Pigments—copper-based greens and blues Švarcová, Silvie; Hradil, David; Hradilová, Janka ...
Archaeological and anthropological sciences,
11/2021, Volume:
13, Issue:
11
Journal Article
Peer reviewed
Since antiquity, various copper-containing substances have been used as green and blue pigments. Their exceptional diversity, reflecting their various chemical and phase composition, chemical ...stability as well as their origin, makes their correct identification challenging. The review focuses on copper-based pigments used in ancient and mediaeval works of art, especially in wall paintings and/or related polychromed decorations or statues—siliceous copper pigments (Egyptian blue and green, Han blue and purple, chrysocolla), copper carbonates (azurite, malachite, blue and green verditers), copper chlorides (atacamite-group, cumengeite, calumetite), copper sulphates (posnjakite, brochantite) and—to a lesser extent—copper acetates (verdigris) and other organometallics. Particular attention is given to the necessity of the detailed study of accompanying phases which can serve as useful indicators of natural and/or artificial origin of copper pigments. Factors affecting the stability of copper pigments in wall paintings—salt attack, oxalic acid, alkalinity and heat—are overviewed. A suitable analytical approach based on complemental combination of in situ and laboratory analyses for proper identification and differentiation of copper pigments is proposed.
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•A rare wood ash glass tessera from Malbork Madonna was studied in detail.•It was found to be original mediaeval, from the area north of Alps, coloured by Co.•Opacification was ...achieved by Ca-phosphate grains, a Mediterranean technology.•Two phases detected in tessera for the first time: leucite and pseudowollastonite.•Pseudowollastonite indicates production temperature above ca. 1125 °C.
While the natron and plant ash glass tesserae may be found on places of importance across the former Roman and Byzantine empires, wood ash glass tesserae are scarce. This is the first time a wood ash glass tessera is studied in detail. It was part of a magnificent 8-metres tall statue of Madonna in Malbork, Poland, created at the end of the 14th century and destroyed at the end of World War Two. It was found to be coloured by cobalt with possible impact of copper, and opacified by Ca-phosphate. Processes previously described in sodium-rich glasses were observed also in the studied potassium-rich wood ash glass tessera, such as diffusion of the respective alkali metal into the Ca-phosphate grains. The elemental composition of the tessera indicates that it is original – mediaeval, from the area north of Alps. Two phases were identified for the first time, to authors’ best knowledge, in any glass tessera – leucite (tetragonal KAlSi2O6) and pseudowollastonite (monoclinic CaSiO3). As pseudowollastonite is a high-temperature phase, it may serve as an indicator of production temperature, which was further supported by the study of polymerisation index of model glasses. This study contributes to the knowledge of old technologies and showed that the know-how for opacification was imported from the Mediterranean, while the raw materials employed for the base glass preparation were from the area north of Alps.
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•An analytical procedure for identification of Cu pigments in artworks is presented.•This procedure is efficient for both mineral and verdigris-type pigments.•It consists of detailed ...elemental and structural analyses and is non-destructive.•Preliminary study of the verdigris’ loss of crystallinity has been performed.
An unambiguous identification of pigments in paint layers of works of art forms a substantial part of the description of a painting technique, which is essential for the evaluation of the work of art including determination of the period and/or region of its creation as well as its attribution to a workshop or an author. Copper pigments represent a significant group of materials used in historic paintings. Because of their substantial diversity and, on the other hand, similarity, their identification and differentiation is a challenging task. An analytical procedure for unambiguous determination of both mineral-type (azurite, malachite, posnjakite, atacamite, etc.) and verdigris-type (copper acetates) copper pigments in the paint layers is presented, including light microscopy under VIS and UV light, electron microscopy with elemental microanalysis, Fourier transformed infrared micro-spectroscopy (micro-FTIR), and X-ray powder micro-diffraction (micro-XRD). Micro-Raman measurements were largely hindered by fluorescence. The choice of the analytical methods meets the contemporary requirement of a detailed description of various components in heterogeneous and minute samples of paint layers without their destruction. It is beneficial to use the combination of phase sensitive methods such as micro-FTIR and micro-XRD, because it allows the identification of both mineral-type and verdigris-type copper pigments in one paint layer. In addition, preliminary results concerning the study of the loss of crystallinity of verdigris-type pigments in proteinaceous binding media and the effect of lead white and lead tin yellow as highly absorbing matrix on verdigris identification in paint layers are reported.
A growing body of literature shows that psychological distress is not only a major threat to psychological well-being but can also have a significant impact on physical health. In cancer patients, it ...can negatively affect prognosis and posttreatment recovery processes. Since face-to-face psychological interventions are often inaccessible to cancer patients, researchers have recently been focusing on the effectiveness of eHealth adaptations of well-established approaches. In this context, there has been a call for high-quality randomised controlled trials that would allow for a direct comparison of different approaches, potentially addressing different needs and preferences of patients, and also for more systematic research focusing on how psychological interventions affect not only psychological but also biological markers of stress. Both of these questions are addressed in the present study.
A randomised controlled trial will be carried out to test and compare the effectiveness of three eight-week eHealth programmes for the mental health support of cancer patients. All programmes will be delivered through the same application for mobile devices MOU MindCare. N = 440 of breast cancer survivors will be recruited at the end of their adjuvant treatment (chemotherapy, radiotherapy, or both) and randomly assigned to one of the three interventions – Mindfulness-Based Cognitive Therapy for Cancer (MBCT-Ca), Positive Psychology (PP), or Autogenic Training (AT) – or the treatment-as-usual (TAU) control group. Psychological and biological markers of stress and adaptive functioning will be assessed at baseline (T0), post-treatment (T1), three-month follow-up (T2), and nine-month follow-up (T3). Primary outcomes will include heart-rate variability and self-report measures of depression, anxiety, perceived stress, general quality of life, and positive mental health. Secondary outcomes will include the levels of serum cortisol and immunomarkers, sleep quality, fatigue, common health symptoms, and several transdiagnostic psychological variables that are expected to be specifically affected by the MBCT-Ca and PP interventions, including dispositional mindfulness, emotion regulation, self-compassion, perceived hope, and gratitude. The data will be analysed using the mixed model repeated measures (MMRM) approach.
This trial is unique in comparing three different eHealth interventions for cancer patients based on three well-established approaches to mental health support delivered on the same platform. The study will allow us to examine whether different types of interventions affect different indicators of mental health. In addition, it will provide valuable data regarding the effects of stress-reducing psychological interventions on the biomarkers of stress playing an essential role in cancer recovery processes and general health.
•A randomised controlled study is conducted to test a new eHealth application for cancer patients•The study compares three well-established stress-reduction interventions•Intervention effects on both psychological and biological markers of stress are tested
Twenty one mock-up samples containing inorganic pigments primarily used at the turn of the 19th and 20th century were selected for comparative study and measured by micro-Raman and portable Raman ...spectrometers. They included pure grounds (chalk-based, earth-based and lithopone-based), grounds covered by resin-based varnish, and different paint layers containing mixtures of white, yellow, orange, red, green, blue and black pigments, usually in combination with white pigments (titanium, zinc and barium whites or chalk). In addition, ten micro-samples obtained from seven paintings of two world-famous modern painters Edvard Munch and František Kupka have been investigated. Infrared reflection spectroscopy (FTIR), portable X-ray fluorescence (XRF) and scanning electron microscopy with energy dispersive spectroscopy (SEM–EDS) were used as supplementary methods. The measurements showed that blue pigments (ultramarine, Prussian blue and azurite), vermilion and ivory black in mixture with whites provided characteristic Raman spectra, while Co-, Cd- and Cr- pigments' bands were suppressed by fluorescence. The best success rate of micro-Raman spectroscopy has been achieved using the 780nm excitation, however, the sensitivity of this excitation laser in a portable Raman instrument significantly decreased. The analyses of micro-samples of paintings by E. Munch and F. Kupka showed that micro-Raman spectroscopy identified pigments which would remain unidentified if analyzed only by SEM–EDS (zinc yellow, Prussian blue). On the other hand, chromium oxide green and ultramarine were not detected together in a sample due to overlap of their main bands. In those cases, it is always necessary to complement Raman analysis with other analytical methods.
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•Mock-up samples of modern inorganic pigments with organic binders were analyzed.•The efficiency of micro-Raman and portable Raman spectrometry was evaluated.•Different Raman excitation wavelengths were tested, 780nm found to be versatile.•Results compared with micro-analysis of paintings by E. Munch and F. Kupka.
Green clay and chrysoprase samples from the Ni-laterite deposit in Szklary, Poland, were studied by X-ray diffraction (XRD), electron microprobe analysis (EMPA), Raman, infrared and UV–VIS–NIR ...absorption spectroscopies. The clay samples proved to be Ni-rich “kerolite” and “pimelite”, and as these minerals are currently discredited, their nature was studied in more detail by high-temperature X-ray diffraction and thermal analysis coupled with mass spectrometry. These methods showed that “kerolite” and “pimelite” contain interlayer water, i.e. they differ from the non-hydrated talc–willemseite mineral series. Subsequently, the XRD and EMPA analyses of Szklary chrysoprase indicated that chrysoprase’s colouring agent is “pimelite”, which was further corroborated by Raman and UV–VIS–NIR spectroscopies. In addition, the Szklary chrysoprase, which has been quarried since the Middle Ages and used in jewellery and wall decorations (e.g. in the Prague Cathedral), was described from the gemmological point of view.
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•Temperature-related degradation of vivianite is presented.•Already temperatures around 70°C are harmful, 90°C start vivianite’s oxidation.•At 80°C, ground natural vivianite paint ...layer sample turns from blue to grey.•The colour change corresponds with the one described in works of art.•Conservation treatments using heat (like relining) should be performed with care.
Temperature-related degradation of pure synthetic as well as partly oxidised natural vivianite has been studied by high-temperature X-ray diffraction (HT-XRD) covering the whole extent of the temperature-related stability of its structure. While temperatures around 70°C are already damaging to vivianite, exposition to 160°C results in complete amorphisation of both the vivianite and its oxidation products. As indicated by Mössbauer spectroscopy, temperature-induced oxidation of vivianite starts at 90°C. To study the occurring structural as well as accompanying colour changes in more detail, model vivianite paint layer samples with different historic binders were prepared and subjected to increased temperatures. Exposition to 80°C caused pronounced colour changes of all the samples: ground natural blue vivianite became grey – a colour change which has been described in actual works of art. Regarding the binders, the oil seemed to facilitate the transfer of heat to vivianite’s grains. To simulate conditions of conservation treatment under which the painting is exposed to increased temperatures, oil-on-canvas mock-ups with vivianite were prepared and relined in a traditional way using iron. The treatment affected preferentially larger grains of vivianite; the micro-samples documented their change to grey, and their Raman spectra showed the change from vivianite to metavivianite.
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