax fibers and no wooden fiber was used in paper making. FTIR data confirmed the presence of cellulose and hemi-cellulose and lack of lignin within all paper samples. Moreover, sizing material used for paper making was polysaccharide type, i.e., starch. TGA and DSC analyses results showed that depending on its thermal and chemical history, each sample had peculiar thermal behavior. Furthermore, compared to cellulose, hemi-cellulose possessed lower thermal stability. Overall, the results of this study revealed that dating of unknown samples through combination of thermal analysis and other characterization methods is possible, so the unknown samples belong to Safavid period. It is to be mentioned that the main goal of this research was dating unknown samples made of papers materials, which in this case all of them were similar. Although some samples may belong to different period, other parameters such as type of contents, differences in aesthetics, type of script, and etc. may be used to distinguish the sampled belonging to the same period. The data obtained in this research can be used in preparation of database for possible identification and dating of unknown historic samples.
In the present study, we explore Dynamic Mechanical Thermal Analysis (DMTA) as a tool for assessing the physical performance in 19th century paints and to evaluate the parameters that influence the mechanical properties of the paint films. This data is particularly important for accurate life-time predictions as well as better conservation treatments. DMTA is used to study the thermophysical properties of chrome yellow (PbCrO4) oil paints under the influence of common fillers found in 19th century chrome yellow oil paints: calcium carbonate (CaCO3), barium sulphate (BaSO4) and gypsum (CaSO4·2H2O). Oil paint mock-ups were dry to touch and included oil plus the single paint components (chrome yellow pigment and the three fillers) that were compared with 19th c. Winsor & Newton historic paint formulations. The fillers selected were applied with a ratio to pigment ranging from 10 to 40% in weight.
In this work, active infrared thermography was applied to study a seventeenth-century painting on paper, namely the Chigi's family tree, housed at Palazzo Chigi in Ariccia (Rome). Thermography was performed before and after restoration to obtain information used in planning the restoration and also to assess its effectiveness. Infrared thermography provided important information on the artifact structure, areas of damage, structural defects, and the state of adhesion between different layers of the composite artifact before and after the treatment.
Kinetic evaluation of thermogravimetry data was used to understand the ageing behavior of beeswax used as an artists’ paint
medium on ancient mummy shrouds and Fayum portraits. Individual components of beeswax were subjected to dynamic thermogravimetry
to assess their evaporation rates, and three methods of kinetic analysis were evaluated for accuracy. The results showed that
although it is impossible to accurately predict the volatility at room temperature for individual components of beeswax due
mostly to their high molecular mass, relative trends and ranking of the volatility of the compounds can be obtained which
may explain compositional changes over time.
Two kilns, one of which collapsed during firing cycle together with its entire pottery load, have been excavated at the Egnazia
site in Southern Italy.
To understand the reason for the collapse, ‘Broad Line’ typology pottery finds were analysed by complementary analytical techniques.
Analytical results not only suggest as cause of collapse sudden overheating in kiln due to uncontrolled increases in temperature,
but also indicate a good technological cycle from the recovery of raw materials to the manufacturing and firing process, which
tends to disprove the common assumption of non-professional production.
Roman ceramics of two hydraulic mortars used to build the pond and water channel of Mithraeum house from Mérida (Spain) have
been studied. The sizes of the ceramic fragments found were different in both of the samples studied, showing different behaviour
in the reactions with the lime. The X-ray diffraction of the ceramic shows the presence of quartz, mica (biotite), anorthite
and hematite accompanied by amorphous phase, being observed scarce vitrification. The presence of mica confirms a firing temperature
for manufacturing the ceramic below 900°C. In one of the ceramics studied, X-ray diffraction did not show calcite. However,
in the FTIR appear bands that could be assigned to carbonates absorptions and likewise, carbonates were identified in the
DTA-TG curves. Ca and small quantities of Si and Al were also identified by SEM-EDX on the surface of the pores that could
be due to an amorphous phase formed in the reaction of lime with the Si and Al of the ceramic. On the other hand, in other
ceramic samples carbonates (about 10%) were detected. The carbonates have been found filling the pores, sometimes accompanied
by a new calcium-aluminium-silicate phase produced by the reaction between the lime and the amorphous phase of the ceramic.
The carbonates and the new phases formed inside the pores are responsible for the decrease of the porosity and for the formation
of new phases during the heating of the ceramics.
The properties of hydraulic mortars were studied by means of simultaneous thermal analysis (STA), according to a procedure
proposed in the literature. Hydraulic limes, cement and/or slaked lime were mixed using different proportions of both inert
and reactive aggregates, in order to test the effectiveness of such procedure in distinguishing the different degree of hydraulicity
of such samples. The use of the normalized coordinates suggested in the literature results in overlapping of the clusters
of different kinds of mortars. Modified coordinates are proposed, which give promising results in view of outlining a ‘master
curve’ of hydraulicity.
M. Odlyha from the of Structural and Molecular Biology, Department of Biological Sciences, Birkbeck, University of London, UK, shares her views on contribution of thermal analysis to the preservation of cultural heritage and its continuing vital role. She has described a number collaborative projects undertaken jointly with major museums, art galleries, and conservation centers to achieve the objectives. Some of these projects include the application of the full range of thermoanalytical techniques, differential scanning calorimetry (DSC), thermogravimetry (TG), thermomechanical analysis (TMA), dielectric analysis, dynamic mechanical analysis (DMA), and micro-thermal analysis (μ-TA). M. Odlyha states that thermal analysis offers methods for problem solving in this area and evidence of this given in one of latest articles published in a journal.
Long aged mortars from ancient hydraulic constructions of Sicily, i.e. the Roman aqueduct of Thermae and the Punic cisterns
and traditional water supply systems in Pantelleria, have been characterised by means of XRD analysis, optical microscopy
and simultaneous thermal analysis to correlate the hydraulic properties to the texture and to their different role in the
construction, i.e. lining, covering, roofing and joint mortars.
According to a procedure proposed in the literature all of the samples, but two air hardening ones, show high hydraulicity,
which somehow can be related to the characteristics of aggregates.
A comprehensive investigation has been made of a set of 14th to 16th-century parchment bookbindings from the Historical Archives of the City of Turin. Advanced physico-chemical techniques, such
as thermal analysis (DSC, TG and DTA), spectroscopy (FTIR and UV-Vis-NIR), scanning electron microscopy (SEM) and unilateral
nuclear magnetic resonance (NMR-ProFiler) were employed to assess specific deterioration processes occurring at different
levels in the hierarchical structure of parchment. Changes in the measured physical and chemical parameter values of parchment
due to interaction with the environment were used to identify possible deterioration pathways.
The present article focuses on an interdisciplinary research on cultural heritage concerning the microanalysis of Gothic mural paintings made during the 15th century in Slovenia. The samples were chosen from the churches of Crngrob (1453), Mirna (1463–1465), Mevkuž (1465) and Mače (1467), attributed to two of the most important Gothic painters of that period of time: Master Bolfgang and Master of Mače. The chemical and phase composition of all the mortars, number of their layers and selection of the pigments were of interest. For this purpose, fragments of mural paintings were studied with several instrumental techniques: optical microscopy (OM), SEM-EDX, x-ray powder diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). In early artworks, the mortar was made using a mixture of lime and more or less clean sand. Later, crushed lime-rock or marble instead of sand was added to lime. The pigments identified by EDX microanalysis of cross sections previously studied by OM, are of earth or mineral origin. Therefore, they are durable in fresco and lime techniques: lime white, yellow and red natural or burned ochres, green earth and azurite. The results confirmed the high technical quality of both painters and the relationships between the teacher and the disciple. Master Bolfgang and Master of Mače combine three basic techniques of mural painting: fresco, secco and lime techniques. This kind of investigation and methodology allow us to know better the Central European Art and the Slovenian Art in the Adriatic zone, as well as the general map of European Art in the 14–15th centuries. Copyright © 2008 John Wiley & Sons, Ltd.
Chemical changes observed in wood as a result of fungal decay have been studied. The development and transformation of the
decayed wood was evaluated by thermal analysis (thermogravimetry) and derivative thermogravimetry and scanning electron microscopy.
Samples of wood beams showing different deterioration stages from the coffered ceiling of the cloister of St. Francesc (15th
century) (Palma de Mallorca, Spain) were characterized. As decay develops, cellulose and lignin disappear and inorganic salts
are formed. Furthermore, the secretion of oxalic acid by fungi and the presence of organic pollutants lead to the precipitation
of authigenic salts. Therefore, the biomineralization process is strongly favoured by fungi that act as calcification nuclei.
At the final stage of fungal colonization, crystals of calcium salts appear in the surroundings of decayed wood fibres. The
thermal behaviour of these samples is the consequence of biodeterioration and weathering processes.
the purpose of this meeting is to present new and current research which: shares an empirical methodology of observation and measurement; concerns interdisciplinary studies of art, archaeology, architecture, ancient technology, and conservation; and uses the knowledge, methods and tools of materials science and engineering. Druzik introduced the symposium as follows: It is not inaccurate to say that Materials Issues in Art and Archaeology II is a continuing experiment. It is an experiment in the sense that conservation scientists, materials scientists who usually deal with the properties and processing of modern technology, and those who study the materials and processing of ancient cultures seldom have an opportunity to experience each other's unique problems. While the conservation of artistic and cultural properties often involves the very same objects as those studied by students of ancient technology these two specialized species seldom, if ever, attend the same meetings, publish in the same journals, or can even name a paltry subset of the other discipline's more famous characters and controversies. And, what do the Real Material Scientists think of these two odd birds. Well, that's what we really want to find out. Because it's certainly clear to myself and my co-organizers that the MRS has undreamed of potential and wealth to help solve many of the questions we pose about past cultures, their tools, their aesthetic sensibilities and their preservation for future generations were we only imaginative enough to exploit it.
This study evaluates the possibilities and limitations of the investigation of paint media by differential scanning calorimetry (DSC). For the first time, particular care was taken to include a large number of samples and a large range of media, and to examine thoroughly the influence of the pigments present. The investigation was carried out on samples from test panels which date from the beginning of this century. The simple experimental procedure, without any sample preparation, allowed a rough characterization of most paint media. The limitations are discussed in detail. Differential scanning calorimetry shows promise as an addition to common techniques of paint media analysis.
This research focuses on the characterization of historical mortars collected from a covered dockyard, called tezone 105, erected in the Arsenal of Venice during the XVI century. The mortars date back to different building phases. A stratigraphical analysis of tezone 105 has proposed a chronology of building interventions. The building phases recognized by the stratigraphical analysis belong to the original structure (XVI century) and to later interventions from XVI to XX century. Mortar samples are investigated by granulometric analysis, infrared spectroscopy (FT-IR), simultaneous thermal analysis (DSC/TG) and X-ray diffraction analysis (XRD) in order to identify the technology peculiar of each building phase. Mortar sampling was carried out on indoor masonry and foundation. Masonry mortars appeared to be characterized by the application of air-hardening binders, whereas foundation mortars were characterized by hydraulic binders.
Summary Many of Sydney’s heritage buildings and monuments were built as a result of the first European settlement in the 1800s. These buildings not only display the richness of the Australian culture, but also capture the architectural and historical values of its past. Although many of these buildings still appear to be strong and sound, many signs of deterioration have been detected in recent years. Conservators from various disciplines such as science, architecture and engineering are working closely together to develop suitable solutions to stop or at least slow down the degradation process of these precious buildings. This study demonstrates the usefulness of thermal analysis in determining the weathering mechanisms of marble and sandstone taken from two of Sydney’s landmarks, the Captain Arthur Phillips Monument at Sydney’s Botanic Gardens and Sydney’s St Mary’s Cathedral. This paper reports the findings of the weathering behaviours of both marble and sandstone samples determined using thermal analysis techniques.
A molecular, thermal, structural and mechanical characterisation of two different commercial water-dispersed polymers, i.e. an unreactive aliphatic polyetherurethane (trade name Akeogard AT40) and a VDF/HFP/TFE terpolymer (trade name Fluorobase T300) has been performed by means of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA), Fourier transform infrared spectroscopy (FTIR) and Fourier transform nuclear magnetic resonance (FT NMR), wide and small angle X-ray scattering (WAXS and SAXS) techniques and an Instron machine. Such polymers were selected from among the available products used for conservation and restoration by Cultural Heritage, with the view of using water-based polyurethanes and fluorinated copolymers as coatings for artefacts belonging to Cultural Heritage, consisting of natural fibrous polymers, mainly textiles. The results obtained so far suggest that a comparatively higher potential for the conservation and restoration of textiles with a cultural value is shown by AT40 polyurethane. Notwithstanding this, the structural properties assessed in water-cast films for both the polymers indicate that desired properties could be conferred by suitably selecting the chemical and molecular structure of the starting monomeric units.
Thermal analysis (thermogravimetry (TG) and derivative thermogravimetry (DTG)) has been applied to study the composition of commercially available base grounds. In several samples an additional XRD analysis was required for full characterisation purposes. Thermoanalytical curves of grounds, belonging to two works of art were also carried out. The results obtained by thermal analysis were related to the nature and composition of the ground layers providing useful information in further studies on grounds used in canvas, sculpture and altarpieces.
Mortars collected from the Cheops pyramid, the Sphinx and the Chephren pyramid, all at Giza, Egypt, have been compared with recently found mortars of a cult building of the aceramic neolithic at Nevali üori (south east of Urfa, province Hilvan, Turkey), probably one of the earliest sites of civilization. As methods of investigation thermal analysis, X-ray diffraction as well as analytical scanning and transmission electron microscopy have been used. The egyptian mortars have been found to be primarily made up of gypsum, anhydrite and calcite. The comparative results with mortar of the recently detected temple site at Nevali Con, Turkey, give evidence that the burning or otherwise chemical treatment of limestone as crucial ingredient for the fabrication of mortar has been performed at a very early period (10'000 - 8000 B.C.). In order to further confirm the described findings 14C dating measurements have been carried out. The results of the described studies raise many questions concerning early civilizations and their knowledge of technologies as well as the transfer mechanisms of this knowledge.
Different ancient mortar samples of Pamplona cathedral have been analysed to characterize their binder and aggregate fractions. A complete characterization has been carried out including chemical (complete macrochemical analysis, analysis of the soluble fraction in hot HCl (1:5) and of the insoluble residue, trace elements and soluble salts, using traditional chemical procedures, ion chromatography and spectrophotometry techniques), mineralogical (structural characterization, granulometric studies and X-ray diffraction) and thermal studies (simultaneous DTA and TG analysis). A lime binder with a silica aggregate has been established. The approximate original compositions of the classes of mortars have been determined using the TG results. A good agreement with the other characterization techniques has been showed by the thermoanalytical techniques. An incomplete carbonation in a sample has been discovered by the thermal analysis.
The elaborate characterisation and specification of materials used for decorating statues and buildings can be achieved by means of complementary methods of investigation such as analytical light and electron microscopy, thermal analysis, X-ray and neutron diffractometry, and various types of spectroscopy. The results cannot only reveal the historically relevant exploration and refinement techniques of natural resources, but also the types of application on different supports. In addition deterioration and erosion processes can be monitored and eventually conservation and restoration procedures may be improved.Here, we present results of investigations on materials, i.e. pigments which have been applied for the decoration of Nefertete’s bust and—practically in the same period—for the illumination of the so-called Talatat blocks of the then dismantled temple erected at Karnak under the reign of Akhenaten. Special attention was paid to the blue pigments, which—in both cases—could be identified unambiguously by means of X-ray diffractometry and Raman spectroscopy with the so-called Egyptian Blue, CaCuSi4O10. Other materials used in the polychromatic decorations are iron oxides (red), amorphous carbon/quartz (yellow) as well as the organic composite soot/bee wax mixtures (black). Obviously these mentioned pigments are chemically inert and therefore still visible, whereas other pigments such as green may have vanished more or less completely. In summary our investigations confirm and further reveal the skill of the Egyptian artisans and may elucidate a more detailed “life cycle analysis” of the used materials, spreading from the natural resources to the production and application and they finally may yield some useful hints for the advancement of our present reconstruction of historical developments in Egypt.
Cold pressed linseed oil and paints prepared using the inorganic pigments; lead white and red lead, were characterized using non-isothermal differential scanning calorimetry (DSC) in an air atmosphere to determine the effect of the pigment on the oxidative polymerisation of the drying oil medium. For each paint sample, the onset temperature for oxidation was reduced from 166C to the range 50 to 60C when a heating rate of 5 K min-1 was used. In order to determine the rate of drying, the non-isothermal experiments were carried out using a range of heating rates. A change in the mechanism oxidative polymerization was observed as the heating rate was increased.
The hyphenated thermal analysis-mass spectrometry
technique (TA-MS) was applied for the investigation of the thermal behavior
of reference and aged parchment samples. The kinetic parameters of the process
were calculated independently from all recorded TA and MS signals. The kinetic
analysis showed the distinct dependence of the activation energy on the reaction
progress. Such behavior is characteristic for the multistage mechanism of
the reaction.
The comparison of the kinetic parameters calculated
from the different signals i.e. TG, DSC, MS for H2O,
NO and CO2, however, indicated that they were differently
dependent on the aging of the sample. For the parchment samples, the aging
almost does not change the kinetics of the decomposition calculated from the
DSC data: the influence of aging seems to be too negligible to be detected
by these techniques. On the other hand, the much more sensitive mass spectrometric
technique applied to the kinetic analysis allowed monitoring of visible changes
in the thermal behavior of the parchment samples due to the aging process.
The influence of aging was especially visible when the MS signals of water
and nitric oxide were applied for the determination of the kinetic parameters.
The applied method of the kinetic analysis allowed also the prediction
of the thermal behaviour of reference and aged parchment samples under isothermal
and modulated temperature conditions. Presented results have confirmed the
usefulness of thermoanalytical methods for investigating behaviour of such
complicated systems as leather or parchment.
Different ancient mortar samples were analyzed to characterize their binder fraction. Thermal analyses (TG, DSC) proved to be very useful in the identification of three different species of lime composed of: (a) only calcite; (b) calcite and magnesite; (c) calcite, hydromagnesite and magnesite. The hydromagnesite is well identified in the DSC curve showing the peaks corresponding to the three-step thermal decomposition. Also the same mineral was detected by FTIR and/or micro-FTIR analyses, depending on its amount in the binder fraction of the mortar. Actually, the two absorption peaks characteristic of the hydromagnesite were often hidden by the wider peaks due to the asymmetric stretching of the carbonate ion, observed for the calcite and magnesite.
10 pages (final publisher version), 23 pages (attached post-print version). Two different types of ancient bricks (12th to 14th centuries) collected from historical buildings of Toledo (Spain) were characterised by optical microscopy, scanning electron microscopy/energy-dispersive X-ray spectrometers (SEM/EDS), electron probe microanalysis (EM), X-ray diffraction (XRD), differential thermal analysis (DTA) and 57Fe-Mössbauer spectroscopy. Physical properties such as water absorption and suction, porosity, density and compression strength were also determined. Several minerals found in the brick matrix, such as garnet, let us infer raw material sources; calcite, dolomite, illite and neoformed gehlenite and diopside phases, on temperature reached in firing; secondary calcite, on first cooling scenarios; and manganese micronodules, on late pollution environments. XRD and DTA of original and refired samples supply information about firing temperatures. Additional data on firing conditions and type of the original clay are provided by the Mössbauer study. Physical properties of both types of bricks were compared and correlated with raw materials and fabric and firing technology employed. The physicochemical characterisation of these bricks provides valuable data for restoration purposes to formulate new specific bricks using neighbouring raw materials. The authors are especially indebted to Josefo Bedoya, technician of the Museo de Ciencias Naturales (Madrid), who took the beautiful SEM microphotographs for this work and was killed in a car accident during the preparation of this manuscript. We are also grateful to Carlos Sánchez (Faculty of Chemistry Sciences, Ciudad Real) for the XRD analyses. The Spanish project MCYT IFD 1997-0561 and agreement CICYT-JCCM (2002) supported the work. Peer reviewed
Materials Issues in Art and Archaeology III Cultural Atlas of China
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- I Navarro
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DOI: 10.1007/s10973-004-6775-0
- Accepted
Accepted: November 16, 2006 DOI: 10.1007/s10973-004-6775-0 J. Therm. Anal. Cal., 87, 2007
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