Abstract
Glass has been used in widespread applications within several sectors since ancient times and it has been systematically studied under different perspectives. However, its thermodynamic ...properties and the variety of its compositions, several aspects related to its durability and its alteration mechanisms remain still open to debate. This literature review presents an overview of the most relevant studies on glass corrosion and the interaction between glass and the environment. The review aims to achieve two objectives. On one hand, it aims to highlight how far research on glass corrosion has come by studying model systems created in the laboratory to simulate different alteration conditions and glass compositions. On the other, it seeks to point out what are the critical aspects that still need to be investigated and how the study of ancient, altered glass can add to the results obtained in laboratory models. The review intends also to demonstrate how advanced analytical techniques commonly used to study modern and technical glass can be applied to investigate corrosion marks on ancient samples.
In this research, a comprehensive multi-technique analysis, including synchrotron-based X-ray micro-computed tomography, is used to visualize the microstructure of alteration in a very particular ...Roman glass fragment, in which millennia of corrosion history have not significantly impacted the integrity of the fragment itself. This exceptionally rare occurrence has allowed for the maximization of meaningful data acquisition, by examining the alteration structures from the macro to the nanoscale. This study elucidates the intricate mechanisms underlying glass corrosion when in contact with soil, providing quantitative data and phase correlations in the alteration structures. These findings validate and refine existing predictive corrosion models.
This research combines 3D and surface methods on corroded glass, shedding light on perfectly preserved alteration structures and corrosion processes across scales.
•Cultural heritage glass artefacts suffer from several degradation processes.•Different consolidation and coating treatments have been proposed against corrosion.•A literature overview is essential ...to critically assess the existing treatments.•This review provides a perspective for the development of new consolidation products.
Consolidation and coating treatments are two types of interventions that form part of the active conservation actions developed for historical and archaeological glass over the years. While thermoplastic and thermosetting resins are widely adopted by conservators worldwide, issues related to the toxicity and the material compatibility of these products remains unsolved. To address these issues, efforts have been made to develop new formulations that can functionally replace or exhibit performance advantages with respect to these canonical polymeric materials. In this review, we discuss the main classes of materials applied thus far for protection and consolidation aims in the cultural heritage glass field, starting from the beginning of the 19th century and continuing until present days. We also assess the potential of hybrid organic-inorganic materials and full inorganic materials as alternative solutions to the limitations of organic materials in application. Finally, we provide our perspectives on future directions for the development of consolidation products that meet the specific requirements of the cultural heritage field.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
•The combined use of SIMS and XPS enables to examine composition of glass surfaces.•XPS and SIMS analyses show composition gradient of fresh soda-lime glass surfaces.•Artificial ageing induces ...chemical and compositional modification of glass surfaces.•An articulated analysis approach is used to shed light on glass corrosion.
This study reports important analytical evidence of an unusual non-uniform element distribution in the superficial layers of glass matrices (from few nm up to 1 µm). The unforeseen observation was made on silica-soda-lime glass mock-ups before and after their artificial ageing, using secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS) surface analysis techniques. The analyses showed a marked non-homogeneous element distribution at the glass surface. The results indicated a very low concentration of Na at the surface up to a depth of around 500 nm below the surface, where its concentration increases reaching a plateau. In addition, the profile distribution of H in the first 200 nm of the pristine glass surface indicated a diffusion of hydrogen from the surrounding environment to the glass network. Additional modifications during the glass ageing process related to external factors (such as temperature and humidity) were also identified in relation to sodium atoms, with atoms on the glass surface showing a different chemical state from those in the bulk. This study confirms that glass composition as well as glass alteration are non-homogeneous locally supporting the importance of studying glass surface as region of interaction with surrounding environment.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
5.
Photonic crystals built by time in ancient Roman glass Guidetti, Giulia; Zanini, Roberta; Franceschin, Giulia ...
Proceedings of the National Academy of Sciences - PNAS,
09/2023, Volume:
120, Issue:
39
Journal Article
Peer reviewed
Open access
Ancient glass objects typically show distinctive effects of deterioration as a result of environmentally induced physicochemical transformations of their surface over time. Iridescence is one of the ...distinctive signatures of aging that is most commonly found on excavated glass. In this work, we present an ancient glass fragment that exhibits structural color through surface weathering resulting in iridescent patinas caused by silica reprecipitation in nanoscale lamellae. This archaeological artifact reveals an unusual hierarchically assembled photonic crystal with extremely ordered nanoscale domains, high spectral selectivity, and reflectivity (~90%), that collectively behaves like a gold mirror. Optical characterization paired with nanoscale elemental analysis further underscores the high quality of this structure providing a window into this sophisticated natural photonic crystal assembled by time.
Abstract
Magnetic materials are crucial for the efficiency of the conversion-storage-transport-reconversion energy chain, and the enhancement of their performance has an important impact on ...technological development. The present work explores the possibility of preparing hetero-nano-structured ceramics based on magnetic oxides, by coupling a ferrimagnetic phase (F) with an antiferromagnetic one (AF) on the nanometric scale. The field-assisted sintering technique or SPS (Spark-Plasma Sintering), adopted at this purpose, ensures the preservation of nano-sized crystals within the final solid structure. The aim is to establish how exchange bias may affect the resulting nano-consolidates and to investigate the potential of this process to increase the total magnetic anisotropy of the CoFe
2
O
4
grains, and thus their coercive field, while keeping the saturation magnetization the same. The structure, microstructure and magnetic properties of the ceramics obtained were studied by several techniques. The results show that the sintering process, along with its typical reductive atmosphere, modifies the composition of the constituents. A new metallic phase appears as a consequence of the reciprocal diffusion of Co and Ni cations, leading to a change in the amount and structure of the AF phase. We propose a schematic representation of the atomic movements that hinder an exchange bias effect between the F and AF phases.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
•μXCT accelerates the numismatic identification process, outperforming current protocols.•It is performed on coins prior physical cleaning, without sample preparation.•Enables virtual reconstruction, ...preventing risks linked to manual handling.•Digitisation allows for information preservation and guides further cleaning.
This study utilises X-ray Computed Micro-Tomography (μXCT) as a non-destructive and non-invasive method to recover the original surface features and reveal the characteristics of encrusted, illegible Roman copper-based coins before any physical cleaning process is performed. The coins were retrieved from the topsoil during an archaeological survey in the countryside of the ancient city of Aquileia, Italy, and were severely degraded, covered with accumulated matter and pronounced encrustations developed over centuries of aging buried in soil. Despite their condition, most of the coins were identified from a numismatic standpoint using tomographic data alone, with the aid of reference images. They were subsequently cleaned using traditional manual methods and the results compared with μXCT. X-ray Fluorescence (XRF) analysis of the coins after the physical cleaning confirmed their numismatic attribution and revealed information regarding the influence of different alloy compositions on the applicability of the μXCT method, as well as on the corrosion process of the coins.
This study showcases how the application of μXCT on fragile corroded metal artifacts prior to any intrusive manual procedures can expedite the identification process, mitigating the risk of information loss caused by physical handling and cleaning. This approach proves particularly valuable when dealing with large numbers of coins that would typically require restoration for identification purposes. It also emphasises the numerous advantages of using μXCT for coin identification, provenance determination, dating, virtual restoration, digitisation, and long-term preservation.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Abstract
Hetero-nanostructures based on magnetic contrast oxides have been prepared as highly dense nanoconsolidates. Cobalt ferrite-cobalt oxide core-shell type nanoparticles (NPs) were synthesized ...by seed mediated growth in polyol and subsequently consolidated by Spark Plasma Sintering (SPS) at 500 °C for a few minutes while applying a uniaxial pressure of 100 MPa. It is interesting to note that the exchange bias feature observed in the core-shell NPs is reproduced in their ceramic counterparts, or even attenuated. A systematic structural characterization was then carried out to elucidate the decrease in the exchange magnetic field, involving mainly advanced X-ray diffraction, zero-field and in-field
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Fe Mössbauer spectrometry, magnetic measurements and electron microscopy.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Récemment, les recherches scientifiques ont attiré son attention sur les domaines liés à l'énergie en raison de la consommation croissante d'énergie qui a affecté les dernières décennies. Les ...matériaux magnétiques sont déterminants dans les applications basées sur l'énergie et l'amélioration de leurs performances joue un rôle primordial dans le développement technologique. Le présent travail explore la possibilité de préparer des composites céramiques magnétiques hétéro-nano-structurés à base de constituants d'oxydes. Un oxyde ferromagnétique (F) a été couplé à un antiferromagnétique (AF) à l'échelle nanométrique pour étudier les propriétés magnétiques résultantes, en accordant une importance primordiale au couplage d'échange entre les deux phases. L’établissement de l’effet de biais d’échange à l’interface des phases F-AF est souhaitable pour augmenter l’anisotropie magnéto-cristalline du système et le produit énergétique relatif BHmax. Dans ce but, deux oxydes F différents ont été pris en compte, le Fe3O4 et le CoFe2O4, et trois oxydes différents de la AF, CoO, NiO et l'hématite α-Fe2O3. Des nanoparticules d'oxyde de chaque composant ont été préparées par synthèse de polyol, avec une bonne qualité cristalline et une morphologie uniforme. Ils ont ensuite été utilisés pour préparer des échantillons de céramique de consolidation par la technique SPS. Pour chaque échantillon, un oxyde F a été mélangé à l'un des oxydes AF. Les céramiques résultantes ont été formées selon différents rapports de masse F / AF, variant entre 0,75 / 0,25, 0,5 / 0,5 et 0,25 / 0,75, et selon différentes combinaisons entre les oxydes F et AF considérés. Tous les échantillons ont été frittés à 500 ° C et 100 MPa pendant 5 minutes. Toutes les céramiques ont été étudiées en profondeur, notamment en ce qui concerne leur structure, leur microstructure et leurs propriétés magnétiques. L’analyse HR-TEM réalisée sur des lames raffinées de céramiques Fe3O4-CoO, Fe3O4-NiO et CoFe2O4-NiO, ainsi que des résultats de diffraction XR, a mis en évidence une importante variation de la composition des échantillons après frittage. Une nouvelle phase métallique est formée après frittage dans l'atmosphère fortement réductrice au cours du processus SPS, modifiant ainsi la composition relative des phases F et AF individuelles. L’établissement d’effets de biais d’échange n’a guère été observé à cause de la diffusion des atomes qui affecte l’échantillon. En effet, les nanoparticules AF d'hématite se sont révélées instables dans une large plage de températures et donc inappropriées pour ce type d'application. En particulier, une transformation de phase se produisant à environ 380 ° C a été observée lorsqu'un champ magnétique externe est appliqué. Une telle transition a été étudiée au moyen d’une caractérisation par magnétomètre, d’une analyse HR-TEM et d’une analyse EELS et a révélé qu’elle impliquait la transformation de l’hématite en magnétite. Le mécanisme de cette transformation n’a pas encore été compris et fait l’objet d’une enquête plus approfondie.
Recently the scientific research led its attention towards energy related fields because of the increasing energy consumption that affected the last few decades. Magnetic materials are determining in energy-based applications and the enhancement of their performances has a primary role on the technological development. The present work explores the possibility to prepare hetero-nano-structured magnetic ceramic composites based on oxide constituents. A ferromagnetic oxide (F) was coupled with an antiferromagnetic one (AF) at a nanometric size scale to study the resulting magnetic properties, above all concerting the exchange coupling between the two different phases. The establishing of the exchange-bias effect at the F-AF phases interface is desirable in order to increase the magneto-crystalline anisotropy of the system and the relative energy product BHmax. At this aim, two different F oxides were took into account, the Fe3O4 and the CoFe2O4, and three different AF oxides, CoO, NiO and hematite α-Fe2O3. Oxide nanoparticles of each component were prepared by polyol synthesis, with a good crystalline quality and uniform morphology. They were then employed to prepare consolidate ceramic samples by SPS technique. For each sample, one F oxide was mixed with one of the AF oxides. The resulting ceramics were formed by different F/AF mass ratio, varying between 0,75/0,25, 0,5/0,5 and 0,25/0,75, and by different combinations between the considered F and AF oxides. All the samples were sintered at 500°C and 100 MPa for 5 minutes. All the ceramics were deeply studied, above all concerning their structure, microstructure and magnetic properties. HR-TEM analysis performed on FIB-refined slides of the Fe3O4-CoO, Fe3O4-NiO and CoFe2O4-NiO ceramic samples, together with XRD results, highlighted an important variation of samples’ composition after sintering. A new metallic phase is formed after sintering cause to the strongly reductive atmosphere during the SPS process, thus modifying the relative composition of the single F and AF phases too. The establishing of exchange-bias effects was hardly observed exactly because of the atoms diffusion that affects the sample. The hematite AF nanoparticles, indeed, were found to be unstable in a wide temperature range and thus unsuitable for this kind of application. In particular, a phase transformation occurring at about 380°C was observed when an external magnetic field is applied. Such a transition was studied by mean of magnetometer characterisation, HR-TEM and EELS analysis and was found to involve hematite transforming into magnetite. The mechanism of such transformation hasn’t been understood yet and is under further investigation
Conventional methods for sintering magnetic biased granular solids are generally known to induce severe grain growth and coarsening, thus making any evidence of exchange bias (EB) hard to detect in ...the resulting consolidates. This work explores the possibility of preparing a hetero-nanoconsolidate starting from an exchange-biased nanopowder and using Spark Plasma Sintering (SPS), in order to overcome that microstructural limitation. It also investigates the capability of the resulting solid to establish EB. The nanopowder consists of an intimate nanocrystalline mixture of the antiferromagnetic NiO and ferrimagnetic CoFe
2
O
4
phases. It exhibits a significant broadening of the hysteresis loop at room temperature when measured under field cooling (FC) conditions. X-ray diffraction coupled to high resolution transmission electron microscopy and
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Fe Mössbauer spectrometry shows that sintering induces a drastic atomic diffusion leading to the replacement of the starting NiO and CoFe
2
O
4
phases by their Ni
1−
x
Co
x
O and Co
1−
x
Ni
x
Fe
2
O
4
solid solutions (
x
value close to 0.25). As a result, exchange-bias is hindered at 300 K but always expressed at lower temperatures, far below the Néel temperature of the new antiferromagnet. The maximum EB value for the ceramics is measured at 5 K and is calculated about 48 mT under a cooling magnetic field of 7 T. This value decreases when the temperature increases, but it remains different from zero up to 200 K.
The evolution of the exchange bias at room temperature is studied between a nanopowder and its ceramic counterpart.
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